USOO7635662B2

(12) United States Patent (10) Patent No.: US 7,635,662 B2 Kabashima et al. (45) Date of Patent: Dec. 22, 2009

(54) COMPOUND FOR COLOR-PRODUCING Sep. 4, 2000 (JP) ...... 2OOO-267467 COMPOSITION, AND RECORDING MATERAL (51) Int. Cl. 75 B4LM 5/20 (2006.01) (75) Inventors: Kazuo Kabashima, Yokohama (JP). C07D 257/00 (2006.01) Hiroshi Kobayashi, Yokohama (JP): C07F 9/28 (2006.01) Tetsurou Iwaya, Kawasaki (JP) C07D 209/10 (2006.01) (73) Assignee: Chemipro Kasei Kaisha, Ltd., Kobe-shi C07D 209/6 (2006.01) (JP) C07D 209/18 (2006.01) (*) Notice: Subject to any disclaimer, the term of this 52 Sion "E, 2: 548/506: 548/507: patent is extended or adjusted under 35 (52) U.S. Cl...... s s s U.S.C. 154(b) by 1737 days 548/495; 548/253: 548/118; 560/157; 560/158: M YW- 560/163; 560/165 (21) Appl. No.: 09/796,471 (58) Field of Classification Search ...... 548/506, 548/507,495,253,118; 560/157, 158, 163, (22) Filed: Mar. 2, 2001 560/165; 503/208,214, 222; 524/591 See application file for complete search history. (65)65 PriorO PublicationDO Dat (56) References Cited US 2001 FOO44553 A1 Nov. 22, 2001 U.S. PATENT DOCUMENTS Related U.S. Application Data 3,539,375 A 11/1970 Baum (63) Continuation-in-part of application No. PCT/JP99/ (Continued) 04776, filed on Sep. 3, 1999. FOREIGN PATENT DOCUMENTS (30) Foreign Application Priority Data EP O138769 A2 4, 1985 Sep. 4, 1998 (JP) ...... 10-250671 (Continued) Apr. 27, 1999 (JP) ...... 11-12O683 Mar. 2, 2000 (JP) ...... 2000-057538 Primary Examiner Taylor Victor Oh Mar. 2, 2000 (JP) ------2OOO-O57693 (74) Attorney, Agent, or Firm—Birch, Stewart, Kolasch & Mar. 3, 2000 (JP) ...... 2000-058249 Birch, LLP Mar. 3, 2000 (JP) ...... 2OOO-O58279 (57) ABSTRACT Mar. 3, 2000 (JP) - - - - - 2OOO-O58468 Mar. 3, 2000 (JP) - - - - - 2OOO-O58594 Aurea-urethane compound having one or more urea groups Mar. 3, 2000 (JP) - - - - - 2000-058770 and one or more urethane groups in the molecular structure, Mar. 3, 2000 (JP) - - - - - 2OOO-O58823 the number of said urea groups (A) and the number of said Mar. 3, 2000 (JP) - - - - - 2OOO-O58861 urethane groups (B) satisfying the following numerical for Mar. 3, 2000 (JP) ...... 2OOO-O58891 mula: Mar. 3, 2000 (JP) ...... 2OOO-O59047 Mar. 3, 2000 (JP) ...... 2OOO-O59216 102 (A+B)23 Mar. 3, 2000 (JP) ...... 2OOO-O59298 wherein each of A and B is an integer of 1 or more. May 31, 2000 (JP) ...... 2000-162679 Sep. 4, 2000 (JP) ...... 2OOO-2673O2 22 Claims, 2 Drawing Sheets

100

5O W.

4000 2000 1500 1000 WAVENUMBER(cm) US 7,635,662 B2 Page 2

U.S. PATENT DOCUMENTS JP 45-2594 1, 1970 JP 59-30919 2, 1984 4.203,883 A * 5/1980 Hangauer, Jr...... 524,591 JP 59-115887 T 1984 4,314,924. A * 2/1982 Haubennestel et al...... 524/779 JP 59-174838 A 10, 1984 4,384,102 A 5, 1983 Rasshofer et al. JP 60-104055 6, 1985 4,388,238 A 6/1983 Heitkamper et al. JP 61-35444 A 2, 1986 4,520,377 A * 5/1985 Iwakura et al...... 503/208 JP 2-141288 5, 1990 4,521,793 A 6, 1985 Kabashima et al. JP 4-69278 3, 1992 4.550,329 A * 10/1985 Gonda et al...... 503/214 JP 05-068873 3, 1993 5,055,567 A 10, 1991 Liechti et al. JP 05-116459 5, 1993 5,441,743 A 8, 1995 McGinniss et al. JP 08-002111 1, 1996 5,780.483. A 7, 1998 Widdowson et al. JP 08-002112 1, 1996 5,854,183 A 12/1998 Hasegawa et al. JP 8-3 11357. A 11, 1996 JP 1O-310633. A 11, 1998 FOREIGN PATENT DOCUMENTS WO WO90,06975 A1 6, 1990 EP O160402 11, 1985 WO 92/2O747 11, 1992 EP O 535,887 A1 4f1993 WO 98,035.18 1, 1998 EP O 633. 145 A1 1, 1995 WO WO99,51692 A1 10, 1999 EP O 709 225 A1 5, 1996 WO WOOO 14058 A1 3, 2000 EP O769391 * 4f1997 EP O 832 757 A1 4f1998 * cited by examiner U.S. Patent Dec. 22, 2009 Sheet 1 of 2 US 7,635,662 B2

O O O t LO

O O O s O L6) (1%)3ONWLLIWSNWhil U.S. Patent Dec. 22, 2009 Sheet 2 of 2 US 7,635,662 B2

3 8

s s

(1%) ONWLLIWSNW US 7,635,662 B2 1. 2 COMPOUND FOR COLOR-PRODUCING ment sensitivity. The heat-sensitive recording method is COMPOSITION, AND RECORDING advantageous, for example, in that an apparatus used in the MATERAL method is Small, requires no maintenance and produces no noise. Therefore, the range of use of the heat-sensitive record CROSS-REFERENCE TO RELATED 5 ing method have been increased in various fields of, for APPLICATION instance, recorders for measurement, facsimiles, printers, ter minals of computer, labels, and automatic vending machines This application is a continuation-in-part of PCT/JP99/ for railroad tickets or the like. 04776 filed Sep. 3, 1999, the content of which is herein In the heat-sensitive recording method, a recording mate incorporated by reference. 10 rial obtained by forming on a Substrate a color-producing layer containing a two-component color-producing composi BACKGROUND OF THE INVENTION tion is mainly used, and the components of the heat-sensitive 1. Field of the Invention composition are brought into contact with each other by treat The present invention relates to a novel urea-urethane com- 15 ing the recording material with heat Supplied as recording pound. The present invention relates also to a novel color energy from a thermal head, a hot stamp, laser beams or the producing composition obtained by using the urea-urethane like. Many of compositions used as the color-producing com compound, and a recording material obtained by using the position are those obtained by using a colorless or light color-producing composition. colored, electron-donating dye precursor (in particular, a The color-producing composition of the present invention 20 leuco dye) and an acidic developer Such as a phenolic com is useful as a color-producing composition for recording pound. An example of recording material obtained by using a materials used by means of recording energy Such as heat, leuco dye is thermal paper obtained by using a combination of pressure or the like, and the present invention relates to, in Crystal Violet lactone and 4,4'-isopropylidenediphenol particular, a color-producing composition capable of giving (bisphenol A) as a heat-sensitive color-producing composi an improved storage stability to an uncolored portion (an 25 tion (see U.S. Pat. No. 3,539,375, etc.). original recording material Surface) and a developed color As the dye precursor and developer used in each of the image, and a recording material, in particular, a heat-sensitive recording methods described above, an electron-donating recording material, which is obtained by using the color compound and an electron-accepting compound, respec producing composition. tively, are mainly used. This is because the electron-donating 2. Description of the Related Art 30 compound and the electron-accepting compound have, for Various chemical color-producing systems used by means example, the following excellent characteristics: the dye pre of recording energy such as heat, pressure or the like have cursor as electron-donating compound and the developer as been known. Of these systems, color-producing systems usu electron-accepting compound come into contact with each ally composed of a two-component color-producing system other to give a developed color image with a high density in a consisting of a colorless or light-colored dye precursor and a 35 moment; and a nearly white appearance can be obtained and developer capable of causing color development on contact various hues such as red, orange, yellow, green, blue, black, with the dye precursor have been known since early times and etc. can be obtained. However, the developed color image are commonly utilized in recording materials. There are, for obtained is so poor in chemical resistance that the record example, pressure-sensitive recording materials used by disappears easily on contact with a plasticizer contained in a means of pressure energy, heat-sensitive recording materials 40 plastic sheet or an eraser, or a chemical contained in food or used by means of heat energy, and light-sensitive recording cosmetics, and the developed color image is so poor in record materials used by means of light energy. storage stability that the record fades or, what is worse, dis Pressure-sensitive recording materials used by means of appears when exposed to Sunlight for a relatively short period pressure energy have been very generally used as if they were of time. Therefore, color-producing compositions compris plane paper. In general, the pressure-sensitive recording 45 ing the dye precursor and the developer are limited in their use material is obtained by dissolving a dye precursorina Suitable to a considerable extent, and their improvement is eagerly Solvent, emulsifying the resulting solution to several microns, desired. and making the emulsion into microcapsules. Upper paper In recent years, phenolic compounds represented by obtained by coating a Substrate with the microcapsules and bisphenol A are considered unsuitable for use because they under paper obtained by coating another Substrate with a 50 are likely to be endocrine disrupters, and hence a non-phe developer layer containing a developer are placed one upon nolic developer is requested. the other so that the microcapsule-coated Surface and the For fulfilling such a request, for example, JP-A-59-115, developer-coated surface may face each other. When a pres 887 and U.S. Pat. No. 4,521,793 disclose recording materials Sure is applied to the resulting assembly by writing, striking comprising a combination of color-producing compositions or the like, the microcapsules are destroyed to release the 55 comprising an aromatic isocyanate and an imino compound, contents including the dye precursor. The dye precursor trans as recording materials having a high shelf stability. These fers to the developer layer to come into contact with the references disclose various recording materials in which the developer, so that color development reaction occurs, result two color-producing compositions are brought into contact ing in recording of an image. with each other to be reacted, by application of recording In recent years, aheat-sensitive recording method compris- 60 energy Such as heat, pressured, light or the like. The refer ing recording by means of heatenergy has been often adopted ences describe the fact that various colors such as red, orange, in various information machines such as facsimiles, printers, yellow, light brown, dark brown, etc. can be developed by recorders and the like. A heat-sensitive recording material properly selecting the color-producing compositions. How used in the heat-sensitive recording method has many excel ever, in the inventions disclosed in the references, the devel lent characteristics Such as a high whiteness, appearance and 65 opment of a black color is not yet sufficient which is eagerly feel which are similar to those of plane paper, and excellent desired in the case of recording materials commonly used at aptitudes for recording, for example, a high color develop present. US 7,635,662 B2 3 JP-A-8-2,111 and JP-A-8-2,112 disclose heat-sensitive recording materials having a color-producing layer contain ing a colorless or light-colored dye precursor and a urea (I) compound, as heat-sensitive recording materials obtained by using a non-phenolic developer. These recording materials, however, give a low coloring density and have an insufficient shelf stability. JP-A-5-116,459 discloses aheat-sensitive recording mate rial having a heat-sensitive color-producing layer containing wherein X and Z are independently an aromatic compound a colorless or light-colored dye precursor and a Sulfonylurea 10 residue, a heterocyclic compound residue or an aliphatic compound. This recording material, however, gives a low compound residue, each of the residues being able to have one whiteness and has an insufficient shelf stability. or more Substituents, and Yo is a group selected from the group consisting of tolylene group, Xylylene group, naphth ylene group, hexamethylene group and -(p-CH(p- group SUMMARY OF THE INVENTION 15 wherein -qp- is a phenylene group;

The present invention is intended to provide a novel urea (II) urethane compound or urea-urethane composition that exhib its excellent performance characteristics when used as devel oper in a color-producing composition. The present invention is also intended to provide a novel color-producing composition excellent in image preservabil ity and coloring density, and a recording material, in particu 25 wherein X and Y are independently an aromatic compound lar, a heat-sensitive recording material, which is obtained by residue, a heterocyclic compound residue or an aliphatic the use of the color-producing composition, by using any of compound residue, each of the residues being able to have one various urea-urethane compounds or urea-urethane composi or more Substituents; tions. In addition, the present invention relates to a novel color 30 producing composition possessing further improved perfor (III) mance characteristics by virtue of the addition of various additives to a urea-urethane compound or a urea-urethane X-O-C-N-Y-N-C- composition and a dye precursor, and a recording material H obtained by using said color-producing composition. 35 The present inventors earnestly investigated the synthesis of various compounds for color-producing composition and wherein X and Y are independently an aromatic compound consequently found that specific compounds exhibit Surpris residue, a heterocyclic compound residue or an aliphatic ingly excellent performance characteristics, whereby the compound residue, C. is a residue having a Valence of 2 or present invention has been accomplished. Furthermore, the 40 more, and n is an integer of 2 or more, each of the residues present inventors found that specific compounds exhibit Sur being able to have one or more substituents; prisingly excellent performance characteristics in combina tion with a dye precursor, whereby the present invention has been accomplished. (IV) That is, the present invention is as follows. 45 A first aspect of the invention is directed to a urea-urethane compound having one or more urea groups and one or more urethane groups in the molecular structure, the number of said urea groups (A) and the number of said urethane groups (B) 50 wherein Z and Y are independently an aromatic compound satisfying the following numerical formula: residue, a heterocyclic compound residue or an aliphatic compound residue, B is a residue having a valence of 2 or more, and n is an integer of 2 or more, each of the residues wherein each of A and B is an integer of 1 or more. being able to have one or more substituents;

(V) O N NHO-C-N-H 1s H -II-?h--- 8-N-H (n--- --N--O- 2 "Ne 2 N-4 " 2 H 21

A second aspect of the invention is directed to a urea- 65 wherein at least one hydrogenatom of each benzene ring may urethane compound represented by any of the following for be replaced by a substituent group, which is preferably an mulas (I) to (VI): aromatic compound residue, an aliphatic compound residue US 7,635,662 B2 5 or a heterocyclic compound residue or which may be a nitro group, a hydroxyl group, a carboxyl group, a nitroso group, a nitrile group, a carbamoyl group, a ureido group, an isocyan (c) ate group, a mercapto group, a Sulfo group, a Sulfamoyl group or a halogenatom, each of the residues may have one or more 5 Substituents, Y is a group selected from the group consisting of SO , O—, (S), , (CH), , CO , —CONH- and any of groups represented by the formulas (a): wherein R is an aliphatic compound residue, A and A are 10 independently an aromatic compound residue, the nitrogen atoms of the urea group are directly bonded to the carbon (a) atoms, respectively, of the aromatic rings of A and A, and R. A and A may have one or more substituents. A fourth aspect of the invention is directed to a urea urethane compound characterized by being represented by the following formula (d): t -o-O--O-o- (d) CH3 N CH3 CH3 N 21 --O)-- 25 CH3 wherein R is an aliphatic compound residue, at least one hydrogen atom of each benzene ring may be replaced by an aromatic compound residue, an aliphatic compound residue, 30 a heterocyclic compound residue, a hydroxyl group, a nitro group, a nitrile group, a carbamoyl group, a Sulfamoyl group. a carboxyl group, a nitroso group, an amino group, an oxyamino group, a nitroamino group, a hydrazino group, a ureido group, an isocyanate group, a mercapto group, a Sulfo group or a halogen atom, and R may have one or more Sub stituents.

(VI) 1s N N 2. -N-C-' NH 2 wherein at least one hydrogenatom of each benzene ring may A fifth aspect of the invention is directed to a urea-urethane be replaced by a substituent group, which is preferably an compound characterized in that it is represented by the fol aromatic compound residue, an aliphatic compound residue lowing formula (e) or (f), has at least one urethane group and or a heterocyclic compound residue or which may be a at least one urea group in a total number of not more than 10 hydroxyl group, a nitro group, a nitrile group, a carbamoyl and not less than 3, and has a molecular weight of 5,000 or group, a Sulfamoyl group, a carboxyl group, a nitroso group. less: an amino group, an oxyamino group, a nitroamino group, a hydrazino group, a ureido group, an isocyanate group, a mer capto group, a Sulfo group or a halogen atom, each of the 55 (e) residues may have one or more Substituents, Ö is a group selected from the group consisting of —SO —O—, (S), , —(CH), , —CO , —CONH-, -NH-, —CH(COOR)— —C(CF). and CRR - or is 60 absent, each of R. R. and R is an alkyl group, and n is 1 or 2. wherein R is an aliphatic compound residue. Y is an aromatic A third aspect of the invention is directed to aurea-urethane compound residue, a heterocyclic compound residue or an compound characterized in that it is represented by the fol 65 aliphatic compound residue, C. is an aromatic compound lowing formula (c) and has a molecular weight of 5,000 or residue, heterocyclic compound residue or aliphatic com less: pound residue which is different from Y and has a valence of US 7,635,662 B2 7 8 2 or more, n is an integer of 2 or more, and each of the residues may have one or more Substituents; or (a)

(f)

H 10 t

CH3 wherein Z and Y are independently an aromatic compound CH3 CH3 residue or a heterocyclic compound residue, B is an aliphatic 15 76. compound residue having a valence of 2 or more, n is an integer of 2 or more, and each of the residues may have one or –CH CH - U - more Substituents. A sixth aspect of the invention is directed to a urea-ure thane compound characterized by being represented by the following formula (g) or (h):

25 (g) or is absent, each of R, R2 and R is an alkyl group, and n is 1 or 2. Nii 30 Another aspect of the invention is directed to a urea-ure thane composition comprising a urea-urethane compound having at least one urea group and at least one urethane group in a total number of 2 to 10 in the molecular structure and having a molecular weight of 5,000 or less and 0.0001 to 50 wherein at least one hydrogenatom of each benzene ring may 35 wt % of a diluent based on the total of the urea-urethane be replaced by an aromatic compound residue, an aliphatic compound and the diluent. compound residue, a heterocyclic compound residue, a Yet another aspect of the invention is directed to a urea hydroxyl group, a nitro group, a nitrile group, a carbamoyl urethane composition according to the above another aspect group, a Sulfamoyl group, a carboxyl group, a nitroso group. 40 of the invention, wherein the diluent is a urea compound an amino group, an oxyamino group, a nitroamino group, a and/or a urethane compound. hydrazino group, a ureido group, an isocyanate group, a mer Still yet another aspect of the invention is directed to a capto group, a Sulfo group or a halogenatom, B is analiphatic urea-urethane composition according to the above another compound residue having a valence of 2 or more, n is an aspect of the invention, wherein the diluent is a compound integer of 2 or more, and each of the residues may have one or obtained by reacting a polyisocyanate compound with a more Substituents; or hydroxy compound or an amino compound.

(h) O O O - 1s - 1s N H N-4 H wherein RS are independently analiphatic compound residue, A seventh aspect of the invention is directed to a urea at least one hydrogen atom of each benzene ring may be 6 urethane composition obtained by reacting a polyisocyanate replaced by an aromatic compound residue, an aliphatic com compound with a hydroxy compound and an amino com pound residue or a heterocyclic compound residue, each of pound, which is characterized by comprising 50 wt % or more the residues may have one or more substituents, Y is a group selected from the group consisting of —SO —O—, of a urea-urethane compound having at least one urea group (S), , —(CH) , —CO , —CONH , NH 65 and at least one urethane group in a total number of 2 to 10 in —CH(COOR)— —C(CF)— —CRR- and any of the molecular structure and having a molecular weight of groups represented by the formulas (a): 5,000 or less. US 7,635,662 B2 10 An eighth aspect of the invention is directed to a urea out the reaction for forming one or more urethane groups and urethane composition according to the seventh aspect of the the reaction for forming one or more urea groups, by the use invention, wherein the hydroxy compound is a phenol com of the same solvent. pound. An eighteenth aspect of the invention is directed to a pro A ninth aspect of the invention is directed to a urea-ure cess for producing a urea-urethane composition according to thane composition according to the seventh aspect of the any one of the twelfth to seventeenth aspects of the invention, invention, wherein the hydroxy compound is an alcohol com wherein the reaction for forming one or more urethane groups pound. and/or the reaction for forming one or more urea groups are A tenth aspect of the invention is directed to a urea-ure carried out at a temperature of 0-300° C. thane composition according to any one of the seventh to 10 ninth aspects of the invention, wherein the amino compound A nineteenth aspect of the invention is directed to a process is an aromatic amino compound. for producing a urea-urethane composition according to any An eleventh aspect of the invention is directed to a urea one of the twelfth to eighteenth aspects of the invention, urethane-composition according to any one of the seventh to wherein the reaction for forming one or more urethane groups tenth aspects of the invention, wherein the polyisocyanate 15 and/or the reaction for forming one or more urea groups are compound is an aromatic polyisocyanate compound. carried out in the presence of a catalyst. Atwelfth aspect of the invention is directed to a process for A twentieth aspect of the invention is directed to a color producing a urea-urethane composition which is character producing composition comprising a developer comprising a ized by reacting a polyisocyanate compound with a hydroxy urea-urethane compound, and a colorless or light-colored dye compound so that the ratio of the number of moles of the precursor. polyisocyanate compound to the number of hydroxyl equiva A twenty-first aspect of the invention is directed to a color lents of the hydroxy compound may be 100/1 to 1/2, to form producing composition according to the twentieth aspect of one or more urethane groups from Some of the isocyanate the invention, wherein said developer is aurea-urethane com groups of the polyisocyanate compound, and then adding an pound according to the first aspect of the invention. amino compound thereto to react the same with the remaining 25 isocyanate groups of the polyisocyanate compound to form A twenty-second aspect of the invention is directed to a one or more urea groups. color-producing composition according to the twentieth A thirteenth aspect of the invention is directed to a process aspect of the invention, wherein said developer is a urea for producing a urea-urethane composition which is charac urethane compound according to the second aspect of the terized by reacting a polyisocyanate compound with an 30 invention or a urea-urethane compound represented by the amino compound so that the ratio of the number of moles of following formula (VII): the polyisocyanate compound to the number of amino equiva lents of the amino compound may be 100/1 to 1/2, to form one or more urea groups from Some of the isocyanate groups of (VII) the polyisocyanate compound, and then adding a hydroxy 35 compound thereto to react the same with the remaining iso cyanate groups of the polyisocyanate compound to form one or more urethane groups. A fourteenth aspect of the invention is directed to a process wherein X,Y and Zare independently an aromatic compound for producing a urea-urethane composition according to the 40 residue, a heterocyclic compound residue or an aliphatic compound residue, each of the residues being able to have one twelfth or thirteenth aspect of the invention, which is charac or more substituents, and each of X,Y and Z being preferably terized by Successively carrying out the reaction for forming an aromatic compound residue or a heterocyclic compound one or more urethane groups and the reaction for forming one residue. or more urea groups. 45 A fifteenth aspect of the invention is directed to a process A twenty-third aspect of the invention is directed to a for producing a urea-urethane composition which comprises color-producing composition according to the twentieth reacting an amino compound with a polyisocyanate adduct aspect of the invention, wherein said developer is a urea obtained by the reaction of a polyisocyanate compound with urethane compound according to any one of the third to sixth aspects of the invention or a urea-urethane composition a hydroxy compound, so that the equivalent ratio of isocyan 50 ate group to amino group may be 2/1 to 1/100, to form one or according to any one of the seventh to eleventh aspects of the more urea groups, and then removing the unreacted amino invention. compound. A twenty-fourth aspect of the invention is directed to a A sixteenth aspect of the invention is directed to a process color-producing composition according to any one of the for producing a urea-urethane composition which comprises 55 twentieth to twenty-third aspects of the invention, wherein the reacting a hydroxy compound with a polyisocyanate adduct colorless or light-colored dye precursor is a leuco dye. obtained by the reaction of a polyisocyanate compound with A twenty-fifth aspect of the invention is directed to a color an amino compound, so that the equivalent ratio of isocyanate producing composition according to the twenty-fourth aspect group to hydroxyl group may be 2/1 to 1/100, to form one or of the invention, which is characterized in that the leuco dye more urethane groups, and then removing the unreacted 60 is at least one leuco dye selected from triarylmethane type hydroxy compound. leuco dyes, fluoran type leuco dyes, fluorene type leuco dyes A seventeenth aspect of the invention is directed to a pro and diphenylmethane type leuco dyes. cess for producing a urea-urethane composition according to A twenty-sixth aspect of the invention is directed to a any one of the twelfth to sixteenth aspects of the invention, color-producing composition according to the twenty-fourth which is characterized by carrying out the reaction for form 65 aspect of the invention, which is characterized in that the ing one or more urethane groups and/or the reaction for form leuco dye is a compound represented by the following for ing one or more urea groups, without a solvent, or carrying mula (i): US 7,635,662 B2 11 12 A twenty-eighth aspect of the invention is directed to a (i) color-producing composition according to any one of the twentieth to twenty-seventh aspects of the invention, which is characterized in that the melting point of the urea-urethane compound developer is not higher than 500° C. and not lower than 40° C. A twenty-ninth aspect of the invention is directed to a color-producing composition according to any one of the twentieth to twenty-eighth aspects of the invention, which 10 further comprises a heat-meltable material. A thirtieth aspect of the invention is directed to a color producing composition according to the twenty-ninth aspect of the invention, which is characterized in that the heat meltable material is at least one material selected from wherein both Y and Y are alkyl groups or alkoxyalkyl 15 B-naphthylbenzyl ether, p-benzylbiphenyl, 1,2-di(m-meth groups, Y is a hydrogen atom, an alkyl group or an alkoxy ylphenoxy)ethane, di-p-methylbenzyl oxalate, 1,2-diphe group, and each of Ys and Y is a hydrogen atom, a halogen noxymethylbenzene, m-terphenyl and Stearamide. atom, an alkyl group or an alkoxy group. A thirty-first aspect of the invention is directed to a color A twenty-seventh aspect of the invention is directed to a producing composition according to the twenty-ninth aspect color-producing composition according to the twenty-fourth of the invention, wherein the heat-meltable material is that aspect of the invention, which is characterized in that the represented by the following structural formula (XVIII): leuco dye is a compound represented by the following for mula (): (XVIII) () 25 (O)--(O)

30 wherein Y is any of —SO. , —(S), , —O , —CO—, —CH2—, —CH(CHs)—, C(CH) , COCO , - CO. , COCHCO-, -COOCH , – CONH-, —OCH-and-NH-, n is 1 or 2, and at least one hydrogen atom of each benzene ring may be replaced by a halogen 35 atom, a hydroxyl group, a nitro group, a nitroso group, a wherein each of Rs and R is a group represented by the nitrile group, an isocyanate group, an isothiocyanate group, a formula (k) or the formula (1): mercapto group, a Sulfamoyl group, a Sulfonic acid group, an amino group, an aromatic compound residue, an aliphatic (k) compound residue or a heterocyclic compound residue. 40 A thirty-second aspect of the invention is directed to a color-producing composition according to the thirty-first aspect of the invention, wherein the heat-meltable material is that represented by the following structural formula (XIX):

45 (XIX) (wherein each of R through Rs is a hydrogen atom, a halogen atom, an alkyl group of 1 to 8 carbon atoms, an alkoxy group of 1 to 8 carbon atoms, or —NRR, wherein 50 each of R and R, is an alkyl group of 1 to 8 carbonatoms), O wherein at least one hydrogenatom of each benzene ring may (l) be replaced by a halogen atom, a hydroxyl group, a nitro 55 group, a nitroso group, a nitrile group, an isocyanate group, an isothiocyanate group, a mercapto group, a Sulfamoyl group, a Sulfonic acid group, an amino group, an aromatic compound residue, an aliphatic compound residue or a heterocyclic compound residue. 60 A thirty-third aspect of the invention is directed to a color producing composition according to any one of the twentieth (wherein each of Rs and Rio is a hydrogen atom, an alkyl to thirtieth aspects of the invention, which further comprises group of 1 to 8 carbonatoms, or a phenyl group), and each of an isocyanate compound. R, through Ro is a hydrogen atom, a halogen atom, an alkyl A thirty-fourth aspect of the invention is directed to a group of 1 to 8 carbonatoms, analkoxy group of 1 to 8 carbon 65 color-producing composition according to any one of the atoms, or—NRoR wherein each of Ro and R is an alkyl twentieth to thirtieth aspects of the invention, which further group of 1 to 8 carbon atoms. comprises an isocyanate compound and an imino compound. US 7,635,662 B2 13 14 A thirty-fifth aspect of the invention is directed to a color is formed on the substrate on the side reverse to the side producing composition according to any one of the twentieth having the color-producing layer formed thereon. to thirty-second aspects of the invention, which further com A forty-ninth aspect of the invention is directed to a record prises an amino compound. ing material according to the forty-eighth aspect of the inven A thirty-sixth aspect of the invention is directed to a color tion, which is characterized in that the back coating layer producing composition according to any one of the twentieth comprises a water-soluble polymer. to thirty-fifth aspects of the invention, wherein the developer A fiftieth aspect of the invention is directed to a recording further comprises an acidic developer. material according to either of the forty-eighth and forty A thirty-seventh aspect of the invention is directed to a ninth aspects of the invention, which is characterized in that color-producing composition according to the thirty-sixth 10 the back coating layer comprises an inorganic pigment and/or aspect of the invention, which is characterized in that the an organic pigment. acidic developer is at least one developer selected from 2.2- A fifty-first aspect of the invention is directed to a recording bis(4-hydroxyphenyl)-propane, 4-isopropyloxyphenyl-4- material according to any one of the fortieth to fiftieth aspects hydroxyphenylsulfone, bis(3-ally-4-hydroxyphenyl)sulfone, of the invention, which is characterized by using at least one 2,4'-dihydroxy-diphenylsulfone and 4,4'-oxybis(ethyl 15 material selected from water-soluble polymers and anionic eneoxy-p-phenylenesulfonyl) diphenol. Surfactants, as a dispersing agent for the urea-urethane com A thirty-eighth aspect of the invention is directed to a pound. color-producing composition according to any one of the A fifty-second aspect of the invention is directed to a twentieth to thirty-seventh aspects of the invention, which recording material according to any one of the fortieth to further comprises a fluorescent dye. fiftieth aspects of the invention, which is characterized by A thirty-ninth aspect of the invention is directed to a color using at least one material selected from poly(vinyl alcohol)S. producing composition according to any one of the twentieth modified poly(vinyl alcohol)s, methyl cellulose, hydroxypro to thirty-eighth aspects of the invention, which further com pylmethyl cellulose, sodium condensed naphthalene prises a preservability-imparting agent. Sulfonate, polycarboxylic acid ammonium salts, water A fortieth aspect of the invention is directed to a recording 25 soluble low-molecular weight copolymers, and Sodium material comprising a Substrate and a color-producing layer 2-ethylhexyl-SulfoSuccinate, as a dispersing agent for the formed thereon, said color-producing layer comprising a urea-urethane compound. urea-urethane compound according to any one of the first and A fifty-third aspect of the invention is directed to a record second aspects of the invention or the third to sixth aspects of ing material according to any one of the fortieth to fifty the invention, or a urea-urethane composition according to 30 second aspects of the invention, which is characterized by any one of the seventh to eleventh aspects of the invention, or using at least one material selected from water-soluble poly comprising a color-producing composition according to any mers, nonionic surfactants and anionic surfactants, as a dis one of the twentieth to thirty-ninth aspects of the invention. persing agent for a leuco dye. A forty-first aspect of the invention is directed to a record A fifty-fourth aspect of the invention is directed to a record ing material according to the fortieth aspect of the invention, 35 ing material according to any one of the fortieth to fifty which is characterized in that a protective layer for the color second aspects of the invention, which is characterized by producing layer is formed on the color-producing layer. using at least one material selected from methyl cellulose, A forty-second aspect of the invention is directed to a hydroxypropylmethyl cellulose, polyethylene glycol fatty recording material according to the forty-first aspect of the acid esters, polyoxyethylene alkyl ether Sulfates and sodium invention, which is characterized in that the protective layer 40 2-ethylhexylsulfoSuccinate, as a dispersing agent for a leuco comprises a water-soluble polymer. dye. A forty-third aspect of the invention is directed to a record A fifty-fifth aspect of the invention is directed to a record ing material according to either of the forty-first and forty ing material according to any one of the fortieth to fifty-fourth second aspects of the invention, which is characterized in that aspects of the invention, which is a heat-sensitive recording the protective layer comprises an inorganic pigment and/oran 45 material. organic pigment. A fifty-sixth aspect of the invention is directed to a heat A forty-fourth aspect of the invention is directed to a sensitive recording material according to the fifty-fifth aspect recording material according to any one of the forty-first and of the invention, which is characterized in that the average forty-third aspects of the invention, which is characterized in particle size of the urea-urethane compound is not more than that the protective layer comprises a lubricant. 50 5um and not less than 0.05um. A forty-fifth aspect of the invention is directed to a record A fifty-seventh aspect of the invention is directed to a ing material according to the fortieth aspect of the invention, heat-sensitive recording material according to the fifty-fifth which is characterized in that an intermediate layer is formed aspect of the invention, which is characterized in that a liquid on the Substrate and that the color-producing layer is formed temperature at grinding of the urea-urethane compound is 60° on said intermediate layer. 55 C. or lower. A forty-sixth aspect of the invention is directed to a record A fifty-eighth aspect of the invention is directed to a heat ing material according to the forty-fifth aspect of the inven sensitive recording material according to the fifty-seventh tion, which is characterized in that the intermediate layer aspect of the invention, which is characterized in that a pH at comprises a water-soluble polymer. grinding of the urea-urethane compound is 5 to 10. A forty-seventh aspect of the invention is directed to a 60 A fifty-ninth aspect of the invention is directed to a heat recording material according to either of the forty-sixth and sensitive recording material according to any one of the fifty forty-seventh aspects of the invention, which is characterized fifth to fifty-eighth aspects of the invention, which is charac in that the intermediate layer comprises an inorganic pigment terized by using at least one material selected from water and/or an organic pigment. soluble polymers and anionic Surfactants, as a dispersing A forty-eighth aspect of the invention is directed to a 65 agent for a heat-meltable material. recording material according to the fortieth aspect of the A sixtieth aspect of the invention is directed to a heat invention, which is characterized in that a back coating layer sensitive recording material according to any one of the fifty US 7,635,662 B2 15 16 fifth to fifty-eighth aspects of the invention, which is charac heat-sensitive recording layers are formed on one side of the terized by using at least one material selected from poly(vinyl Substrate, said recording material being characterized in that alcohol)s, modified poly(vinyl alcohol)s, methyl cellulose, at least one of said heat-sensitive recording layers comprises hydroxypropylmethyl cellulose, Sodium condensed naphtha a urea-urethane compound developer. lenesulfonate, polycarboxylic acid ammonium salts, water A seventy-fourth aspect of the invention is directed to a soluble low-molecular weight copolymers, and sodium multicolor heat-sensitive recording material according to the 2-ethylhexylsulfoSuccinate, as a dispersing agent for a heat seventy-third aspect of the invention, which is characterized meltable material. in that an intermediate layer is formed between the heat A sixty-first aspect of the invention is directed to a heat sensitive recording layers. sensitive recording material according to any one of the fifty 10 A seventy-fifth aspect of the invention is directed to a fifth to fifty-eighth aspects of the invention, which is charac multicolor heat-sensitive recording material characterized by terized in that the urea-urethane compound and a heat comprising a substrate and two heat-sensitive recording lay meltable material are finely ground at the same time. erSlaminated on one side of the substrate which have different A sixty-second aspect of the invention is directed to a color development temperatures, respectively, and undergo heat-sensitive recording material according to any one of the 15 color development in different color tones, respectively, the fifty-fifth to sixty-first aspects of the invention, which is char upper heat-sensitive recording layer comprising either an acterized in that the pH of the substrate surface to be coated agent used both as developer and tone reducer, or a reversible with the heat-sensitive recording layer of the heat-sensitive developer, and the lower heat-sensitive recording layer com recording material is 3 to 9. prising a urea-urethane compound developer. A sixty-third aspect of the invention is directed to a process A seventy-sixth aspect of the invention is directed to a for producing aheat-sensitive recording material according to multicolor heat-sensitive recording material according to the any one of the fifty-fifth to sixty-second aspects of the inven seventy-fifth aspect of the invention, which is characterized in tion, which is characterized by applying on a Substrate a that of the two heat-sensitive recording layers, the upper layer heat-sensitive coating liquid of pH 5 to 12 for forming the is a low-temperature color-producing layer capable of under heat-sensitive recording layer of the heat-sensitive recording 25 going color development at a low temperature and undergo material. ing achromatizationata high temperature, and the lower layer A sixty-fourth aspect of the invention is directed to a is a high-temperature color-producing layer capable of under recording material according the fortieth aspect of the inven going color development at a high temperature. tion, which is a heat-sensitive magnetic recording material. A seventy-seventh aspect of the invention is directed to an A sixty-fifth aspect of the invention is directed to a heat 30 article for laser marking characterized by having on the Sur sensitive magnetic recording material characterized by com face aheat-sensitive recording layer comprising a colorless or prising a substrate, a heat-sensitive recording layer compris light-colored dye precursor, a urea-urethane compound ing a urea-urethane compound developer and formed on one developer and a recording sensitivity improving agent. side of the Substrate, and a magnetic recording layer formed on the other side of the substrate. 35 A seventy-eighth aspect of the invention is directed to an A sixty-sixth aspect of the invention is directed to a railroad article for laser marking according to the seventy-seventh ticket that is a heat-sensitive magnetic recording material aspect of the invention, which is characterized by having on according to the sixty-fourth or sixty-fifth aspect of the inven the heat-sensitive recording layer a protective layer compris tion. ing an aqueous binder having a glass transition point of 20-80° C. A sixty-seventh aspect of the invention is directed to a 40 ticket that is a heat-sensitive magnetic recording material A seventy-ninth aspect of the invention is directed to an according to the sixty-fourth or sixty-fifth aspect of the inven article for laser marking according to either of the seventy tion. seventh and seventy-eighth aspects of the invention, wherein A sixty-eighth aspect of the invention is directed to a the recording sensitivity improving agent is at least one mate recording material according to the fortieth aspect of the 45 rial selected from aluminum hydroxide, muscovite, wollas invention, which is a label for heat-sensitive recording. tonite and kaolin. A sixty-ninth aspect of the invention is directed to a label An eightieth aspect of the invention is directed to an article for heat-sensitive recording characterized by comprising a for laser marking according to any one of the seventy-seventh Substrate, a heat-sensitive recording layer comprising a urea to seventy-ninth aspects of the invention, which is any of urethane compound developer and formed on one side of the 50 labels, packaging materials and containers. substrate, and an adhesive layer formed on the other side of An eighty-first aspect of the invention is directed to a the substrate. process for producing an article for laser marking which is A seventieth aspect of the invention is directed to a label for characterized by applying on a Substrate a color-producing heat-sensitive recording according to the sixty-ninth aspect of marking agent comprising a colorless or light-colored dye the invention, characterized in that a back coating layer is 55 precursor, aurea-urethane compound developer and a record formed between the adhesive layer and the substrate. ing sensitivity improving agent, and drying the thus treated A seventy-first aspect of the invention is directed to a label substrate. for heat-sensitive recording according to either of the sixty An eighty-second aspect of the invention is directed to a ninth and seventieth aspects of the invention, characterized in method for marking an article, which is characterized by that an intermediate layer is formed between the heat-sensi 60 irradiating the heat-sensitive recording layer of an article for tive recording layer and the Substrate. laser marking according to any one of the seventy-seventh to A seventy-second aspect of the invention is directed to a eightieth aspects of the invention, with laser beams. recording material according the fortieth aspect of the inven An eighty-third aspect of the invention is directed to a tion, which is a multicolor heat-sensitive recording material. color-producing marking agent characterized by comprising A seventy-third aspect of the invention is directed to a 65 a colorless or light-colored dye precursor, a urea-urethane multicolor heat-sensitive recording material according the compound developer and a recording sensitivity improving seventy-second aspect of the invention, wherein at least two agent. US 7,635,662 B2 17 18 BRIEF DESCRIPTION OF THE DRAWINGS In this case, a urea-urethane compound having at least one urea group and at least one urethane group in a total number FIG. 1 is an IR spectrum of the white crystals obtained in of 3 to 10 can be obtained by using an isocyanate compound Example 1. having two or more isocyanate groups, as the isocyanate to be FIG. 2 is an IR spectrum of the white crystals obtained in 5 lastly reacted, and repeating a procedure of reacting the Example 8. remaining isocyanate group(s) with a compound containing two or more OH groups oran amine compound having two or PREFERRED EMBODIMENT OF THE more amino groups. INVENTION The starting isocyanate is not particularly limited so longas 10 it has two or more isocyanate groups. The starting isocyanate includes, for example, p-phenylene diisocyanate, 2.5- The present invention is explained below in detail. dimethoxybenzene-1,4-diisocyanate, 2,4-toluene diisocyan The urea-urethane compound of the first aspect of the ate, 2,6-toluene diisocyanate, diphenylmethane diisocyanate, present invention which satisfies the numeral formula: o-tolidine diisocyanate, diphenyl ether diisocyanate, 1.5- 15 naphthylene diisocyanate, dianisidine diisocyanate, 9-ethyl carbazole-3,6-diisocyanate, 3,3'-dimethyl-4,4'-diphenyl methane diisocyanate, hexamethylene diisocyanate, wherein each of A and B is an integer of 1 or more, is a isophorone diisocyanate, triphenylmethane triisocyanate, tris compound having a molecular structure in which at least one (4-phenylisocyanate) thiophosphate, 4,4',4'-triisocyanato-2, urea group ( NHCONH group) and at least one urethane 5-dimethoxytriphenylamine, 4,4',4'-triisocyanatotripheny group (-NHCOO— group) are present in a total number of lamine, m-xylylene diisocyanate, lysine diisocyanate, dimer not more than 10 and not less than 3. acid diisocyanate, isopropylidene bis-4-cyclohexyl-isocyan Such a compound has not been known and is a quite novel ate, dicyclohexylmethane diisocyanate and methylcyclohex compound. This novel compound is useful in the case of ane diisocyanate. As the starting isocyanate, there may also be recording materials used by means of recording energy Such used diisocyanate dimers such as N,N'-(4,4'-dimethyl-3,3'- as heat, pressure or the like. The molecular weight of the 25 diphenyl-diisocyanato)urethodione (Desmodur TT, a trade urea-urethane compound is preferably 5,000 or less, more name), a toluene diisocyanate dimer; and diisocyanate trim preferably 2,000 or less. The ratio ofurea group(s) to urethane ers such as 4,4',4'-trimethyl-3.3',3'-triisocyanato-2,4,6- group(s) in the molecular structure of the urea-urethane com triphenylcyanurate. There may also be used water adduct pound is preferably 1:3 to 3:1, in particular, 1:2 to 2:1. isocyanates of toluene diisocyanate, diphenyl-methane diiso A process for synthesizing the urea-urethane compound of 30 cyanate and the like. Such as 1,3-bis(3-isocyanato-4-meth the first aspect of the present invention is not particularly ylphenyl)urea; polyol adducts such as trimethylolpropane limited so long as at least one urea group (-NHCONH adduct of toluene diisocyanate (Desmodur L., a trade name); group) and at least one urethane group (-NHCOO— group) and amine adducts. There may also be used compounds hav are formed in a total number of 3 to 10. A process in which the ing two or more isocyanate groups, among the isocyanate 35 compounds and isocyanate adduct compounds described in urea-urethane compound is produced by the reaction of an the specification of JP-A-10-76,757 and the specification of OH group-containing compound with an amine compound is JP-A-10-95,171 (the contents of these references are hereby preferable because of its ease. incorporated herein by reference). In detail, as the urea-urethane compound of the first aspect Especially preferable examples of the starting isocyanate of the present invention, aurea-urethane compound having at 40 are toluene diisocyanates. Of the toluene diisocyanates, 2,4- least one urea group and at least one urethane group in a total toluene diisocyanate is preferable. Besides 2,4-toluene diiso number of at least 3 can be obtained, for example, by using an cyanate, mixtures of 2,4-toluene diisocyanate and 2,6-toluene isocyanate having at least two isocyanate groups, as a starting diisocyanate are generally on the market and available at a material, reacting all the isocyanate groups except at least one low price and may also be used as the staring isocyanate. The with an OH group-containing compound to form one or more 45 mixtures of these toluene diisocyanate isomers are liquid at urethane groups, and then reacting the remaining isocyanate ordinary temperature. groups of two molecules of the resulting urethane compound As the amine compound that is reacted with the starting with each other by the use of water to bond them to each other. isocyanate for the urea-urethane compound to form one or In addition, a urea-urethane compound having at least one more urea groups, any compound may be used so long as it urea group and at least one urethane group in a total number 50 has one or more amino groups. The amine compound of at least 3 can be obtained, for example, by using an isocy includes, for example, aromatic amines such as aniline, anate having at least two isocyanate groups, as a starting o-toluidine, m-toluidine, p-toluidine, o-anisidine, p-anisi material, reacting all the isocyanate groups except at least one dine, p-phenetidine, N,N-dimethyl-aniline, N,N-diethyla with an OH group-containing compound to form one or more niline, N,N-dimethyl-p-phenylene-diamine, N,N-diethyl-p- urethane groups, reacting the remaining isocyanate group(s) 55 phenylene-diamine, 2,4-dimethoxyaniline, 2.5- with an amine compound having two or more amino groups, dimethoxyaniline, 3,4-dimethoxy-aniline, to form one or more urea groups, and reacting the remaining p-aminoacetanilide, p-aminobenzoic acid, o-aminophenol, amino group(s) with an isocyanate compound. m-aminophenol, p-aminophenol. 2.3-Xylidine, 2,4-Xylidine, 3,4-Xylidine, 2,6-Xylidine, 4-aminobenzonitrile, anthranilic Furthermore, a urea-urethane compound having at least acid, p-cresidine, 2,5-dichloroaniline, 2,6-dichloroaniline, one urea group and at least one urethane group in a total 60 3,4-dichloro-aniline, 3,5-dichloroaniline, 2,4,5-trichloroa number of at least 3 can be obtained also by reacting all the niline, C.-naphthylamine, aminoanthracene, o-ethylaniline, isocyanate groups except at least one with an amine com o-chloroaniline, m-chloroaniline, p-chloroaniline, N-methy pound at first to form one or more urea groups, reacting the laniline, N-ethylaniline, N-propylaniline, N-butylaniline, remaining isocyanate group(s) with a compound containing N,N-diglycidylaniline, N,N-diglycidyl-o-toluidine, two or more OH groups, to form one or more urethane groups, 65 acetoacetic acid anilide, trimethylphenyl-ammonium bro and then reacting the resulting compound with an isocyanate mide, 4,4'-diamino-3,3'-diethyldiphenyl-methane, 4,4'-di compound. aminobenzanilide, 3.5-diaminochloro-benzene, diamino US 7,635,662 B2 19 20 diphenyl ether, 3,3'-dichloro-4,4'-diaminodiphenylmethane, niline, 1,8-naphthalene-diamine, sodium naphthionate, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, tolidine base, Tobias acid, H acid, Jacid, phenyl Jacid, 1,4-diaminoan o-phenylene-diamine, m-phenylenediamine, p-phenylenedi thraquinone, 1,4-diamino-2,3-dichloroanthraquinone, etc.; amine, 2-chloro-p-phenylenediamine, dianisidine, methyl heterocyclic compound amines such as 3-amino-1,2,4-triaz p-aminobenzoate, ethyl p-aminobenzoate, n-propyl p-ami ole, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, nobenzoate, isopropyl p-aminobenzoate, butyl p-aminoben C.-amino-e-caprolactam, acetoguanamine, 2,4-diamino-6- Zoate, dodecyl p-aminobenzoate, benzyl p-aminobenzoate, 2-methylimidazolyl-(1)ethyl-S-triazine, 2,3-diamino-pyri o-aminobenzophenone, m-aminoaceto-phenone, p-aminoac dine, 2,5-diaminopyridine, 2,3,5-triaminopyridine, 1-amino etophenone, m-aminobenzamide, o-aminobenzamide, 4-methylpiperazine, 1-(2-aminoethyl)piperazine, bis p-aminobenzamide, p-amino-N-methylbenzamide, 3-amino 10 (aminopropyl)piperazine, N-(3-aminopropyl)-morpholine, 4-methylbenzamide, 3-amino-4-methoxybenzamide, etc.; and aliphatic amines such as methylamine, ethylamine, 3-amino-4-chlorobenzamide, p-(N-phenylcarbamoyl) dimethylamine, diethylamine, Stearylamine, allylamine, dial aniline, p-N-(4-chlorophenyl)-carbamoylaniline, p-N-(4- lylamine, isopropylamine, diisopropylamine, 2-ethylhexy aminophenyl)carbamoyl-aniline, 2-methoxy-5-(N-phenyl lamine, ethanolamine, 3-(2-ethylhexyloxy)propylamine, carbamoyl)aniline, 2-methoxy-5-N-(2-methyl-3- 15 3-ethoxypropylamine, diisobutylamine, 3-(diethylamino) chlorophenyl)carbamoyl-aniline, 2-methoxy-5-N-(2- propylamine, di-2-ethylhexylamine, 3-(dilbutylamino)propy chlorophenyl)carbamoyl-aniline, 5-acetylamino-2- methoxyaniline, 4-acetylaminoaniline, 4-(N-methyl-N- lamine, t-butylamine, propylamine, 3-(methylamino)propy acetylamino)aniline, 2,5-diethoxy-4-(N-benzoylamino) lamine, 3-(dimethylamino)propylamine, aniline, 2,5-dimethoxy-4-(N-benzoylamino)aniline, 3-methoxypropylamine, methylhydrazine, 1-methylbuty 2-methoxy-4-(N-benzoyl-amino)-5-methylaniline, 4-sulfa lamine, methanediamine, 1,4-diaminobutane, cyclohex moylaniline, 3-sulfamoylaniline, 2-(N-ethyl-N-phenylami anemethylamine, cyclohexyl-amine, 4-methylcyclohexy nosulfonyl)-aniline, 4-dimethylaminosulfonylaniline, 4-di lamine, 2-bromoethylamine, 2-methoxyethylamine, ethyl-aminosulfonylaniline, Sulfathiazole, 4-aminodiphenyl 2-ethoxymethylamine, 2-amino-1-propanol, 2-aminobu sulfone, 2-chloro-5-N-phenylsulfamoylaniline, 2-methoxy tanol, 3-amino-1,2-propanediol. 1,3-diamino-2-hydroxypro 5-N,N-diethylsulfamoylaniline, 2,5-dimethoxy-4-N- 25 pane, 2-aminoethanethiol, ethylenediamine, diethylenetri phenysulfamoylaniline, 2-methoxy-5-benzylsulfonyl amine, hexamethylene-diamine, etc. aniline, 2-phenoxysulfonylaniline, 2-(2-chlorophenoxy) Of the above-exemplified amine compounds, aniline sulfonylaniline, 3-anilinosulfonyl-4-methylaniline, bis4 derivatives having at least one amino group and represented (m-aminophenoxy)phenyl Sulfone, bis4-(p- by the following formula (VIII) are especially preferable: aminophenoxy)phenyl Sulfone, bis3-methyl-4-(p- 30 aminophenoxy)phenyl sulfone, 3,3'-dimethoxy-4,4'- diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'- (VIII) dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl, 2,2'5,5'- tetrachloro-4,4'-diaminobiphenyl, o-tolidine sulfone, 2,4'- diaminobiphenyl, 2,2'-diaminobiphenyl, 4,4'- diaminobiphenyl, 2,2'-dichloro-4,4'-diamino-biphenyl, 3,3'- 35 dichloro-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'- O-O. diaminobiphenyl, 4,4'-thiodianiline, 2,2'-dithiodianiline, 4,4'-dithiodianiline, 4,4'-diaminodiphenyl ether, 3,3'-diami nodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diamino wherein R. R. R. and Ra are independently a hydrogen diphenyl-methane, 3,4'-diaminodiphenylmethane, bis(3- 40 atom, a halogen atom, an alkyl group, an alkoxy group or an amino-4-chlorophenyl) sulfone, bis(3,4-diaminophenyl) amino group, X and X are independently an amino group or sulfone, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl a group represented by the formula (b): sulfone, 3,4'-diaminodiphenyl sulfone, 3,3'-diamino-diphe nylmethane, 4.4-diaminodiphenylamine, 4,4'-ethylenedi aniline, 4,4'-diamino-2,2'-dimethyldibenzyl, 3,3'-diami 45 nobenzophenone, 4,4'-diaminobenzophenone, 1,4-bis(4- (b) aminophenoxy)benzene, 1,3-bis(4-amino-phenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 9.9-bis(4-aminophenyl) fluorene, 2.2-bis(4-aminophenoxy-phenyl)propane, 4,4'-bis --O). (4-aminophenoxy)diphenyl, 3.3',4,4-tetraaminodiphenyl 50 ether, 3.3',4,4-tetraaminodiphenyl sulfone, 3,3',4,4-tet raaminobenzo-phenone, 3-aminobenzonitrile, 4-phenoxya and Y, is any of—SO. , —O— —(S) , —(CH), , niline, 3-phenoxyaniline, 4,4'-methylenebis-o-toluidine, —CO—, —CONH and a group represented by any of the 4,4'-(p-phenyleneisopropylidene)-bis-(2,6-Xylidine), formulas (a): o-chloro-p-nitroaniline, o-nitro-p-chloroaniline, 2,6- 55 dichloro-4-nitroaniline, 5-chloro-2-nitroaniline, 2-amino-4- chlorophenol, o-nitroaniline, m-nitroaniline, p-nitroaniline, (a) 2-methyl-4-nitroaniline, m-nitro-p-toluidine, 2-amino-5-ni trobenzonitrile, Metol. 2,4-diaminophenol, N-(B-hydroxy ethyl)-o-aminophenol Sulfate, Sulfanilic acid, metanilic acid, 4B acid, C acid, 2B acid, p-fluoroaniline, o-fluoroaniline, 60 3-chloro-4-fluoroaniline, 2,4-difluoroaniline, 2,3,4-trifluo roaniline, m-aminobenzotrifluoride, m-toluylene-diamine, CO 2-aminothiophenol, 2-amino-3-bromo-5-nitrobenzonitrile, CH diphenylamine, p-aminodiphenylamine, octylated dipheny lamine, 2-methyl-4-methoxydiphenyl-amine, N,N-diphenyl 65 p-phenylenediamine, dianisidine, 3,3'-dichlorobenzidine, CH3 4,4'-diaminostilbene-2,2'-disulfonic acid, benzylethyla US 7,635,662 B2 21 22 3-hexanol, tert-butanol, tert-amyl alcohol, methyl Cello -continued solve, butyl Cellosolve, methyl Carbitol, allyl alcohol, 2-me thyl-2-propen-1-ol, benzyl alcohol, 4-pyridinemethanol, t th 76. phenyl Cellosolve, furfuryl alcohol, cyclohexanol, cyclo hexyl-methanol, cyclopentanol, 2-chloroethanol. 1-chloro-3- --O)--CH3 CH3 -o-O-o-N-4 hydroxypropane, glycerin, glycerol, etc.; polyether type polyols such as polypropylene glycols, polytetra-methylene ether glycols, adipate-derived polyols, epoxy-modified poly ols, polyether ester polyols, polycarbonate polyols, polyca 10 prolactone diols, phenolic polyols, amine-modified polyols, etc.; and polyols such as ethylene glycol, diethylene glycol, 1,3-propanediol. 1.2-propanediol, propylene glycol, dipropy -o-O- -O-o- lene glycol, 1,4-butanediol, 1.5-pentanediol, 1.6-hexanediol. 1.6-hexane glycol, 1.9-nonanediol, acryl polyols, fluoro-car 15 bon polyols, polybutadiene polyols, polyhydroxy polyols, trimethylolpropane, trimethylolethane, hexanetriol, phos or is absent, and n is 1 or 2. phoric acid, neopentylglycol, pentaerythritol, castor-oil-de As the OH group-containing compound that is reacted with rived polyols, polymer polyols, methylpentanediol, halogen the isocyanate to form one or more urethane groups, any containing polyols, phosphorus-containing polyols, compound may be used so long as it contains one or more OH ethylenediamine, C.-methylglucoside, Sorbitol. Sucrose, etc. groups. The OH group-containing compound includes, for The urea-urethane compound represented by any of the example, phenols such as phenol, cresol. Xylenol, p-ethylphe formulas (I) to (VI) of the second aspect of the present inven nol, o-isopropyl-phenol, resorcinol, p-tert-butylphenol, tion is also a quite novel compound. This novel compound is p-tert-octylphenol, 2-cyclohexylphenol, 2-allylphenol, 4-in useful in the case of for example, recording materials used by danol, thymol, 2-naphthol, p-nitrophenol, o-chloro-phenol, 25 means of recording energy Such as heat, pressure or the like. p-chlorophenol. 2.2-bis(4-hydroxyphenyl)-propane, 2.2-bis A process for producing the urea-urethane compound rep (hydroxyphenyl)butane, 2.2-bis(hydroxy-phenyl)pentane, resented by the formula (I) of the second aspect of the present 2.2-bis(hydroxyphenyl)heptane, catechol, 3-methylcatechol, invention is not limited. This compound can be obtained, for 3-methoxycatechol, pyrogallol, hydroquinone, methylhydro example, by reacting an OH group-containing compound of quinone, 4-phenylphenol, p.p'-biphenol, 4-cumylphenol, 30 the following general formula (IX) with an isocyanate com butyl bis(4-hydroxyphenyl)acetate, benzyl bis(4-hydrox pound of the following general formula (X) and an amine yphenyl)acetate, bis(4-hydroxyphenyl) sulfone, bis(3-me compound of the following general formula (XI) according thyl-4-hydroxyphenyl) sulfone, bis(3,5-dimethyl-4-hydrox to, for instance, the reaction formula (A) shown below: yphenyl) Sulfone, 4-hydroxyphenyl-4'-methylphenyl X-OH (DX) sulfone, 3-chloro-4-hydroxyphenyl-4'-methylphenyl sul 35 fone, 3,4-dihydroxyphenyl-4'-methylphenyl sulfone, 4-iso propyloxyphenyl-4'-hydroxyphenyl Sulfone, bis(2-allyl-4- OCN-Y-NCO (X) hydroxyphenyl) Sulfone, 4-hydroxyphenyl-4- Z-NH (XI) benzyloxyphenyl Sulfone, 4-isopropylphenyl-4- hydroxyphenyl Sulfone, 4-hydroxy-4-isopropoxydiphenyl 40 wherein X and Z are independently an aromatic compound sulfone, bis(2-methyl-3-tert-butyl-4-hydroxyphenyl)sulfide, residue, a heterocyclic compound residue or an aliphatic 4,4'-dihydroxydiphenyl ether, 4,4'-thiodiphenol. 4,4'-dihy compound residue, each of the residues being able to have one droxybenzophenone, 2.2-bis(4-hydroxyphenyl)hexafluoro or more Substituents, and Yo is a group selected from the propane, 4,4'-dihydroxydiphenylmethane, 3,3'-dihydroxy group consisting of tolylene group, Xylylene group, naphth diphenylamine, bis(4-hydroxy-3-methylphenyl) sulfide, bis 45 ylene group, hexamethylene group and -(p-CH2-p-group (4-(2-hydroxy)phenyl) Sulfone, 2,4- wherein -qp- is a phenylene group. dihydroxybenzophenone, 2,2',4,4'- The term “aliphatic” used herein includes the term “alicy tetrahydroxybenzophenone, phenyl salicylate, salicylanilide, clic”. methyl 4-hydroxybenzoate, benzyl 4-hydroxybenzoate, (4'- chlorobenzyl) 4-hydroxybenzoate, ethyl 12-bis(4-hydroxy 50 benzoate), penty1 1.5-bis(4-hydroxybenzoate), hexyl 1,6-bis (A) (4'-hydroxybenzoate), dimethyl 3-hydroxyphthalate, stearyl X-OH + OCN-Y-NCO gallate, lauryl gallate, methyl gallate, 4-methoxyphenol, O 4-(benzyloxy)phenol, 4-hydroxybenzaldehyde, 4-n-octylox ysalicylic acid, 4-n-butyloxysalicylic acid, 4-n-pentylox 55 X-O-C-N-Y-NCO ysalicylic acid, 3-n-dodecyloxysalicylic acid, 3-n-octanoy loxysalicylic acid, 4-n-octyloxy-carbonylaminosalicylic acid, 4-n-octanoyloxy-carbonylaminosalicylic acid, etc. X-O-C-N-Y-NCO + z-NH. -- However, as such phenols, those having an amino group are O O not desirable. Since the amino group has a higher reactivity 60 X-O-C-N-Yo N-C-N-Z with an isocyanate group than does an OH group, the amino H H H group reacts with the isocyanate group before the OH group, so that it is difficult in some cases to obtain a desired com A process for producing the urea-urethane compound rep pound. The OH group-containing compound also includes resented by the formula (II) of the second aspect of the present alcohols such as methanol, ethanol, propanol, butanol, pen 65 invention is not limited. This compound can be obtained, for tanol, hexanol, heptanol, octanol, isopropanol, iosbutanol, example, by reacting an OH group-containing compound of isoheptanol, 2-ethyl-1-hexanol. 1-decanol, 2-pentanol, the general formula (IX) with an isocyanate compound of the US 7,635,662 B2 23 24 following general formula (XII) and water according to, for general formula (XII) and an OH group-containing com instance, the reaction formula (B) shown below: pound of the following general formula (XIV) according to, OCN-Y-NCO (XII) for instance, the reaction formula (E) or (F) shown below: f-(-OH), (XIV) wherein Y is an aromatic compound residue, a hetero-cyclic 5 compound residue oran aliphatic compound residue, each of wherein B is a residue having a Valence of 2 or more, and n is the residues being able to have one or more substituents. an integer of 2 or more.

(B) 10 (E) X-OH + OCN-Y-NCO - a Z-NH + OCN-Y-NCO - - O

Z-N-C-N-Y-NCO H H 15 Z-N-C-N-Y-NCO) + p--OH), --

A process for producing the urea-urethane compound rep resented by the formula (III) of the second aspect of the present invention is not limited. This compound can be obtained, for example, by reacting an OH group-containing 25 compound of the general formula (IX) with an isocyanate compound of the general formula (XII) and an amine com pound of the following general formula (XIII) according to, for instance, the reaction formula (C) or (D) shown below: 30 wherein C. is a residue having a valence of 2 or more, and n is an integer of 2 or more. 35

(C) The compounds of the general formulas (IX) to (XIV) are X-OH + OCN-Y-NCO - - explained below in further detail which can be used for syn O thesis of the urea-urethane compounds of the above formulas 40 (I) to (IV). X-O-C-N-Y-NCO The OH group-containing compound of the general for mula (IX) is not particularly limited so long as it has one or He more OH groups. This compound includes, for example, " X-O- -N-Y-NCO + o- (NH) monophenols such as phenol, cresol, Xylenol, p-ethylphenol, 45 o-isopropylphenol, resorcinol, p-tert-butylphenol, p-tert-oc tylphenol, 2-cyclohexylphenol, 2-allylphenol, 4-indanol, thymol, 2-naphthol, p-nitrophenol, o-chlorophenol, p-chloro-phenol, 4-phenylphenol, 4-hydroxyphenyl-4'-me a-NH2) + n (OCN-Y-NCO) thylphenyl sulfone, 3-chloro-4-hydroxyphenyl-4'-meth 50 ylphenyl Sulfone, 4-isopropylphenyl-4'-hydroxyphenyl Sul fone, 4-isopropyloxyphenyl-4'-hydroxyphenyl Sulfone, 4-hydroxyphenyl-4'-benzyloxyphenyl sulfone, 4-isopropyl phenyl-4'-hydroxyphenyl Sulfone, 4-hydroxy-4-isopropoxy diphenyl sulfone, phenyl salicylate, salicylanilide, methyl 55 4-hydroxybenzoate, benzyl 4-hydroxybenzoate, (4'-chlo robenzyl) 4-hydroxybenzoate, ethyl 12-bis(4-hydroxyben Zoate), pentyl 1.5-bis(4-hydroxybenzoate), hexyl 1,6-bis(4- hydroxybenzoate), dimethyl 3-hydroxyphthalate, 4-methoxyphenol, 4-(benzyloxy)phenol, 4-hydroxybenzal 60 dehyde, 4-n-octyloxysalcylic acid, 4-n-butyloxysalcylic acid, 4-n-pentyloxysalcylic acid, 3-n-dodecyloxysalcylic acid, 3-n-octanoyloxysalcylic acid, 4-n-octyloxycarbony A process for producing the urea-urethane compound rep lamino-salcylic acid, 4-n-octanoyloxycarbonylaminosalcylic resented by the formula (IV) of the second aspect of the acid, etc. The compound of the general formula (IX) also present invention is not limited. This compound can be 65 includes diphenols such as 2.2-bis(4-hydroxy-phenyl)pro obtained, for example, by reacting an amine compound of the pane, 2.2-bis(hydroxyphenyl)butane, 2.2-bis(hydroxyphe general formula (XI) with an isocyanate compound of the nyl)pentane, 2.2-bis(hydroxyphenyl)-heptane, catechol, US 7,635,662 B2 25 26 3-methylcatechol, 3-methoxycatechol, pyrogallol, hydro such as N,N'-(4,4'-dimethyl-3,3'-diphenyldiisocyanato)ure quinone, methylhydroquinone, 4-phenylphenol. 4,4'-biphe thodione (Desmodur TT, a trade name), a toluene diisocyan nol, 4-cumylphenol, butyl bis(4-hydroxyphenyl)acetate, ben ate dimer, and diisocyanate trimers such as 4,4',4'-trimethyl Zyl bis(4-hydroxy-phenyl)acetate, bis(4-hydroxyphenyl) 3.3',3'-triisocyanato-2,4,6-triphenyl-cyanurate. There may sulfone, bis(3-methyl-4-hydroxyphenyl) sulfone, bis(3,5- also be used water adduct isocyanates of toluene diisocyan dimethyl-4-hydroxyphenyl) sulfone, 3,4-dihydroxyphenyl ate, diphenylmethane diisocyanate and the like. Such as 1,3- 4'-methylphenyl sulfone, bis(2-allyl-4-hydroxyphenyl) sul bis(3-isocyanato-4-methylphenyl)urea; polyol adducts Such fone, bis(2-methyl-3-tert-butyl-4-hydroxyphenyl) sulfide, as trimethylolpropane adduct of toluene diisocyanate (Des 4,4'-dihydroxydiphenyl ether, 4,4'-thiodiphenol. 4,4'-dihy modur L., a trade name); and amine adducts. There may also droxybenzophenone, 2.2-bis(4-hydroxyphenyl)hexafluoro 10 be used compounds having two or more isocyanate groups, propane, 4,4'-dihydroxy-diphenylmethane, 3,3'-dihydroxy among the isocyanate compounds and isocyanate adduct diphenylamine, bis(4-hydroxy-3-methylphenyl) sulfide, etc. compounds described in the specifications of JP-A-10-76757 However, as Such OH group-containing compounds, those and JP-A-10-95171. An especially preferable example of the having an amino group are not desirable. When the amino isocyanate compound of the general formula (XII) is toluene group is present together with the OH group(S), the amino 15 diisocyanate. group has a higher reactivity with an isocyanate group than The amine compound of the general formula (XI) is not does the OH group and hence reacts with the isocyanate group particularly limited so long as it has one or more amino before the OH group, so that it is difficult in some cases to groups. This compound includes, for example, aromatic obtain a desired compound. The compound of the general monoamines Such as aniline, o-toluidine, m-toluidine, formula (IX) further includes monohydric alcohols such as p-toluidine, o-anisidine, p-anisidine, p-phenetidine, 2,4- methanol, ethanol, propanol, butanol, pentanol, hexanol, hep dimethoxyaniline, 2,5-dimethoxyaniline, 3,4-dimethoxya tanol, octanol, isopropanol, isobutanol, isopentanol, 2-ethyl niline, p-aminoacetanilide, p-aminobenzoic acid, o-ami 1-hexanol. 1-decanol, 2-pentanol, 3-hexanol, tert-butanol, nophenol, m-aminophenol, p-aminophenol. 2.3-Xylidine, tert-amyl alcohol, methyl Cellosolve, butyl Cellosolve, 2,4-Xylidine, 3,4-Xylidine, 2,6-Xylidine, 4-aminobenzoni methyl Carbitol, allyl alcohol, 2-methyl-2-propen-1-ol, ben 25 trile, anthranilic acid, p-cresidine, 2,5-dichloroaniline, 2.6- Zyl alcohol, 4-pyridinemethanol, phenyl Cellosolve, furfuryl dichloroaniline, 3,4-dichloroaniline, 3,5-dichloro-aniline, alcohol, cyclohexanol, cyclohexylmethanol, cyclo-pentanol, 2,4,5-trichloroaniline, C.-naphthylamine, aminoanthracene, 2-chloroethanol. 1-chloro-3-hydroxypropane, glycerin, glyc o-ethylaniline, o-chloroaniline, m-chloroaniline, p-chloroa erol, etc. As the compound of the general formula (IX), there niline, methyl p-aminobenzoate, ethyl p-aminobenzoate, may also be used polyether type polyols such as polypropy 30 n-propyl p-aminobenzoate, isopropyl p-aminobenzoate, lene glycols, polytetra-methylene ether glycols, adipate-de butyl p-aminobenzoate, dodecyl p-aminobenzoate, benzyl rived polyols, epoxy-modified polyols, polyether ester poly p-aminobenzoate, o-aminobenzophenone, m-aminoac ols, polycarbonate polyols, polycaprolactone diols, phenolic etophenone, p-aminoaceto-phenone, m-aminobenzamide, polyols, amine-modified polyols, etc.; and polyols such as o-aminobenzamide, p-aminobenzamide, p-amino-N-methyl ethylene glycol, diethylene glycol, 1,3-propanediol. 1,2-pro 35 benzamide, 3-amino-4-methylbenzamide, 3-amino-4-meth panediol, propylene glycol, dipropylene glycol, 1,4-butane oxybenzamide, 3-amino-4-chlorobenzamide, p-(N-phenyl diol. 1.5-pentanediol, 1.6-hexanediol, 1.6-hexane glycol, 1.9- carbamoyl)aniline, p-N-(4-chlorophenyl)carbamoyl nonanediol, acryl polyols, fluoro-carbon polyols, aniline, p-N-(4-aminophenyl)-carbamoylaniline, polybutadiene polyols, polyhydroxy polyols, trimethylolpro 2-methoxy-5-(N-phenylcarbamoyl)-aniline, 2-methoxy-5- pane, trimethylolethane, hexanetriol, phosphoric acid, neo 40 N-(2-methyl-3'-chlorophenyl)-carbamoylaniline, 2-meth pentyl glycol, pentaerythritol, castor-oil-derived polyols, oxy-5-N-(2-chlorophenyl)-carbamoylaniline, 5-acety polymer polyols, methylpentanediol, halogen-containing lamino-2-methoxyaniline, 4-acetylaminoaniline, polyols, phosphorus-containing polyols, ethylenediamine, 2-methoxy-4-(N-benzoylamino)-5-methylaniline, 4-sulfa C.-methylglucoside, Sorbitol. Sucrose, etc. of these, the moylaniline, 3-sulfamoylaniline, 2-(N-ethyl-N-phenyl-ami monophenols are preferably used. 45 nosulfonyl)aniline, 4-dimethyl-aminosulfonylaniline, 4-di The isocyanate compound of the general formula (X) ethylaminosulfonylaniline, Sulfathiazole, 4-aminodiphenyl includes 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, sulfone, 2-chloro-5-N-phenylsulfamoylaniline, 2-methoxy diphenylmethane diisocyanate, hexamethylene diisocyanate, 5-N,N-diethyl-sulfamoylaniline, 2,5-dimethoxy-4-N- 1.5-naphthylene diisocyanate, m-xylylene diisocyanate, etc. phenysulfamoyl-aniline, 2-methoxy-5-benzylsulfonyla of these, the toluene diisocyanates are preferable. 50 niline, 2-phenoxysulfonylaniline, 2-(2-chlorophenoxy)- The isocyanate compound of the general formula (XII) is Sulfonylaniline, 3-anilinosulfonyl-4-methylaniline, not particularly limited so long as it has two or more isocy o-chloro-p-nitroaniline, o-nitro-p-chloroaniline, 2,6- anate groups. This compound includes, for example, p-phe dichloro-4-nitroaniline, 5-chloro-2-nitroaniline, 2-amino-4- nylene diisocyanate, 2,5-dimethoxybenzene-1,4-diisocyan chlorophenol, o-nitroaniline, m-nitroaniline, p-nitroaniline, ate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 55 2-methyl-4-nitroaniline, m-nitro-p-toluidine, 2-amino-5-ni diphenylmethane diisocyanate, o-tolidine diisocyanate, 1.5- trobenzonitrile, sulfanilic acid, metanilic acid, 4B acid, C naphthylene diisocyanate, dianisidine diisocyanate, 9-ethyl acid, 2B acid, p-fluoro-aniline, o-fluoroaniline, 3-chloro-4- carbazole-3,6-diisocyanate, 3,3'-dimethyl-4,4'-diphenyl fluoroaniline, 2,4-difluoroaniline, 2,3,4-trifluoroaniline, methane diisocyanate, hexamethylene diisocyanate, m-aminobenzotrifluoride, 2-amino-3-bromo-5-nitroben isophorone diisocyanate, triphenylmethane triisocyanate, tris 60 Zonitrile, etc.; and aromatic diamines Such as 4,4'-diamino (4-phenylisocyanato)thiophosphate, 4,4',4'-triisocyanato-2, 3,3'-diethyldiphenylmethane, 4,4'-diaminobenzanilide, 3.5- 5-dimethoxytriphenylamine, 4,4',4'-triisocyanatotripheny diaminochlorobenzene, diaminodiphenyl ether, 3,3'- lamine, m-xylylene diisocyanate, lysine diisocyanate, dimer dichloro-4,4'-diamino-diphenyl-methane, 3,3'-dimethyl-4, acid diisocyanate, isopropylidene bis-4-cyclohexyl-isocyan 4'-diaminodiphenylmethane, tolidine base, dianisidine, bis ate, dicyclohexylmethane diisocyanate and methylcyclohex 65 4-(m-aminophenoxy)phenyl Sulfone, bis4-(p- ane diisocyanate. As the isocyanate compound of the general aminophenoxy)-phenyl Sulfone, bis3-methyl-4-(p- formula (XII), there may also be used diisocyanate dimers aminophenoxy)phenyl Sulfone, 3,3'-dimethoxy-4,4'- US 7,635,662 B2 27 28 diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'- dimethyl-dibenzyl, 3,3'-diaminobenzophenone, 4,4'- dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl, 2.2.5.5'-tet diaminobenzo-phenone, 1,4-bis(4-aminophenoxy)benzene, rachloro-4,4'-diaminobiphenyl, o-tolidine sulfone, 2,4'- 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophe diaminobiphenyl, 2,2'-diaminobiphenyl, 4,4'-diamino noxy)benzene, 9.9-bis(4-aminophenyl)fluorene, 2.2-bis(4- biphenyl, 2,2'-dichloro-4,4'-diaminobiphenyl, 3,3'-dichloro- 5 aminophenoxy-phenyl)propane, 4,4'-bis(4-aminophenoxy) 4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, diphenyl, dianisidine, 3,3'-dichlorobenzidine, tolidine base, 4,4'-thiodianiline, 2,2'-dithiodi-aniline, 4,4'-dithiodianiline, o-phenylenediamine, m-phenylenediamine, p-phenylene-di 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'- amine, etc. Of the above-exemplified amine compounds, diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 3,4'- aniline derivatives having at least two amino groups and diamino-diphenylmethane, bis(3-amino-4-chlorophenyl) 10 represented by the following formula (VIII) are especially Sulfone, bis(3,4-diaminophenyl) sulfone, 4,4'-diaminodiphe preferable: nyl sulfone, 3,3'-diaminodiphenyl sulfone, 3,4'-diamino diphenyl Sulfone, 3,3'-diaminodiphenylmethane, 4,4'-diami nodiphenylamine, 4,4'-ethylenedianiline, 4,4'-diamino-2,2'- (VIII) dimethyldibenzyl, 3,3'-diamino-benzophenone, 4,4'- 15 diaminobenzophenone, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophe noxy)benzene, 9.9-bis(4-aminophenyl)-fluorene, 2.2-bis(4- aminophenoxyphenyl)propane, 4,4'-bis(4-aminophenoxy) O-O. diphenyl, dianisidine, 3,3'-dichlorobenzidine, etc. The amine 20 compound of the general formula (XI) also includes, for wherein R. R. R. and Ra are independently a hydrogen example, heterocyclic compound amines such as 3-amino-1, atom, a halogen atom, an alkyl group, an alkoxy group or an 2,4-triazole, 2-aminopyridine, 3-aminopyridine, 4-aminopy amino group, X and X are independently an amino group or ridine, C.-amino-e-caprolactam, acetoguanamine, 2,4-di a group represented by the formula (b): amino-6-2'-methylimidazolyl-(1)ethyl-S-triazine, 2,3- 25 diaminopyridine, 2,5-diaminopyridine, 2,3,5- triaminopyridine, 1-amino-4-methylpiperazine, 1-(2- (b) aminoethyl)piperazine, bis(aminopropyl)piperazine, N-(3- aminopropyl)morpholine, etc.; and aliphatic amines such as methylamine, ethylamine, Stearylamine, allyl-amine, isopro- 30 pylamine, 2-ethylhexylamine, ethanolamine, 3-(2-ethyl --O). hexyloxy)propylamine, 3-ethoxypropylamine, 3-(diethy lamino)propylamine, 3-(dibutylamino)propylamine, and Y is any of —SO , —O— —(S), , —(CH), , t-butylamine, propylamine, 3-(methylamino)propylamine, —CO—, —CONH and a group represented by any of the 3-(dimethylamino)propylamine, 3-methoxypropylamine, 35 formulas (a): methylhydrazine, 1-methylbutylamine, methanediamine, 1,4-diaminobutane, cyclohexanemethylamine, cyclohexyl amine, 4-methylcyclohexylamine, 2-bromoethylamine, 2-methoxyethylamine, 2-ethoxymethylamine, 2-amino-i- propanol, 2-aminobutanol, 3-amino-1,2-propanediol. 1,3-di- 40 amino-2-hydroxypropane, 2-aminoethanethiol, ethylene-di amine, diethylenetriamine, hexamethylenediamine, etc. Of these, the aromatic monoamines are preferably used. CO The amine compound of the general formula (XIII) is not particularly limited so long as it has two or more amino 45 CH groups. This compound includes, for example, aromatic amines such as 4,4'-diamino-3,3'-diethyldiphenylmethane, -o-O--O-o- 4,4'-diaminobenzanilide, 3.5-diaminochlorobenzene, diami hi, nodiphenyl ether, 3,3'-dichloro-4,4'-diaminodiphenyl CH CH methane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, toli- 50 dine base, dianisidine, bis4-(m-aminophenoxy)phenyl --O)-- – ?o Sulfone, bis4-(p-aminophenoxy)phenyl Sulfone, bis3-me it, hi, N-4 thyl-4-(p-aminophenoxy)phenyl Sulfone, 3,3'-dimethoxy-4, 4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diamino-5,5-dimethoxybiphenyl, 2.2".5, 55 5'-tetrachloro-4,4'-diaminobiphenyl, o-tolidine sulfone, 2,4'- diaminobiphenyl, 2,2'-diaminobiphenyl, 4,4'-diaminobiphe nyl, 2,2'-dichloro-4,4'-diamino-biphenyl, 3,3'-dichloro-4,4'- diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 4,4'- thiodianiline, 2,2'-dithiodianiline, 4,4'-dithiodianiline, 4,4'- 60 diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'- diaminodiphenyl ether, 4,4'-diaminodiphenyl-methane, 3,4'- or is absent, and n is 1 or 2. diaminodiphenylmethane, bis(3-amino-4-chlorophenyl) The OH group-containing compound of the general for Sulfone, bis(3,4-diaminophenyl) sulfone, 4,4'-diaminodiphe mula (XIV) is not particularly limited so long as it has two or nyl sulfone, 3,3'-diaminodiphenyl sulfone, 3,4'-diamino- 65 more OH groups. This compound includes, for example, diphenyl Sulfone, 3,3'-diaminodiphenylmethane, 4,4'-diami diphenols such as 2.2-bis(4-hydroxyphenyl)propane, 2.2-bis nodiphenylamine, 4,4'-ethylenedianiline, 4,4'-diamino-2,2'- (hydroxyphenyl)butane, 2.2-bis(hydroxyphenyl)pentane, US 7,635,662 B2 29 30 2.2-bis(hydroxyphenyl)-heptane, catechol, 3-methylcat wherein at least one hydrogenatom of each benzene ring may echol, 3-methoxycatechol, pyrogallol, hydroquinone, meth be replaced by a substituent group, which is preferably an ylhydroquinone, p.p'-biphenol, butyl bis(4-hydroxyphenyl) aromatic compound residue, an aliphatic compound residue acetate, benzyl bis(4-hydroxyphenyl)acetate, bis(4- or a heterocyclic compound residue or which may be a nitro hydroxyphenyl) sulfone, bis(3-methyl-4-hydroxyphenyl) group, a hydroxyl group, a carboxyl group, a nitroso group, a sulfone, bis(3,5-dimethyl-4-hydroxyphenyl) sulfone, 3,4-di hydroxyphenyl-4'-methylphenyl sulfone, bis(2-allyl-4-hy nitrile group, a carbamoyl group, a ureido group, an isocyan droxyphenyl) sulfone, bis(2-methyl-3-tert-butyl-4-hydrox ate group, a mercapto group, a Sulfo group, a Sulfamoyl group yphenyl) sulfide, 4,4'-dihydroxydiphenyl ether, 4,4'- or a halogenatom, each of the residues may have one or more thiodiphenol, 4,4'-dihydroxybenzophenone, 2.2-bis(4- 10 Substituents, and Y is any of —SO , —O— —(S), , hydroxyphenyl)hexafluoropropane, 4,4'- (CH), , —CO , —CONH- and a group represented dihydroxydiphenylmethane, 3,3'-dihydroxydiphenylamine, by any of the formulas (a): bis(4-hydroxy-3-methylphenyl) sulfide, etc. However, as Such diphenols, those having an amino group are not desir able. Since the amino group has a higher reactivity with an 15 isocyanate group than does an OH group, the amino group reacts with the isocyanate group before the OH group, so that it is difficult in some cases to obtain a desired compound. The OH group-containing compound of the general formula (XIV) also includes polyether type polyols such as polypro CO pylene glycols, polytetramethylene ether glycols, adipate derived polyols, epoxy-modified polyols, polyether ester polyols, polycarbonate polyols, polycaprolactone diols, phe nolic polyols, amine-modified polyols, etc.; and polyols such as ethylene glycol, diethylene glycol, 1,3-propanediol. 1.2- 25 propanediol, propylene glycol, dipropylene glycol, 1,4-bu tanediol. 1.5-pentanediol, 1.6-hexanediol. 1.6-hexane glycol, CH3 1.9-nonanediol, acryl polyols, fluorocarbon polyols, polyb utadiene polyols, polyhydroxy polyols, trimethylolpropane, trimethylolethane, hexanetriol, phosphoric acid, neopentyl 30 glycol, pentaerythritol, castor-oil-derived polyols, polymer polyols, methylpentanediol, halogen-containing polyols, st th phosphorus-containing polyols, ethylenediamine, C.-methyl --O--CH CH --O-o-N4 glucoside, Sorbitol, Sucrose, etc. A process for producing the urea-urethane compound rep 35 resented by the formula (V) of the second aspect of the present invention is not limited. This compound can be obtained, for example, by reacting a monophenol compound with an aromatic diisocyanate compound and a diamine com pound of the following general formula (XV) according to the 40 reaction formula (G) or (H) shown below:

(XV) 45

(G) ho -- of-sco He 2 N-4 O

2 21 N-4 N 1s 1s 2 -O-C-N-H"Ne -N-C-N-N-4 US 7,635,662 B2 31 32

-continued

2 o-Co21 -- re-C-O-2 21 He O ce-?h---fN-4 Ne ------Sue N4lso (H) OH O of------f lso + 2 / \ He Nuel Nuel Sue 21 o 1) O ------1-1-1)----O O O

A process for producing the urea-urethane compound rep wherein at least one hydrogenatom of each benzene ring may resented by the formula (VI) of the second aspect of the be replaced by a substituent group, which is preferably an present invention is not limited. This compound can be aromatic compound residue, an aliphatic compound residue obtained, for example, by reacting an aniline derivative with or a heterocyclic compound residue or which may be a an aromatic diisocyanate compound and a dihydroxy com hydroxyl group, a nitro group, a nitrile group, a carbamoyl pound of the following general formula (XVI) according to group, a Sulfamoyl group, a carboxyl group, a nitroso group. the reaction formula (J) or (K) shown below: an amino group, an oxyamino group, a nitroamino group, a hydrazino group, a ureido group, an isocyanate group, a mer (XVI) capto group, a Sulfo group or a halogen atom, each of the residues may have one or more Substituents, Ö is any of i?), ?). SO , O—, (S), , (CH2) , CO , N-4 (N4 35 – CONH-, -NH , —CH(COOR) , —C(CF) and —CRR - or is absent, R, R2 and Rs are independently an alkyl group, and n is 1 or 2.

(J) hi, -- o-?, sco -> s-HN--N-H 1s HNCO 21 N-4 2 Ne

O 2 21 -----soN-4 )

O O O

e ------i ti e ii N-4 2 21 21 ?), ?o . US 7,635,662 B2 33 34

-continued (K) NH2 O on-?-s-s-?-s-?-----soN-4 Nel Nue N-4 + 2 /o \ Her N__ () () () () N e i t e N-4 N-4 "Nel" Ne

The compounds usable for synthesis of the urea-urethane 15 diisocyanates. Of the toluene diisocyanates, 2,4-toluene compounds represented by the formulas (V) and (VI) of the diisocyanate is preferable. Besides 2,4-toluene diisocyanate, second aspect of the present invention are explained below in mixtures of 2.4-toluene diisocyanate and 2,6-toluene diiso detail. cyanate are generally on the market and available at a low The phenol compound usable for synthesizing the urea price and may also be used as the aromatic diisocyanate. The urethane compound of the formula (V) is not particularly mixtures of these toluene diisocyanate isomers are liquid at limited so long as it has one or more OH groups on the ordinary temperature. benzene ring. In addition, at least one hydrogen atom of the The diamine compound of the general formula (XV) which benzene ring may be replaced by a substituent other than OH is usable for synthesizing the urea-urethane compound of the group, Such as an aromatic compound residue, an aliphatic formula (V) includes, for example, aromatic diamines such as compound residue, a heterocyclic compound residue, a nitro 25 4,4'-diamino-3,3'-diethyl-diphenylmethane, 4,4'-diami group, a carboxyl group, a nitroso group, a nitrile group, a nobenzanilide, 3,5-diaminochlorobenzene, diaminodiphenyl carbamoyl group, a ureido group, an isocyanate group, a ether, 3,3'-dichloro-4,4'-diaminodiphenylmethane, 3,3'-dim mercapto group, a Sulfo group, a Sulfamoyl group or a halo ethyl-4,4'-diaminodiphenylmethane, tolidine base, dianisi gen atom. The preferable phenol compound includes, for dine, bis4-(m-aminophenoxy)phenyl Sulfone, bis4-(p- example, phenols such as phenol, cresol. Xylenol, p-ethylphe 30 aminophenoxy)phenyl Sulfone, bis3-methyl-4-(p- nol, o-isopropylphenol, resorcinol, p-tert-butylphenol, p-tert aminophenoxy)phenyl Sulfone, 3,3'-dimethoxy-4,4'- octylphenol, 2-cyclohexylphenol, 2-allylphenol, 4-indanol, diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'- thymol, 2-naphthol, nitro-Substituted phenols (e.g. p-nitro dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl, 2,2'5,5'- phenol), halogen-substituted phenols (e.g. o-chlorophenol tetrachloro-4,4'-diaminobiphenyl, o-tolidine sulfone, 2,4'- and p-chlorophenol), 4-phenylphenol, 4-hydroxyphenyl-4- 35 diaminobiphenyl, 2,2'-diaminobiphenyl, 4,4'- methylphenyl sulfone, 3-chloro-4-hydroxyphenyl-4'-meth diaminobiphenyl, 2,2'-dichloro-4,4'-diamino-biphenyl, 3,3'- ylphenyl Sulfone, 4-isopropylphenyl-4'-hydroxyphenyl Sul dichloro-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'- fone, 4-isopropyloxyphenyl-4'-hydroxyphenyl Sulfone, diaminobiphenyl, 4,4'-thiodianiline, 2,2'-dithiodianiline, 4-hydroxyphenyl-4-benzyloxy-phenyl Sulfone, 4-isopropy 4,4'-dithiodianiline, 4,4'-diaminodiphenyl ether, 3,3'-diami lphenyl-4'-hydroxyphenyl Sulfone, 4-hydroxy-4-isopro 40 nodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diamino poxydiphenyl Sulfone, phenyl salicylate, salicylanilide, diphenyl-methane, 3,4'-diaminodiphenylmethane, bis(3- methyl 4-hydroxy-benzoate, benzyl 4-hydroxybenzoate, (4'- amino-4-chlorophenyl) sulfone, bis(3,4-diaminophenyl) chlorobenzyl) 4-hydroxybenzoate, dimethyl 3-hydroxyph sulfone, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl thalate, 4-methoxyphenol, 4-(benzyloxy)phenol, 4-hydroxy sulfone, 3,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphe benzaldehyde, 4-n-octyloxysalicylic acid, 4-n- 45 nylmethane, 4,4'-diaminodiphenylamine, 4,4'-ethylenedi butyloxysalicylic acid, 4-n-pentyloxysalicylic acid, 3-n- aniline, 4,4'-diamino-2,2'-dimethyl-dibenzyl, 3,3'-diami dodecyloxysalicylic acid, 3-n-octanoyloxysalicylic acid, 4-n- nobenzophenone, 4,4'-diaminobenzo-phenone, 1,4-bis(4- octyloxycarbonylaminosalicylic acid, 4-n- aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, octanoyloxycarbonylaminosalicylic acid, etc. The phenol 1,3-bis(3-amino-phenoxy)benzene, 9.9-bis(4-aminophenyl) compound also includes phenol compounds having one or 50 fluorene, 2.2-bis(4-amino-phenoxyphenyl)propane, 4,4'-bis more substituents including carboxyl group, nitroso group, (4-aminophenoxy)-diphenyl, dianisidine, 3,3'-dichloroben nitrile group, carbamoyl group, ureido group, isocyanate Zidine, etc. group, mercapto group, Sulfo group, Sulfamoyl group, etc. The aniline derivative usable for synthesizing the urea However, as such phenols, those having an amino group are urethane compound of the formula (VI) is not particularly not desirable. Since the amino group has a higher reactivity 55 limited so long as it is an aniline compound having one or with an isocyanate group than does an OH group, the amino more amino groups on the benzene ring. In addition, at least group reacts with the isocyanate group before the OH group, one hydrogenatom of the benzene ring may be replaced by an so that it is difficult in some cases to obtain a desired com aromatic compound residue, an aliphatic compound residue, pound. a heterocyclic compound residue, a hydroxyl group, a nitro The aromatic diisocyanate compound usable for synthesiz 60 group, a nitrile group, a carbamoyl group, a Sulfamoyl group. ing the urea-urethane compound of the formula (V) or (VI) is a carboxyl group, a nitroso group, an amino group, an not particularly limited so long as it has two isocyanate oxyamino group, a nitroamino group, a hydrazino group, a groups bonded to its benzene ring. The aromatic diisocyanate ureido group, an isocyanate group, a mercapto group, a Sulfo compound includes, for example, p-phenylene diisocyanate, group or a halogen atom. The preferable aniline derivative 2,5-dimethoxy-benzene-1,4-diisocyanate, 2,4-toluene diiso 65 includes, for example, aniline, o-toluidine, m-toluidine, cyanate and 2,6-toluene diisocyanate. Especially preferable p-toluidine, o-anisidine, p-anisidine, p-phenetidine, N.N- examples of the aromatic diisocyanate compound are toluene dimethyl-p-phenylene-diamine, N,N-diethyl-p-phenylenedi US 7,635,662 B2 35 36 amine, 2,4-dimethoxy-aniline, 2,5-dimethoxyaniline, 3,4- nitroso group, oxyamino group, nitroamino group, hydrazino dimethoxyaniline, p-aminoacetanilide, carboxy-Substituted group, ureido group, isocyanate group, mercapto group, Sulfo anilines (e.g. p-aminobenzoic acid), hydroxyl-substituted group, etc. anilines (e.g. o-aminophenol, m-aminophenol, 2-amino-4- The dihydroxy compound of the general formula (XVI) chlorophenol and p-aminophenol), 2.3-Xylidine, 2,4-Xyli which is usable for synthesizing the urea-urethane compound dine, 3,4-xylidine, 2,6-Xylidine, nitrile-substituted anilines of the formula (VI) includes diphenols such as 2.2-bis(4- (e.g. 4-aminobenzonitrile), anthranilic acid, p-cresidine, hydroxyphenyl)propane, 2.2-bis(hydroxyphenyl)butane, halogen-substituted anilines (e.g. 2,5-dichloroaniline, 2.6- 2.2-bis(hydroxyphenyl)-pentane, 2.2-bis(hydroxyphenyl) dichloroaniline, 3,4-dichloro-aniline, 3,5-dichloroaniline, heptane, 4,4'-biphenol, butyl bis(4-hydroxyphenyl)acetate, 2,4,5-trichloroaniline, o-chloroaniline, m-chloroaniline and 10 benzyl bis(4-hydroxyphenyl)acetate, bis(4-hydroxyphenyl) p-chloroaniline), C.-naphthylamine, aminoanthracene, sulfone, bis(3-methyl-4-hydroxyphenyl) sulfone, bis(3,5- o-ethylaniline, methyl p-aminobenzoate, ethyl p-aminoben dimethyl-4-hydroxyphenyl) sulfone, bis(2-allyl-4-hydrox Zoate, n-propyl p-aminobenzoate, isopropyl p-aminoben yphenyl) sulfone, bis(2-methyl-3-tert-butyl-4-hydroxyphe Zoate, butyl p-aminobenzoate, dodecyl p-aminobenzoate, benzyl p-aminobenzoate, o-aminobenzophenone, m-ami 15 nyl)sulfide, 4,4'-dihydroxydiphenyl ether, 4,4'-thiodiphenol, noacetophenone, p-aminoacetophenone, m-aminobenza 4,4'-dihydroxybenzophenone, 2.2-bis(4-hydroxyphenyl) mide, o-aminobenzamide, p-aminobenzamide, p-amino-N- hexafluoropropane, 4,4'-dihydroxydiphenylmethane, 3,3'-di methyl-benzamide, 3-amino-4-methylbenzamide, 3-amino hydroxydiphenylamine, bis(4-hydroxy-3-methylphenyl) sul 4-methoxybenzamide, 3-amino-4-chlorobenzamide, fide, etc. However, as Such diphenols, those having an amino carbamoyl-anilines (e.g. p-(N-phenylcarbamoyl)aniline, group are not desirable. Since the amino group has a higher p-N-(4-chlorophenyl)carbamoylaniline, p-N-(4-ami reactivity with an isocyanate group than does an OH group, nophenyl)-carbamoylaniline, 2-methoxy-5-(N-phenylcar the amino group reacts with the isocyanate group before the bamoyl)-aniline, 2-methoxy-5-N-(2-methyl-3-chlorophe OH group, so that it is difficult in Some cases to obtain a nyl)-carbamoylaniline and 2-methoxy-5-N-(2- 25 desired compound. chlorophenyl)-carbamoylaniline), 5-acetylamino-2- methoxyaniline, 4-acetylaminoaniline, 4-(N-methyl-N- The urea-urethane compound of the second aspect of the acetylamino)aniline, 2,5-diethoxy-4-(N-benzoylamino) present invention may be obtained by mixing the isocyanate aniline, 2,5-dimethoxy-4-(N-benzoyl-amino)aniline, with the corresponding reactants in an organic solvent or 2-methoxy-4-(N-benzoylamino)-5-methylaniline, sulfamoy without a solvent, reacting them, and then collecting the lanilines (e.g. 4-sulfamoylaniline, 3-sulfamoylaniline, 30 resulting crystals by filtration. As each of the reactants, one or 2-chloro-5-N-phenylsulfamoylaniline, 2-methoxy-5-N,N- more compounds may be used depending on purposes. As the diethyl-sulfamoylaniline and 2,5-dimethoxy-4-N-phenysul Solvent, any solvent may be used so long as it does not react famoyl-aniline), 2-(N-ethyl-N-phenylaminosulfonyl)aniline, with an isocyanate group and the functional groups of the 4-dimethylaminosulfonylaniline, 4-diethylaminosulfonyl 35 reactants. The solvent includes, for example, aliphatic hydro aniline, Sulfathiazole, 4-aminodiphenyl Sulfone, 2-methoxy carbons, alicyclic hydro-carbons, aromatic hydrocarbons, 5-benzylsulfonylaniline, 2-phenoxysulfonyl-aniline, 2-(2- chlorinated aliphatic hydrocarbons, chlorinated aromatic chlorophenoxy)Sulfonylaniline, 3-anilinosulfonyl-4- hydrocarbons, chlorinated alicyclic hydrocarbons, and methylaniline, nitro-substituted anilines (e.g. o-chloro-p- ketones. Especially preferable are methyl ethyl ketone, tolu nitroaniline, o-nitro-p-chloroaniline, 2,6-dichloro-4- 40 nitroaniline, 5-chloro-2-nitroaniline, o-nitroaniline, ene and the like, which dissolve the isocyanate and in which m-nitroaniline, p-nitroaniline, 2-methyl-4-nitroaniline, m-ni the reaction product has a low solubility. The reaction product tro-p-toluidine and 2-amino-5-nitrobenzonitrile), p-fluoro obtained by the above reaction procedure is not always a aniline, o-fluoroaniline, 3-chloro-4-fluoroaniline, 2,4-difluo single compound, but is obtained as a mixture of compounds roaniline, 2,3,4-trifluoroaniline, m-aminobenzotrifluoride 45 different in the position of a Substituent, in Some cases. and 2-amino-3-bromo-5-nitrobenzonitrile. Specific examples of the urea-urethane compound of the The aniline derivative also includes aniline derivatives hav second aspect of the present invention are the following com ing one or more Substituents including carboxyl group, pounds (E-1) to (E-43)).

(E-1) (E-2) O O

(O)---H H CH3 N-C-NH H CH3

HN HN V V CO CO V O O OCH3

US 7,635,662 B2 53 54

-continued (E-43) H3C O O O | | | HC N-C-N S N-C-N

O Os NH HN 2 O / V O NH

4. 2

NH2 (E-44) O O-C-N CH3 H

NH V OC V NH V CHCH

The urea-urethane compound of the second aspect of the through at least one compound residue (such a structure por present invention is useful in the case of for example, record tion is hereinafter referred to as a urea-urethane structure ing materials. 40 portion). It is preferable that only one compound residue be Each of the urea-urethane compounds of the third to sixth present between the urea group and the urethane group. In aspects of the present invention has both at least one urea addition, this residue is preferably an aromatic ring. group and at least one urethane group. Although a mechanism by which the urea-urethane com In the urea-urethane compounds of the third to sixth pounds of the third to sixth aspects of the present invention aspects of the present invention, an aliphatic compound resi 45 have a function as a developer is unknown, it is conjectured due is bonded to the terminal oxygen atom of the urethane that the function is due to the interaction between the urea group. Therefore, the urea-urethane compounds can be group and the urethane group in the urea-urethane structure obtained as compounds excellent in physical and chemical portion. The number of urea-urethane structure portions is stability, in particular, heat stability. Moreover, the urea-ure two or more in the formulas (e) and (f). On the other hand, the thane compounds can be obtained by using relatively inex 50 number of urea-urethane structure portions is one in some pensive materials. cases in the urea-urethane compound of the formula (c) or (d). Preferable forms at the ends of the urea group vary depend In this case, the following is conjectured: in the urea-urethane ing on the molecular size of the urea-urethane compound. In compound of the formula (c) or (d), a residue to be bonded to the urea-urethane compound of the formula (c), each end of each end of the urethane group is limited to the most prefer the urea group should be bonded to an aromatic compound 55 able residue, i.e., an aromatic compound residue in order to residue. The aromatic compound residue is preferably an enable the compound to perform its function as a developerto aromatic ring shown in the formula (d). In the urea-urethane a cetain extent; on the other hand, in the formulas (e) and (f), compounds of the formulas (e) and (f) having a relatively a residue to be bonded to each end of the urethane group need large molecular size, a group at each end of the urea group is, not always be an aromatic compound residue. for example, as follows: in the formula (e), the group at the 60 It is sufficient that the number of urea-urethane structure end may be any of an aromatic compound residue, a hetero portions present in the molecule is 1 to 10, preferably 1 to 5, cyclic compound residue and an aliphatic compound residue, more preferably 2 to 4. and in the formula (f), the group at the end may be either an The urea-urethane compound may have in the molecule aromatic compound residue or a heterocyclic compound resi one or more other urea groups and urethanegroups in addition due. In both the formulas (e) and (f), each end of the urea 65 to the urea-urethane structure portion(s). group is preferably an aromatic compound residue. The urea The term “aliphatic' used in the case of the third to sixth group and the urethane group are adjacent to each other aspects of the present invention includes the term “alicyclic”. US 7,635,662 B2 55 The term “aliphatic compound residue' used in the case of the third to sixth aspects of the present invention means a residue bonded by the carbonatom of the aliphatic hydrocar (A) bon portion in the residue. The term “aromatic compound R-OH + OCN-A-NCO -- residue used therein means a residue bonded by the carbon atom of the aromatic ring Such as benzene ring in the residue. C The term "heterocyclic compound residue' used therein R-01 SN-A-NCO means a residue bonded by the carbon atom forming the hetero-cyclic ring in the residue. 10 1CN Preferable examples of the substituents of the aliphatic R-O N-A-NCO + A-NH - - compound residue, the heterocyclic compound residue and the aromatic compound residue are alkyl groups, cycloalkyl groups, phenyl group, amide group, alkoxyl groups, nitro R-O1 C SN-A-N1 C SN-A, group, nitrile group, halogen atoms, formyl group, dialky 15 H H H (B) lamino groups, toluenesulfonyl group and methanesulfonyl A-NH + OCN-A-NCO -- group. When it is considered that the urea-urethane compounds of the third to sixth aspects of the present invention are used as OCN-A-N1 C SN-A. a developer or in a heat-sensitive recording material, the total H H number of one or more aliphatic urethane groups and one or more urea groups, which are present in the molecular struc -CN R-OH + OCN-A-N N-A -> H H ture of each of the urea-urethane compounds is not more than 25 11 and not less than 2, preferably not more than 11 and not O less than 3, more preferably not more than 11 and not less than 4. The ratio of the urethane group(s) to the urea group(s) is R-O ls N-A-N1 C SN-A. preferably 1:3 to 3:1, more preferably 1:2 to 2:1, most pref H H H erably 1:1. The molecular weight of the urea-urethane com 30 pounds is 5,000 or less, preferably 2,000 or less. Although a process for producing the urea-urethane com pound of the formula (d) of the fourth aspect of the present In a heat-sensitive recording material, a compound having invention is not particularly limited, this compound can be a melting point is preferably used. The melting poing or the obtained, for example, by reacting an alcohol compound of urea-urethane compounds of the third to sixth aspects of the 35 the formula (m) with an isocyanate compound of the follow present invention ranges preferably from 40°C. to 500° C. ing formula (p) and an amine compound of the following more preferably from 60° C. to 300° C., most preferably from formula (q) according to, for example, the reaction formula 60° C. to 250° C. (C) or (D") shown below: Although a process for synthesizing each of the urea-ure 40 thane compounds of the third to sixth aspects of the present (p) invention is not particularly limited, a process in which the urea-urethane compound is synthesized by the reaction of an isocyanate compound with an alcohol and an amine com pound is preferably because of its ease. 45 That is, although a process for producing the urea-urethane compound of the formula (c) of the third aspect of the present wherein at least one hydrogen atom of the benzene ring may invention is not particularly limited, this compound can be be replaced by an aromatic compound residue, an aliphatic obtained, for example, by reacting an alcohol compound of compound residue, a heterocyclic compound residue, a the following formula (m) with an isocyanate compound of 50 hydroxyl group, a nitro group, a nitrile group, a carbamoyl the following formula (n) and an amine compound of the group, a Sulfamoyl group, a carboxyl group, a nitroso group. following formula (o) according to, for example, the reaction an amino group, an oxyamino group, a nitroamino group, a formula (A') or (B") shown below: hydrazino group, a ureido group, an isocyanate group, a mer capto group, a Sulfo group or a halogen atom, and each of the R-OH (m) 55 residues may have one or more Substituents; and wherein R is an aliphatic compound residue which may have one or more substituents; (q) N OCN-A-NCO (n) 60 o NH2 wherein A is an aromatic compound residue which may have 2 one or more substituents; and A-NH2 (o) wherein at least one hydrogen atom of the benzene ring may 65 be replaced by an aromatic compound residue, an aliphatic wherein A is an aromatic compound residue which may have compound residue or a heterocyclic compound residue, and one or more substituents. each of the residues may have one or more substituents. US 7,635,662 B2 57 58

(C)

R-OH + OCN-Y-NCO -> R-OH + OCN- N-4- - -NCO —- 5 R-01 C SN-Y-NCO C N 10 R-O1 S-Clso21 in R-O 1CN N-Y-NCO + o- (-NH) - > 1Cn ? N N R-O N- --NCO + --NH -> 15 H N-4 21 C C R-01 SN-Y-N1H H Y--aH (F) 1CN 1s 1CN ? N it, it - o-NH) + OCN-Y-NCO -- (D') C OCN-Y-N1 SN-a,H his -- on-?n-so --- 25 2 2 N-4 1CN nR-OH + OCN-Y-N N-Ho -- H H 1) -'s 1s 30 H N-4 21 C C R-O1 YN-Y-N1H H y--aH O 35 Although a process for producing the urea-urethane com R-OH + OCN-H 1stN1 SN-H 1s He pound of the formula (f) of the fifth aspect of the present N-4 2 invention is not particularly limited, this compound can be obtained, for example, by reacting an amine compound of the following general formula (t) with an isocyanate compound 40 of the general formula (r) and an alcohol compound of the following general formula (u) according to, for example, the --s ?y-'s ( N reaction formula (G) or (H) shown below: H N-4 H 21 Z-NH- (t) 45 wherein Z is is an aromatic compound residue or a hetero Although a process for producing the urea-urethane com cyclic compound residue, each of the residues being able to pound of the formula (e) of the fifth aspect of the present have one or more Substituents; and invention is not particularly limited, this compound can be B--OH (u) obtained, for example, by reacting an alcohol compound of 50 the general formula (m) with an isocyanate compound of the wherein B is an aliphatic compound residue which has a following general formula (r) and an amine compound of the Valence of 2 or more and may have one or more Substituents, following general formula (S) according to, for example, the and n is an integer of 2 or more. reaction formula (E') or (F") shown below: 55 OCN-YCO (r) G wherein Y is an aromatic compound residue, a hetero-cyclic Z-NH + OCN-Y-NCO -> compound residue oran aliphatic compound residue, each of the residues being able to have one or more Substituents; and 60 OCN-Y-N1 C y-Z, C-(-NH2). (s) H wherein C. is an aromatic compound residue, aliphatic com pound residue or heterocyclic compound residue having a 65 1.On Valence of 2 or more, n is an integer of 2 or more, and each of niOCN-Y-N N-Z, B-FOH), —- the residues may have one or more Substituents. US 7,635,662 B2 59 60

-continued -continued O O | || N N f O1 SN-Y-N1 y-Z, H H ofsN-4 21 (H) M B -OH + m1 OCN-Y-NCO - - N C N O of-s).N-4 2 | B -OH) - - B-01 SN-Y-NCO 15 O 1Cn 1s 1n ? N 1CN B O N N N B-O N-Y-NCO + nZ-NH -- N-4 2

O O Although a process for producing the urea-urethane com B--O1 J. SN-Y-N1J. y-Z, pound of the formula (h) of the sixth aspect of the present H H H invention is not particularly limited, this compound can be obtained, for example, by reacting an amine compound of the 25 following formula (XVII) with an isocyanate compound of Although a process for producing the urea-urethane com the formula (p) and an alcohol compound of the general pound of the formula (g) of the sixth aspect of the present formula (m) according to, for example, the reaction formula invention is not particularly limited, this compound can be (K) or (L) shown below: obtained, for example, by reacting an alcohol compound of 30 the formula (u) with an isocyanate compound of the formula (p) and an amine compound of the formula (q) according to, (XVII) for example, the reaction formula (i') or (J) shown below: N N NH-i - - o NH2 35 2 21 (i) wherein at least one hydrogenatom of each benzene ring may B -OH + noCN- 1s- - -NCO - - be replaced by an aromatic compound residue, an aliphatic 40 compound residue, a heterocyclic compound residue, a nitro N-4 group, a hydroxyl group, a carboxyl group, a nitroso group, a nitrile group, a carbamoyl group, a ureido group, an isocyan ate group, a mercapto group, a Sulfo group, a Sulfamoyl group 1Cn 1s or a halogenatom, each of the residues may have one or more B--O U21 45 Substituents, Y is a group selected from the group consisting of —SO. , —O— —(S), , —(CH), , —CO—, - CONH-, -NH-, -CH(COOR) , —C(CF) , —CRR - and any of groups represented by the formulas 1CN 1s (a): B -O NiN-4 -NCO + 50 N l --NH -- 21 55 1.On 1s 1CN ? N OO | U2 it 21 60 (J') -O-O-CH3 h 2 -- or ?he He 2 N-4 65 --O)-- CH3 --O-- US 7,635,662 B2 61 62 thyl-2-pentanol, heptanol, isoheptanol, octanol, 2-ethyl-1- -continued hexanol, capryl alcohol, nonyl alcohol, isononyl alcohol, decanol, undecyl alcohol, dodecyl alcohol, tridecyl alcohol, tetradecyl alcohol, hexadecyl alcohol, octadecyl alcohol, isostearyl alcohol, etc.; unsaturated aliphatic alcohols such as ally alcohol, 2-methyl-2-propen-1-ol, crotyl alcohol, propar gyl alcohol, etc.; aliphatic alcohols having an aromatic com pound residue bonded thereto. Such as benzyl alcohol, cin | namyl alcohol, etc.; aliphatic alcohols having a heterocyclic 10 compound residue bonded thereto, such as 2-pyridinemetha nol, 3-pyridine-methanol, 4-pyridinemethanol, furfuryl alco or is absent, each of R, R2 and R is an alkyl group, and n is hol, etc.; halogenated aliphatic alcohols such as 2-chloroet 1 or 2. hanol. 1-chloro-3-hydroxypropane, etc.; glycol ethers such as

(K) 1s I -N AO 1s R-OH + ost 21into He- R-O1 it 21is 2 R-O1 it is -- ?) ?) . . . 21 2 -sO in-sinO n-snO O

(L)

HN-- -- Y - - -NH2 + 2OCN-- --NCO --

O O ... ?y's| ?y?yl-(N.

OCN--1s --N 1CN N--1s - Y 1s- -HN 1CN N--1s - NCO + 2R-OH -- --'sO (N-1).O 1r) -'sO (N-s,O

The compounds of the formulas (m) to (u) which can be ethylene glycol monomethyl ether, ethylene glycol monoet used for synthesis of the urea-urethane compounds of the hyl ether, ethylene glycol monopropyl ether, ethylene glycol above formulas (c) to (h)are explained below infurther detail. monoisopropyl ether, ethylene glycol monobutyl ether, eth As the alcohol compound of the general formula (m), any ylene glycol monoisobutyl ether, ethylene glycol monohexyl alcohol compound having at least one OH group bonded to ether, ethylene glycol monophenyl ether, diethylene glycol the carbon atom of an aliphatic compound may be used. monomethyl ether, diethylene glycol monoethyl ether, dieth Examples of the alcohol compound are the alcohols described to ylene glycol monopropyl ether, diethylene glycol monoiso in Solvent Handbook, Kodansha Scientific Co., Ltd., the propyl ether, diethylene glycol monobutyl ether, diethylene ninth impression (1989), pp. 327-420 and pp. 772-817. The glycol monoisobutyl ether, diethylene glycol monohexyl alcohol compound includes, for example, aliphatic alcohols ether, diethylene glycol monophenyl ether, propylene glycol Such as methanol, ethanol, propanol, isopropanol, n-butanol, monomethyl ether, propylene glycol monoethyl ether, propy isobutanol, sec-butanol, tert-butanol, pentanol, cyclopen 65 lene glycol monopropyl ether, propylene glycol monoisopro tanol, tert-amyl alcohol. 2-pentanol, isoamyl alcohol, hex pyl ether, propylene glycol monobutyl ether, propylene gly anol, 3-hexanol, cyclohexanol, cyclohexyl-methanol, 4-me col monoisobutyl ether, propylene glycol monophenyl ether, US 7,635,662 B2 63 64 dipropylene glycol monomethyl ether, dipropylene glycol diphenyl ether diisocyanate, 1.5-naphthylene diisocyanate, monoethyl ether, dipropylene glycol monopropyl ether, triphenyl-methane triisocyanate, N,N'-(4,4'-dimethyl-3,3'- dipropylene glycol monoisopropyl ether, dipropylene glycol diphenyldiisocyanato)urethodione (Desmodur TT, a trade monobutyl ether, dipropylene glycol monoisobutyl ether, name), 4,4',4'-trimethyl-3,3',3'-triisocyanato-2,4,6-triph dipropylene glycol monophenyl ether, etc.; diols such as eth enylcyanurate, 1,3-bis(3-isocyanato-4-methyl-phenyl)urea, ylene glycol, diethylene glycol, triethylene glycol. 1,3-pro and trimethylolpropane adducts of toluene diisocyanate panediol. 1,2-propanediol, propylene glycol, dipropylene (Desmodur L and Coronate L, trade names). Especially pref glycol, tripropylene glycol, 1,4-butanediol. 1.5-pentanediol. erable examples of the isocyanate compound of the formula 1.6-hexanediol, hexylene glycol, 1.9-nonanediol, neopentyl (n) are toluene diisocyanates. Of the toluene diisocyanates, glycol, methyl-pentanediol, etc.; aliphatic polyols such as 10 glycerin, castor oil, trimethylolpropane, trimethylolethane, 2.4-toluene diisocyanate is preferable. Besides 2.4-toluene hexanetriol, pentaerythritol, C.-methyl glucoside, Sorbitol, diisocyanate, mixtures of 2.4-toluene diisocyanate and 2.6- Sucrose, etc.; polyols such as polyethylene glycols, polypro toluene diisocyanate are generally on the market and avail pylene glycols, polytetramethylene glycols, adipate-derived able at a low price and may also be used as the isocyanate polyols, epoxy-modified polyols, polyether ester polyols, 15 compound of the formula (n). polycarbonate polyols, polycaprolactone diols, amine-modi As the amine compound of the general formula (o), there fied polyols, polyether polyols obtained by adding one of or a are mentioned, for example, aromatic amines Such as aniline, o-toluidine, m-toluidine, p-toluidine, o-anisidine, p-anisi mixture of two or more of alkylene oxides (e.g. ethylene dine, p-phenetidine, N,N-dimethyl-p-phenylenediamine, oxide and propylene oxide) to one of or a mixture of two or N,N-diethyl-p-phenylenediamine, 2,4-dimethoxyaniline, more of polyhydric alcohols (glycerin and propylene glycol), 2,5-dimethoxyaniline, 3,4-dimethoxyaniline, p-aminoaceta acryl polyols, fluorinated polyols, polybutadiene polyols, nilide, p-aminobenzoic acid, o-aminophenol, m-aminophe polyhydroxy polyols, castor oil-derived polyols, polymer nol, p-aminophenol. 2.3-Xylidine, 2,4-Xylidine, 3,4-Xylidine, polyols, halogen-containing polyols, phosphorus-containing 2,6-Xylidine, 4-aminobenzonitrile, anthranilic acid, p-cresi polyols, etc.; and alkanolamines such as N,N-dialkylethanol dine, 2,5-dichloroaniline, 2,6-dichloroaniline, 3,4-dichloroa amines, N,N-dialkylisopropanolamines, N-alkyl-diethanola 25 niline, 3,5-dichloroaniline, 2,4,5-trichloroaniline, C.-naph mines, N-alkyldiisopropanolamines, triethanolamine, triiso thylamine, aminoanthracene, o-ethylaniline, o-chloroaniline, propanolamine, N.N.N',N'-tetrakis(2-hydroxyethyl) m-chloroaniline, p-chloroaniline, N-methylaniline, N-ethy ethylenediamine, N.N.N',N'-tetrakis(2-hydroxypropyl) laniline, N-propylaniline, N-butylaniline, acetoacetic acid ethylenediamine, etc. Of the above-exemplified alcohol anilide, trimethyl-phenylammonium bromide, 4,4'-diamino compounds, monoalcohols having one OH group are prefer 30 3,3'-diethyl-diphenylmethane, 4,4'-diaminobenzanilide, 3.5- able, and aliphatic alcohols and glycol ethers, which have 10 diaminochlorobenzene, diaminodiphenyl ether, 3,3'- or less carbon atoms are more preferable. dichloro-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'- The isocyanate compound of the formula (n) is not particu diaminodiphenylmethane, tolidine base, larly limited so long as it is an aromatic isocyanate having two o-phenylenediamine, m-phenylenediamine, p-phenylene-di amine, 2-chloro-p-phenylenediamine, dianisidine, methyl or more isocyanate groups bonded to carbon atoms, respec 35 p-aminobenzoate, ethyl p-aminobenzoate, n-propyl p-ami tively. This compound includes, for example, p-phenylene nobenzoate, isopropyl p-aminobenzoate, butyl p-aminoben diisocyanate, m-phenylene diisocyanate, o-phenylene diiso Zoate, dodecyl p-aminobenzoate, benzyl p-aminobenzoate, cyanate, 2,5-dimethoxy-benzene-1,4-diisocyanate, 2,4-tolu o-aminobenzophenone, m-aminoaceto-phenone, p-aminoac ene diisocyanate, 2,6-toluene diisocyanate, diphenylmethane etophenone, m-aminobenzamide, o-aminobenzamide, diisocyanate, o-tolidine diisocyanate, diphenyl ether diisocy 40 p-aminobenzamide, p-amino-N-methyl-benzamide, anate, 1.5-naphthylene diisocyanate, dianisidine diisocyan 3-amino-4-methylbenzamide, 3-amino-4-methoxybenza ate, 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, triph mide, 3-amino-4-chlorobenzamide, p-(N-phenylcarbamoyl) enylmethane triisocyanate, tris(4-phenyl-isocyanate) aniline, p-N-(4-chlorophenyl)-carbamoylaniline, p-N-(4- thiophosphate, 4.41 .4"-triisocyanato-2,5-dimethoxytriph aminophenyl)carbamoyl-aniline, 2-methoxy-5-(N- enylamine and 4,4',4'-triisocyanato-triphenylamine. As the 45 phenylcarbamoyl)aniline, 2-methoxy-5-N-(2-methyl-3- isocyanate compound of the formula (n), there may also be chlorophenyl)carbamoyl-aniline, 2-methoxy-5-N-(2- used diisocyanate dimers such as N,N'-(4,4'-dimethyl-3,3'- chlorophenyl)carbamoyl-aniline, 5-acetylamino-2- diphenyl-diisocyanato)urethodione (Desmodur TT, a trade methoxyaniline, 4-acetylamino-aniline, 4-(N-methyl-N- name), a toluene diisocyanate dimer, and diisocyanate trim acetylamino)aniline, 2,5-diethoxy-4-(N-benzoylamino) ers such as 4,4',4'-trimethyl-3.3',3'-triisocyanato-2,4,6- 50 aniline, 2,5-dimethoxy-4-(N-benzoylamino)aniline, triphenylcyanurate. There may also be used water adduct 2-methoxy-4-(N-benzoylamino)-5-methylaniline, 4-sulfa isocyanates oftoluene diisocyanate, diphenyl-methane diiso moylaniline, 3-sulfamoylaniline, 2-(N-ethyl-N-phenylami cyanate and the like, such as 1,3-bis(3-isocyanato-4-meth nosulfonyl)aniline, 4-dimethyl-aminosulfonylaniline, 4-di ylphenyl)urea; polyol adducts such as trimethylolpropane ethylaminosulfonylaniline, Sulfathiazole, 4-aminodiphenyl sulfone, 2-chloro-5-N-phenylsulfamoylaniline, 2-methoxy adducts of toluene diisocyanate (Desmodur L and Coronate 55 5-N,N-diethyl-sulfamoylaniline, 2,5-dimethoxy-4-N- L. trade names); and amine adducts. There may also be used phenysulfamoyl-aniline, 2-methoxy-5-benzylsulfonyla compounds having two or more isocyanate groups, among niline, 2-phenoxysulfonylaniline, 2-(2-chlorophenoxy) the isocyanate compounds and isocyanate adduct compounds Sulfonyl-aniline, 3-anilinosulfonyl-4-methylaniline, bis4 described in the specification of JP-A-10-76757 and the (m-aminophenoxy)phenyl Sulfone, bis4-(p- specification of JP-A-10-95171 (the contents of these refer 60 aminophenoxy)-phenyl Sulfone, bis3-methyl-4-(p- ences are hereby incorporated herein by reference). aminophenoxy)phenyl Sulfone, 3,3'-dimethoxy-4,4'- Of the above-exemplified isocyanate compounds, aromatic diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'- isocyanates having isocyanate groups bonded to a benzene dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl, 2,2'5,5'- ring are preferable. More preferable are p-phenylene diiso tetrachloro-4,4'-diaminobiphenyl, o-tolidine sulfone, 2,4'- cyanate, m-phenylene diisocyanate, o-phenylene diisocyan 65 diaminobiphenyl, 2,2'-diaminobiphenyl, 4,4'-diamino ate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, biphenyl, 2,2'-dichloro-4,4'-diaminobiphenyl, 3,3'-dichloro diphenylmethane diisocyanate, o-tolidine diisocyanate, 4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, US 7,635,662 B2 65 66 4,4'-thiodianiline, 2,2'-dithiodi-aniline, 4,4'-dithiodianiline, mide, o-aminobenzamide, p-aminobenzamide, p-amino-N- 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'- methylbenzamide, 3-amino-4-methylbenzamide, 3-amino diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 3,4'- 4-methoxybenzamide, 3-amino-4-chlorobenzamide, diamino-diphenylmethane, bis(3-amino-4-chlorophenyl) carbamoyl-anilines (e.g. p-(N-phenylcarbamoyl)aniline, Sulfone, bis(3,4-diaminophenyl) sulfone, 4,4'-diaminodiphe p-N-(4-chlorophenyl)carbamoylaniline, p-N-(4-ami nyl sulfone, 3,3'-diaminodiphenyl sulfone, 3,4'-diamino nophenyl)-carbamoylaniline, 2-methoxy-5-(N-phenylcar diphenyl Sulfone, 3,3'-diaminodiphenylmethane, 4.4-diami bamoyl)-aniline, 2-methoxy-5-N-(2-methyl-3-chlorophe nodiphenylamine, 4,4'-ethylenedianiline, 4,4'-diamino-2,2'- nyl)-carbamoylaniline and 2-methoxy-5-N-(2- dimethyldibenzyl, 3,3'-diaminobenzo-phenone, 4,4'- chlorophenyl)-carbamoylaniline), 5-acetylamino-2- diaminobenzophenone, 1,4-bis(4-aminophenoxy)benzene, methoxyaniline, 4-acetylaminoaniline, 2-methoxy-4-(N- 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophe 10 benzoylamino)-5-methylaniline, Sulfamoylanilines (e.g. noxy)benzene, 9.9-bis(4-aminophenyl)-fluorene, 2.2-bis(4- 4-sulfamoyl-aniline, 3-sulfamoylaniline, 2-chloro-5-N-phe aminophenoxyphenyl)propane, 4,4'-bis(4-aminophenoxy) nyl-sulfamoylaniline, 2-methoxy-5-N,N-diethylsulfamoyl diphenyl, 3.3',4,4-tetraamino-diphenyl ether, 3.31.4,4'- aniline and 2,5-dimethoxy-4-N-phenysulfamoylaniline), tetraaminodiphenyl Sulfone, 3,3'44'- 2-(N-ethyl-N-phenylaminosulfonyl)aniline, 4-dimethyl tetraaminobenzophenone, 3-aminobenzonitrile, 15 aminosulfonylaniline, 4-diethylaminosulfonylaniline, Sul 4-phenoxyaniline, 3-phenoxyaniline, 4,4'-methylenebis-o- fathiazole, 4-aminodiphenyl sulfone, 2-methoxy-5-benzyl toluidine, 4,4'-(p-phenyleneisopropylidene)-bis-(2,6-Xyli Sulfonylaniline, 2-phenoxysulfonylaniline, 2-(2- dine), o-chloro-p-nitroaniline, o-nitro-p-chloro-aniline, 2.6- chlorophenoxy)Sulfonylaniline, 3-anilinosulfonyl-4- dichloro-4-nitroaniline, 5-chloro-2-nitroaniline, 2-amino-4- methylaniline, nitro-substituted anilines (e.g. o-chloro-p- chlorophenol, o-nitroaniline, m-nitroaniline, p-nitroaniline, nitroaniline, o-nitro-p-chloroaniline, 2,6-dichloro-4- 2-methyl-4-nitro-aniline, m-nitro-p-toluidine, 2-amino-5-ni nitroaniline, 5-chloro-2-nitroaniline, o-nitroaniline, trobenzo-nitrile, Metol. 2,4-diaminophenol, N-(B-hydroxy m-nitroaniline, p-nitroaniline, 2-methyl-4-nitroaniline, m-ni ethyl)-o-aminophenol Sulfate, Sulfanilic acid, metanilic acid, tro-p-toluidine and 2-amino-5-nitrobenzonitrile), sulfanilic 4B acid, C acid, 2B acid, p-fluoroaniline, o-fluoro-aniline, acid, metanilic acid, 4B acid, Cacid, 2B acid, p-fluoroaniline, 3-chloro-4-fluoroaniline, 2,4-difluoroaniline, 2,3,4-trifluo 25 o-fluoro-aniline, 3-chloro-4-fluoroaniline, 2,4-difluoroa roaniline, m-aminobenzotrifluoride, m-toluylenediamine, niline, 2,3,4-trifluoroaniline, m-aminobenzotrifluoride, 2-aminothiophenol, 2-amino-3-bromo-5-nitrobenzonitrile, 2-amino-3-bromo-5-nitrobenzonitrile, etc., aromatic diphenylamine, p-aminodiphenylamine, octylated dipheny monoamines having one or more Substituents including car lamine, 2-methyl-4-methoxydiphenyl-amine, N,N-diphenyl boxyl group, nitroso group, oxyamino group, nitroamino p-phenylenediamine, dianisidine, 3,3'-dichlorobenzidine, group, hydrazine group, ureido group, isocyanate group, mer 4,4'-diaminostilbene-2,2'-disulfonic acid, benzylethyla 30 capto group, Sulfo group, etc.; aromatic diamines such as niline, 1.8-naphthalene-diamine, sodium naphthionate, 4,4'-diamino-3,3'-diethyl-diphenylmethane, 4,4'-diami Tobias acid, Hacid, Jacid, phenyl Jacid, 1,4-diamino-an nobenzanilide, 3,5-diaminochlorobenzene, diaminodiphenyl thraquinone, 1,4-diamino-2,3-dichloroanthraquinone, etc. ether, 3,3'-dichloro-4,4'-diaminodiphenylmethane, 3,3'-dim The aromatic isocyanate compound of the formula (p) ethyl-4,4'-diaminodiphenylmethane, tolidine base, dianisi includes 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 35 dine, bis4-(m-aminophenoxy)phenyl Sulfone, bis4-(p- m-phenylene diisocyanate, p-phenylene diisocyanate, o-phe aminophenoxy)phenyl Sulfone, bis3-methyl-4-(p- nylene diisocyanate, etc. Of these, the toluene diisocynates aminophenoxy)phenyl Sulfone, 3,3'-dimethoxy-4,4'- are preferable, and 2,4-toluene diisocyanate is more prefer diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'- able. dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl, 2,2'5,5'- 40 tetrachloro-4,4'-diaminobiphenyl, o-tolidine sulfone, 2,4'- The aromatic amine compound of the formula (q) is not diaminobiphenyl, 2,2'-diaminobiphenyl, 4,4'- particularly limited so long as it has at least one amino group diaminobiphenyl, 2,2'-dichloro-4,4'-diamino-biphenyl, 3,3'- directly bonded to the carbon atom of the benzene ring. In dichloro-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'- addition, the hydrogen atom of the benzene ring may be diaminobiphenyl, 4,4'-thiodianiline, 2,2'-dithiodianiline, replaced by an aromatic compound residue, an aliphatic com 4,4'-dithiodianiline, 4,4'-diaminodiphenyl ether, 3,3'-diami pound residue, a heterocyclic compound residue, a hydroxyl 45 nodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diamino group, a nitro group, a nitrile group, a carbamoyl group, a diphenyl-methane, 3,4'-diaminodiphenylmethane, bis(3- Sulfamoyl group, a carboxyl group, a nitroso group, an amino-4-chlorophenyl) sulfone, bis(3,4-diaminophenyl) oxyamino group, a nitroamino group, a hydrazino group, a sulfone, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl ureido group, an isocyanate group, a mercapto group, a Sulfo sulfone, 3,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphe group or a halogen atom. The aromatic amine compound of 50 the formula (q) includes, for example, aniline, o-toluidine, nylmethane, 4,4'-diaminodiphenylamine, 4,4'-ethylenedi m-toluidine, p-toluidine, o-anisidine, p-anisidine, p-pheneti aniline, 4,4'-diamino-2,2'-dimethyl-dibenzyl, 3,3'-diami dine, 2,4-dimethoxy-aniline, 2,5-dimethoxyaniline, 3,4- nobenzophenone, 4,4'-diamino-benzophenone, 1,4-bis(4- dimethoxyaniline, p-aminoacetanilide, carboxy-Substituted aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, aniline (e.g. p-aminobenzoic acid), hydroxyl-substituted 1,3-bis(3-aminophenoxy)-benzene, 9.9-bis(4-aminophenyl) anilines (e.g. o-aminophenol, m-aminophenol, p-aminophe 55 fluorene, 2.2-bis(4-aminophenoxyphenyl)propane, 4,4'-bis nol and 2-amino-4-chlorophenol), 2.3-Xylidine, 2,4-Xylidine, (4-aminophenoxy)-diphenyl, dianisidine, 3,3'-dichloroben 3,4-Xylidine, 2,6-Xylidine, nitrile-substituted aniline (e.g. Zidine, etc. Of these, the aromatic monoamines are preferably 4-aminobenzonitrile), anthranilic acid, p-cresidine, halogen used, and aniline or the aniline derivatives are more prefer Substituted anilines (e.g. 2,5-dichloroaniline, 2,6-dichloroa ably used. niline, 3,4-dichloro-aniline, 3,5-dichloroaniline, 2,4,5- 60 The isocyanate compound of the formula (r) is not particu trichloroaniline, o-chloroaniline, m-chloroaniline and larly limited so long as it has two or more isocyanate groups p-chloroaniline), C.-naphthylamine, aminoanthracene, bonded to carbon atoms, respectively. This compound o-ethylaniline, methyl p-aminobenzoate, ethyl p-aminoben includes, for example, p-phenylene diisocyanate, m-phe Zoate, n-propyl p-aminobenzoate, isopropyl p-aminoben nylene diisocyanate, o-phenylene diisocyanate, 2.5- Zoate, butyl p-aminobenzoate, dodecyl p-aminobenzoate, 65 dimethoxybenzene-1,4-diisocyanate, 2,4-toluene diisocyan benzyl p-aminobenzoate, o-aminobenzophenone, m-ami ate, 2,6-toluene diisocyanate, diphenylmethane diisocyanate, noaceto-phenone, p-aminoacetophenone, m-aminobenza o-tolidine diisocyanate, diphenyl ether diisocyanate, 1.5- US 7,635,662 B2 67 68 naphthylene diisocyanate, dianisidine diisocyanate, 9-ethyl diphenyl Sulfone, 3,3'-diamino-diphenylmethane, 4,4'-diami carbazole-3,6-diisocyanate, 3,3'-dimethyl-4,4'-diphenyl nodiphenylamine, 4,4'-ethylenedianiline, 4,4'-diamino-2,2'- methane diisocyanate, hexamethylene diisocyanate, dimethyldibenzyl, 3,3'-diaminobenzophenone, 4,4'- isophorone diisocyanate, triphenylmethane triisocyanate, tris diaminobenzophenone, 1,4-bis(4-aminophenoxy)benzene, (4-phenylisocyanate) thiophosphate, 4,4',4'-triisocyanato-2, 5-dimethoxytriphenylamine, 4,4',4'-triisocyanatotripheny 1,3-bis(4-amino-phenoxy)benzene, 1,3-bis(3-aminophe lamine, m-xylylene diisocyanate, lysine diisocyanate, dimer noxy)benzene, 9.9-bis(4-aminophenyl)fluorene, 2.2-bis(4- acid diisocyanate, isopropylidene bis-4-cyclohexyl-isocyan aminophenoxy-phenyl)propane, 4,4'-bis(4-aminophenoxy) ate, dicyclohexylmethane diisocyanate and methylcyclohex diphenyl, dianisidine, 3,3'-dichlorobenzidine, tolidine base, ane diisocyanate. As the isocyanate compound of the formula 10 o-phenylenediamine, m-phenylenediamine, p-phenylene-di (r), there may also be used diisocyanate dimers such as N,N'- amine, etc.; heterocyclic compound amines such as guan (4,4'-dimethyl-3,3'-diphenyldiisocyanato)urethodione (Des amine, acetoguanamine, 2,4-diamino-6-2'-methylimida modur TT, a trade name), a toluene diisocyanate dimer; and Zolyl-(1)ethyl-S-triazine, 2,3-diaminopyridine, 2.5- diisocyanate trimers such as 4,4',4'-trimethyl-3.3',3'-triiso diaminopyridine, 2,3,5-triaminopyridine, bis(aminopropyl) cyanato-2,4,6-triphenylcyanurate. There may also be used 15 piperazine, etc.; and aliphatic amines such as water adduct isocyanates of toluene diisocyanate, diphenyl methanediamine, 1,2-diamino-propane, 1,3-diaminopro methane diisocyanate and the like, such as 1,3-bis(3-isocy anato-4-methylphenyl)urea; polyol adducts such as trimethy pane, 1,4-diaminobutane, 1,3-diamino-2-hydroxypropane, lolpropane adducts oftoluene diisocyanate (Desmodur Land ethylenediamine, diethylene-triamine, triethylenetetramine, Coronate L, trade names); and amine adducts. There may also tetraethylenepentamine, N-methyl-3,3'-iminobis(propy be used compounds having two or more isocyanate groups, lamine), hexamethylene-diamine, bis(aminomethyl)cyclo among the isocyanate compounds and isocyanate adduct hexane, isophorone-diamine, isopropylidenebis(aminocy compounds described in the specification of JP-A-10-76,757 clohexane), 4,4'-diaminodicyclohexylmethane, and the specification of JP-A-10-95,171 (the contents of these xylylenediamine, etc. Of the above-exemplified amine com references are hereby incorporated herein by reference). 25 pounds, the aromatic amines are preferable, and aniline Of the above-exemplified isocyanate compounds, aromatic derivatives having at least two amino groups and represented isocyanates having isocyanate groups bonded to a benzene ring are preferable. More preferable are p-phenylene diiso by the following formula (VIII) are especially preferable: cyanate, m-phenylene diisocyanate, o-phenylene diisocyan ate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 30 diphenylmethane diisocyanate, o-tolidine diisocyanate, (VIII) diphenyl ether diisocyanate, 1.5-naphthylene diisocyanate, triphenyl-methane triisocyanate, N,N'-(4,4'-dimethyl-3,3'- diphenyldiisocyanato)urethodione (Desmodur TT, a trade name), 4,4',4'-trimethyl-3.3',3'-triisocyanato-2,4,6-triph 35 O-C. enylcyanurate, 1,3-bis(3-isocyanato-4-methyl-phenyl)urea, and trimethylolpropane adducts of toluene diisocyanate (Desmodur L and Coronate L, trade names). Especially pref wherein R. R. R. and Ra are independently a hydrogen erable examples of the isocyanate compound of the formula atom, a halogen atom, an alkyl group, an alkoxy group or an (r) are toluene diisocyanates. Of the toluene diisocyanates, 40 amino group, X and X are independently an amino group or 2.4-toluene diisocyanate is preferable. Besides 2.4-toluene a group represented by the formula (b): diisocyanate, mixtures of 2.4-toluene diisocyanate and 2.6- toluene diisocyanate are generally on the market and avail able at a low price and may also be used as the isocyanate (b) compound of the formula (r). 45 The amine compound of the general formula (S) is not particularly limited so long as it has two or more amino --O). groups. This compound includes, for example, aromatic amines such as 4,4'-diamino-3,3'-diethyldiphenylmethane, 4,4'-diaminobenzanilide, 3.5-diaminochlorobenzene, diami 50 nodiphenyl ether, 3,3'-dichloro-4,4'-diaminodiphenyl and Y, is any of —SO. , —O— —(S), , —(CH), , methane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, toli CO , CONH , NH , CH(COOR) , dine base, dianisidine, bis4-(m-aminophenoxy)phenyl —C(CF) , —CRR- and a group represented by any of Sulfone, bis4-(p-aminophenoxy)phenyl Sulfone, bis3-me the formulas (a): thyl-4-(p-aminophenoxy)phenyl Sulfone, 3,3'-dimethoxy-4, 55 4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diamino-5,5-dimethoxybiphenyl, 2.2.5. (a) 5'-tetrachloro-4,4'-diaminobiphenyl, o-tolidine sulfone, 2,4'- diaminobiphenyl, 2,2'-diaminobiphenyl, 4,4'-diaminobiphe nyl, 2,2'-dichloro-4,4'-diamino-biphenyl, 3,3'-dichloro-4,4'- 60 diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 4,4'- thiodianiline, 2,2'-dithiodianiline, 4,4'-dithiodianiline, 4,4'- CO diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'- CH diaminodiphenyl ether, 4,4'-diaminodiphenyl-methane, 3,4'- diaminodiphenylmethane, bis(3-amino-4-chlorophenyl) 65 -o-O- O Sulfone, bis(3,4-diaminophenyl) sulfone, 4,4'-diaminodiphe CH nyl sulfone, 3,3'-diaminodiphenyl sulfone, 3,4'-diamino US 7,635,662 B2 69 70 diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'- -continued dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl, 2.2.5.5'-tet rachloro-4,4'-diaminobiphenyl, o-tolidine sulfone, 2,4'-di t t 76. aminobiphenyl, 2,2'-diaminobiphenyl, 4,4'-diamino 5 biphenyl, 2,2'-dichloro-4,4'-diaminobiphenyl, 3,3'-dichloro --O--CH3 CH3 -o-O-o-N-4 4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 4,4'-thiodianiline, 2,2'-dithiodianiline, 4,4'-dithiodianiline, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'- -o-O-O-o- diaminodiphenyl ether, 4,4'-diaminodiphenyl-methane, 3,4'- 10 diaminodiphenylmethane, bis(3-amino-4-chlorophenyl) sul fone, bis(3,4-diaminophenyl) sulfone, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl Sulfone, 3,3'-diamino-diphenylmethane, 4.4-diaminodiphe nylamine, 4,4'-ethylenedianiline, 4,4'-diamino-2,2'-dimeth 15 yldibenzyl, 3,3'-diaminobenzophenone, 4,4'-diaminoben or is absent, each of R. R. and R is an alkyl group, and n is Zophenone, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4- 1 or 2. amino-phenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, The amine compound of the general formula (t) includes 9.9-bis(4-aminophenyl)fluorene, 2.2-bis(4-aminophenoxy aromatic amines such as aniline, o-toluidine, m-toluidine, phenyl)propane, 4,4'-bis(4-aminophenoxy)diphenyl, 3.3.4. p-toluidine, o-anisidine, p-anisidine, p-phenetidine, N.N- 4-tetraaminodiphenyl ether, 3.3',4,4-tetraaminodiphenyl dimethyl-p-phenylenediamine, N,N-diethyl-p-phenylenedi Sulfone, 3.3',4,4-tetraamino-benzophenone, 3-aminoben amine, 2,4-dimethoxyaniline, 2,5-dimethoxyaniline, 3,4- Zonitrile, 4-phenoxyaniline, 3-phenoxyaniline, 4,4'-methyl dimethoxyaniline, p-amino-acetanilide, p-aminobenzoic enebis-o-toluidiner 4,4'-(p-phenyleneisopropylidene)-bis-(2, acid, o-aminophenol, m-aminophenol, p-aminophenol, 2.3- 6-Xylidine), o-chloro-p-nitroaniline, o-nitro-p-chloroaniline, Xylidine, 2,4-Xylidine, 3,4-Xylidine, 2,6-Xylidine, 4-ami 25 2,6-dichloro-4-nitroaniline, 5-chloro-2-nitroaniline, nobenzonitrile, anthranilic acid, p-cresidine, 2,5-dichloroa 2-amino-4-chlorophenol, o-nitroaniline, m-nitroaniline, niline, 2,6-dichloroaniline, 3,4-dichloroaniline, 3.5- p-nitroaniline, 2-methyl-4-nitroaniline, m-nitro-p-toluidine, dichloroaniline, 2,4,5-trichloroaniline, C.-naphthyl-amine, 2-amino-5-nitrobenzonitrile, Metol. 2,4-diaminophenol, aminoanthracene, o-ethylaniline, o-chloro-aniline, m-chlo N-(B-hydroxyethyl)-o-aminophenol sulfate, sulfanilic acid, roaniline, p-chloroaniline, N-methylaniline, N-ethylaniline, 30 metanilic acid, 4B acid, C acid, 2B acid, p-fluoroaniline, N-propylaniline, N-butylaniline, N,N-diglycidylaniline, o-fluoroaniline, 3-chloro-4-fluoroaniline, 2,4-difluoroa N,N-diglycidyl-o-toluidine, acetoacetic acid anilide, trim niline, 2,3,4-trifluoroaniline, m-aminobenzotrifluoride, ethyl-phenylammonium bromide, 4,4'-diamino-3,3'-diethyl m-toluylenediamine, 2-aminothiophenol, 2-amino-3-bromo diphenylmethane, 4,4'-diaminobenzanilide, 3.5-diami 5-nitrobenzonitrile, diphenylamine, p-aminodiphenylamine, nochlorobenzene, diaminodiphenyl ether, 3,3'-dichloro-4,4'- 35 octylated diphenylamine, 2-methyl-4-methoxydiphenyl diaminodiphenylmethane, 3,3'-dimethyl-4,4'- amine, N,N-diphenyl-p-phenylenediamine, dianisidine, 3,3'- diaminodiphenylmethane, tolidine base, dichlorobenzidine, 4,4'-diaminostilbene-2,2'-disulfonic acid, o-phenylenediamine, m-phenylenediamine, p-phenylene-di benzylethylaniline, 1.8-naphthalene-diamine, sodium naph amine, 2-chloro-p-phenylenediamine, dianisidine, methyl thionate, Tobias acid, H acid, Jacid, phenyl J acid, 1,4- p-aminobenzoate, ethyl p-aminobenzoate, n-propyl p-ami 40 diaminoanthraquinone, 1,4-diamino-2,3-dichloroan nobenzoate, isopropyl p-aminobenzoate, butyl p-aminoben thraquinone, etc.; and heterocyclic compoundamines such as Zoate, dodecyl p-aminobenzoate, benzyl p-aminobenzoate, 3-amino-1,2,4-triazole, 2-aminopyridine, 3-aminopyridine, o-aminobenzophenone, m-aminoaceto-phenone, p-aminoac 4-aminopyridine, C.-amino-e-caprolactam, acetoguanamine, etophenone, m-aminobenzamide, o-aminobenzamide, 2,4-diamino-6-2'-methylimidazolyl-(1)ethyl-S-triazine, p-aminobenzamide, p-amino-N-methylbenzamide, 3-amino 45 2,3-diaminopyridine, 2,5-diaminopyridine, 2,3,5-triami 4-methylbenzamide, 3-amino-4-methoxybenzamide, nopyridine, 1-amino-4-methylpiperazine, 1-(2-aminoethyl) 3-amino-4-chlorobenzamide, p-(N-phenylcarbamoyl) piperazine, bis(aminopropyl)piperazine, N-(3-aminopropyl) aniline, p-N-(4-chlorophenyl)-carbamoylaniline, p-N-(4- morpholine, etc. Of these, the aromatic monoamines are aminophenyl)carbamoyl-aniline, 2-methoxy-5-(N-phenyl preferably used. carbamoyl)aniline, 2-methoxy-5-N-(2-methyl-3- 50 The alcohol compound of the general formula (u) is not chlorophenyl)carbamoyl-aniline, 2-methoxy-5-N-(2- particularly limited so long as it is a polyol compound having chlorophenyl)carbamoyl-aniline, 5-acetylamino-2- two or more OH groups. The alcohol compound includes methoxyaniline, 4-acetyl-aminoaniline, 4-(N-methyl-N- diols such as ethylene glycol, diethylene glycol, triethylene acetylamino)aniline, 2,5-diethoxy-4-(N-benzoylamino) glycol. 1,3-propanediol. 1,2-propanediol, propylene glycol, aniline, 2,5-dimethoxy-4-(N-benzoylamino)aniline, 55 dipropylene glycol, tripropylene glycol, 1,4-butanediol. 1.5- 2-methoxy-4-(N-benzoylamino)-5-methylaniline, 4-sulfa pentanediol, 1.6-hexanediol, hexylene glycol, 1.9- moylaniline, 3-sulfamoylaniline, 2-(N-ethyl-N-phenylami nonanediol, neopentyl glycol, methyl-pentanediol, etc.; ali nosulfonyl)aniline, 4-dimethyl-aminosulfonylaniline, 4-di phatic polyols such as glycerin, castor oil, ethylaminosulfonylaniline, Sulfathiazole, 4-aminodiphenyl trimethylolpropane, trimethylolethane, hexanetriol, pen sulfone, 2-chloro-5-N-phenylsulfamoylaniline, 2-methoxy 60 taerythritol, C.-methylglucoside, Sorbitol. Sucrose, etc.; poly 5-N,N-diethyl-sulfamoylaniline, 2,5-dimethoxy-4-N- ols such as polyethylene glycols, polypropylene glycols, phenysulfamoyl-aniline, 2-methoxy-5-benzylsulfonyla polytetramethylene glycols, adipate-derived polyols, epoxy niline, 2-phenoxysulfonylaniline, 2-(2-chlorophenoxy) modified polyols, polyether ester polyols, polycarbonate Sulfonyl-aniline, 3-anilinosulfonyl-4-methylaniline, bis4 polyols, polycaprolactone diols, amine-modified polyols, (m-aminophenoxy)phenyl Sulfone, bis4-(p- 65 polyether polyols obtained by adding one of or a mixture of aminophenoxy)-phenyl Sulfone, bis3-methyl-4-(p- two or more of alkylene oxides (e.g. ethylene oxide and aminophenoxy)phenyl sulfone, 3,3'-dimethoxy-4,4'- propylene oxide) to one of or a mixture of two or more of US 7,635,662 B2 71 72 polyhydric alcohols (e.g. glycerin and propylene glycol), (4-aminophenoxy)diphenyl, dianisidine, 3,3'-dichlorobenzi acryl polyols, fluorinated polyols, polybutadiene polyols, dine, etc. Amine compounds of the general formula (XVII) in polyhydroxy polyols, castor oil-derived polyols, polymer which Y is a Sulfonyl group or a methylene group are prefer polyols, halogen-containing polyols, phosphorus-containing able. polyols, etc.; and alkanolamines such as N-alkyldiethanola- 5 mines, N-alkyldiisopropanolamines, triethanolamine, triiso For obtaining each of the urea-urethane compounds of the propanolamine, N.N.N',N'-tetrakis(2-hydroxyethyl)ethyl third to sixth aspects of the present invention, an isocyanate enediamine, N.N.N',N'-tetrakis(2-hydroxypropyl) and the corresponding reactants are mixed to be reacted in an ethylenediamine, etc. Of these, the diols, the aliphatic crganic Solvent or without a solvent, after which the resulting polyols, the alkanol-amines, and polyols having a molecular 10 crystals are collected by filtration, crystallization, solvent weight of 2,000 or less are preferably used. elimination, etc. to obtain the desired compound. The reac The amine compound of the general formula (XVII) tion may be carried out by a method in which a material includes, for example, aromatic diamines such as 4,4'-di- having two or more groups in the molecule is used in large amino-3,3'-diethyldiphenylmethane, 4,4'-diamino-benzanil- excess and another material to be reacted with the groups is ide,3,5-diaminochlorobenzene, diaminodiphenyl ether, 3,3'- 15 added thereto in Smallportions. When this method is adopted, dichloro-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'- it is possible to react only one of the two or more groups. In the diaminodiphenylmethane, tolidine base, dianisidine, bis4- addition, it is preferable to stir the system thoroughly to effect (m-aminophenoxy)phenyl Sulfone, bis4-(p- sufficient dispersion of the added material immediately after aminophenoxy)phenyl Sulfone, bis3-methyl-4-(p- the addition. The above applies to any of the urea-urethane aminophenoxy)phenyl sulfone, 3,3'-dimethoxy-4,4'- 20 compounds exemplified herein. A method for the reaction is diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'- not limited to the above method and any method may be dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl, 2,2'5,5'- adopted so long as the same result as above can be obtained. tetrachloro-4,4'-diaminobiphenyl, o-tolidine sulfone, 2,4'- AS each of the reactants, one or more compounds may be used diaminobiphenyl, 2,2'-diaminobiphenyl, 4,4'- depending on purposes. As the solvent, any solvent may be diaminobiphenyl, 2,2'-dichloro-4,4'-diamino-biphenyl, 3,3'- 25 used so long as it does not react with isocyanate group and the dichloro-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'- functional groups of the reactants. The solvent includes, for diaminobiphenyl, 4,4'-thiodianiline, 2,2'-dithiodianiline, example, aliphatic hydrocarbons, alicyclic hydrocarbons, 4,4'-dithiodianiline, 4,4'-diaminodiphenyl ether, 3,3'-diami- aromatic hydrocarbons, chlorinated aliphatic hydro-carbons, nodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diamino- chlorinated aromatic hydrocarbons, chlorinated alicyclic diphenyl-methane, 3,4'-diaminodiphenylmethane, bis(3- 30 hydrocarbons, and ketones. Especially preferable a methyl amino-4-chlorophenyl) sulfone, bis(3,4-diaminophenyl) ethyl ketone, toluene and the like, which dissolve the isocy sulfone, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl anate and in which the reaction product has a low solubility. sulfone, 3,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphe- The product obtained by the above reaction procedure is not nylmethane, 4,4'-diaminodiphenylamine, 4,4'-ethylenedi- always a single compound but is obtained as a mixture of aniline, 4,4'-diamino-2,2'-dimethyl-dibenzyl, 3,3'-diami- 35 compounds different in the position of a Substituent, in some nobenzophenone, 4,4'-diaminobenzo-phenone, 1,4-bis(4- CaSCS. aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, Specific examples of the urea-urethane compounds of the 1,3-bis(3-aminophenoxy)benzene, 9.9-bis(4-aminophenyl) third to sixth aspects of the present invention are the following fluorene, 2.2-bis(4-aminophenoxy-phenyl)propane, 4,4'-bis compounds (S-1) to (S-70)).

(S-1) (S-2) H3C H3C

H3CNo1 C NN N1 C NN CH*"No.1 C ns N1 C NN H H H H H H (S-3) (S-4) H3C H3C O O O O | | | | "CH-N1n N 1n i-Cahs.1 ns N 1n H H H H H H (S-5) (S-6) H3C H3C O O O O | | | | "Cities1n N 1n i-Cities1 ns N 1n H H H H H H (S-7) (S-8)

US 7,635,662 B2 85 86

-continued (S-67) (S-68) CH HC O O O O| ls C-N N N C-N N N H H H H H H CH H3C i-o O HC-O O O HC-O-C-N ls CH-C-O-C-N| H N N H N N HC-O HC-O H H H H CH3 HC O an \ 3 O C-NH ls 21 C-N| H N ls N

H H H H (S-69) (S-70)

CH3 CH3 O O N----O--NH. H. i N1 NN C-C-O--Nit, it N1 | NN H 3 H 4 H H H H

Each of the urea-urethane compositions according to the iting excellent color-developing capability and preserving seventh to nineteenth aspects of the present invention com capability which are required of a color-producing composi prises 50 wt % or more, preferably 60 wt % or more, more tion. In addition, as the urea-urethane compound, either a preferably 70 wt % or more of a urea-urethane compound 35 single compound or a mixture of two or more compounds having in the molecule at least one urethane group (-NH including isomers may be used. The mixture of two or more COO group) and at least one urea group (-NHCONH urea-urethane compounds including isomers may be used for group) in a total number of 2 to 10 and having a molecular the purpose of enhancing color-producing sensitivity and weight of 5,000 or less. Such a urea-urethane composition storage stability, etc. can be used in combination with a colorless or light-colored dye precursor in order to obtain a color-producing composi 40 On the other hand, the urea-urethane compound of the tion for a heat-sensitive recording material or a pressure present invention can be optionally diluted with a material(s) sensitive recording material. This color-producing composi which does not inhibit the effect of the invention. The diluent tion is so effective that it is excellent in both color-producing for this purpose includes, for example, a heat-meltable mate capability and print preservability. 45 rial, an acidic developer, an amine compound, an isocyanate The urea-urethane compound as the main constituent of the compound, a urea compound and a urethane compound. urea-urethane composition has at least one urea group and at Among them, a urea compound and a urethane compound, least one urethane group in the molecule. The urea group and which are similar in molecular structure to the urea-urethane the urethane group are preferably adjacent to each other compound, are preferable because they can increase the sen through at least one compound residue (such a structure por 50 sitivity. More preferable is a compound obtained by reacting tion is hereinafter referred to as a urea-urethane structure a polyisocyanate compound with a hydroxy compound or an portion). The total number of the urethane group(s) and the amino compound. These diluents are preferably contained in urea group(s) is not more than 10 and not less than 2, prefer a content of 0.0001 to 50 wt % based on the total of the ably not more than 10 and not less than 3, more preferably not urea-urethane compound and the diluent. The diluent content more than 10 and not less than 4. 55 is more preferably 40 wt % or less, further preferably 30 wt % The ratio of urethane group(s) to urea group(s) in a mol or less to show better storage stability. The diluent content is ecule of the urea-urethane compound is preferably 1:3 to 3:1, also more preferably 0.01 wt % or more, further preferably 1 more preferably 1:2 to 2:1, most preferably 1:1. wt % or more to increase the sensitivity. Some diluents may The molecular weight of the urea-urethane compound is be produced during a reaction for synthesizing the urea-ure preferably 5,000 or less, more preferably 2,000 or less. 60 thane compound. Some diluents, however, may be preferably The content of the urea-urethane compound in each of the added to the synthesis reaction to increase the sensitivity. The urea-urethane compositions of the seventh to nineteenth same effect can be obtained in the compositions according to aspects of the present invention is 50 wt % or more. Such a the seventh to nineteenth aspects of the present invention. urea-urethane composition can be produced by a relatively Each of the urea-urethane compositions of the seventh to simple production process. On the other hand, it can exhibit 65 nineteenth aspects of the present invention is preferably a excellent performance characteristics because of the high colorless or light-colored solid having a melting point, from proportion of the urea-urethane compound capable of exhib the viewpoint of utility in a heat-sensitive recording material. US 7,635,662 B2 87 88 The melting point of the composition is preferably 40° C. to present in the reaction system in an excess amount over amino 300° C., more preferably 60° C. to 260° C. group. Such an adding method is preferable particularly when As a process for producing the urea-urethane composition the reaction is carried out at a ratio of the number of moles of of the present invention, there is preferably adopted a process the polyisocyanate compound to the number of amino equiva of forming one or more urethane groups from at least one of 5 lents of the amino compound of near 1/1, for example, 5/1 to the isocyanate groups of a polyisocyanate compound and the 1/2. hydroxyl group(s) of a hydroxy compound, and then forming In a process for producing the urethane-urea composition one or more urea groups from the remaining unreacted iso of the present invention, the reaction of a polyisocyanate cyanate groups of the same polyisocyanate compound and the compound with a hydroxy compound for forming one or amino group(s) of an amino compound; or a process of form 10 more urethane groups is preferably carried out without a ing one or more urea groups from at least one of the isocyan Solvent or by adding, dropping or pouring the hydroxy com ate groups of a polyisocyanate compound and the amino pound without a solvent, a dilution of the hydroxy compound group(s) of an amino compound, and then forming one or with a solvent or a dispersion of the hydroxy compound in a more urethane groups from the remaining unreacted isocyan Solvent continuously or by portions to a dilution of the poly ate groups of the same polyisocyanate compound and the 15 isocyanate compound with a solvent or a dispersion of the hydroxyl group(s) of a hydroxy compound. polyisocyanate compound in a solvent. Similarly, the reaction When one or more urethane groups are formed from a of a polyisocyanate compound with an amino compound for polyisocyanate compound and a hydroxy compound, the forming one or more urea groups may be carried out without urea-urethane composition can be efficiently obtained by a solvent or by adding, dropping or pouring the amino com using the polyisocyanate compound in an excess amount over pound without a solvent, a dilution of the amino compound hydroxyl group, bonding the polyisocyanate compound to the with a solvent or a dispersion of the amino compound in a hydroxy compound in an amount of one molecule per Solvent continuously or by portions to a dilution of the poly hydroxyl group of the hydroxy compound to react only one of isocyanate compound with a solvent or a dispersion of the the isocyanate groups of the polyisocyanate compound and polyisocyanate compound in a solvent. leave at least one of the isocyanate groups unreacted, and then 25 The above production process comprising adding a reacting unreacted isocyanate group(s) with an amino com hydroxy compound oran amino compound to a polyisocyan pound to form one or more urea groups. In this case, it is ate compound in Small portions is preferable particularly in preferable to form one or more urethane groups by reacting the following case: in a reaction process for the production of the polyisocyanate compound with the hydroxy compound so the urea-urethane composition, while leaving at least one of that the ratio of the number of moles of the polyisocyanate 30 the isocyanate groups in molecule of the polyisocyanate com compound to the number of hydroxyl equivalents of the pound, the other isocyanate group(s) is reacted with the hydroxy compound may be 100/1 to 1/2. It is preferable to hydroxy compound or the amino compound to form one or form one or more urethane groups by a reaction with a ratio of more urethane groups or urea groups, respectively. Moreover, the number of isocyanate equivalents of the polyisocyanate said production process is preferable when a hydroxy com compound to the number of hydroxyl equivalents of the 35 pound having two or more hydroxyl groups or an amino hydroxy compound being 1000/1 to 1/1. compound having two or more amino groups is reacted with In adding the hydroxy compound to the poly-isocyanate a polyisocyanate compound having two or more isocyanate compound, the hydroxy compound is preferably added in groups. Small portions so that the polyisocyanate compound may be In carrying out the above reactions, it is preferable to stir always present in the reaction system in an excess amount 40 the system thoroughly so that the hydroxy or amino com over hydroxyl group. Such an adding method is preferable pound added, dropped or poured to the polyisocyanate may particularly when the reaction is carried out at a ratio of the be immediately and sufficiently dispersed. It is preferable to number of moles of the polyisocyanate compound to the stir the reaction system sufficiently, for example, by adjusting number of hydroxyl equivalents of the hydroxy compound of the stirring rate in a reactor, choosing an agitating blade or near 1/1, for example, 5/1 to 1/2. 45 setting a baffle plate. Similarly, when one or more urea groups are formed from It is preferable to carry out the reaction for forming one or a polyisocyanate compound and an amino compound, the more urethane groups and the reaction for forming one or urea-urethane composition can be efficiently obtained by more urea groups, individually and Successively. When they using the polyisocyanate compound in an excess amount over are carried out at the same time, the urea-urethane compound amino group, bonding the polyisocyanate compound to the 50 content of the urea-urethane composition is undesirably amino compound in an amount of one molecule per amino decreased. It is preferable to carry out these urethane group group of the amino compound to react one of the isocyanate forming reaction and urea group forming reaction continu groups of the polyisocyanate compound and leave at least one ously. In the process of the present invention, since separation of the isocyanate groups unreacted, and then reacting unre and purification steps are not necessary in the course of the acted isocyanate group(s) with a hydroxy compound to form 55 production, the production can be simplified by carrying out one or more urethane groups. Also in this case, it is preferable the two reaction steps continuously. to form one or more urea groups by reacting the polyisocy In the production of the urea-urethane composition of the anate compound with the amino compound so that the ratio of present invention, when a polyisocyanate adduct with a the number of moles of the polyisocyanate compound to the hydroxy compound is used which is an isocyanate already number of amino equivalents of the amino compound may be 60 having one or more urethane groups in the molecule, the 100/1 to 1/2. It is preferable to form one or more urea groups urea-urethane composition can be obtained by reacting this by a reaction with a ratio of the number of isocyanate equiva adduct with an amino compound. In this case, it is preferable lents of the polyisocyanate compound to the number of amino to form one or more urea groups by carrying out the reaction equivalents of the amino compound being 1000/1 to 1/1. at an equivalent ratio of isocyanate group to amino group of In adding the amino compound to the poly-isocyanate 65 2/1 to 1/100, and remove the unreacted amino compound. compound, the amino compound is preferably added in Small In the production of the urea-urethane composition of the portions so that the polyisocyanate compound may be always present invention, when a polyisocyanate adduct with an US 7,635,662 B2 89 90 amino compound is used which is an isocyanate already o-tolidine diisocyanate, diphenyl ether diisocyanate, 1.5- having one or more urea groups in the molecule, the urea naphthylene diisocyanate, dianisidine diisocyanate, 9-ethyl urethane composition can be obtained by reacting this adduct carbazole-3,6-diisocyanate, 3,3'-dimethyl-4,4'-diphenyl with a hydroxy compound. In this case, it is preferable to form methane diisocyanate, hexamethylene diisocyanate, one or more urethane groups by carrying out the reactionatan 5 isophorone diisocyanate, triphenylmethane triisocyanate, tris equivalent ratio of isocyanate group to hydroxyl group of 2/1 (4-phenyl-isocyanate) thiophosphate, 4,4',4'-triisocyanato to 1/100, and remove the unreacted hydroxy compound. 2,5-dimethoxytriphenylamine, 4,4',4'-triisocyanato-triph When a solvent is used for carrying out the reactions in the enylamine, m-xylylene diisocyanate, lysine diisocyanate, production of any of the urea-urethane compositions of the dimeracid diisocyanate, isopropylidene bis-4-cyclohexyliso seventh to nineteenth aspects of the present invention, the 10 cyanate, dicyclohexylmethane diisocyanate and methylcy Solvent is not particularly limited so long as it does not react clohexane diisocyanate. As the polyisocyanate compound, with isocyanate group and the like. The solvent includes, for there may also be used diisocyanate dimers such as N,N'-(4. example, aliphatic hydrocarbons, alicyclic hydro-carbons, 4'-dimethyl-3,3'-diphenyldiisocyanato)urethodione (Desmo aromatic hydrocarbons, chlorinated aliphatic hydrocarbons, dur TT, a trade name), a toluene diisocyanate dimer, and chlorinated aromatic hydrocarbons, chlorinated alicyclic 15 diisocyanate trimers such as 4,4',4'-trimethyl-3.3',3'-triiso hydrocarbons, ketones and phosphoric esters. Especially cyanato-2,4,6-triphenylcyanurate. There may also be used preferable are acetone, methyl ethyl ketone, toluene and the water adduct isocyanates of toluene diiso-cyanate, diphenyl like, which dissolve the isocyanate and in which the reaction methane diisocyanate and the like, such as 1,3-bis(3-isocy product has a low solubility. When a high dissolving power anato-4-methylphenyl)urea; polyol adducts such as trimethy for both the isocyanate and the reaction product is necessary, lolpropane adducts oftoluene diisocyanate (Desmodur Land the phosphoric esters, in particular, trimethyl phosphate are Coronate L, trade names); and amine adducts. There may also preferable. be used compounds having two or more isocyanate groups, When such a solvent is used, the formation of one or more among the isocyanate compounds and isocyanate adduct urethane groups and the formation of one or more urea groups compounds described in the specification of JP-A-10-76,757 are preferably carried out in one and the same solvent in order 25 and the specification of JP-A-10-95171 (the contents of these to make it easy to reuse the solvent and carry out the reaction references are hereby incorporated herein by reference). The for the urea group formation and the reaction for the urethane above-exemplified compounds may be used singly or in com group formation continuously. bination. of the above-exemplified compounds, preferable The reaction temperature at which a polyisocyanate is examples of the polyisocyanate compound are aromatic poly reacted with a hydroxy compound and/or an amino com 30 isocyanates having isocyanate groups bonded to a benzene pound to form one or more urethane groups and/or one or ring, such as p-phenylene diisocyanate, m-phenylene diiso more urea groups is 0°C. to 300° C., preferably 5° C. to 200° cyanate, o-phenylene diisocyanate, 2,4-toluene diisocyanate, C., more preferably 10°C. to 150° C. The reaction tempera 2,6-toluene diisocyanate, diphenylmethane diisocyanate, ture is properly adjusted depending on the polyisocyanate o-tolidine diisocyanate, diphenyl ether diisocyanate, 1.5- compound, hydroxy compound and amino compound 35 naphthylene diisocyanate, triphenylmethane triisocyanate, selected. It is also possible to carry out the urethane group N,N'-(4,4'-dimethyl-3,3'-diphenyldiiso-cyanato)urethodione formation and the urea group formation at different tempera (Desmodur TT, a trade name), 4,4',4'-trimethyl-3.3',3'-tri tures suitable for the formations, respectively. isocyanato-2,4,6-triphenylcyanurate, 1,3-bis(3-isocyanato A catalyst may be used for reacting a polyisocyanate with 4-methyl-phenyl)urea, trimethylolpropane adducts of tolu a hydroxy compound and/oran amino compound to form one 40 ene diisocyanate (Desmodur Land Coronate L, trade names), or more urethane groups and/or one or more urea groups. The etc. Especially preferable examples of the polyisocyanate catalyst includes, for example, tertiary amine compounds compound are toluene diisocyanates. Of the toluene diisocy Such as triethyl-amine, 1,4-diazabicyclo(2.2.2).octane, etc.; anates, 2.4-toluene diisocyanate is preferable. Besides 2.4- organic acid tin salts such as dibutyltin dilaurate, etc. Usually, toluene diisocyanate, mixtures of 2.4-toluene diisocyanate the catalyst concentration is 1 to 10,000 ppm, preferably 10 to 45 and 2,6-toluene diisocyanate are generally on the market and 2,000 ppm, relative to the isocyanate compound. Of the available at a low price and may also be used as the polyiso above-exemplified catalysts, the tertiary amine compounds cyanate compound. are preferable. As the hydroxy compound that is reacted with the polyiso A urea-urethane composition containing a urea-urethane cyanate compound to form one or more urethane groups, compound having a plurality of urea-urethane structure por 50 phenol compounds and alcohol compounds are mentioned. tions in the molecule can be obtained by repeating the steps of The phenol compounds include, for example, phenol, the production process of the present invention two or more cresol, Xylenol, p-ethylphenol, o-isopropyl-phenol, resorci times by using, for example, an amino compound having two nol, p-tert-butylphenol, p-tert-octylphenol, 2-cyclohexylphe or more amino groups and a hydroxy compound having two nol, 2-allylphenol, 4-indanol, thymol, 2-naphthol, p-nitro or more hydroxyl groups. Since a sufficiently high yield from 55 phenol, o-chloro-phenol, p-chlorophenol. 2.2-bis(4- reaction can be attained in each step, the production process hydroxyphenyl)-propane, 2.2-bis(hydroxyphenyl)butane, of the present invention permits relatively easy production of 2.2-bis(hydroxy-phenyl)pentane, 2.2-bis(hydroxyphenyl) a urea-urethane composition having high performance char heptane, catechol, 3-methylcatechol, 3-methoxycatechol, acteristics. pyrogallol, hydroquinone, methylhydroquinone, 4-phe The polyisocyanate compound used in each of the seventh 60 nylphenol, p.p'-biphenol, 4-cumylphenol, butyl bis(4-hy to nineteenth aspects of the present invention is not particu droxyphenyl)acetate, benzyl bis(4-hydroxy-phenyl)acetate, larly limited so long as it has two or more isocyanate groups bis(4-hydroxyphenyl) sulfone, bis(3-methyl-4-hydroxyphe bonded to carbon atoms, respectively. The polyisocyanate nyl) sulfone, bis(3,5-dimethyl-4-hydroxyphenyl) sulfone, compound includes, for example, p-phenylene diisocyanate, 4-hydroxyphenyl-4'-methylphenyl sulfone, 3-chloro-4-hy m-phenylene diisocyanate, o-phenylene diisocyanate, 2.5- 65 droxyphenyl-4'-methylphenyl sulfone, 3,4-dihydroxyphe dimethoxybenzene-1,4-diisocyanate, 2,4-toluene diisocyan nyl-4'-methylphenyl Sulfone, 4-isopropyloxyphenyl-4-hy ate, 2,6-toluene diisocyanate, diphenylmethane diisocyanate, droxyphenyl sulfone, bis(2-allyl-4-hydroxyphenyl) sulfone, US 7,635,662 B2 91 92 4-hydroxyphenyl-4-benzyloxyphenyl Sulfone, 4-isopropy hydrocarbon portion in the residue. The term “aromatic com lphenyl-4'-hydroxyphenyl Sulfone, 4-hydroxy-4-isopro pound residue' used therein means a residue bonded by the poxydiphenyl sulfone, bis(2-methyl-3-tert-butyl-4-hydrox carbon atom of the aromatic ring Such as benzene ring in the yphenyl) sulfide, 4,4'-dihydroxydiphenyl ether, 4,4'- residue. The term "heterocyclic compound residue' used thiodiphenol, 4,4'-dihydroxybenzophenone, 2.2-bis(4- 5 therein means a residue bonded by the carbon atom forming hydroxyphenyl)hexafluoropropane, 4,4'-dihydroxy the heterocyclic ring in the residue. diphenylmethane, 3,3'-dihydroxydiphenylamine, bis(4- Preferable examples of the substituent of the aliphatic hydroxy-3-methylphenyl) sulfide, bis(4-(2-hydroxy)- compound residue, heterocyclic compound residue or aro phenyl) sulfone, 2,4-dihydroxybenzophenone, 2.2',4,4'- matic compound residue are alkyl groups, cycloalkyl groups, tetrahydroxybenzophenone, phenyl salicylate, salicylanilide, 10 phenyl group, amide group, alkoxyl groups, nitro group, methyl 4-hydroxybenzoate, benzyl 4-hydroxybenzoate, (4'- nitrile group, halogen atoms, formyl group, dialkylamino chlorobenzyl) 4-hydroxybenzoate, ethyl 12-bis(4-hydroxy groups, toluenesulfonyl group and methanesulfonyl group. benzoate), penty1 1.5-bis(4-hydroxybenzoate), hexyl 1,6-bis As the alcohol compounds, compounds having at least one (4'-hydroxybenzoate), dimethyl 3-hydroxyphthalate, stearyl OH group bonded to the carbon atom of an aliphatic com gallate, lauryl gallate, methyl gallate, 4-methoxyphenol, 15 pound are mentioned. Examples of the alcohol compounds 4-(benzyloxy)phenol, 4-hydroxybenzaldehyde, 4-n-octylox are the alcohols described in Solvent Handbook, Kodansha ysalicylic acid, 4-n-butyloxysalicylic acid, 4-n-pentylox Scientific Co., Ltd., the ninth impression (1989), pp. 327-420 ysalicylic acid, 3-n-dodecyloxysalicylic acid, 3-n-octanoy and pp. 772-817. The alcohol compound includes, for loxysalicylic acid, 4-n-octyloxy-carbonylaminosalicylic acid example, aliphatic alcohols such as methanol, ethanol, pro and 4-n-octanoyloxy-carbonylaminosalicylic acid. panol, isopropanol, n-butanol, isobutanol, Sec-butanol, tert Of the above-exemplified phenol compounds, phenol, phe butanol, pentanol, cyclopentanol, tert-amyl alcohol. 2-pen nol derivatives represented by the following formula (w) and tanol, isoamyl alcohol, hexanol, 3-hexanol, cyclo-hexanol, diphenol compounds represented by the following formula cyclohexylmethanol, 4-methyl-2-pentanol, heptanol, isohep (XVI) are preferable. tanol, octanol, 2-ethyl-1-hexanol, capryl alcohol, nonyl alco 25 hol, isononyl alcohol, decanol, undecyl alcohol, dodecyl alcohol, tridecyl alcohol, tetradecyl alcohol, hexadecyl alco (W) hol, octadecyl alcohol, isostearyl alcohol, etc.; unsaturated aliphatic alcohols such as ally alcohol, 2-methyl-2-propen-1- ol, crotyl alcohol, propargyl alcohol, etc.; aliphatic alcohols ( )—o 30 having an aromatic compound residue bonded thereto. Such as benzyl alcohol, cinnamyl alcohol, etc.; aliphatic alcohols having a heterocyclic compound residue bonded thereto, such wherein at least one hydrogen atom of the benzene ring may as 2-pyridinemethanol, 3-pyridinemethanol, 4-py be replaced by an alkyl group, a cycloalkyl group, a phenyl ridinemethanol, furfuryl alcohol, etc.; halogenated aliphatic group, an amide group, an alkoxyl group, a nitro group, a 35 alcohols such as 2-chloroethanol. 1-chloro-3-hydroxypro nitrile group, a halogenatom, a formyl group, a dialkylamino pane, etc.; glycol ethers such as ethylene glycol monomethyl group, a toluenesulfonyl group, a methanesulfonyl group or a ether, ethylene glycol monoethyl ether, ethylene glycol OH group; and monopropyl ether, ethylene glycol monoisopropyl ether, eth ylene glycol monobutyl ether, ethylene glycol monoisobutyl 40 ether, ethylene glycol monohexyl ether, ethylene glycol (XVI) monophenyl ether, diethylene glycol monomethyl ether, N N diethylene glycol monoethyl ether, diethylene glycol mono HO-I I-8-4 --OH propyl ether, diethylene glycol monoisopropyl ether, diethyl 21 2 ene glycol monobutyl ether, diethylene glycol monoisobutyl 45 ether, diethylene glycol monohexyl ether, diethylene glycol monophenyl ether, propylene glycol monomethyl ether, pro wherein at least one hydrogenatom of each benzene ring may pylene glycol monoethylether, propylene glycol monopropyl be replaced by a substituent group, which is preferably an ether, propylene glycol monoisopropyl ether, propylene gly aromatic compound residue, an aliphatic compound residue col monobutyl ether, propylene glycol monoisobutyl ether, or a heterocyclic compound residue or which may be a 50 propylene glycol monophenyl ether, dipropylene glycol hydroxyl group, a nitro group, a nitrile group, a carbamoyl monomethyl ether, dipropylene glycol monoethyl ether, group, a Sulfamoyl group, a carboxyl group, a nitroso group. dipropylene glycol monopropyl ether, dipropylene glycol an amino group, an oxyamino group, a nitroamino group, a monoisopropyl ether, dipropylene glycol monobutyl ether, hydrazino group, a ureido group, an isocyanate group, a mer dipropylene glycol monoisobutyl ether, dipropylene glycol capto group, a Sulfo group or a halogen atom, each of the 55 monophenyl ether, etc.; diols such as ethylene glycol, dieth residues may have one or more Substituents, Ö is a group ylene glycol, triethylene glycol. 1,3-propanediol. 1,2-pro selected from the group consisting of —SO —O—, panediol, propylene glycol, dipropylene glycol, tripropylene (S), , —(CH), , —CO , —CONH-, -NH-. glycol, 1,4-butanediol. 1.5-pentanediol, 1.6-hexanediol. —CH(COOR)— —C(CF)— and —CRR- or is hexylene glycol, 1.9-nonanediol, neopentylglycol, methyl absent, each of R. RandR is independently an alkyl group, 60 pentanediol, etc.; aliphatic polyols such as glycerin, castor and n is 1 or 2. oil, trimethylol-propane, trimethylolethane, hexanetriol, pen The term “aliphatic” used in the case of the seventh to taerythritol, C.-methylglucoside, Sorbitol. Sucrose, etc.; poly nineteenth aspects of the present invention includes the term ols such as polyethylene glycols, polypropylene glycols, “alicyclic”. polytetramethylene glycols, adipate-derived polyols, epoxy The term “aliphatic compound residue' used in the case of 65 modified polyols, polyether ester polyols, polycarbonate the seventh to nineteenth aspects of the present invention polyols, polycaprolactone diols, amine-modified polyols, means a residue bonded by the carbon atom of the aliphatic polyether polyols obtained by adding one of or a mixture of US 7,635,662 B2 93 94 two or more of alkylene oxides (e.g. ethylene oxide and niline, 2-phenoxysulfonylaniline, 2-(2-chlorophenoxy) propylene oxide) to one of or a mixture of two or more of Sulfonyl-aniline, 3-anilinosulfonyl-4-methylaniline, bis4 polyhydric alcohols (glycerin and propylene glycol), acryl (m-aminophenoxy)phenyl Sulfone, bis4-(p- polyols, fluorinated polyols, polybutadiene polyols, polyhy aminophenoxy)-phenyl Sulfone, bis3-methyl-4-(p- droxy polyols, castor oil-derived polyols, polymer polyols, aminophenoxy)phenyl Sulfone, 3,3'-dimethoxy-4,4'- halogen-containing polyols, phosphorus-containing polyols, diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'- etc.; and alkanolamines Such as N,N-dialkylethanolamines, dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl, 2,2'5,5'- N,N-dialkyliso-propanolamines, N-alkyldiethanolamines, tetrachloro-4,4'-diaminobiphenyl, o-tolidine sulfone, 2,4'- N-alkyldiisopropanolamines, triethanolamine, triisopro diamino-biphenyl, 2,2'-diaminobiphenyl, 4,4'- panolamine, N.N.N',N'-tetrakis(2-hydroxyethyl)ethylenedi 10 diaminobiphenyl, 2,2'-dichloro-4,4'-diaminobiphenyl, 3,3'- amine, N.N.N',N'-tetrakis(2-hydroxypropyl)ethylenedi dichloro-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'- amine, etc. diaminobiphenyl, 4,4'-thiodianiline, 2,2'-dithiodianiline, Of the above-exemplified alcohol compounds, aliphatic 4,4'-dithiodianiline, 4,4'-diaminodiphenyl ether, 3,3'-diami alcohols having 10 or less carbonatoms, the glycol ethers, the nodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diamino diols, the aliphatic polyols, polyols having a molecular 15 diphenylmethane, 3,4'-diaminodiphenyl-methane, bis(3- weight of 2,000 or less, and the alkanolamines are preferable. amino-4-chlorophenyl) sulfone, bis(3,4-diaminophenyl) The above-exemplified alcohol compounds may be used sulfone, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl singly or in combination, and the above-exemplified phenol sulfone, 3,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphe compounds may also be used singly or in combination. nylmethane, 4.4-diamino-diphenylamine, 4,4'-ethylenedi As the amino compound that is reacted with the polyiso aniline, 4,4'-diamino-2,2'-dimethyldibenzyl, 3,3'-diami cyanate compound to form one or more urea groups, any nobenzophenone, 4,4'-diaminobenzophenone, 1,4-bis(4- compound may be used so long as it has one or more amino aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, groups bonded to carbon atoms, respectively. The amino 1,3-bis(3-amino-phenoxy)benzene, 9.9-bis(4-aminophenyl) compound includes, for example, aromatic amines Such as fluorene, 2.2-bis(4-aminophenoxyphenyl)propane, 4,4'-bis aniline, o-toluidine, m-toluidine, p-toluidine, o-anisidine, 25 (4-amino-phenoxy)diphenyl, 3.3',4,4-tetraaminodiphenyl p-anisidine, p-phenetidine, N,N-dimethyl-p-phenylenedi ether, 3.3',4,4-tetraaminodiphenyl sulfone, 3,3',4,4-tet amine, N,N-diethyl-p-phenylenediamine, 2,4-dimethoxya raaminobenzophenone, 3-aminobenzonitrile, 4-phenoxya niline, 2,5-dimethoxyaniline, 3,4-dimethoxyaniline, niline, 3-phenoxyaniline, 4,4'-methylenebis-o-toluidine, p-amino-acetanilide, p-aminobenzoic acid, o-aminophenol, 4,4'-(p-phenyleneisopropylidene)-bis-(2,6-Xylidine), m-aminophenol, p-aminophenol. 2.3-Xylidine, 2,4-Xylidine, 30 o-chloro-p-nitroaniline, o-nitro-p-chloroaniline, 2,6- 3,4-Xylidine, 2,6-Xylidine, 4-aminobenzonitrile, anthranilic dichloro-4-nitroaniline, 5-chloro-2-nitroaniline, 2-amino-4- acid, p-cresidine, 2,5-dichloroaniline, 2,6-dichloroaniline, chlorophenol, o-nitroaniline, m-nitroaniline, p-nitroaniline, 3,4-dichloroaniline, 3,5-dichloroaniline, 2,4,5-trichloroa 2-methyl-4-nitro-aniline, m-nitro-p-toluidine, 2-amino-5-ni niline, C.-naphthylamine, aminoanthracene, o-ethylaniline, trobenzo-nitrile, Metol. 2,4-diaminophenol, N-(B-hydroxy o-chloroaniline, m-chloroaniline, p-chloroaniline, N-methy 35 ethyl)-o-aminophenol sulfate, Sulfanilic acid, metanilic acid, laniline, N-ethylaniline, N-propylaniline, N-butylaniline, 4B acid, C acid, 2B acid, p-fluoroaniline, o-fluoro-aniline, N,N-diglycidylaniline, N,N-diglycidyl-o-toluidine, 3-chloro-4-fluoroaniline, 2,4-difluoroaniline, 2,3,4-trifluo acetoacetic acid anilide, trimethylphenyl-ammonium bro roaniline, m-aminobenzotrifluoride, m-toluylenediamine, mide, 4,4'-diamino-3,3'-diethyldiphenyl-methane, 4,4'-di 2-aminothiophenol, 2-amino-3-bromo-5-nitrobenzonitrile, aminobenzanilide, 3.5-diaminochloro-benzene, diamino 40 diphenylamine, p-aminodiphenylamine, octylated dipheny diphenyl ether, 3,3'-dichloro-4,4'-diaminodiphenylmethane, lamine, 2-methyl-4-methoxydiphenyl-amine, N,N-diphenyl 3,3'-dimethyl-4,4'-diaminodiphenylmethane, tolidine base, p-phenylenediamine, dianisidine, 3,3'-dichlorobenzidine, o-phenylene-diamine, m-phenylenediamine, p-phenylenedi 4,4'-diaminostilbene-2,2'-disulfonic acid, benzylethyla amine, 2-chloro-p-phenylenediamine, dianisidine, methyl niline, 1,8-naphthalene-diamine, sodium naphthionate, p-aminobenzoate, ethyl p-aminobenzoate, n-propyl p-ami 45 Tobias acid, Hacid, Jacid, phenyl Jacid, 1,4-diamino-an nobenzoate, isopropyl p-aminobenzoate, butyl p-aminoben thraquinone, 1,4-diamino-2,3-dichloroanthraquinone, etc.; Zoate, dodecyl p-aminobenzoate, benzyl p-aminobenzoate, heterocyclic compound amines such as 3-amino-1,2,4-triaz o-aminobenzophenone, m-aminoaceto-phenone, p-aminoac ole, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, etophenone, m-aminobenzamide, o-aminobenzamide, C.-amino-e-caprolactam, acetoguanamine, 2,4-diamino-6- p-aminobenzamide, p-amino-N-methylbenzamide, 3-amino 50 2-methylimidazolyl-(1)ethyl-S-triazine, 2,3-diamino-pyri 4-methylbenzamide, 3-amino-4-methoxybenzamide, dine, 2,5-diaminopyridine, 2,3,5-triaminopyridine, 1-amino 3-amino-4-chlorobenzamide, p-(N-phenylcarbamoyl) 4-methylpiperazine, 1-(2-aminoethyl)piperazine, bis aniline, p-N-(4-chlorophenyl)-carbamoylaniline, p-N-(4- (aminopropyl)piperazine, N-(3-aminopropyl)-morpholine, aminophenyl)carbamoyl-aniline, 2-methoxy-5-(N-phenyl etc.; and aliphatic amines such as methylamine, ethylamine, carbamoyl)aniline, 2-methoxy-5-N-(2-methyl-3- 55 dimethylamine, diethylamine, Stearylamine, allylamine, dial chlorophenyl)carbamoyl-aniline, 2-methoxy-5-N-(2- lylamine, isopropylamine, diisopropylamine, 2-ethylhexy chlorophenyl)carbamoyl-aniline, 5-acetylamino-2- lamine, ethanolamine, 3-(2-ethylhexyloxy)propylamine, methoxyaniline, 4-acetyl-aminoaniline, 4-(N-methyl-N- 3-ethoxypropylamine, diisobutylamine, 3-(diethylamino) acetylamino)aniline, 2,5-diethoxy-4-(N-benzoylamino) propylamine, di-2-ethylhexylamine, 3-(dilbutylamino)propy aniline, 2,5-dimethoxy-4-(N-benzoylamino)aniline, 60 lamine, t-butylamine, propylamine, 3-(methylamino)propy 2-methoxy-4-(N-benzoylamino)-5-methylaniline, 4-sulfa lamine, 3-(dimethylamino)propylamine, moylaniline, 3-sulfamoylaniline, 2-(N-ethyl-N-phenylami 3-methoxypropylamine, methylhydrazine, 1-methylbuty nosulfonyl)aniline, 4-dimethyl-aminosulfonylaniline, 4-di lamine, methanediamine, 1,4-diaminobutane, cyclohex ethylaminosulfonylaniline, Sulfathiazole, 4-aminodiphenyl anemethylamine, cyclohexyl-amine, 4-methylcyclohexy sulfone, 2-chloro-5-N-phenylsulfamoylaniline, 2-methoxy 65 lamine, 2-bromoethylamine, 2-methoxyethylamine, 5-N,N-diethyl-sulfamoylaniline, 2,5-dimethoxy-4-N- 2-ethoxymethylamine, 2-amino-1-propanol, 2-aminobu phenysulfamoyl-aniline, 2-methoxy-5-benzylsulfonyla tanol, 3-amino-1,2-propanediol. 1,3-diamino-2-hydroxypro US 7,635,662 B2 95 96 pane, 2-aminoethanethiol, ethylene-diamine, diethylenetri amine, hexamethylenediamine, etc. -continued In addition, of the above-exemplified amino compounds, the aromatic amines are preferable, and aniline derivatives having at least one amino group and represented by the fol 5 lowing formula (Z) or (VIII) are specially preferable: O or is absent, each of R, R2 and R is an alkyl group, and n is (Z) 10 1 or 2. Such amine compounds may be used singly or in combi nation. The urea-urethane compound used as developer in the twentieth aspect of the present invention refers to a compound 15 having at least one urea group (-NHCONH-group) and at least one urethane group ( NHCOO group) in the mol ecule. wherein R and R are independently a hydrogen atom, a It has been known that compounds having one or more urea halogen atom, an alkyl group, an alkoxy group or an amino groups have color-developing effect, but they have not been group; or practical because they give a low coloring density and have an insufficient shelf stability. However, surprisingly, a urea-ure thane compound having both at least one urea group and at (VIII) least one urethane group in the molecule is an excellent devel oper for a colorless or light-colored dye precursor, and a 25 color-producing composition comprising the urea-urethane compound and the dye precursor and a recording material CO-C. obtained by using the color-producing composition give a high coloring density and have an excellent shelf stability. Although a mechanism by which such a urea-urethane wherein R. R. R. and Ra are independently a hydrogen 30 compound exhibits an excellent color-developing effect is atom, a halogen atom, an alkyl group, an alkoxy group or an unknown, it is conjectured that the effect is due to the inter amino group, X and X are independently an amino group or action between the urea group(s) and the urethane group(s) in a group represented by the formula (b): the molecule. As the urea-urethane compound used as developer in the 35 twentieth aspect of the present invention, any compound may (b) be used so long as it has both at least one urea group (-NH CONH group) and at least one urethane group ( NH COO-group) in the molecule. The urea-urethane compound is preferably an aromatic compound or a heterocyclic com --O). 40 pound. In addition, the urea-urethane compound is preferably a compound in which an aromatic compound residue or het erocyclic compound residue is directly bonded to each end of and Yi is any of —SO , —O— —(S), , —(CH), , each of the urea group(s) and the urethane group(s). It is more CO , CONH , NH CH(COOR) , preferable that besides the urea group(s) ( NHCONH —C(CF) , —CRR- and a group represented by any of 45 group(s)) and urethane group(s) (—NHCOO— group(s)), the formulas (a): one or more Sulfonic acid groups (—SO - groups), amide groups (-NHCO— groups) or isopropylidene groups (—C (CH)—groups) be present in the molecule without binding (a) directly to the urea group(s). The molecular weight of the urea-urethane compound is preferably 5,000 or less, more preferably 2,000 or less. The total number of urea group(s) and urethane group(s) in the urea-urethane compound is preferably 20 or less, more pref 55 erably 10 or less. The ratio of urea group(s) to urethane OO group(s) in the molecular structure of the urea-urethane com pound is preferably 1:3 to 3:1, in particular, 1:2 to 2:1. When used in a heat-sensitive recording material, the urea CH urethane compound is preferably one that has a melting point. 60 The melting point ranges preferably from 40°C. to 500°C., in t th 76. particular, from 60° C. to 300° C. A process for synthesizing the urea-urethane compound --O--CH CH -o-O-o-N-4 used as developer in the twentieth aspect of the present inven tion is not particularly limited so long as at least one urea 65 group (-NHCONH group) and at least one urethane group (-NHCOO— group) are formed. A process in which the urea-urethane compound is produced by the reaction of an US 7,635,662 B2 97 98 isocyanate compound with an OH group-containing com o-chloroaniline, m-chloroaniline, p-chloroaniline, N-methy pound and an amine compound is preferable because of its laniline, N-ethylaniline, N-propylaniline, N-butylaniline, CaSC. N,N-diglycidylaniline, N,N-diglycidyl-o-toluidine, In detail, in the case of the urea-urethane compound used as acetoacetic acid anilide, trimethylphenylammonium bro developer in the present invention, an isocyanate having at 5 mide, 4,4'-diamino-3,3'-diethyldiphenylmethane, 4,4'-diami least two isocyanate groups is used as a starting material and nobenzanilide, 3,5-diaminochlorobenzene, diaminodiphenyl one or more urethane groups are formed by reacting all the ether, 3,3'-dichloro-4,4'-diaminodiphenylmethane, 3,3'-dim isocyanate groups except at least one with an OH group ethyl-4,4'-diaminodiphenylmethane, tolidine base, o-phe containing compound, after which one or more urea groups nylenediamine, m-phenylenediamine, p-phenylene-diamine, can be formed by reacting the remaining isocyanate group(s) 10 2-chloro-p-phenylenediamine, dianisidine, methyl p-ami with an amine compound. It is also possible to form one or nobenzoate, ethyl p-aminobenzoate, n-propyl p-aminoben more urea groups by reacting all the isocyanate groups except Zoate, isopropyl p-aminobenzoate, butyl p-aminobenzoate, at least one with an amine compound at first, and then form dodecyl p-aminobenzoate, benzyl p-aminobenzoate, o-ami one or more urethane groups by reacting the remaining iso nobenzophenone, m-aminoaceto-phenone, p-aminoac cyanate group(s) with an OH group-containing compound. 15 etophenone, m-aminobenzamide, o-aminobenzamide, The starting isocyanate is not particularly limited so longas p-aminobenzamide, p-amino-N-methyl-benzamide, it has two or more isocyanate groups. The starting isocyanate 3-amino-4-methylbenzamide, 3-amino-4-methoxybenza includes, for example, p-phenylene diisocyanate, 2.5- mide, 3-amino-4-chlorobenzamide, p-(N-phenylcarbamoyl) dimethoxybenzene-1,4-diisocyanate, 2,4-toluene diisocyan aniline, p-N-(4-chlorophenyl)-carbamoylaniline, p-N-(4- ate, 2,6-toluene diisocyanate, diphenylmethane diisocyanate, 20 aminophenyl)carbamoyl-aniline, 2-methoxy-5-(N- o-tolidine diisocyanate, diphenyl ether diisocyanate, 1.5- phenylcarbamoyl)aniline, 2-methoxy-5-N-(2-methyl-3- naphthylene diisocyanate, dianisidine diisocyanate, 9-ethyl chlorophenyl)carbamoyl-aniline, 2-methoxy-5-N-(2- carbazole-3,6-diisocyanate, 3,3'-dimethyl-4,4'-diphenyl chlorophenyl)carbamoyl-aniline, 5-acetylamino-2- methane diisocyanate, hexamethylene diisocyanate, methoxyaniline, 4-acetyl-aminoaniline, 4-(N-methyl-N- isophorone diisocyanate, triphenylmethane triisocyanate, tris 25 acetylamino)aniline, 2,5-diethoxy-4-(N-benzoylamino) (4-phenylisocyanato)thiophosphate, 4.4.4.4"-triisocyanato aniline, 2,5-dimethoxy-4-(N-benzoylamino)aniline, 2,5-dimethoxytriphenylamine, 4,4',4'-triisocyanatotriph 2-methoxy-4-(N-benzoylamino)-5-methylaniline, 4-sulfa enylamine, m-xylylene diisocyanate, lysine diisocyanate, moylaniline, 3-sulfamoylaniline, 2-(N-ethyl-N-phenylami dimeracid diisocyanate, isopropylidene bis-4-cyclohexyliso nosulfonyl)aniline, 4-dimethyl-aminosulfonylaniline, 4-di cyanate, dicyclohexylmethane diisocyanate and methylcy- 30 ethylaminosulfonylaniline, Sulfathiazole, 4-aminodiphenyl clohexane diisocyanate. As the starting isocyanate, there may sulfone, 2-chloro-5-N-phenylsulfamoylaniline, 2-methoxy also be used diisocyanate dimers such as N,N'-(4,4'-dimethyl 5-N,N-diethyl-sulfamoylaniline, 2,5-dimethoxy-4-N- 3,3'-diphenyldiisocyanato)urethodione (Desmodur TT, a phenysulfamoyl-aniline, 2-methoxy-5-benzylsulfonyla trade name), a toluene diisocyanate dimer; and diisocyanate niline, 2-phenoxy-Sulfonylaniline, 2-(2-chlorophenoxy) trimers such as 4,4',4'-trimethyl-3,3',3'-triisocyanato-2,4,6- 35 sulfonylaniline, 3-anilinosulfonyl-4-methylaniline, bis4 triphenylcyanurate. There may also be used water adduct (m-aminophenoxy)phenyl Sulfone, bis4-(p- isocyanates of toluene diisocyanate, diphenylmethane diiso aminophenoxy)-phenyl Sulfone, bis3-methyl-4-(p- cyanate and the like, such as 1,3-bis(3-isocyanato-4-meth aminophenoxy)phenyl Sulfone, 3,3'-dimethoxy-4,4'- ylphenyl)urea; polyol adducts such as trimethylolpropane diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'- adduct of toluene diisocyanate (Desmodur L., a trade name); 40 dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl, 2,2'5,5'- and amine adducts. There may also be used compounds hav tetrachloro-4,4'-diaminobiphenyl, o-tolidine sulfone, 2,4'- ing two or more isocyanate groups, among the isocyanate diaminobiphenyl, 2,2'-diaminobiphenyl, 4,4'-diamino compounds and isocyanate adduct compounds described in biphenyl, 2,2'-dichloro-4,4'-diaminobiphenyl, 3,3'-dichloro the specification of JP-A-8-225,445 and the specification of 4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, JP-A-8-250,623. 45 4,4'-thiodianiline, 2,2'-dithiodianiline, 4,4'-dithiodianiline, Especially preferable examples of the starting isocyanate 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'- are toluene diisocyanates. Of the toluene diisocyanates, 2.4- diaminodiphenyl ether, 4,4'-diaminodiphenyl-methane, 3,4'- toluene diisocyanate is preferable. Besides 2.4-toluene diiso diaminodiphenylmethane, bis(3-amino-4-chlorophenyl) sul cyanate, mixtures of 2.4-toluene diisocyanate and 2,6-toluene fone, bis(3,4-diaminophenyl) sulfone, 4,4'-diaminodiphenyl diisocyanate are generally on the market and available at a 50 sulfone, 3,3'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl low price and may also be used as the staring isocyanate. Sulfone, 3,3'-diamino-diphenyl-methane, 4.4-diaminodiphe As the amine compound that is reacted with the starting nylamine, 4,4'-ethylenedianiline, 4,4'-diamino-2,2'-dimeth isocyanate for the urea-urethane compound as developer to yldibenzyl, 3,3'-diaminobenzophenone, 4,4'-diaminoben form one or more urea groups, any compound may be used so Zophenone, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4- long as it has one or more amino groups. The amine com- 55 amino-henoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, pound includes, for example, aromatic amines such as 9.9-bis(4-aminophenyl)fluorene, 2.2-bis(4-aminophenoxy aniline, o-toluidine, m-toluidine, p-toluidine, o-anisidine, phenyl)propane, 4,4'-bis(4-aminophenoxy)diphenyl, 3.3.4. p-anisidine, p-phenetidine, N,N-dimethylaniline, N,N-di 4-tetraaminodiphenyl ether, 3.3',4,4-tetraaminodiphenyl ethylaniline, N,N-dimethyl-p-phenylenediamine, N,N-di Sulfone, 3.3,4,4-tetraamino-benzophenone, 3-aminoben ethyl-p-phenylenediamine, 2,4-dimethoxyaniline, 2.5- 60 Zonitrile, 4-phenoxyaniline, 3-phenoxyaniline, 4,4'-methyl dimethoxy-aniline, 3,4-dimethoxyaniline, enebis-o-toluidine, 4,4'-(p-phenyleneisopropylidene)-bis-(2, p-aminoacetanilide, p-aminobenzoic acid, o-aminophenol, 6-Xylidine), o-chloro-p-nitroaniline, o-nitro-p-chloroaniline, m-aminophenol, p-aminophenol. 2.3-Xylidine, 2,4-Xylidine, 2,6-dichloro-4-nitroaniline, 5-chloro-2-nitroaniline, 3,4-Xylidine, 2,6-Xylidine, 4-aminobenzonitrile, anthranilic 2-amino-4-chlorophenol, o-nitroaniline, m-nitroaniline, acid, p-cresidine, 2,5-dichloroaniline, 2,6-dichloroaniline, 65 p-nitroaniline, 2-methyl-4-nitroaniline, m-nitro-p-toluidine, 3,4-dichloroaniline, 3,5-dichloroaniline, 2,4,5-trichloroa 2-amino-5-nitrobenzonitrile, Metol. 2,4-diaminophenol, niline, C.-naphthylamine, aminoanthracene, o-ethylaniline, N-(B-hydroxyethyl)-o-aminophenol sulfate, sulfanilic acid, US 7,635,662 B2 99 100 metanilic acid, 4B acid, C acid, 2B acid, p-fluoroaniline, o-fluoroaniline, 3-chloro-4-fluoroaniline, 2,4-difluoroa niline, 2,3,4-trifluoroaniline, m-aminobenzotrifluoride, (a) m-toluylenediamine, 2-aminothiophenol, 2-amino-3-bromo 5-nitrobenzonitrile, diphenylamine, p-aminodiphenylamine, octylated diphenylamine, 2-methyl-4-methoxydiphenyl amine, N,N-diphenyl-p-phenylenediamine, dianisidine, 3,3'- dichlorobenzidine, 4,4'-diaminostilbene-2,2'-disulfonic acid, benzylethylaniline, 1.8-naphthalene-diamine, sodium naph 10 CO thionate, Tobias acid, H acid, Jacid, phenyl J acid, 1,4- diamino-anthraquinone, 1,4-diamino-2,3-dichloroan CH thraquinone, etc.; heterocyclic compound amines such as 3-amino-1,2,4-triazole, 2-aminopyridine, 3-aminopyridine, st th 76. 4-aminopyridine, C.-amino-e-caprolactam, acetoguanamine, 15 2,4-diamino-6-2'-methylimidazolyl-(1)ethyl-S-triazine, --O--CH CH -o-O-o-N-4 2,3-diamino-pyridine, 2,5-diaminopyridine, 2,3,5-triami nopyridine, 1-amino-4-methylpiperazine, 1-(2-aminoethyl) piperazine, bis(aminopropyl)piperazine, N-(3-aminopro -O-O-O-o- pyl)-morpholine, etc.; and aliphatic amines such as O methylamine, ethylamine, dimethylamine, diethylamine, Stearylamine, allylamine, diallylamine, isopropylamine, diisopropylamine, 2-ethylhexylamine, ethanolamine, 3-(2- O ethylhexyloxy)propylamine, 3-ethoxypropylamine, diisobu 25 tylamine, 3-(diethylamino)propylamine, di-2-ethylhexy lamine, 3-(dibutylamino)propylamine, t-butylamine, or is absent, and n is 1 or 2. propylamine, 3-(methylamino)propylamine, 3-(dimethy As the OH group-containing compound that is reacted with lamino)propylamine, 3-methoxypropylamine, methylhydra the isocyanate to form one or more urethane groups, any 30 compound may be used so long as it contains one or more OH Zine, 1-methylbutylamine, methanediamine, 1,4-diaminobu groups. The OH group-containing compound includes, for tane, cyclohexanemethylamine, cyclohexyl-amine, example, phenols such as phenol, cresol, xylenol, p-ethylphe 4-methylcyclohexylamine, 2-bromoethylamine, 2-methoxy nol, o-isopropyl-phenol, resorcinol, p-tert-butylphenol, ethylamine, 2-ethoxymethylamine, 2-amino-1-propanol, p-tert-octylphenol, 2-cyclohexylphenol, 2-allylphenol, 4-in 2-aminobutanol, 3-amino-1,2-propanediol. 1,3-diamino-2- 35 danol, thymol, 2-naphthol, p-nitrophenol, o-chlorophenol, hydroxypropane, 2-aminoethanethiol, ethylene-diamine, p-chlorophenol. 2.2-bis(4-hydroxyphenyl)-propane, 2.2-bis diethylenetriamine, hexamethylenediamine, etc. (hydroxyphenyl)butane, 2.2-bis(hydroxy-phenyl)pentane, 2.2-bis(hydroxyphenyl)heptane, catechol, 3-methylcatechol, Of the above-exemplified amine compounds, aniline 3-methoxycatechol, pyrogallol, hydroquinone, methylhydro derivatives having at least one amino group and represented 40 quinone, 4-phenylphenol, p.p'-biphenol, 4-cumylphenol, by the following formula (VIII) are especially preferable: butyl bis(4-hydroxyphenyl)acetate, benzyl bis(4-hydroxy phenyl)acetate, bis(4-hydroxyphenyl) sulfone, bis(3-methyl 4-hydroxyphenyl) sulfone, bis(3,5-dimethyl-4-hydroxyphe (VIII) nyl) sulfone, 4-hydroxyphenyl-4'-methylphenyl Sulfone, 45 3-chloro-4-hydroxyphenyl-4'-methylphenyl sulfone, 3,4-di hydroxyphenyl-4'-methylphenyl Sulfone, 4-isopropylox yphenyl-4'-hydroxyphenyl sulfone, bis(2-allyl-4-hydrox yphenyl) sulfone, 4-hydroxyphenyl-4'-benzyloxyphenyl CO-C. Sulfone, 4-isopropylphenyl-4'-hydroxyphenyl sulfone, 4-hy 50 droxy-4-isopropoxydiphenyl sulfone, bis(2-methyl-3-tert butyl-4-hydroxyphenyl) sulfide, 4,4'-dihydroxydiphenyl wherein R. R. R. and Ra are independently a hydrogen ether, 4,4'-thiodiphenol. 4,4'-dihydroxybenzophenone, 2.2- atom, a halogen atom, an alkyl group, an alkoxy group or an bis(4-hydroxyphenyl)hexafluoropropane, 4,4'-dibydroxy amino group, X and X are independently an amino group or diphenylmethane, 3,3'-dihydroxydiphenylamine, bis(4-hy a group represented by the formula (b): 55 droxy-3-methylphenyl) sulfide, bis(4-(2-hydroxy)-phenyl) Sulfone, 2,4-dihydroxybenzophenone, 2.2',4,4-tetrahy droxybenzophenone, phenyl salicylate, Salicylanilide, methyl 4-hydroxybenzoate, benzyl 4-hydroxybenzoate, (4'- (b) chlorobenzyl) 4-hydroxybenzoate, ethyl 12-bis(4-hydroxy 60 benzoate), penty1 1.5-bis(4-hydroxybenzoate), hexyl 1,6-bis (4'-hydroxybenzoate), dimethyl 3-hydroxyphthalate, stearyl --O). gallate, lauryl gallate, methyl gallate, 4-methoxyphenol, 4-(benzyloxy)phenol, 4-hydroxybenzaldehyde, 4-n-octylox ysalicylic acid, 4-n-butyloxysalicylic acid, 4-n-pentylox and Y is any of —SO —O— —(S), , —(CH), , 65 ysalicylic acid, 3-n-dodecyloxysalicylic acid, 3-n-octanoy —CO—, —CONH and a group represented by any of the loxysalicylic acid, 4-n-octyloxy-carbonylaminosalicylic formulas (a): acid, 4-n-octanoyloxycarbonyl-aminosalicylic acid, etc. US 7,635,662 B2 101 102 However, as such phenols, those having an amino group are amide group, alkoxyl groups, nitro group, nitroso group. not desirable. Since the amino group has a higher reactivity nitrile group, toluenesulfonyl group, methanesulfonyl group, with an isocyanate group than does an OH group, the amino acetyl group, halogen atoms, formyl group, dialkylamino group reacts with the isocyanate group before the OH group, groups and isocyanate group are preferable. so that it is difficult in some cases to obtain a desired com Of Such urea-urethane compounds of the general formulas pound. The OH group-containing compound also includes (I) to (VII) as developer, compounds of the general formulas alcohols such as methanol, ethanol, propanol, butanol, pen (II) to (VI) are preferable and compounds of the general tanol, hexanol, heptanol, octanol, isopropanol, iosbutanol, formulas (V) and (VI) are especially preferable. isopentanol, 2-ethyl-1-hexanol. 1-decanol, 2-pentanol, In the case of the urea-urethane compound used as devel 3-hexanol, tert-butanol, tert-amyl alcohol, methyl Cello 10 oper in the twentieth aspect of the present invention and the solve, butyl Cellosolve, methyl Carbitol, allyl alcohol, 2-me compounds of any of the general formulas (I) to (VI) and the thyl-2-propen-1-ol, benzyl alcohol, 4-pyridinemethanol, general formula (VII) as developer, if a residue bonded to phenyl Cellosolve, furfuryl alcohol, cyclohexanol, cyclo their urea group or urethane group is an aliphatic compound hexylmethanol, cyclopentanol, 2-chloroethanol, 1-chloro-3- residue, the coloring density and the print-preserving capa hydroxypropane, glycerin, glycerol, etc.; polyether type 15 bility are deteriorated in some cases. Therefore, the residue polyols such as polypropylene glycols, polytetramethylene bonded to the urea group or urethane group is preferably an ether glycols, adipate-derived polyols, epoxy-modified poly aromatic compound residue or a heterocyclic compound resi ols, polyether ester polyols, polycarbonate polyols, polyca due. However, the deterioration of the coloring density and prolactone diols, phenolic polyols, amine-modified polyols, the print-preserving capability which is likely to be caused by etc.; and polyols such as ethylene glycol, diethylene glycol, the introduction of an aliphatic compound residue is reduced 1,3-propanediol. 1.2-propanediol, propylene glycol, dipropy by an increase in the total number of the urea group(s) and lene glycol, 1,4-butanediol, 1.5-pentanediol, 1.6-hexanediol. urethane group(s). In the case of compounds of the formula 1.6-hexane glycol, 1.9-nonanediol, acryl polyols, fluorocar (III) and the formula (IV), even if an aliphatic compound bon polyols, polybutadiene polyols, polyhydroxy polyols, residue is among residues bonded to the urea group(s) or trimethylolpropane, trimethylolethane, hexanetriol, phos 25 urethane group(s), almost no problem about performance phoric acid, neopentylglycol, pentaerythritol, castor-oil-de characteristics is caused. rived polyols, polymer polyols, methylpentanediol, halogen The urea-urethane compound used as developer in the containing polyols, phosphorus-containing polyols, present invention is usually a colorless or light-colored com ethylenediamine, C.-methylglucoside, Sorbitol. Sucrose, etc. pound that is solid at ordinary temperature. As the urea-urethane compound used as developer in the 30 The molecular weight of the urea-urethane compound used twenty-first aspect of the present invention, the urea-urethane as developer in the present invention is preferably 5,000 or compound of the first aspect of the present invention can be less, more preferably 2,000 or less. used. A process for synthesizing this compound is as already The total number of urea group(s) and urethane group(s) in described in detail in the explanation of the first aspect of the the urea-urethane compound used as developer in the present present invention. 35 invention is preferably 20 or less, more preferably 10 or less. As the urea-urethane compound used as developer in the The ratio of urea group(s) to urethane group(s) in the molecu twenty-second aspect of the present invention, the urea-ure lar structure of the urea-urethane compound is preferably 1:3 thane compound represented by any of the general formulas to 3:1, in particular, 1:2 to 2:1. (I) to (VI) of the second aspect of the present invention and a When used in a heat-sensitive recording material, the melt urea-urethane compound represented by the general formula 40 ing point of urea-urethane compound used as developer in the (VII) can be used. A process for synthesizing the urea-ure present invention is preferably a compound having a melting thane compound represented by any of the general formulas point, and its melting point ranges preferably from 40°C. to (I) to (VI) is as already described in detail in the explanation 500° C., in particular, from 60° C. to 300° C. of the second aspect of the present invention. A process for For producing a recording material by using the urea synthesizing the urea-urethane compound of the general for 45 mula (VII) is not particularly limited. This compound can be urethane compound as developer, the urea-urethane com obtained, for example, by reacting an OH group-containing pound of one kind or, if necessary, a combination of the compound of the general formula (IX) with an isocyanate urea-urethane compounds of two or more kinds may be used. compound of the general formula (XII) and an amine com As the urea-urethane compound or urea-urethane compo 50 sition used as developer in the twenty-third aspect of the pound of the general formula (XI) according to, for instance, present invention, any of the urea-urethane compounds of the the following reaction formula (L). third to sixth aspects of the present invention or any of the urea-urethane compositions of the seventh to eleventh aspects (L) of the present invention can be used. Synthesis processes of X-OH + OCN-Y-NCO -- 55 these compounds and compositions are as already described O in detail in the explanations of the third to eleventh aspects of H X-O-C-N-Y-NCO the present invention. O The colorless or light-colored dye precursor used in the H present invention is a compound well known as a color former X-O-C-N-Y-NCO + Z-NH -- 60 used in pressure-sensitive recording materials and heat-sen O O sitive recording materials and is not particularly limited. As the dye precursor, basic dye precursors are preferable and electron-donating dye precursors are more preferable. Leuco dyes, in particular, triarylmethane type leuco dyes, fluoran As the substituent of Xbonded to the urethane group of the 65 type leuco dyes, fluorene type leuco dyes, diphenyl-methane urea-urethane compound of the general formula (VII), alkyl type leuco dyes and the like are still more preferable. Typical groups, alkenyl groups, phenyl group, cycloalkyl groups. examples of the dye precursor are given below. US 7,635,662 B2 103 104 (1) Triarylmethane Type Compounds Of the above-exemplified dye precursors, triarylmethane 3.3-bis(p-dimethylaminophenyl)-6-dimethyl-aminoph type leuco dyes, fluoran type leuco dyes, fluorene type leuco thalide (Crystal Violet lactone), 3.3-bis(p-dimethylami dyes and diphenylmethane type leuco dyes are preferable nophenyl)phthalide, 3-(p-dimethyl-aminophenyl)-3-(1,2- from the viewpoint of sensitivity and plasticizer resistance, dimethylindol-3-yl)phthalide, 3-(p-dimethylaminophenyl)- and compounds having a structure represented by the follow 3-(2-methylindol-3-yl)phthalide, 3-(p- dimethylaminophenyl)-3-(2-phenylindol-3-yl)phthalide, ing chemical formula (i) or () are more preferable: 3.3-bis(1,2-dimethylindol-3-yl)-5-dimethylaminophthalide, (i)

3.3-bis(1,2-dimethylindol-3-yl)-6-dimethylaminophthalide, 3.3-bis(9-ethylcarbazol-3-yl)-5-dimethylaminophthalide, 10 3.3-bis(2-phenylindol-3-yl)-5-dimethylaminophthalide, 3-p- dimethylamino-phenyl-3-(1-methylpyrrol-2-yl)-6-dimethy lamino-phthalide, etc.

(2) Diphenylmethane Type Compounds 15 4,4'-bis-dimethylaminophenylbenzhydryl benzyl ether, N-halophenyleucoauramines, N-2,4,5-trichloro-phenylleu coauramine, etc. (3) Xanthene Type Compounds Rhodamine Banilinolactam, Rhodamine B-p-chloroanili nolactam, 3-diethylamino-7-dibenzylamino-fluoran, 3-di ethylamino-7-octylaminofluoran, 3-diethylamino-7-phe wherein both Y and Y are alkyl groups or alkoxyalkyl nylfluoran, 3-diethylamino-7-chlorofluoran, 3-diethylamino groups, Y is a hydrogen atom, an alkyl group or an alkoxy 6-chloro-7-methylfluoran, 3-diethylamino-7-(3,4- group, and each of Ys and Y is a hydrogen atom, a halogen dichloroanilino).uoran, 3-diethylamino-7-(2- 25 atom, an alkyl group or an alkoxy group; or chloroanilino) fluoran, 3-diethylamino-6-methyl-7- anilinofluoran, 3-(N-ethyl-N-tolyl)amino-6-methyl-7- () anilinofluoran, 3-piperidino-6-methyl-7-anilinofluoran, R6 Rs 3-(N-ethyl-N-tolyl)amino-6-methyl-7-phenethylfluoran, 3-diethylamino-7-(4-nitroanilino) fluoran, 3-dibutylamino-6- 30 methyl-7-anilinofluoran, 3-(N-methyl-N-propyl)amino-6- R7 "VCEO methyl-7-anilinofluoran, 3-(N-ethyl-N-isoamyl)amino-6- methyl-7-anilinofluoran, 3-(N-methyl-N-cyclohexyl)amino 6-methyl-7-anilinofluoran, 3-(N-ethyl-N-tetrahydrofuryl)- Rs R10 amino-6-methyl-7-anilinofluoran, etc. 35 (4) Thiazine Type Compounds benzoyleucomethylene blue, p-nitrobenzoyl-leucometh wherein each of Rs and R is a group represented by the ylene blue, etc. 40 formula (k) or the formula (1): (5) Spiro-compounds 3-methylspirodinaphthopyran, 3-ethylspiro-dinaphthopy (k) ran, 3.3-dichloroSpirodinaphthopyran, 3-benzylspirodinaph thopyran, 3-methylnaphtho-(3-methoxybenzo)Spiropyran, 3-propylspirobenzopyran, etc. 45 The dye precursor also includes, for example, the follow ing compounds that can absorb a near infrared ray: 3.6-bis (dimethylamino)fluorene-9-spiro-3'-(6'-dimethylamino-ph thalide), 3-diethylamino-6-dimethyl-aminofluorene-9-spiro 3'-(6'-dimethylaminophthalide), 3,6-bis(diethylamino)- 50 fluorene-9-spiro-3'-(6'-dimethyl-aminophthalide), (wherein each of R through Rs is a hydrogen atom, a 3-dibutylamino-6-dimethylamino-fluorene-9-spiro-3'-(6'- halogen atom, a C-C alkyl group, a C-C alkoxy group or dimethylaminophthalide), 3-dibutylamino-6-diethylaminof NRR, wherein each of RandR, is a C-C alkyl group); luorene-9-spiro-3'-(6'-dimethylaminophthalide), 3,6-bis O (dimethylamino)-fluorene-9-spiro-3'-(6'- 55 diethylaminophthalide), 3-diethylamino-6- dimethylaminofluorene-9-spiro-3'-(6'- (l) diethylaminophthalide), 3-dibutylamino-6-dimethyl aminofluorene-9-spiro-3'-(6'-diethylaminophthalide), 3.6- bis(diethylamino)fluorene-9-spiro-3'-(6'- 60 diethylaminophthalide), 3,6-bis(dimethylamino) fluorene-9- spiro-3'-(6'-dibutylaminophthalide), 3-dibutylamino-6- diethylaminofluorene-9-spiro-3'-(6'-diethylamino phthalide), 3-diethylamino-6-dimethylaminofluorene-9- spiro-3'-(6'-dibutylaminophthalide), 3.3-bis(2-(4- 65 dimethylaminophenyl)-2-(4-methoxyphenyl)ethenyl-4,5,6, (wherein each of Rs and Rio is a hydrogen atom, a C-Cs 7-tetrachlorophthalide, etc. alkyl group or a phenyl group), and each of R, through Ro is US 7,635,662 B2 105 106 a hydrogen atom, a halogen atom, a C-Cs alkyl group, a coloring density is high. When the proportion of the isocyan C-C alkoxy group or NRoR wherein each of Ro and R ate compound is 500 parts by weight or less, the isocyanate is a C-C alkyl group. compound hardly remains as a Surplus, and this is economi Such colorless or light-colored leuco dyes may be used in cally advantageous and hence preferable. combination of two or more thereof if necessary. 5 The urea-urethane compound as developer is used in a The incorporation of an imino compound into the color proportion of preferably 5 to 1,000 parts by weight, more producing composition of the present invention further preferably 20 to 500 parts by weight, per 100 parts by weight improves the shelf stability. of the colorless or light-colored dye precursor. As the propor The imino compound that can be incorporated into the tion of the urea-urethane compound as developer, 5 parts by 10 color-producing composition of the present invention is a weight or more is sufficient to allow the dye precursor to colorless or light-colored compound that has at least one develop a color. At Such a proportion, the coloring density is imino group and is solidat ordinary temperature. Two or more high. When the proportion of the urea-urethane compound as imino compounds may be incorporated in combination, developer is 1,000 parts by weight or less, the urea-urethane depending on purposes. As the imino compound, those compound as developerhardly remains as a Surplus, and this 15 described in JP-A-9-142,032 can be mentioned, and the con is economically advantageous and hence preferable. tents of this reference are hereby incorporated herein by ref The incorporation of an isocyanate compound into the erence. Of the imino compounds described in the reference, color-producing composition of the present invention iminoisoindoline derivatives are preferable, and 1,3-diimino improves the shelf stability of the composition. The isocyan 4,5,6,7-tetrachloroisoindoline, 3-imino-4,5,6,7-tetrachlor ate compound incorporated into the color-producing compo oisoindolin-1-one and 1,3-diimino-4,5,6,7-tetrabromoisoin sition of the present invention refers to a colorless or light colored, aromatic or heterocyclic isocyanate compound that doline are more preferable. is solid at ordinary temperature. For example, one or more of The imino compound is used in a proportion of preferably the following isocyanate compounds are used. 5 to 500 parts by weight, more preferably 20 to 200 parts by The isocyanate compound incorporated includes 2.6- 25 weight, per 100 parts by weight of the colorless or light dichlorophenyl isocyanate, p-chlorophenyl isocyanate, 1.3- colored dye precursor. When the proportion of the imino phenylene diisocyanate, 1,4-phenylene diisocyanate, 1.3- compound is 5 parts by weight or more, an improving effect dimethylbenzene-4,6-diisocyanate, 1,4-dimethylbenzene-2, on the shelf stability is obtained. When the proportion of the 5-diisocyanate, 1-methoxybenzene-2,4-diisocyanate, imino compound is 500 parts by weight or less, the imino 1-methoxybenzene-2,5-diisocyanate, 1-ethoxybenzene-2,4- 30 compound hardly remains as a Surplus, and this is economi diisocyanate, 2,5-dimethoxybenzene-1,4-diisocyanate, 2.5- cally advantageous and hence preferable. diethoxylbenzene-1,4-diisocyanate, 2,5-dibutoxybenzene-1, In addition, the incorporation of an amino compound into 4-diisocyanate, azobenzene-4,4'-diisocyanate, diphenyl the color-producing composition of the present invention ether-4,4'-diisocyanate, naphthalene-1,4-diisocyanate, naph improves the preservability of an original recording material thalene-1,5-diisocyanate, naphthalene-2,6-diisocyanate, 35 naphthalene-2,7-diisocyanate, 3,3'-dimethyl-biphenyl-4,4'- Surface and print. The amino compound that can be incorpo diisocyanate, 3,3'-dimethoxy-biphenyl-4,4'-diisocyanate, rated is a colorless or light-colored Substance having at least diphenylmethane-4,4'-diisocyanate, diphenyldimethyl one primary, secondary or tertiary amino group. AS Such an methane-4,4'-diisocyanate, benzophenone-3,3'-diisocyanate, amino compound, those described in JP-A-9-142,032 can be fluorene-2,7-diisocyanate, anthraquinone-2,6-diisocyanate, 40 mentioned. Of the amino compounds described in this refer 9-ethylcarbazole-3,6-diisocyanate, pyrene-3,8-diisocyanate, ence, aniline derivatives having at least one amino group and naphthalene-1,3,7-triisocyanate, biphenyl-2,4,4-triisocyan represented by the following formula (VIII) are especially ate, 4,4',4'-triisocyanato-2,5-dimethoxytriphenylmethane, preferable: 4,4',4'-triisocyanato-triphenylamine, p-dimethylaminophe nyl isocyanate, tris(4-phenylisocyanato)thiophosphate, etc. 45 If necessary, these isocyanates may be used in the form of a (VIII) so-called block isocyanate, i.e., an addition compound with a phenol, lactam, oxime or the like, they may be used in the form of a diisocyanate dimer Such as 1-methylbenzene-2,4- diisocyanate dimmer, or a diisocyanurate trimeras an isocya 50 CO-C. nurate, and they may be used in the form of a polyisocyanate obtained as an adduct by the use of any of various polyols and the like. There may also be used water adduct isocyanates of wherein R. R. R. and Ra are independently a hydrogen 2,4-toluene diisocyanate, diphenylmethane diisocyanate and atom, a halogen atom, an alkyl group, an alkoxy group or an the like, Such as 1,3-bis(3-isocyanato-4-methylphenyl)urea; 55 amino group, X and X are independently an amino group or polyol adducts such as trimethylol-propane adduct of toluene a group represented by the formula (b): diisocyanate (Desmodur L., a trade name); phenol adduct isocyanates; amine adduct isocyanates; and the isocyanate compounds and isocyanate adduct compounds described in (b) the specification of JP-A-10-76,757 and the specification of 60 JP-A-10-95,171. The isocyanate compound is used in a proportion of pref --O). erably 5 to 500 parts by weight, more preferably 20 to 200 parts by weight, per 100 parts by weight of the colorless or light-colored dye precursor. When the proportion of the iso 65 and Y is any of —SO , —O— —(S), , —(CH), , cyanate compound is 5 parts by weight or more, a sufficient —CO—, —CONH and a group represented by any of the improving effect on the shelf stability can be obtained and the formulas (a): US 7,635,662 B2 107 108 droxybenzoate), hexyl 1,6-bis(4-hydroxybenzoate), dim ethyl 3-hydroxyphthalate, Stearyl gallate, lauryl gallate, etc. (a) The salicylic acid derivatives include 4-n-octyloxysalicylic acid, 4-n-butyloxysalicylic acid, 4-n-pentyloxysalicylic acid, 3-n-dodecyloxysalicylic acid, 3-n-octanoyloxysalicylic acid, 4-n-octyloxycarbonylaminosalicylic acid, 4-n-octanoyloxy carbonylaminosalicylic acid, etc. The Sulfonylurea deriva tives include, for example, compounds containing one or more arylsulfonyl-aminoureido groups, such as 4.4-bis(p- CO toluene-Sulfonylaminocarbonylamino)diphenylmethane, 4.4-bis(o-toluenesulfonylaminocarbonylamino)diphenyl methane, 4.4-bis(p-toluenesulfonylaminocarbonylamino) CH3 diphenyl sulfide, 4.4-bis(p-toluenesulfonylaminocarbonyl -O-O- amino)diphenyl ether, N-(p-toluenesulfonyl)-N'-phenylurea, th 76. 15 etc. Further, 4,4'-oxybis(ethyleneoxy-p-phenylenesulfo --O--CH CH -o-O-o-N4 nyl) diphenol, a mixture containing it as a main component (for example, D-90 (trade name) made by Nippon Soda Co., Ltd.) or the like can be used. Among them, 2.2-bis(4-hydroxyphenyl)propane, 4-iso propyloxyphenyl-4'-hydroxyphenylsulfone, bis(3-allyl-4- hydroxyphenyl)sulfone, 2,4'-dihydroxydiphenyl-sulfone and 4.4"-oybis(ethyleneoxy-p-phenylene-Sulfonyl) diphenol are particularly preferable because they enhance the sensitivity to produce a heat-sensitive recording material capable of clear 25 color production. In order to improve fog, the thermal response and the like, or is absent, and n is 1 or 2. it is also possible to add phenolic compounds such as These amino compounds may be used singly or as a mix N-stearyl-N'-(2-hydroxyphenyl)urea, N-stearyl-N'-(3-hy ture thereof. For improving the print preservability in the droxyphenyl)urea, N-stearyl-N'-(4-hydroxyphenyl)urea, plasticizer resistance, the proportion of the amino compound 30 p-Stearoylaminophenol, o-stearoyl-aminophenol, p-lauroy is preferably 1 to 500 parts by weight per 100 parts by weight laminophenol, p-butyrylamino-phenol, m-acetylaminophe of the colorless or light-colored dye precursor. When the nol, o-acetylaminophenol, p-acetylaminophenol, o-buty content of the amino compound is 1 part by weight or more laminocarbonylphenol, o-stearylaminocarbonylphenol, perpart of the urea-urethane compound, the print preservabil p-stearylaminocarbonyl-phenol, 1,1,3-tris(3-tert-butyl-4-hy ity can be improved. When the content is 500 parts by weight 35 droxy-6-methylphenyl)butane, 1,1,3-tris(3-tert-butyl-4-hy or less, performance characteristics of the resulting compo droxy-6-ethylphenyl)butane, 1,1,3-tris(3,5-di-tert-butyl-4- sition can be sufficiently improved and Such a content is hydroxyphenyl)butane, 1,1,3-tris(3-tert-butyl-4-hydroxy-6- advantageous from the viewpoint of cost. methylphenyl)propane, 1,2,3-tris(3-tert-butyl-4-hydroxy-6- The incorporation of also an acidic developer into the methylphenyl)butane, 1,1,3-tris(3-phenyl-4-hydroxyphenyl) color-producing composition of the present invention 40 butane, 1,1,3-tris(3-cyclohexyl-4-hydroxy-5-methylphenyl) improves the sensitivity and enables the color-producing butane, 1,1,3-tris(3-cyclohexyl-4-hydroxy-6-methylphenyl) composition to produce a brilliant color. butane, 1,1,3-tetra(3-phenyl-4-hydroxyphenyl)propane, 1.3, As the acidic developer that is used when the color-pro 3-tetra(3-cyclohexyl-4-hydroxy-6-methylphenyl)propane, ducing composition of the present invention is used in a 1,1-bis(3-tert-butyl-4-hydroxy-6-methylphenyl)butane, 1,1- heat-sensitive recording material, conventional electron-ac 45 bis(3-cyclohexyl-4-hydroxy-6-methylphenyl)butane, etc. cepting materials are used and, in particular, phenol deriva The above-mentioned acidic developer is used in a propor tives; aromatic carboxylic acid derivatives or their metalcom tion of preferably 5 to 500 parts by weight, more preferably 20 pounds; salicylic acid derivatives or their metal salts; N.N- to 200 parts by weight, per 100 parts by weight of the color diaryl-thiourea derivatives; sulfonylurea derivatives; etc. are less or light-colored dye precursor. When the proportion of preferable. The phenol derivatives are especially preferable. 50 the acidic developer is 5 parts by weight or more, the color Specific examples of the phenol derivatives are 2.2-bis(4- development of the dye precursor is satisfactory and the col hydroxyphenyl)propane, 2.2-bis(hydroxyphenyl)butane, oring density is high. When the proportion of the acidic devel 2.2-bis(hydroxyphenyl)-pentane, 2.2-bis(hydroxyphenyl) oper is 500 parts by weight or less, the acidic developerhardly heptane, 1,1-bis(4-hydroxyphenyl)cyclohexane, butyl bis(4- remains, and this is economically advantageous and hence hydroxyphenyl)-acetate, benzyl bis(4-hydroxyphenyl)ac 55 preferable. etate, bis(4-hydroxyphenyl) sulfone, bis(3-methyl-4- Also when the color-producing composition of the present hydroxyphenyl) sulfone, 4-hydroxyphenyl-4'-methylphenyl invention is used in a pressure-sensitive recording material, sulfone, 3-chloro-4-hydroxyphenyl-4'-methylphenyl sul the incorporation of an acidic developer into the color-pro fone, 3,4-dihydroxyphenyl-4'-methylphenyl sulfone, 4-iso ducing composition improves the coloring density and propylphenyl-4'-hydroxyphenyl Sulfone, 4-isopropylox 60 enables the pressure-sensitive recording material to produce a yphenyl-4-hydroxyphenyl Sulfone, bis(2-allyl-4- brilliant color. hydroxyphenyl) Sulfone, 4-hydroxyphenyl-4- Also as this acidic developer, an electron-accepting mate benzyloxyphenyl Sulfone, 4-isopropylphenyl-4- rial is used. The acidic developer includes, for example, inor hydroxyphenyl Sulfone, bis(2-methyl-3-tert-butyl-4- ganic compounds Such as acid clay, activated clay, attapulg hydroxyphenyl) sulfide, methyl 4-hydroxybenzoate, benzyl 65 ite, bentonite, Zeolite, colloidal silica, magnesium silicate, 4-hydroxybenzoate, (4-chlorobenzyl) 4-hydroxybenzoate, talc, aluminum silicate, etc.; phenol, cresol, butylphenol, ethyl 12-bis(4-hydroxybenzoate), pentyl 1.5-bis(4-hy octyl-phenol, phenylphenol, chlorophenol, Salicylic acid and US 7,635,662 B2 109 110 the like, or aldehyde condensation novolak resins derived droxy-5'-octyloxycarbonylethylphenyl)-5-chlorobenzotriaz therefrom and their metal salts; and salicylic acid derivatives ole and the like: 4-hydroxy-, 4-methoxy-, 4-Octoxy-, Such as 3-isopropylsalicylic acid, 3-phenylsalicylic acid, 4-decyloxy-, 4-dodecyloxy-, 4-benzyloxy-, 4.2',4'-trihy 3-cyclohexylsalicylic acid,3,5-di-t-butylsalicylic acid,3,5-di droxy-, 2-hydroxy-4,4'-dimethoxy- or 4-(2-ethylhexyloxy)- (C.-methylbenzyl)-salicylic acid, 3,5-di-t-octylsalicylic acid, 2-hydroxybenzophenone derivatives and the like: 4-t-bu 3-methyl-5-benzylsalicylic acid, 3.5-di(O.C.-dimethylben tylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, Zyl)-salicylic acid, 3-phenyl-5-(C.C.-dimethylbenzyl)-sali dibenzoylresorcinol, bis(4-t-butylbenzoyl)resorcinol, 2,4-di cylic, etc. and metal salts thereof. t-butylphenyl 3,5-di-t-butyl-4-hydroxybenzoate, hexadecyl The incorporation of also a fluorescent dye improves the 3,5-di-t-butyl-4-hydroxybenzoate and the like; ethyl C-cy whiteness. As the fluorescent dye to be incorporated into the 10 ano-B.f3-diphenylacrylate, isooctyl C-cyano-B.B-dipheny color-producing composition of the present invention, Vari lacrylate, methyl C-carbomethoxy-cinnamate, methyl C-cy ous well-known ones can be used, and there are mentioned ano-3-methyl-p-methoxycinnamate and the like; bis(2.2.6.6- stilbene derivatives, coumarin derivatives, pyrazoline deriva tetramethyl-4-piperidyl) sebacate, bis(2.2.6,6-tetramethyl-4- tives, bisstyrylbiphenyl derivatives, naphthalimide deriva piperidyl) Succinate, bis(1.2.2.6,6-pentamethyl-4-piperidyl) tives, bisbenzoxazolyl derivatives, etc. Although fluorescent 15 sebacate, bis(1-octyloxy-2.2.6,6-tetramethyl-4-piperidyl) dye is not limited to them, diaminostilbenesulfonic acid sebacate, bis(1.2.2.6,6-pentamethyl-4-piperidyl) adipate and derivatives are especially preferable. the like; 4,4'-di-octyloxy-oxanilide, 2,2'-diethoxyoxyoxanil As to the amount of the fluorescent dye used, the fluores ide, 2,2'-di-octyloxy-5,5'-di-t-butyloxanilide, 2,2'-di-dode cent dye is made present in an amount of preferably 0.01 to 3 cyloxy-5.5'-di-t-butyloxanilide, 2-ethoxy-2-ethyloxanilide, wt %, more preferably 0.1 to 2 wt %, based on the total weight N,N'-bis(3-dimethylaminopropyl)oxanilide, 2-ethoxy-5-t- (in terms of dry solids) of the color-producing composition. butyl-2'-ethoxyoxanilide and the like; and 2,4,6-tris(2-hy When the amount of the fluorescent dye used is more than 3 droxy-4-octyloxyphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-oc wt %, the color-producing composition is colored in some tyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, cases. When the amount is less than 0.01 wt %, the effect of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3, the fluorescent dye on the whiteness is lessened. 25 5-triazine, 2,4-bis(2-hydroxy-4-propyloxyphenyl-6-(2,4- Next, the color-producing composition of the present dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-dodecylox invention may contain shelf-life-imparting agents. The shelf yphenyl)-4,6-bis(2,4-dimethyl-phenyl)-1,3,5-triazine and life-imparting agents usable in the present invention are addi the like. Usually, these light stabilizers are used in a propor tives such as image-stabilizing agents, light stabilizers, anti tion of preferably 5 to 1,000 parts by weight, more preferably oxidants, etc. By using these shelf-life-imparting agents in 30 10 to 500 parts by weight, per 100 parts by weight of the combination with the urea-urethane compound developerand colorless or light-colored dye precursor. When the proportion the colorless and light-colored dye precursor, the light resis of the light stabilizers is 5 parts by weight or more, the light tance of the color-producing composition can be improved resistance is good and the coloring density is high. When the and a recording material excellent in light resistance can be proportion of the light stabilizers is more than 1,000 parts by obtained. 35 weight, their effect on the light resistance is not heightened The image-Stabilizing agents as preferable examples of the and moreover, Such a proportion is economically disadvanta shelf-life-imparting agents used in the present invention geous. include, for example, 1,1,3-tris(2-methyl-4-hydroxy-5-tert The antioxidants as preferable examples of the shelf-life butylphenyl)butane, 1,1,3-tris(2-methyl-4-hydroxy-5-cyclo imparting agents used in the present invention include, for hexylphenyl)butane, hindered phenol compounds e.g. 4,4'- 40 example, 2,6-di-t-butyl-4-methylphenol, 2-t-4,6-dimeth butylidenebis(2-tert-butyl-5-methylphenol), 4,4'-thiobis(2- ylphenol. 2,6-di-t-butyl-4-ethylphenol. 2,6-di-t-butyl-4-n- tert-butyl-5-methylphenol), 2,2'-thiobis(6-tert-butyl-4- butylphenol. 2,6-di-t-butyl-4-isobutylphenol. 2,6-dicyclo methylphenol) and 2,2'-methylenebis(6-tert-butyl-4- pentyl-4-methyl-phenol, 2-(C.-methylcyclohexyl)-4,6- methylphenol). 4-benzyloxy-4-(2-methylglycidyloxy)- dimethylphenol. 2,6-dioctadecyl-4-methylphenol, 2.4.6- diphenyl Sulfone, 4,4'-diglycidyloxydiphenyl Sulfone, 1,4- 45 tricyclohexylphenol. 2,6-dinonyl-4-methylphenol. 2,6-di-t- diglycidyloxybenzene, Sodium 2,2'-methylenebis(4,6-di butyl-4-methoxy-methylphenol. 2,4-dimethyl-6-(1'-methyl tert-butylphenyl)phosphate, 2-propanol derivatives and undeca-1-yl)-phenol. 2,4-dimethyl-6-(1'-methyl-heptadeca salicylic acid derivatives. Usually, these image-stabilizing 1'-yl)-phenol, 2,4-dimethyl-6-(1'-methyl-trideca-1-yl)- agents are used in a proportion of preferably 5 to 1,000 parts phenol and mixtures thereof 2,4-di-octylthiomethyl-6-t- by weight, more preferably 10 to 500 parts by weight, per 100 50 butylphenol. 2,4-di-octylthiomethyl-6-methylphenol. 2,4-di parts by weight of the colorless or light-colored dye precur octylthiomethyl-6-ethylphenol. 2,6-di-dodecylthiomethyl-4- sor. When the proportion of the image-stabilizing agents is 5 nonylphenol and mixtures thereof; 2,6-di-t-butyl-4- parts by weight or more, the light resistance is good and the methoxyphenol. 2,5-di-t-butylhydro-quinone, 2,5-di-t- coloring density is high. When the proportion of the image amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol, stabilizing agents is more than 1,000 parts by weight, their 55 2,6-di-t-butylhydroquinone, 2,5-di-t-butyl-4-hydroxyani effect on the light resistance is not heightened and moreover, sole, 3,5-di-t-butyl-4-hydroxy-anisole, 3,5-di-t-butyl-4-hy Such a proportion is economically disadvantageous. droxyphenyl stearate, bis(3,5-di-t-butyl-4-hydroxyphenyl) The light stabilizers as preferable examples of the shelf adipate and mixtures thereof 2,4-bis-octylmercapto-6-(3.5- life-imparting agents used in the present invention include, di-t-butyl-4-hydroxyanilino)-1,3,5-triazine, 2-octylmer for example, 2-(2-hydroxy-5'-methylphenyl)benzotriazole, 60 capto-4,6-bis(3,5-di-t-butyl-4-hydroxy-anilino)-1,3,5-triaz 2-(3',5'-di-t-butyl-2'-hydroxyphenyl)benzotriazole, 2-(5'-t- ine, 2-octylmercapto-4,6-bis(3,5-di-t-butyl-4- butyl-2'-hydroxyphenyl)benzotriazole, 2-2'-hydroxy-5'-(1, hydroxyphenoxy)-1,2,3-triazine, 1,3,5-tris(3,5-di-t-butyl-4- 1,3,3-tetramethylbutyl)phenylbenzotriazole, 2-(3',5'-di-t- hydroxybenzyl)isocyanurate, 1,3,5-tris(4-t-butyl-3- butyl-2'-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3'-t- hydroxy-2,6-dimethylbenzyl)-isocyanurate, 2,4,6-tris(3,5- butyl-2'-hydroxy-5'-methylphenyl)-5-chlorobenzo-triazole, 65 di-t-butyl-4-hydroxy-phenylethyl)-1,3,5-triazine, 1,3,5-tris 2-(2-hydroxy-4-Octoxyphenyl)benzotriazole, 2-(3',5'-di-t- (3,5-di-t-butyl-4-hydroxyphenyl-propionyl)hexahydro-1,3, pentyl-2'-hydroxyphenyl)benzotriazole, 2-(3'-t-butyl-2'-hy 5-triazine, 1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)- US 7,635,662 B2 111 112 isocyanurate and the like: 2,2'-methylenebis(6-t-butyl-4-me cially preferable. The above-exemplified surfactants may be thylphenol), 2,2'-methylenebis(6-t-butyl-4-ethylphenol), used singly or as a mixture thereof. 2,2'-ethylidenebis(4,6-di-t-butylphenol), 2,2'-ethylidenebis When the urea-urethane compound developer according to (6-t-butyl-4-isobutylphenol), 4,4'-methylenebis(2,6-di-t-bu the present invention is used in a heat-sensitive recording tylphenol), 4,4'-methylenebis-(6-t-butyl-2-methylphenol), 5 material, the adjustment of the average particle size of the 1,1-bis(5-t-butyl-4-hydroxy-2-methylphenyl)butane, ethyl urea-urethane compound developer to not more than 5 um C glycol bis(3,3'-bis(3'-t-butyl-4'-hydroxyphenyl) and not less than 0.05 um makes it possible to obtain a butyrate and the like; 1,3,5-tris(3,5-di-t-butyl-4-hydroxy heat-sensitive recording material which has a sufficient color benzyl)-2,4,6-trimethylbenzene, 1,4-bis(3,5-di-t-butyl-4-hy development sensitivity, gives a very stable printed developed droxybenzyl)-2,3,5,6-tetramethylbenzene, 2,4,6-tris(3,5-di- 10 color image, and has a good plasticizer resistance. The aver t-butyl-4-hydroxybenzyl)phenol and the like. Usually, these age particle size is more preferably not more than 3 um and antioxidants are used in a proportion of preferably 5 to 1,000 not less than 0.1 Lum. When the average particle size is less parts by weight, more preferably 10 to 500 parts by weight, than 0.05 um, the preservability of the original recording per 100 parts by weight of the colorless or light-colored dye material Surface against plasticizers is deteriorated. On the precursor. When the proportion of the antioxidants is 5 parts 15 other hand, when the average particle size is more than 5um, by weight or more, the light resistance is good and the color the sensitivity of the heat-sensitive recording material is ing density is high. When the proportion of the antioxidants is decreased. more than 1,000 parts by weight, their effect on the light Particularly when the urea-urethane compound is sub resistance is not heightened and moreover, Such a proportion jected to wet grinding in an aqueous medium, the temperature is economically disadvantageous. 2O of the aqueous medium is preferably 60° C. or lower. At the The color-producing composition of the present invention time of the grinding, the urea-urethane compound developer can be made into a recording material by forming a color comes into contact with water, so that hydrolysis of its ure producing layer of the composition on Some Substrate by a thane group(s) proceeds depending on conditions. Therefore, method such as coating. The structure of the recording mate the sensitivity of a heat-sensitive recording material obtained rial is varied depending on the kind of the recording material. 25 by the use of the urea-urethane compound developer tends to The color-producing composition of the present invention be decreased. Particularly when the medium temperature at can be used in any of various recording materials such as the grinding is higher than 60°C., the sensitivity is remark heat-sensitive recording materials, pressure-sensitive record ably decreased. The medium temperature at the grinding is ing materials and the like, and is Suitable particularly for the more preferably 40°C. or lower. heat-sensitive recording materials. 30 In addition, when the urea-urethane compound developer When the color-producing composition is used in a heat is ground, it is preferably ground in a neutral pH range of 5 to sensitive recording material, a heat-sensitive recording layer 10. When the pH at the grinding is lower than 5, an inorganic capable of producing a color on heating is formed on a Sub pigment and the like are decomposed in the production of a strate. Specifically, the above-mentioned urea-urethane com heat-sensitive coating liquid, so that the sensitivity tends to be pound, the above-mentioned colorless or light-colored dye 35 decreased. On the other hand, when the pH is higher than 10, precursor Such as a leuco dye, and the heat-meltable material the urea-urethane compound developer is hydrolyzed, so that described hereinafter, and the like should be applied on a the sensitivity is decreased in Some cases. substrate, each in the form of a dispersion together with other Specific examples of dispersing agent usable for preparing necessary components to form a heat-sensitive recording a dispersion of the urea-urethane compound developer by layer. The dispersion is prepared by finely grinding one or 40 grinding in the present invention are water-soluble polymers more compounds as each of the components described above, Such as poly(vinyl alcohol)s, carboxylic acid-modified poly with a sandgrinder or the like in an aqueous solution contain (vinyl alcohol)S, Sulfonic acid-modified poly(Vinyl alcohol)S. ing a compound having dispersing capability, Such as a water methyl cellulose, hydroxypropylmethyl cellulose, hydrox soluble polymer, a surfactant or the like. The particle size of ypropyl cellulose, etc.; anionic Surfactants such as condensed each of the dispersions thus obtained is preferably adjusted to 45 naphthalenesulfonates, polyoxyethylene alkyl ether sulfuric 0.1 to 10 um, in particular, to about 1 um. Specific examples acid ester salts (e.g. sodium polyoxyethylene lauryl ether of the compound having dispersing capability which can be Sulfates, Sodium polyoxyethylene alkyl ether Sulfates and used in the present invention are water-soluble polymers such sodium polyoxyethylenealkyl phenyl ether sulfates), dialkyl as poly(vinyl alcohol)S, carboxylic acid-modified poly(vinyl SulfoSuccinic acid ester sodium, alkylphosphates (e.g. dietha alcohol)S, Sulfonic acid-modified poly(vinyl alcohol)S, 50 nolamine alkylphosphates and potassium alkylphosphates), methyl cellulose, hydroxypropylmethyl cellulose, hydrox specialty carboxylic acid-based polymers, etc.; nonionic Sur ypropyl cellulose, etc.; anionic Surfactants such as condensa factants such as polyoxyethylene alkyl phenyl ethers, poly tion naphthalene Sulfonates, polyoxyethylene alkyl ether Sul oxyethylene Sorbitan fatty acid esters, fatty acid monoglyc furic acid ester salts (e.g. sodium polyoxyethylene lauryl erides, polyethylene glycol fatty acid esters, etc.; and cationic ether sulfates, sodium polyoxyethylene alkyl ether sulfates 55 Surfactants such as dicyanamidopolyamines, tertiary amine and Sodium polyoxyethylene alkyl phenyl ether Sulfates), salts, quaternary ammonium salts, etc. Of these, the water dialkylsulfoSuccinic acid ester Sodium, alkylphosphates (e.g. soluble polymers and the anionic Surfactants are especially diethanolamine alkylphosphates and potassium alkylphos preferable because they make it possible to obtain a heat phates), specialty carboxylic acid-based polymers, etc.; non sensitive recording material that has a high sensitivity irre ionic Surfactants such as polyoxyethylene alkyl ethers, poly- 60 spective of conditions of dispersing the urea-urethane com oxyethylene alky phenyl ethers, polyoxyethylene Sorbitan pound developer and has an improved preservability of the fatty acid esters, fatty acid monoglycerides, polyethylene gly original recording material Surface against plasticizers irre col fatty acid esters, etc.; and cationic Surfactants such as spective of the average particle size of the urea-urethane dicyanamidopolyamines, tertiary amine salts, quaternary compound developer. The poly(vinyl alcohol)s, modified ammonium salts, etc. Of these, the polyvinyl alcohols, car- 65 poly(vinyl alcohol)s, methyl cellulose, hydroxypropylmethyl boxylic acid-modified polyvinyl alcohols, sulfonic acid cellulose, sodium condensed naphthalenesulfonate, polycar modified polyvinyl alcohols and methyl cellulose are espe boxylic acid ammonium salts, water-soluble low-molecular US 7,635,662 B2 113 114 weight copolymers and Sodium 2-ethylhexylsulfoSuccinate The surface pH of the substrate is preferably 3 to 9, more are more preferable. of these, the methyl cellulose, hydrox preferably 5 to 9, most preferably 6 to 8. When the surface pH ypropylmethyl cellulose, Sodium condensed naphthalene of the substrate is lower than 3, fog tends to occur. When the Sulfonate, water-soluble low-molecular weight copolymers surface pH of the substrate is higher than 12, the urea-ure are still more preferable, and hydroxypropylmethyl cellulose thane compound developer is decomposed, so that the color is the most preferable. The above-exemplified dispersing ing density is decreased in some cases. agents may be used singly or as a mixture thereof. The heat-sensitive recording layer may be composed of As a dispersing agent usable for preparing a dispersion of either a single layer or two or more layers. The heat-sensitive the colorless or light-colored dye by grinding in the present recording layer may have, for example, a multilayer structure invention, the same compounds as those used as the dispers 10 formed by incorporating each color-producing component ing agent for dispersing the urea-urethane compound devel into one layer. A protective layer composed of a single layer oper can be used. Of such compounds, the water-soluble or two or more layers may be formed on the heat-sensitive polymers, the anionic Surfactants and mixed dispersing recording layer, and an intermediate layer composed of a agents of these two kinds of the Surfactants are especially single layer or two or more layers may also be formed preferable for improving a heat-sensitive recording material 15 between the substrate and the heat-sensitive recording layer. in sensitivity and preservability of the original recording The heat-sensitive recording layer can be obtained by mixing material Surface against plasticizers. Mixed dispersing agents aqueous dispersions prepared by fine grinding of each color consisting of methyl cellulose or hydroxypropylmethyl cel producing component or any other component, with a binder lulose as a water-soluble polymer and a polyoxyethylene and the like, applying the resulting mixture on the Substrate, alkyl ether sulfate or sodium 2-ethylhexylsulfosuccinate as an and drying the mixture. The coating amount of this coating anionic Surfactant are more preferable. A mixed dispersing liquid is preferably 1 to 15 g/m when the coating liquid is in agent of hydroxypropylmethyl cellulose and sodium 2-ethyl a dried State. hexylsulfosuccinate is the most preferable. When the color-producing composition of the present The pH of a coating liquid containing the urea-urethane invention is used in a heat-sensitive recording material, a compound and the colorless or light-colored dye precursor is 25 heat-meltable material may be incorporated into the color preferably 5 to 12. producing composition in order to improve the sensitivity. The heat-sensitive recording layer may contain, besides the The heat-meltable material is preferably one which has a components described above, pigments such as diatomaceous melting point of 60°C. to 180°C., in particular, one which has earth, talc, kaolin, calcined kaolin, calcium carbonate, mag a melting point of 80°C. to 140°C. The heat-meltable mate nesium carbonate, titanium oxide, Zinc oxide, silicon oxide, 30 rial includes, for example, benzyl p-benzyloxybenzoate, aluminum hydroxide, urea-formaldehyde resin, etc. In addi Stearamide or its emulsified product, palmitamide, N-methy tion, the heat-sensitive recording layer may, if necessary, lolstearamide, B-naphthylbenzyl ether, N-stearylurea, N,N'- contain metal salts of higher fatty acids, such as Zinc Stearate, distearylurea, phenyl B-naphthoate, phenyl 1-hydroxy-2- calcium Stearate, etc.; and waxes such as paraffin, oxidized naphthoate, B-naphthol (p-methylbenzyl) ether, 1,4- paraffin, polyethylenes, oxidized polyethylenes, Stearamide, 35 dimethoxynaphthalene, 1-methoxy-4- cator wax, etc., for the purpose of for example, preventing the benzyloxynaphthalene, N-Stearoylurea, p-benzylbiphenyl, wear of a head and sticking. If necessary, the heat-sensitive 1.2-di(m-methylphenoxy)ethane, 1-phenoxy-2-(4-chloro recording layer may also contain dispersing agents such as phenoxy)ethane, 1,4-butanediol phenyl ether, dimethyl sodium dioctylsulfosuccinate, etc.; ultraviolet absorbers of terephthalate, m-terphenyl, dibenzyl oxalate and (p-chlo benzophenone type, benzotriazole type and the like; Surfac 40 robenzyl) oxalate. tants; fluorescent dyes; etc. Also, 4,4'-dimethoxybenzophenone, 4,4'-dichloroben As a binder usable for forming the heat-sensitive recording Zophenone, 4,4'-difluorobenzophenone, diphenyl Sulfone, layer, there can be mentioned, for example, water-soluble 4,4'-dichlorodiphenyl sulfone, 4,4'-difluorodiphenyl sulfone, binders such as starches, hydroxyethyl cellulose, methyl cel 4,4'-dichlorodiphenyl disulfide, diphenylamine, 2-methyl-4- lulose, carboxymethyl cellulose, gelatin, casein, poly(vinyl 45 methoxydiphenyl-amine, N,N'-diphenyl-p-phenylenedi alcohol)s, modified poly(vinyl alcohol)S. sodium poly(acry amine, 1-(N-phenylamino)naphthalene, benzil, 1.3-diphe late)S. acrylamide-acrylic ester copolymers, acrylamide nyl-1,3-propanedione and the like are preferable because they acrylic ester-methacrylic acid terpolymers, alkali salts of sty are highly effective for enhancing the sensitivity. Further, rene-maleic anhydride copolymers, alkali salts of ethylene benzyl 4-hydroxybenzoate, 4-(benzyloxy)phenol. 2,4-dihy maleic anhydride copolymers, etc.; and latex type water 50 droxybenzophenone, 2.2',4,4-tetrahydroxy-benzophenone, insoluble binders of styrene-butadiene copolymers, 4,4'-dihydroxybenzophenone, 2.2-bis(4-hydroxyphenyl)pro acrylonitrile-butadiene copolymers, methyl acrylate-butadi pane, 4,4'-dihydroxydiphenyl sulfone, bis(3-methyl-4-hy ene copolymers, etc. droxyphenyl) sulfone, bis(3,5-dimethyl-4-hydroxyphenyl) As the substrate for the heat-sensitive recording layer, sulfone, 3,4-dihydroxyphenyl-4'-methylphenyl sulfone, bis paper is mainly used, though any of various woven fabrics, 55 (2-methyl-3-tert-butyl-4-hydroxyphenyl) sulfide, 4,4'-dihy nonwoven fabrics, synthetic resin films, laminated papers, droxydiphenyl ether, 4,4'-thiodiphenol, 4,4'-dihydroxydiphe synthetic papers, metal foils, and composite sheets obtained nylmethane, 3,3'-dihydroxydiphenylamine, bis(4-hydroxy by combining two or more of them may be used besides 3-methylphenyl) sulfide, 4-hydroxy-4-isopropoxydiphenyl paper, depending on purposes. The basis weight of the Sub sulfone, 4,4'-thiobisbenzenethiol, salicylanilide, 4,4'-di strate is preferably 40 g/m to 200 g/m. The substrate is 60 amino-3,3'-diethyldiphenylmethane, 4,4'-diaminobenzanil preferably excellent in Surface Smoothness and flatness ide, 3,3'-dichloro-4,4'-diaminodiphenylmethane, 3,3'-dim because a heat-sensitive recording material obtained by the ethyl-4,4'-diaminodiphenylmethane, 4,4'-thiodianiline, 2,2'- use of the Substrate is desired to have as high a flatness as dithiodianiline, 4,4'-dithiodianiline, 4,4'-diamino-diphenyl possible. Therefore, the substrate is preferably subjected to ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl Surface treatment by applying heat and pressure by means of 65 ether, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenyl any of a machine calender, Soft calender, Supercalender and methane, bis(3-amino-4-chloro-phenyl) sulfone, bis(3,4-di the like. aminophenyl) sulfone, 4,4'-diaminodiphenyl Sulfone, 3,3'- US 7,635,662 B2 115 116 diaminodiphenyl sulfone, 3,4'-diaminodiphenyl Sulfone, cizers. The polyevinyl alcohol)s, modified poly(vinyl alco 3.3'-diaminodiphenyl-methane, 4,4'-diaminodiphenylamine, hol)s, methyl cellulose, hydroxypropyl-methyl cellulose, 3.3'-diamino-benzophenone, 4,4'-diaminobenzophenone, Sodium condensed naphthalene-Sulfonate, polycarboxylic acetoacetic o-chloroanilide, acetoacetic anilide, acetoacetic acid ammonium salts, water-soluble low-molecular weight o-toluidide, acetoacetic p-toluidide, acetoacetic o-anisidide, copolymers and sodium 2-ethylhexylsulfo Succinate are more acetoacetic m-Xylidide, p-acetotoluidide etc. can be used. preferable. Of these, the modified poly(vinyl alcohol)s. Of these, diphenyl sulfone, di-p-methylbenzyl oxalate, methyl cellulose, hydroxypropylmethyl cellulose, sodium benzil, B-naphthylbenzyl ether, p-benzyl-biphenyl, 1,2-di(m- condensed naphthalenesulfonate, polycarboxylic acid methylphenoxy)ethane, 1.2-diphenoxymethylbenzene, ammonium salts are still more preferable, and hydroxypro m-terphenyl and Stearamide are preferably used. 10 pylmethyl cellulose is the most preferable. The above-exem In addition, employment of a heat-meltable material of the plified dispersing agents may be used singly or as a mixture following structural formula (XVIII), among the above-ex thereof. emplified heat-meltable materials, in a heat-sensitive record When the urea-urethane compound developer is ground, ing material is markedly effective in increasing the sensitivity fine grinding of the developer together with the above-men of the recording material and improving the plasticizer resis 15 tioned heat-meltable material (co-grinding) further improves tance of a print portion and the heat resistance of the original the sensitivity of a heat-sensitive recording material and recording material Surface. Heat-meltable materials repre improves the plasticizer resistance as compared with fine sented by the structural formula (XIX) shown below are espe grinding of each compound followed by mixing of the ground cially preferable. compounds. The reason why these effects are obtained is not completely clear. Furthermore, the moisture resistance of the non-print por (XVIII) tion (the original Surface) of a heat-sensitive recording mate rial can be improved by using at least one dispersing agent for the urea-urethane compound developer selected from methyl 25 cellulose, hydroxypropylmethyl cellulose, Sodium con densed naphthalenesulfonate and water-soluble low-molecu lar weight copolymers, and at least one dispersing agent for wherein Y is any of —SO. , —(S), , —O , —CO—, the heat-meltable material selected from modified poly(vinyl —CH2—, —CH(CHs)—, C(CH) , COCO , alcohol)s, methyl cellulose, hydroxypropyl-methyl cellulose, —CO, , -COCHCO-, -COOCH-, -CONH-, 30 Sodium condensed naphthalenesulfonate and polycarboxylic —OCH2— and —NH-, n is 1 or 2, and the hydrogen atom acid ammonium salts. of each benzene ring may be replaced by a halogen atom, a The color-producing composition of the present invention hydroxyl group, a nitro group, a nitroso group, a nitrile group, can be used in various heat-sensitive recording materials and an isocyanate group, an isothiocyanate group, a mercapto is especially Suitable for heat-sensitive magnetic recording group, a Sulfamoyl group, a Sulfone group, an amino group. 35 materials, labels for heat-sensitive recording, multicolor an aromatic compound residue, an aliphatic compound resi heat-sensitive recording materials, and heat-sensitive record due or a heterocyclic compound residue. ing materials for laser marking. When the color-producing composition of the present invention is used in a heat-sensitive magnetic recording mate (XIX) 40 rial, the recording material is preferably in a form in which a heat-sensitive recording layer containing the urea-urethane compound developer is formed on one side of a Substrate and a magnetic recording layer is formed on the other side. The magnetic recording layer of the heat-sensitive mag 45 netic recording material is formed by coating a Substrate with a coating material prepared by uniformly dispersing ferro wherein the hydrogen atom of each benzene ring may be magnetic powder Such as barium ferrite, strontium ferrite, replaced by a halogen atom, a hydroxyl group, a nitro group, Co-y-Fe-O, Y-Fe2O, or the like in an aqueous binder Such as a nitroso group, a nitrile group, an isocyanate group, an an aqueous emulsion resin, and drying the coated Substrate. In isothiocyanate group, a mercapto group, a Sulfamoyl group, a 50 this case, various additives Such as antistatic agents (e.g. Sulfone group, an amino group, an aromatic compound resi carbon graphite), lubricants (e.g. wax), color pigments for due, an aliphatic compound residue or a heterocyclic com hue adjustment, coating film flexibilizers e.g. poly(ethylene pound residue. oxide)S. etc. may be added. The above-exemplified heat-meltable materials may be The heat-sensitive magnetic recording material of the used singly or as a mixture thereof. For attaining a sufficient 55 present invention is Suitable as heat-sensitive magnetic thermal response, the heat-meltable material is used in a recording materials used as rail road tickets, tickets, prepaid proportion of preferably 10 to 300 parts by weight, more cards, etc. preferably 20 to 250 parts by weight, per 100 parts by weight When the color-producing composition of the present of the colorless or light-colored dye precursor. invention is used in a label for heat-sensitive recording, the As a dispersing agent usable for preparing a dispersion of 60 label is preferably in a form in which a heat-sensitive record the heat-meltable material by grinding in the present inven ing layer containing the urea-urethane compound developer tion, the same compounds as those used as the dispersing is formed on one side of a Substrate and an adhesive layer is agent for dispersing the urea-urethane compound developer formed on the other side. can be used. Of such compounds, the water-soluble polymers The adhesive layer of this heat-sensitive recording material and the anionic Surfactants are especially preferable for 65 is composed mainly of a pressure-sensitive adhesive. The improving a heat-sensitive recording material in preservabil pressure-sensitive adhesive includes, for example, synthetic ity of the original recording material Surface against plasti rubber-based emulsion type adhesives, acrylic emulsion type US 7,635,662 B2 117 118 adhesives, natural-rubber-based solvent type adhesives, obtained by mixing a white inorganic pigment with any of the acrylic solvent type adhesives and silicon-based solvent type above-exemplified resins, followed by biaxial stretching; and adhesives. Of these, the acrylic emulsion type adhesives are Substrates produced from pulp fiber, Such as woodfree paper, especially preferable. medium-duty paper, machine glazed paper, regenerated When a reverse-side layer (a back coating layer) is, if 5 paper, coated paper, etc. The Substrates made of pulp fiber are necessary, formed between the adhesive layer and the sub preferably coated with a heat-sensitive layer after previous strate in the label for heat-sensitive recording produced by a formation of a coating layer in order to improve the unifor process according to the present invention, taking-out of curl, mity of image. prevention of electrostatic charge, and adjustment of coeffi A heat-sensitive color-producing layer according to the cient of friction are possible in the label for heat-sensitive 10 present invention comprises as its main constituents an adhe recording material. As the components of a coating liquid for sive and a color-producing composition capable of causing the reverse-side layer and a coating method for the coating color development reaction owing to the contact of materials liquid, the same components and method as in a method for with each other made by heating. Specific examples of the forming the heat-sensitive recording layer may be employed. color-producing composition are combinations of a colorless The dry spread ranges preferably from 0.2 to 10.0 g/m. 15 or light-colored dye precursor and the above-mentioned urea The order of coating in the production of the label for urethane developer capable of allowing said dye precursor to heat-sensitive recording material is not particularly limited. develop a color, and combinations of a diazo compound and For example, either of the following orders may be employed: a coupler capable of developing a color by its reaction with a the heat-sensitive recording layer is formed on one side of the diazo compound. If necessary, crosslinking agents, pigments Substrate and then the back coating layer is formed on the and heat-meltable materials may be added. Usually, the coat other side, after which the adhesive layer is formed thereon; ing amount of the heat-sensitive color-producing layer is or the back coating layer is formed on one side of the Substrate preferably 3 to 15 g/m from the viewpoint of color develop and then the heat-sensitive recording layer is formed on the ment sensitivity and coloring density. other side, after which the adhesive layer is formed on the As a dye capable of developing a dye, the colorless or back coating layer. 25 light-colored dye precursor described above is used which As to a method for forming the adhesive layer on the back can develop a color when reacted with the urea-urethane coating layer, a liquid for forming the adhesive layer may be compound developer with heating. directly applied on the back coating layer and dried, or a On the other hand, in a heat-sensitive layer comprising as material obtained by previously applying a liquid for forming its main constituents a diazo compound and a coupler capable the adhesive layer, on release paper, followed by drying may 30 of developing a color by its reaction with said diazo com be attached to the back coating layer side of a heat-sensitive pound, these compounds are a well-known light-decompos recording material having no adhesive layer formed thereon. able diazo compound and a coupler capable of forming a dye In addition, the thermal response can be improved by form by its reaction with said diazo compound. If necessary, a basic ing an intermediate layer composed of a single layer or two or material and the like may be added in order to accelerate the more layers, between the heat-sensitive recording layer and 35 reaction of the diazo compound with the coupler. The coupler the substrate. The intermediate layer is composed mainly of and the basic material are preferably used as a mixture thereof an organic or inorganic pigment, hollow particles and an in proportions of 10 to 1,000 parts by weight and 10 to 2,000 aqueous binder Such as a water-soluble polymer or a latex. As parts by weight, respectively, per 100 parts by weight of the the organic or inorganic pigment and the aqueous binder, the diazo compound. same organic or inorganic pigment and aqueous binder as 40 The term “light-decomposable diazo compound used used in the heat-sensitive recording layer can be used. A herein means a diazo type photosensitive material capable of method for forming the intermediate layer is not particularly forming a dye by its reaction with a coupling component on limited. As this method, the same method as a method for heating. Such as a diazonium salt, diazosulfonate compound, forming the heat-sensitive recording layer can be adopted. A diazoamino compound, quinonediazide compound or the dry spread for forming the intermediate layer ranges prefer 45 ably from 2.0 to 15.0 g/m. like. The diazonium salt refers to a compound represented by When the color-producing composition of the present the general formula: invention is used in a multicolor heat-sensitive recording material, this recording material is preferably in a form in which at least two heat-sensitive recording layers are formed 50 wherein Aris an aromatic portion, N." is a diazonium group. on one side of a Substrate and at least one of said heat and X is a counter anion. Such compounds have various sensitive recording layers contains the urea-urethane com maximum absorption wavelengths, depending on the posi pound developer. tions and kinds of substituents of the Arportion. As the Substrate used, there can be used synthetic paper Specific examples of the diazonium compound used in the produced by kneading a polyolefin resin and a white inor 55 present invention are 4-dimethylamino-benzenediazonium, ganic pigment with heating, extruding the kneaded product 4-diethylaminobenzenediazonium, 4-dipropylaminoben through a die, stretching the extruded product in a lengthwise ZenediaZonium, 4-methylbenzylamino-benzenediaZonium, direction, laminating one or two films made of a polyolefin 4-dibenzylaminobenzenediazonium, 4-ethylhydroxyethy resin and a white inorganic pigment on each side of the laminobenzenediaZonium, 4-diethylamino-2-methoxyben stretched product, and stretching the resulting assembly in a 60 ZenediaZonium, 4-dimethyl-3-methylbenzene-diazonium, crosswise direction to make the same semitransparent or 4-benzoylamino-2,5-diethoxybenzenediaZonium, 4-mor opaque; films obtained by kneading one of or a mixture of two pholinobenzenediaZonium, 4-morpholino-2,5-diethoxyben or more of thermoplastic resins such as polyethylenes, ZenediaZonium, 4-morpholino-2,5-dibutoxybenzenediaZo polypropylenes, ethylene-vinyl acetate copolymer resins, nium, 4-anilinobenzenediaZonium, 4-toluylmercapto-2,5- polylvinyl chloride)S. polystyrenes, polyesters, etc. with 65 diethoxybenzenediaZonium, 4-(N,N-dioctylcarbamoyl) heating, extruding the kneaded product through a die, and benzenediaZonium, 2-octadecyloxy-benzenediazonium, then stretching the kneaded product biaxially; opaque films 4-(4-tert-octylphenoxy)benzene-diazonium, 4-(2,4-di-tert US 7,635,662 B2 119 120 amylphenoxy)benzenediaZonium, 2-(4-tert-octylphenoxy) group, and R' is an aromatic amine. Magenta couplers are, for benzenediaZonium, 5-chloro-2-(4-tert-octylphenoxy)ben example, 1) cyanoacetyl derivatives of cyclic compounds, or ZenediaZonium, 2.5-bis-octadecyloxybenzenediaZonium, 2) heterocyclic compounds having active methylene or any 2.4-bis-octadecyloxy-benzenediaZonium, 4-(N-octyllauroy other coupling portion on the heterocyclic ring, and include, lamino)benzene-diazonium, etc. Specific examples of the for example, pyrazolone compounds and indazolone com counteranion of the diazonium salt used in the present inven pounds. Cyan couplers include, for example, phenols and tion are C1.1/2ZCl, BF, PF, B(ph), CFCOO (n naphthols. is 3 to 9), CFSOT (mis 2 to 8), (CFSO)CH (kis Specific examples of the coupler used in the present inven 1 to 18), etc. tion are 4-(p-toluenesulfonylamino)-()-benzoylacetanilide, The diaZoSulfonate compound used in the present inven 10 C.-benzoyl-o-methoxyacetanilide, 2-cyanoacetyl-couma tion is a compound represented by the general formula: rone, 1-(2,4,6-trichlorophenyl)-3-p-nitroamino-2-pyrazo lon-5-one, resorcin, phloroglucin, 2.3-dihydroxynaphtha lene, 2,6-dibromo-1,5-dihydroxy-naphthalene, N-(o- acetamidophenethyl)-1-hydroxy-2-napthoamide, etc. In wherein Ar is an aromatic portion. Specific examples of the 15 addition, these couplers may be used singly or in combina diazosulfonate compound used in the present invention are tion. Sodium benzenediaZoSulfonates having one or more substitu ents including 2-methoxy. 2-phenoxy, 2-methoxy-4-phe For Smoother progress of the coupling reaction of the diazo noxy, 2,4-dimethoxy, 2-methyl-4-methoxy. 2,4-dimethyl, compound with the coupler under a basic atmosphere, a basic 2,4,6-trimethyl, 2,4,6-trimethoxy. 2,4-dimethoxy-5-chloro, material is preferably incorporated into the heat-sensitive 2-methoxy-5-nitro, 2-methoxy-5-acetamido, 2-methoxy-5- color-producing layer. As the basic material, a slightly water N,N-diethylsulfonamido, 2-methoxy-5-N-phenylcarbamyl. soluble or water-insoluble basic material or a material 3-methyl, 4-methyl, 4-methoxy, 4-ethoxy, 4-phenyl, 4-phe capable of producing an alkali on heating is used. The basic noxy, 4-acetamido, etc.; and benzenediaZoSulfonates having material includes, for example, nitrogen-containing com one or more substituents including 4-(N-ethyl-N-benzy pounds Such as inorganic and organic ammonium salts, 25 organic amines, amides, urea and thiourea and their deriva lamino), 4-(N,N-dimethylamino), 4-(N,N-diethylamino),4- tives, thiazoles, pyrroles, pyrimidines, piperazines, (N,N-diethylamino)-3-chloro, 4-(N-ethylamino)-3-methyl, guanidines, imidazoles, imidazolines, triazoles, morpho 4-(N,N-diethylamino)-2-methyl, 4-(N-ethyl-N-B-hydroxy lines, piperidines, amidines, formamidines, pyridines, etc. ethylamino), 4-pyrrolidino-3-chloro, 4-pyrrolidino-3,5- Specific examples of these compounds are tricyclohexy dichloro, 4-morpholino, 4-morpholino-3-chloro, 4-mor 30 lamine, tribenzylamine, octadodecylbenzyl-amine, Steary pholino-3-methoxy, 4-morpholino-2,5-diethoxy, lamine, allylurea, thiourea, methyl-thourea, allylthiourea, 4-morpholino-2,5-dibutoxy, 4-(4-tolylmercapto)-2,5-dubu ethylenethiourea, 2-benzylimidazole, 4-phenylimidazole, toxy, 4-(4-tolylmercapto)-2,5-diethoxy, 4-(4-methoxyben 2-phenyl-4-methylimidazole, 2-undecylimidazoline, 2,4,5- Zoylamino)-2,5-dibutoxy, 4-diphenylamino, etc. When any trifuryl-2-imidazoline, 1,2-diphenyl-4,4-dimethyl-2-imida of these diaZoSulfonate compounds is used, the diazosul 35 Zoline, 2-phenyl-2-imidazoline, 1,2,3-triphenylguanidine, fonate compound is preferably activated by light irradiation 1.2-dicyclohexylguanidine, 1,2,3-tricyclohexylguanidine, before printing. guanidine trichloroacetate, N,N'-dibenzylpiperazine, 4,4'- The diazoamino compound usable in the present invention dithiomorpholine, morpholinium trichloroacetate, 2-ami is a compound obtained by coupling a diazo group with nobenzothiazole, 2-benzoylhydrazinobenzothiazole, etc. dicyandiamide, sarcosine, methyltaurine, N-ethylanthranilic 40 These basic materials may be used singly or in combination. acid-5-Sulfonic acid, monoethanol-amine, diethanolamine, In the present invention, the storage stability can be guanidine or the like. improved by adding a weakly acidic material Such as citric The quinonediazide used in the present invention is con acid, tartaric acid, oxalic acid, boric acid, phosphoric acid, sidered as an internal-salt type diazonium salt from the view pyrophosphoric acid or the like to the heat-sensitive color point of structure and is, for example, o-quinonediazide or 45 producing layer formed of a combination of the diazo com o-naphthoduinone-diazide. The quinonediazide includes pound and the coupler. salts, esters and amide compounds of 1.2-quinonediazide-4- Needless to say, the color-producing components used in Sulfonic acid, 1.2-naphthoduinonediazide -5-Sulfonic acid, the present invention can be used in a solid dispersion state 1.2-naphthoguinonediazide-4-Sulfonic acid, etc. Specific attained by dispersing the components in an aqueous solution examples of the quinonediazide used in the present invention 50 of a water-soluble polymer, followed by coating and drying, are sodium 1.2-quinonediazide-4-Sulfonate, sodium 1.2- as in a conventional method adopted in heat-sensitive record naphthoduinonediazide-5-Sulfonate, Sodium 1.2-naphtho ing materials. It is also possible to improve the green stability quinonediazide-4-Sulfonate, p-cumylphenyl 12-naphtho by making a color former into microcapsules and preventing quinonediazide-5-Sulfonate, p-cumylphenyl 1.2- the contact of the color former with a developer at ordinary naphthoduinonediazide-4-Sulfonate, methyl 1.2- 55 temperature by utilizing the isolating effect of the capsule naphthoduinonediazide-5-Sulfonate, ethyl 1.2- walls, as described in JP-A-59-190,886, JP-A-60-49,991, naphthoduinonediazide-5-Sulfonate, 1.2-naphthoduinone JP-A-61-169,281, etc. The microcapsules are characterized diazide-5-sulfonic acid dimethylamide, esters of 1.2- in that they enable the color former and the developer to come naphthoduinonediazide-5-Sulfonic acid and a novolak resin, into contact with each other only during heating at a certain etc. In addition, these light-decomposable diazo compounds 60 temperature or higher. The temperature at the starting of the may be used singly or in combination. color former-developer contact can be controlled by properly The coupler used in the present invention is one that reacts choosing a material for the capsule wall, a core material for with the diazo compound to form a dye. For example, typical the capsule, additives, etc. couplers capable of forming a yellow dye are compounds As a material for the walls of the micro-capsules in the which have a methylene group activated by a carbonyl group 65 present invention, there are mentioned conventional materials adjacent thereto and is represented by the general formula for microcapsule wall. Such as polyurethanes, polyureas, RCOCH2CO R' wherein R is an alkyl group or an allyl polyesters, polycarbonates, urea-formaldehyde resins, US 7,635,662 B2 121 122 melamine resins, polystyrenes, styrene-methacrylate copoly dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, gallic mers, gelatin, poly(vinylpyrrolidone)S. poly(vinyl alcohol)S. acid, bis(4-hydroxyphenyl)acetic acid, 3.3-bis(4-hydrox etc. These polymers may be used singly or in combination. yphenyl)propionic acid, etc. In the present invention, as the adhesive contained in the The amine compound that forms the complex Salt together heat-sensitive color-producing layer, either water-soluble with the phenolcarboxylic acid compound includes octy resins or water-dispersible resins may be used. However, lamine, nonylamine, decylamine, laurylamine, tetradecy when any of these resins is mixed with dispersions of the lamine, heptadecylamine, Stearylamine, behenylamine, above-mentioned dye capable of developing a color and 3-methoxypropylamine, hexamethylenediamine, etc. developer, respectively, the resulting mixture should not The reversible developer is, for example, a phenolic com undergo coloration or aggregation and should not have a high 10 pound or a phosphonic acid compound, which have an ali Viscosity. In addition, a coating film formed as heat-sensitive phatic hydrocarbon group of 8 or more carbonatoms. Specific recording layer should be tough and should not have desen examples of such a reversible developer are those mentioned sitizing effect. The content of the adhesive in the heat-sensi below. The reversible developer is not limited to those men tive color-producing layer is preferably 8 to 20% based on the tioned below, and any reversible developer may be used so amount (in terms of Solids) of the heat-sensitive color-pro 15 long as it performs a color-developing function on heating at ducing layer. A content of less than 8% is disadvantageous in a low temperature and performs anachromatizing function on that the strength of the coating film is low. A content of more heating at a high temperature. than 20% involves a problem of sensitivity decrease. In order The reversible developer includes 4-(octadecylthio)phe to improve the water resistance of the heat-sensitive color nol, 4-(dococylthio)phenol, 4-(octadecyloxy)phenol, 4-(do producing layer, a crosslinking agent for curing the resin can cocyloxy)phenol, N-octadecyl-4-hydroxybenzamide, 4'-hy be used. droxydocosane-anilide, N-(4-hydroxyphenyl)-N'-n- In the multicolor heat-sensitive recording material of the octadecylurea, docosylphosphonic acid, etc. When recording present invention, forming an intermediate layer between is conducted with a thermal printer or the like by using the heat-sensitive recording layers is effective in improving the multicolor heat-sensitive recording material of the present thermal partitionment. The intermediate layer comprises the 25 invention, printing by heating at a low temperature causes same resin as the water-soluble or water-dispersible resin color development only in the low-temperature color-produc used as the adhesive in the heat-sensitive recording layers, as ing layer, and printing by heating at a high temperature causes its main constituent and may further comprises pigments, achromatization in the low-temperature color-producing crosslinking agents, etc. The coating amount of the interme layer in a print portion and causes color development only in diate layer is preferably 1.0 to 5.0 g/m. When the coating 30 the high-temperature color-producing layer. amount is less than 1.0 g/m, no sufficient preventive effection Employment of the urea-urethane compound makes it pos diffusion between the recording layers can be obtained, sible to obtain an article for laser marking which is sufficient resulting in a deteriorated quality of image. When the coating in coloring density and gives such a very stable printed devel amount is more than 5.0 g/m, the sensitivity is disadvanta oped color image that the image is hardly discolored or faded geously decreased. 35 even by fats and oil, chemicals, fingerprints, etc. Therefore, As an especially preferable form of the multicolor heat the employment is especially advantageous from the view sensitive recording material of the present invention, there point of long-term preservation of records. can be mentioned a multicolor heat-sensitive recording mate rial in which two heat-sensitive recording layers which have In the present invention, the heat-sensitive recording layer different color development temperatures, respectively, and 40 of the article for laser marking preferably contains a recording undergo color development in different color tones, respec sensitivity improving agent. tively, are laminated on one side of a Substrate, and of the As the recording sensitivity improving agent usable these recording layers, the upper heat-sensitive recording therein, compounds capable of absorbing laser beams used layer contains eitheran agent used both as developerandtone for irradiation are used. Specific examples thereofare various reducer, or a reversible developer, and the lower heat-sensi 45 inorganic compounds such as aluminum hydroxide, wollas tive recording layer contains the urea-urethane compound tonite, bentonite, micas (e.g. muscovite and phlogopite), cal developer. cium silicate, talc, kaolin, clay, and silicate minerals (e.g. Of these, the agent used both as developer and tone reducer foyaite, hornblende and albite). Aluminum hydroxide, mus in the upper heat-sensitive recording layer is an amphoteric covite, Wollastonite and kaolin are especially preferable. compound which has an acidic group having a color-devel 50 These inorganic compounds may be used singly or as a mix oping function and a basic group having an achromatizing ture thereof. function, and performs the color-developing function on The proportions of the colorless or light-colored dye pre heating at a low temperature and performs the achromatizing cursor and recording sensitivity improving agent used in the function on heating at a high temperature. A typical example heat-sensitive recording layer in the present invention are not of the acidic group is phenolic hydroxyl group or carboxyl 55 particularly limited and may be properly chosen depending group. A typical example of the basic group is amino group. on the kinds of the dye precursor and recording sensitivity Although the amphoteric compound may have the basic improving agent used. Usually, the recording sensitivity group as a functional group, it preferably has the basic group improving agent can be used in a proportion of 10 to 5,000 as a portion of a salt compound as in a complex of a phenol parts by weight, preferably 100 to 2,000 parts by weight, per carboxylic acid compound and an amine compound. Specific 60 100 parts by weight of the color former. examples of Such an agent used both as developer and tone The contents of the dye precursor, the urea-urethane com reducer are those mentioned below. The phenolcarboxylic pound developer and the recording sensitivity improving acid compound that constitutes the agent used both as devel agent in the heat-sensitive recording layer can be adjusted as oper and tone reducer includes 2-hydroxybenzoic acid, 3-hy follows: based on the total weight (in terms of solids) of said droxybenzoic acid, 4-hydroxybenzoic acid, 3,4-dihydroxy 65 layer, the content of the dye precursor ranges from 5 to 30 wt benzoic acid, 3,5-dihydroxybenzoic acid, 2,3- %, preferably from 10 to 25 wt %, the content of the urea dihydroxybenzoic acid, 2,4-dihydroxybenzoic acid, 2.5- urethane compound developer ranges from 10 to 60 wt %, US 7,635,662 B2 123 124 preferably 20 to 50 wt %, and the content of the recording using a suitable coater Such as a roll coater, gravure coater, sensitivity improving agent ranges from 5 to 40 wt %, pref micro-gravure coater, knife coater, spray coater or the like. erably 10 to 30 wt %. The thickness of the coating film (the heat-sensitive recording The incorporation of also an acidic developer into the heat layer) obtained by the application and drying can be usually sensitive recording layer of the article for laser marking of the adjusted to 1 to 4 L. When the thickness is less than 1 u, color present invention improves the sensitivity and enables the development by laser irradiation is not sufficient and more article for laser marking to develop a brilliant color. As the over, the coating film tends to be peeled off. On the other acidic developer, the above-exemplified conventional elec hand, when the thickness is more than 4L, drying character tron-accepting materials are used. istics and the label attachability tend to be deteriorated. The For further improving the sensitivity of the article for laser 10 drying is varied depending on coating conditions such as the marking of the present invention, aheat-meltable material can speed of line and may be conducted either at room tempera be incorporated into the heat-sensitive recording layer. The ture or under conditions which do not cause color develop heat-meltable material is preferably one which has a melting ment in the heat-sensitive recording layer. point of 60° C. to 180° C., in particular, 80° C. to 140°C. The protective layer of the article for laser marking of the The color-producing marking agent of the present inven 15 present invention is formed by applying a transparent clear tion can be obtained by using the above-mentioned colorless coating liquid on the heat-sensitive recording layer. The clear or light-colored dye precursor, urea-urethane compound coating liquid is an aqueous composition consisting of an developer, recording sensitivity improving agent and aqueous aqueous binder, water and the like. binder and water as essential constituents, and mixing various As the aqueous binder used in the clear coating liquid for assistants therewith if necessary. the protective layer in the present invention, there are men The water used in the color-producing marking agent has a tioned those obtained by using as a base a per se known pH in a range of 5 to 12, preferably 6 to 9. When the pH is water-soluble or water-dispersible resin used in a coating lower than 5, fog is caused. When the pH is higher than 12, material or ink. Such a resin has a hydrophilic group (e.g. there are likely to be undesirable influences such as loss of the carboxyl group or amino group) optionally introduced there color-developing capability of the urea-urethane compound 25 into for impartment of the water-solubility or water-dispers developer. The water may be used in admixture with a water ibility. As said resin for the aqueous binder, a resin having a soluble organic solvent Such as methanol, ethanol or the like. glass transition temperature in a range of 20-80° C., prefer In addition to the essential constituents described above, ably 35-70° C. is used. When the glass transition temperature various assistants may, if necessary, be incorporated into the is lower than 20°C., the scuff resistance, chemical resistance, color-producing marking agent used in the present invention, 30 water resistance and the like of the protective layer are dete in order to, for example, facilitate application on a Substrate. riorated. On the other hand when the glass transition tempera The various assistants include, for example, dispersing agents ture is higher than 80°C., the protective layer is brittle, is poor (e.g. sodium dioctylsulfoSuccinate, sodium dodecylbenzene in flexibility and the like, and is easily cracked. Therefore, Sulfonate, lauryl alcohol Sulfuric acid ester sodium salt, and both of Such glass transition temperatures are not desirable. If fatty acid metal salts), opacifying agents (e.g. titanium 35 necessary, leveling agents, slip-properties-imparting agents, oxide), defoaming agents, viscosity modifiers, fluorescent dyes, and coloring agents. defoaming agents and the like may be incorporated into said A Substrate on which the color-producing marking agent of clear coating liquid in addition to the components described the present invention is printed (applied) is not particularly above. limited so long as it requires marking. As the Substrate, there 40 As the aqueous binder used in the clear coating liquid, an are mentioned, for example, the predetermined portions of acrylic resin can be obtained by using an alkyl (number of food containers, packaging materials, electronic parts and the carbonatoms: 1 to 24) ester of acrylic acid or methacrylic acid like, and articles (e.g. substrates for label) to be attached as a main component in combination with any of for thereto. As the Substrates for label, papers (e.g. paper and example, unsaturated carboxylic acids such as acrylic acid, synthetic paper), synthetic resin films, plastics, metallized 45 methacrylic acid, maleic acid, etc.; hydroxy-containing paper and synthetic paper, metallized films, metals, wood, unsaturated monomers such as hydroxyethyl acrylate, etc. are properly used depending on purposes. hydroxypropyl methacrylate, etc.; amino-containing unsatur The color-producing marking agent is prepared, for ated monomer Such as acrylamide, methacrylamide, etc.; and example, as follows. The binder is dissolved or dispersed in other unsaturated monomers such as styrene, acrylonitrile, water or a solvent composed mainly of water. Among the 50 vinyl acetate, vinyl chloride, etc., and copolymerizing the color former, the developer, the recording sensitivity improv alkyl ester with Such a comonomer. A polyester resin can be ing agent and the like, components that should be dissolved or obtained by carrying out the ester reaction of a polybasic acid dispersed in water or a solvent composed mainly of water are (including acid anhydrides) having two or more carboxyl treated together or individually in water or an aqueous sol groups in the molecule with a polyhydric alcohol having two vent, which contains a dispersing agent such as a poly(vinyl 55 or more hydroxyl groups in the molecule. The glass transition alcohol), by using a dispersing machine Such as a ball mill, point of Such an aqueous binder can be arbitrarily adjusted by attritor, sand grinder or the like. The average particle size of properly choosing the kinds, combination and proportions of each component after the dispersion is usually about 2 L or components that constitute said binder. less, preferably about 1 L or less. Then, the binder and the Said clear coating liquid is prepared by dissolving or dis dispersions are mixed to obtain the color-producing marking 60 persing the above-mentioned aqueous binder in Suitable agent of the present invention. The Solid content of said color water, and if necessary, it is incorporated with leveling agents, producing marking agent is 20 to 70 wt %, preferably about slip-properties-imparting agents, defoaming agents and the 30 wt % to about 65 wt %. like. The solid content of said clear coating liquid ranges The color-producing marking agent may be applied preferably from 20 to 70 wt %, in particular, 30 to 60 wt %. directly on the substrate, or it may be applied on the substrate 65 Said clear coating liquid can be printed (applied) on the that has been previously subjected to Surface treatment, surface of the dried coating film formed as heat-sensitive undercoating or the like. The application can be carried out by recording layer. A method for the printing (application) is not US 7,635,662 B2 125 126 particularly limited. The application can be carried out by depending on purposes from papers (e.g. paper and synthetic means of a roll coater, gravure coater, micro-gravure coater, paper), synthetic resin films, plastics, metallized paper and spray coater or the like. synthetic paper, metallized films, metals, glass, wood, etc. The thickness of the coating film thus formed can be usu Although said packaging material can be used in all the fields ally adjusted to 3 to 10 L. When the thickness is less than 3 L, of conventional packaging materials, it is preferably used in the protection of the heat-sensitive recording layer afforded the field of, in particular, food, medicine, toiletries, publica by said clear coating is not sufficient and the chemical resis tions, and electric and electronic parts, etc. tance, rub resistance and the like are deteriorated. On the The container as the article for laser marking of the present other hand, when the thickness is more than 10 L, the drying invention is produced by forming a heat-sensitive recording characteristics and physical performance of the coating film 10 layer and a protective layer on a Substrate Such as glass, tend to be deteriorated. Drying of said clear coating liquid is plastic, metal or the like by the above-mentioned methods. varied depending on coating conditions such as the speed of This food container can be used all the fields of conventional line and may be conducted either at room temperature or food containers, such as the fields of bottles for liquors and underconditions which do not cause color development in the refreshing drinks, retort-food containers, instant-food con heat-sensitive recording layer. 15 tainers, cosmetics containers, medicine container, toiletry When the thus formed heat-sensitive recording layer of the products, etc. article for marking is irradiated with laser beams, the irradi When the recording material is a pressure-sensitive record ated portion is heated, so that the urea-urethane compound ing material, it can have, for example, the forms disclosed in developer and the dye precursor react with each other to U.S. Pat. Nos. 2,505,470, 2,712,507, 2,730,456, 2,730,457 develop a color, resulting in marking. Although the amount of and 3,418.250, etc. That is, various forms such as the follow energy of laser beams used for the irradiation is not particu ing forms can be employed: pressure-sensitive recording larly limited, it is preferably 1.4J (joule)/cm or less when the paper obtained by dissolving the dye precursorora mixture of possibility of fracture of the coating film is taken into consid the dye precursors in a solvent consisting of one of or a eration. On the other hand, although the lower limit of the mixture of two or more of alkylated naphthalenes, alkylated amount of energy required for color development is unknown 25 diphenyls, alkylated diphenylmethanes, alkylated diaryle because there is not apparatus capable of producing low thanes, synthetic oils (e.g. chlorinated paraffin), vegetable energy, Sufficient color development takes place at an amount oils, animal oils, mineral oils, etc., dispersing the resulting of energy of 0.4 J/cm. Therefore, the suitable amount of Solution in a binder or incorporating the Solution into micro energy for color development by the irradiation ranges from capsules, applying the dispersion on a Substrate or applying 0.4 to 1.4 J/cm, in particular, from 0.45 to 1.2 J/cm. As a 30 the microcapsules on a Substrate together with a binder, and laser used for the irradiation, a pulsed laser or scanning laser placing the upper paper thus obtained and under paper coated is suitable. As to the kind of the laser, any of, for example, gas with a dispersion of the urea-urethane compound (and an lasers, excimer lasers and semiconductor lasers may be used. amino compound and/or a developer, etc.), one upon the other Specific examples of the laser are carbon dioxide lasers, so that their coated Surfaces may face each other, pressure mixed gas lasers,YAG lasers, ruby lasers, etc. 35 sensitive recording paper obtained by holding, between the As a method for partially irradiatingaportion of a desirable above-mentioned upper paper and under paper, intermediate form with laser beams, there are mentioned a method of paper coated with a dispersion of the urea-urethane com irradiating the coating film with laser beams through a metal pound on one side and the dye precursor on the other side; mask to irradiate the coating film with laser beams corre self-type pressure-sensitive recording paper obtained by sponding to the form of the opening of the metal mask; and a 40 applying the above-mentioned dispersion of the urea-ure method of inputting a desirable form to a computer and irra thane compound (and an amino compound and/or a devel diating the coating film with laser beams in accordance with oper) and the above-mentioned dispersion containing the dye the desirable form in a manner of so-called drawing with a precursor, on the same Surface of a substrate as a mixture or in single stroke. When the heat-sensitive recording layer is irra a multilayer form; and self-type pressure-sensitive recording diated with laser beams, the irradiated portion is increased in 45 paper obtained by making each of the dye precursor and the temperature to undergo color development caused by melting urea-urethane compound (and an amino compound and/or a and mixing of the color-producing components in the heat developer) into microcapsules, and applying a mixture of the sensitive recording layer, resulting in the appearance of letters microcapsules of the two kinds on the same Surface of a or a figure, which has a clear desirable form. This color substrate. change by irradiation can be carried out in a moment because 50 As a process for producing microcapsules, there can be the energy density of laser beams is high. adopted, for example, the coacervation processes disclosed in The label as the article for laser marking of the present U.S. Pat. Nos. 2,800.457 and 2,800.458, the interfacial poly invention can be produced by forming aheat-sensitive record merization processes disclosed in JP-B-38-19,574, JP-B-42 ing layer and a protective layer by the above-mentioned meth 446, JP-B-42-771, etc., the in-situ processes disclosed in ods on a Substrate for label properly selected depending on 55 JP-B-36-9168, JP-B-51-9079, etc., the melt dispersion cool purposes from papers (e.g. paper and synthetic paper), Syn ing processes disclosed in Brit. Patent Nos. 952,807 and thetic resin films, plastics, metallized paper and synthetic 96-5,074, etc., and the spray drying processes disclosed in paper, metallized films, metals, etc. Although the label thus U.S. Pat. No. 311,140, Brit. Patent No. 930,422, etc. obtained can be used in all the fields of conventional labels, it The color-producing composition of the present invention is preferably used in the field of, in particular, food, medicine, 60 corresponds to the combination of a dye precursor and a toiletries, publications, and electric and electronic parts, etc. developer described in each of the above references and the The packaging material as the article for laser marking of like. the present invention is produced by forming a heat-sensitive For forming a pressure-sensitive layer, each component recording layer and a protective layer by the above-men Such as the urea-urethane compound may be used in the form tioned methods on any of various conventional packaging 65 of a solution or dispersion in a solvent. In the case of a materials such as boxes, packing paper and packages, which color-producing system further comprising an amino com are obtained by the use of a substrate properly selected pound and/or a developer, each component may be used in the US 7,635,662 B2 127 128 form of a solution or dispersion in a solvent, or a combination A method for forming the color-producing layer is not of the urea-urethane compound, the amino compound and particularly limited. The color-producing layer is formed, for optionally the developer may be used in the form of a solution example, by applying a coating liquid for the color-producing or dispersion in a solvent. layer on a Substrate by a suitable coating method such as In the above-mentioned interfacial polymerization pro free-fall curtain coating, air-knife coating, Bariber blade cesses adopted for forming microcapsules, a film is formed on coating, Pure blade coating, short-dwell coating or the like, an interface by using two kinds of monomers, i.e., an oil and drying the thus treated Substrate. The coating amount of monomer and a water-soluble monomer. There are known, the coating liquid for the color-producing layer is not particu for example, a process in which a polybasic acid chloride is larly limited and is usually controlled in a range of 1 to 15 used as an oil phase and a polyvalent amine as an aqueous 10 g/m, preferably about 3 to about 10 gim, in terms of dry phase, and a polyamide film is formed on the interface; a weight. process in which a polybasic acid chloride is used as an oil The thermal response can be improved by forming an phase and a polyhydric hydroxy compound as an aqueous intermediate layer between the heat-sensitive recording layer phase, and a polyester film is formed on the interface; a and the Substrate. The intermediate layer is composed mainly process in which a polyvalent isocyanate is used as an oil 15 of an organic or inorganic pigment, hollow particles and an phase and a polyhydric alcohol or a polyhydric phenol as an aqueous binder Such as a water-soluble polymer or a latex. As aqueous phase, and a polyurethane film is formed on the the organic or inorganic pigment and the aqueous binder, the interface; and a process in which a polyvalent isocyanate is same organic or inorganic pigment and aqueous binder as used as an oil phase and a polyvalent amine as an aqueous used in the heat-sensitive recording layer can be used. A phase, and a polyurea film is formed on the interface. Thus, method for forming the intermediate layer is not particularly when the interfacial polymerization process is adopted for limited. As this method, the same method as a method for producing microcapsules, an isocyanate compound is used in forming the heat-sensitive recording layer can be adopted. A Some cases as a reactive monomer for forming a film. dry spread for forming the intermediate layer ranges prefer In this case, said isocyanate compound is consumed in ably from 2.0 to 15.0 g/m. In this case, the surface pH of the forming a film for microcapsules and is not directly con 25 intermediate layer formed on the substrate is preferably 3 to 9, cerned with a developed color image, and it is absolutely more preferably 5 to 9, most preferably 6 to 8. necessary to use a water-soluble monomer together with the In addition, in the present invention, the resistance to rub isocyanate compound. In these points, its employment is bing of recording paper can be improved by forming a pro distinguished from the employment of the isocyanate com tective layer composed mainly of a water-soluble polymer, on pound according to the present invention. 30 the heat-sensitive recording layer if necessary. Specific Dispersions of compounds which are not made into micro examples of the water-soluble polymer in this case are the capsules are prepared by finely grinding one or more com water-soluble polymer binders mentioned in relation to the pounds as each component in an aqueous solution containing above-mentioned heat-sensitive recording layer. The water a compound having dispersing capability, Such as a water soluble polymer can be used together with a conventional 35 waterproofing agent capable of waterproofing the water soluble polymer, a surfactant or the like. The urea-urethane soluble polymer. Specific examples of the waterproofing compound may be dispersed together with an amino com agent are formaldehyde, glyoxal, chrome alum, melamine, pound and an acidic developer. melamine-formaldehyde resins, polyamide resins, polya As the Substrate used in the pressure-sensitive recording mide-epichlorohydrin resins, etc. material, paper is mainly used, though any of various woven 40 Furthermore, pigments, metal Soaps, waxes, crosslinking fabrics, nonwoven fabrics, synthetic resin films, laminated agents, etc. are incorporated into the protective layer for the papers, synthetic papers, metal foils, and composite sheets purpose of for example, improving the matching with a ther obtained by combining two or more of them may be used mal head during printing and improving the water resistance besides paper, depending on purposes. of the protective layer. As a binder, conventional various binders can be used. The 45 The pigments include Zinc oxide, calcium carbonate, binder includes, for example, water-soluble binders such as barium Sulfate, titanium oxide, lithopone, talc, pagodite, starches, hydroxyethyl cellulose, methyl cellulose, car kaolin, aluminum hydroxide, silica, amorphous silica, etc. boxymethyl cellulose, gelatin, casein, poly(vinyl alcohol)S. The amount of the pigments added is 0.5 to 4 times, prefer modified poly(vinyl alcohol)S, Sodium poly(acrylate)S. acry ably 0.8 to 3.5 times, the total weight of the polymers. When lamide-acrylic ester copolymers, acrylamide-acrylic ester 50 the amount is below the lower limit of the above range, the methacrylic acid terpolymers, alkali salts of styrene-maleic pigments are not effective in improving the matching with a anhydride copolymers, alkali salts of ethylene-maleic anhy thermal head. When the amount is above the upper limit, the dride copolymers, etc.; and latex type water-insoluble binders sensitivity of the heat-sensitive recording material is remark of Styrene-butadiene copolymers, acrylonitrile-butadiene ably decreased, so that the commercial value of the recording copolymers, methyl acrylate-butadiene copolymers, etc. 55 material is impaired. In the recording material of the present invention, the The metal Soaps include, for example, emulsions of higher recording layer may contain a hindered phenol compound or fatty acid metal salts such as Zinc Stearate, calcium Stearate, an ultraviolet absorber. The hindered phenol compound or aluminum Stearate, etc. The metal Soaps are added in a pro ultraviolet absorber includes, for example, 1,1,3-tris(3'-cy portion of 0.5 to 20 wt %, preferably 1 to 10 wt %, based on clohexyl-4'-hydroxyphenyl)butane, 1,1,3-tris(2-methyl-4- 60 the total weight of the protective layer. The waxes include, for hydroxy-5-tert-butylpheny)butane, 4,4'-thiobis(3-methyl-6- example, emulsions of paraffin wax, microcrystalline wax, tert-butylphenol), 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert carnauba wax, methylolstearoamide, polyethylene wax, etc. butyl-4-hydroxybenzyl)benzene, 2,2'-dihydroxy-4,4'- The waxes are added in a proportion of 1 to 20 wt %, prefer dimethoxybenzophenone, p-octylphenyl salicylate, 2-(2- ably 1 to 10 wt %, based on the total weight of the protective hydroxy-5'-methylpheny)benzotriazole, ethyl-2-cyano-3,3'- 65 layer. diphenyl acrylate and tetra (2.2.6.6-tetramethyl-4-piperidyl)- Informing the protective layer on the heat-sensitive record 1,2,3,4-butanetetracarbonate. ing layer, a Surfactant is added to a coating liquid for forming US 7,635,662 B2 129 130 the protective layer, in order to obtaina uniform coating layer. cific examples of the fillers, heat-meltable materials and fluo- 10 Hand cream (Atrix, a trade name, mfcd. by Kao Corp.) was rescent dyes are those mentioned in relation to the above thinly applied on the developed color image portion obtained mentioned heat-sensitive recording layer. The dry spread of in the coloring density estimation, and after standing at ordi the protective layer is preferably about 0.5 to about 10 g/m, nary temperature for 7 days, the color density of print portion in particular, about 1 to about 5 g/m. was visually estimated. When there was only a slight decrease When a reverse-side layer (a back coating layer) is, if 15 in a print density, the print preservability was rated as good. necessary, formed on the side reverse to the recording layer of the recording material produced by the process of the present EXAMPLE 1. invention, curling of the resulting recording paper can be To 88.2 g of 2,4-toluene diisocyanate were added 124 g of made difficult. As the components of a coating liquid for the methyl ethyl ketone and 15 g of dimethylformamide as sol reverse-side layer and a coating method for the coating liquid, 20 vents, followed by adding dropwise thereto a dilution of 6.3g the same components and method as in the case of the pro of 4,4'-diaminodiphenyl sulfone with a mixture of 25 g of tective recording layer may be employed. The dry spread methyl ethyl ketone and 3 g of dimethylformamide, and the ranges preferably from 0.2 to 10.0 g/m. reaction was carried out at 25°C. for 8 hours. After comple The present invention is explained in further detail with the tion of the reaction, the methyl ethyl ketone was removed by following examples. 25 concentration and toluene was added to the residue, and the The analyses of materials and the evaluation of physical white solid precipitated was recovered by filtration, washed properties were carried out by the following methods. with toluene and then dried overnight in a vacuum to obtain 10.0 g of a compound as white crystals. Subsequently, 33 g of phenol and 180g of methyl ethyl ketone were added to 8.4g Measured by diffuse reflectance spectroscopy by the use of 30 of the obtained compound, followed by adding thereto 8.5 mg FTIR-8100M manufactured by Shimadzu Corp. of triethylamine, and the reaction was carried out at 25°C. for 7 hours. After completion of the reaction, toluene was added Measured by using JMS-HX100 manufactured by JEOL to the reaction Solution and the crystals precipitated were LTD., nitrobenzyl alcohol as a matrix, and Xenon as a primary is recovered by filtration, washed with toluene and then dried gaS. overnight in a vacuum to obtain 10.0 g of a compound as white crystals. Analytical values of these white crystals were Result of mass spectrum measurement: Aheat-sensitive recording material was held between vinyl 45 M+H as detected at m/z. 785. chloride wrap films or in a vinyl chloride file, and a load of The structural formula of the major component of this 300 g/cm was applied thereto from above. After standing at compound is presumed to be the structural formula of the 40°C. for 24 hours, the coloring density of the printed portion above-mentioned compound (E-24). and the non-printed portion (the original recording material Next, 2 g of this compound was ground together with 8g of surface) was visually estimated. When there was only a slight 50 a 2.5 wt % aqueous Solution of a poly(vinyl alcohol)(Goseran decrease in print density, the print preservability was rated as L-3266, a trade name, mfcd. by The Nippon Synthetic Chemi good. cal Industry Co., Ltd.) in a paint shaker for 45 minutes to be dispersed, whereby a dispersion was obtained. The tempera ture of the dispersion immediately after the dispersing opera Aheat-sensitive recording material was allowed to stand in 55 tion was 25°C. The diameter of dispersed particles of the a circumstance of 60° C. and 25% RH for 24 hours and the compound was 0.9 Lum. degree of fading of print was visually estimated. When the Separately, 70 g of 3-dibutylamino-6-methyl-7-anilinof degree of fading is low, the print preservability was rated as luoran was ground together with 130 g of a 5.4 wt % poly good. (vinyl alcohol) aqueous Solution in a sand grinder (mfl. by In addition, a heat-sensitive recording material was 60 AIMEX CO.,LTD., vessel capacity 400 ml) at a number of allowed to stand in a circumstance of 80° C. and 25% RH for revolution of 2,000 rpm for 3 hours to be dispersed, whereby 24 hours and the degree of fading of print was visually esti a dispersion was obtained. mated. When the degree of fading was low, the print preserv Separately, 70g of diphenyl Sulfone was ground together ability was rated as good. The coloring density of the original with 130 g of a 5.4 wt % poly(vinyl alcohol) aqueous solution recording material surface was also visually estimated. When 65 in a sandgrinder (mfl. by AIMEXCO.,LTD., vessel capacity the color development was slight, the preservability of origi 400 ml) at a number of revolution of 2,000 rpm for 3 hours to nal recording material Surface was rated good. be dispersed, whereby a dispersion was obtained. US 7,635,662 B2 131 132 Separately, 10 g of calcium carbonate was mixed with 30 g nyl in place of diphenyl sulfone, and was evaluated. The of water and dispersed by stirring by the use of a stirrer to results obtained are summarized in Table 1. obtain a dispersion. A coating liquid was obtained by stirring and mixing the EXAMPLE 3 above-mentioned dispersions and other components in the While stirring 31.5g of 2,4-toluene duisocyanate at 60°C., following proportions (dry basis proportions); the dispersion a dilution of 21.5g of 4,4'-diaminodiphenyl sulfone with 120 of the above-mentioned compound in terms of dry solids: 20 ml of methyl ethyl ketone was added dropwise thereto over a parts by weight, the 3-dibutylamino-6-methyl-7-anilinofluo period of 4 hours, and the reaction was continued at 60° C. for ran dispersion in terms of dry solids: 10 parts by weight, the 10 another 2 hours. After completion of the reaction, the reaction diphenyl sulfone dispersion in terms of dry solids: 25 parts by Solution was cooled to room temperature and then toluene weight, the calcium carbonate dispersion in terms of dry was added thereto, and the white solid precipitated was recov Solids: 40 parts by weight, a Zinc Stearate dispersion (solid ered by filtration, washed with toluene and then dried over content: 16 wt %) in terms of dry solids: 20 parts by weight, night in a vacuum to obtain 47 g of a compound as white and a 15 wt % poly(vinyl alcohol) in terms of dry solids: 15 15 crystals. Subsequently, 9.5g of phenol and 95 ml of methyl parts by weight. ethyl ketone were added to 30g of the obtained compound, followed by adding thereto 30 mg of triethylamine, and the The coating liquid was applied on base paper with a basis reaction was carried out at 25°C. for 4 hours. After comple weight of 50 g/m by the use of a bar coater of rod number 10 tion of the reaction, toluene was added to the reaction Solution and dried, followed by Supercalendering, to obtain a heat and the crystals precipitated were recovered by filtration, sensitive recording material. washed with toluene and then dried overnight in a vacuum to The result of sensitivity evaluation was so good that the obtain 38.5g of a compound as white crystals. The result of IR optical density was 1.3. measurement of these white crystals was the same as in The result of estimating the degree of a thermal color Example 1. change of the original recording material Surface (the heat 25 The structural formula of the major component of this resistance) was so good that the color change was slight. The compound is presumed to be the structural formula of the above-mentioned compound (E-24). thermal fading of the print portion was desirably slight. The Next, 2 g of this compound was ground together with 8g of result of evaluating the plasticizer resistance by the use of a 2.5 wt % poly(Vinyl alcohol) aqueous Solution in a paint vinyl chloride wrap films was so good that only a slight color shaker for 45 minutes to be dispersed, whereby a dispersion change was caused. The results are Summarized in Table 1. was obtained. Then, a heat-sensitive recording material was produced in EXAMPLE 2 the same manner as in Example 1 except for using this dis persion of said compound in place of the dispersion of the To 30 g of 2,4-toluene diisocyanate was added 57 g of 35 compound obtained in Example 1, and was evaluated. The methyl ethyl ketone as a solvent, followed by adding drop results obtained are summarized in Table 1. wise thereto a dilution of 2.15 g of 4,4'-diaminodiphenyl sulfone with 12 g of methylethylketone, and the reaction was EXAMPLE 4 carried out at 50° C. for 6 hours. After completion of the reaction, the reaction solution was cooled to room tempera 40 To 10.4 g of 2,4-toluene diisocyanate was added 20 g of ture and then toluene was added thereto, and the white solid methyl ethyl ketone as a solvent, followed by adding thereto precipitated was recovered by filtration, washed with toluene a dilution of 3.7 g of 4,4'-diaminodiphenyl sulfone with 30 g and then dried overnight in a vacuum to obtain 4.1 g of a of methyl ethyl ketone, and the reaction was carried out at compound as white crystals. Subsequently, 11.8g of phenol ordinary temperature for 20 hours. After completion of the 45 reaction, the methyl ethyl ketone was removed by concentra and 78 g of methyl ethyl ketone were added to 3.0 g of the tion and then toluene was added to the residue, and the white obtained compound, followed by adding thereto 3 mg of solid precipitated was recovered by filtration, washed with triethylamine, and the reaction was carried out at 25°C. for 4 hexane and then dried overnightina vacuum to obtain 8.8g of hours. After completion of the reaction, toluene was added to a compound as white crystals. Subsequently, 15 g of phenol the reaction Solution and the crystals precipitated were recov 50 and then a small amount of dibutyltin dilaurate, were added to ered by filtration, washed with toluene and then dried over 4 g of the obtained compound, and the reaction was carried night in a vacuum to obtain 3.9 g of a compound as white out at 50° C. for 4 hours. After completion of the reaction, crystals. The result of IR measurement of these white crystals toluene was added to the reaction Solution and the crystals was the same as in Example 1. precipitated were recovered by filtration, washed with hexane The structural formula of the major component of this 55 and then dried over-night in a vacuum to obtain 5.2 g of a compound is presumed to be the structural formula of the compound as white crystals. above-mentioned compound (E-24). The structural formula of the major component of this Next, 2 g of this compound was ground together with 8g of compound is presumed to be the structural formula of the a 2.5 wt % aqueous solution of a poly(vinyl alcohol)(Gosenol above-mentioned compound (E-24). 60 Next, 2 g of this compound was ground together with 8g of KL-05, a trade name, mfcd. by The Nippon Synthetic Chemi a 2.5 wt % methyl cellulose aqueous solution in a paint shaker cal Industry Co., Ltd.) in a paint shaker for 45 minutes to be for 45 minutes to be dispersed, whereby a dispersion was dispersed, whereby a dispersion was obtained. obtained. Then, a heat-sensitive recording material was produced in Then, a heat-sensitive recording material was produced in the same manner as in Example 1 except for using this dis 65 the same manner as in Example 1 except for using this dis persion of said compound in place of the dispersion of the persion of said compound in place of the dispersion of the compound obtained in Example 1, and using p-benzylbiphe compound obtained in Example 1, and using benzyloxynaph US 7,635,662 B2 133 134 thalene in place of diphenyl sulfone, and was evaluated. The Then, a heat-sensitive recording material was produced in results obtained are summarized in Table 1. the same manner as in Example 1 except for using this dis persion of said compound in place of the dispersion of the EXAMPLE 5 compound obtained in Example 1, and using benzil in place To 30 g of 2,4-toluene diisocyanate was added 30 g of 5 of diphenyl sulfone, and was evaluated. The results obtained toluene as a solvent, followed by adding thereto 3.24 g of are summarized in Table 1. phenol, and the reaction was carried out at 100° C. for 1 hour and 30 minutes. After completion of the reaction, the toluene EXAMPLE 7 was removed by concentration and hexane was added to the 10 residue, and the white solid precipitated was recovered by To 10.4 g of 2,4-toluene diisocyanate was added 20 g of filtration, washed with hexane and then dried overnight in a methyl ethyl ketone as a solvent, followed by adding drop vacuum to obtain 6.9 g of a compound as white crystals. wise thereto a dilution of 3.7 g of 3,3'-diaminodiphenyl sul Subsequently, methyl ethyl ketone was added as a solvent to fone with 30 g of methyl ethyl ketone, and the reaction was 2 g of the obtained compound, followed by adding thereto 0.9 15 carried out at 15° C. for 3 hours. The white crystals precipi g of 4,4'-diaminodiphenyl Sulfone, and the reaction was car tated were recovered by filtration, washed with hexane and ried out at 50° C. for 22 hours. The crystals precipitated were then dried overnight in a vacuum to obtain 6.3 g of a com recovered by filtration, washed with hexane and then dried pound as white crystals. Subsequently, 15 g of phenol and overnight in a vacuum to obtain 2.3 g of a compound as white then 3 mg of dibutyltin dilaurate were added to 3.0 g of the crystals. Analytical values of these white crystals were as obtained compound, and the reaction was carried out at 50° C. follows. for 3 hours. After completion of the reaction, hexane was Result of IR measurement: added to the reaction Solution and the crystals precipitated Characteristic peaks appeared at 550 cm, 1030 cm', were recovered by filtration, washed and then dried overnight 1110 cm, 1150 cm, 1590 cm, 1700 cm and 3300 in a vacuum to obtain 3.3 g of a compound as white crystals. cm. 25 Analytical values of these white crystals were as follows. The structural formula of the major component of this compound is presumed to be the structural formula of the Result of IR measurement: above-mentioned compound (E-22). Characteristic peaks appeared at 520 cm, 880 cm, 1030 Next, 2 g of this compound was ground together with 8g of cm, 1430 cm, 1590 cm, 1710 cm and 3300 cm. a 2.5 wt % poly(Vinyl alcohol) aqueous Solution in a paint 30 The structural formula of the major component of this shaker for 45 minutes to be dispersed, whereby a dispersion compound is presumed to be the structural formula of the was obtained. above-mentioned compound (E-21). Then, a heat-sensitive recording material was produced in the same manner as in Example 1 except for using this dis Next, 2 g of this compound was ground together with 8g of persion of said compound in place of the dispersion of the 35 a 2.5 wt % poly(Vinyl alcohol) aqueous Solution in a paint compound obtained in Example 1, and using di-p-methylben shaker for 45 minutes to be dispersed, whereby a dispersion Zyl oxalate in place of diphenyl sulfone, and was evaluated. was obtained. The results obtained are summarized in Table 1. Then, a heat-sensitive recording material was produced in the same manner as in Example 1 except for using this dis EXAMPLE 6 40 persion of said compound in place of the dispersion of the compound obtained in Example 1, and using 1,2-di(3-meth To 30 g of 2,4-toluene diisocyanate was added 30 g of ylphenoxy)ethane in place of diphenyl Sulfone, and was toluene as a solvent, followed by adding thereto 3.24 g of evaluated. The results obtained are summarized in Table 1. phenol, and the reaction was carried out at 100° C. for 1 hour and 30 minutes. After completion of the reaction, the toluene 45 EXAMPLE 8 was removed by concentration and hexane was added to the residue, and the white solid precipitated was recovered by To 27.8g of 2,4-toluene diisocyanate was added 111 g of filtration, washed with hexane and then dried overnight in a toluene as a solvent, followed by adding dropwise thereto a vacuum to obtain 6.9 g of a compound as white crystals. solution of 7.4 g of aniline in 37 g of toluene, and the reaction Subsequently, methyl ethyl ketone was added as a solvent to 50 was carried out at 10°C. for 8 hours. After completion of the 2 g of the obtained compound, followed by adding thereto 0.9 reaction, the white solid precipitated was recovered by filtra g of 3,3'-diaminodiphenyl Sulfone, and the reaction was car tion and then dried overnight in a vacuum to obtain 20.0 g of ried out at 50° C. for 22 hours. The crystals precipitated were a compound as white crystals. Subsequently, 20g of dimeth recovered by filtration, washed with hexane and then dried ylformamide was added as a solvent to 6.6 g of the obtained overnight in a vacuum to obtain 2.5g of a compound as white 55 compound, followed by adding thereto 2.7 g of 2.2-bis(4- crystals. Analytical values of these white crystals were as hydroxyphenyl)propane, and the reaction was carried out at follows. 15° C. for 5 hours. After completion of the reaction, 8 g of Result of IR measurement: acetone and then 160 g of water were added to the reaction Characteristic peaks appeared at 620 cm, 880 cm, 1030 solution, and the crystals precipitated were recovered by fil cm, 1300 cm, 1590 cm, 1700 cm and 3300 cm. 60 tration and then dried overnight in a vacuum to obtain 9.3 g of The structural formula of the major component of this a compound as white crystals. Analytical values of these compound is presumed to be the structural formula of the white crystals were as follows. above-mentioned compound (E-19). Next, 2 g of this compound was ground together with 8g of Result of IR measurement: a 2.5 wt % poly(Vinyl alcohol) aqueous Solution in a paint 65 Characteristic peaks appeared at 750cm, 840cm, 1020 shaker for 45 minutes to be dispersed, whereby a dispersion cm, 1500 cm, 1600 cm, 1720 cm and 3320 cm. An was obtained. IR spectrum is shown in FIG. 2. US 7,635,662 B2 135 136 Result of mass spectrum measurement: tration, washed with toluene and then dried overnight in a M+H" was detected at m/z 763. vacuum to obtain 42 g of a compound as white crystals. The The structural formula of the major component of this result of IR measurement of these white crystals was the same compound is presumed to be the structural formula of the as in Example 8. above-mentioned compound (E-30). 5 The structural formula of the major component of this Next, 2 g of this compound was ground together with 8g of compound is presumed to be the structural formula of the a 2.5 wt % poly(Vinyl alcohol) aqueous Solution in a paint above-mentioned compound (E-30). shaker for 45 minutes to be dispersed, whereby a dispersion Next, 2 g of this compound was ground together with 8g of was obtained. a 2.5 wt % poly(Vinyl alcohol) aqueous Solution in a paint Then, a heat-sensitive recording material was produced in 10 shaker for 45 minutes to be dispersed, whereby a dispersion the same manner as in Example 1 except for using this dis was obtained. persion of said compound in place of the dispersion of the Then, a heat-sensitive recording material was produced in compound obtained in Example 1, and was evaluated. The the same manner as in Example 1 except for using this dis results obtained are summarized in Table 1. persion of said compound in place of the dispersion of the 15 compound obtained in Example 1, and was evaluated. The EXAMPLE 9 results obtained are summarized in Table 1.

To 12.2 g of 2,4-toluene diisocyanate was added 90 g of EXAMPLE 11 toluene as a solvent, followed by adding dropwise thereto a solution of 5.2 g of aniline in 30 g of toluene, and the reaction To 27.8g of 2,4-toluene diisocyanate was added 111 g of was carried out at 5° C. for 7 hours. After completion of the toluene as a solvent, followed by adding dropwise thereto a reaction, the white solid precipitated was recovered by filtra solution of 7.4 g of aniline in 37 g of toluene, and the reaction tion, washed with toluene and then dried overnight in a was carried out at 10°C. for 8 hours. After completion of the vacuum to obtain 14 g of a compound as white crystals. reaction, the white solid precipitated was recovered by filtra Subsequently, 60 g of toluene was added as a solvent to 4.3g 25 tion and then dried overnight in a vacuum to obtain 20.0 g of of the obtained compound, followed by adding thereto 1.73 g a compound as white crystals. Subsequently, 65 g of toluene of 2.2-bis(4-hydroxyphenyl)propane and 0.043 mg of triethy was added as a solvent to 2.8 g of the obtained compound, lamine, and the reaction was carried out at 70° C. for 8 hours. followed by adding thereto 1.14 g of 2.2-bis(4-hydroxyphe Thereafter, the temperature was raised to 80° C. and the nyl)propane and 2.7 mg of dibutyltin dilaurate, and the reac reaction was continued for another 1 hour. After completion 30 tion was carried out at 60°C. for 7 hours. After completion of of the reaction, the reaction solution was cooled to room the reaction, the reaction Solution was concentrated, followed temperature, and the crystals precipitated were recovered by by adding thereto acetone and then 160 g of water, and the filtration, washed with toluene and then dried overnight in a crystals precipitated were recovered by filtration and dried vacuum to obtain 6.0 g of a compound as white crystals. The overnight in a vacuum to obtain 3.5g of a compound as white result of IR measurement of these white crystals was the same 35 as in Example 8. crystals. The structural formula of the major component of this The structural formula of the major component of this compound is presumed to be the structural formula of the compound is presumed to be the structural formula of the above-mentioned compound (E-30). above-mentioned compound (E-30). Next, 2 g of this compound was ground together with 8g of 40 Next, 2 g of this compound was ground together with 8g of a 2.5 wt % poly(Vinyl alcohol) aqueous Solution in a paint a 2.5 wt % poly(Vinyl alcohol) aqueous Solution in a paint shaker for 45 minutes to be dispersed, whereby a dispersion shaker for 45 minutes to be dispersed, whereby a dispersion was obtained. was obtained. Then, a heat-sensitive recording material was produced in Then, a heat-sensitive recording material was produced in the same manner as in Example 1 except for using this dis 45 the same manner as in Example 1 except for using this dis persion of said compound in place of the dispersion of the persion of said compound in place of the dispersion of the compound obtained in Example 1, and was evaluated. The compound obtained in Example 1, and was evaluated. The results obtained are summarized in Table 1. results obtained are summarized in Table 1.

EXAMPLE 10 50 EXAMPLE 12 To 61 g of 2,4-toluene diisocyanate was added 450 g of To 27.8g of 2,4-toluene diisocyanate was added 111 g of toluene as a solvent, followed by adding dropwise thereto a toluene as a solvent, followed by adding dropwise thereto a solution of 26 g of aniline in 150 g of toluene over a period of solution of 7.4 g of aniline in 37 g of toluene, and the reaction 6 hours, and the reaction was carried out at 5° C. for 7 hours. 55 was carried out at 10°C. for 8 hours. After completion of the After completion of the reaction, the white solid precipitated reaction, the white solid precipitated was recovered by filtra was recovered by filtration, washed with toluene and then tion and then dried overnight in a vacuum to obtain 20.0 g of dried overnight in a vacuum to obtain 70g of a compound as a compound as white crystals. Subsequently, 30 g of methyl white crystals. Subsequently, 365g of toluene was added as a ethyl ketone was added as a solvent to 4.7 g of the obtained solvent to 30g of the obtained compound, followed by adding 60 compound, followed by adding thereto 1.0 g of 2.2-bis(4- thereto 12.2 g of 2.2-bis(4-hydroxyphenyl)propane and 0.3 hydroxyphenyl)propane and 4.7 mg of dibutyltin dilaurate, mg of triethylamine, and the reaction was carried out with and the reaction was carried out at 75° C. for 4 hours. After stirring at 60° C. for 4 hours and then at 70° C. for 3 hours. completion of the reaction, the reaction solution was concen Thereafter, the temperature was raised and the reaction was trated, followed by adding thereto acetone and then 160 g of continued at 80° C. for another 3 hours. After completion of 65 water, and the crystals precipitated were recovered by filtra the reaction, the reaction solution was cooled to room tem tion and then dried overnight in a vacuum to obtain 3.0 g of a perature, and the crystals precipitated were recovered by fil compound as white crystals. US 7,635,662 B2 137 138 The structural formula of the major component of this Result of IR measurement: compound is presumed to be the structural formula of the Characteristic peaks appeared at 750cm, 840 cm, 1020 above-mentioned compound (E-30). cm, 1500 cm, 1600 cm, 1700 cm and 3320 cm. Next, 2 g of this compound was ground together with 8g of The structural formula of the major component of this a 2.5 wt % poly(Vinyl alcohol) aqueous Solution in a paint 5 compound is presumed to be the structural formula of the shaker for 45 minutes to be dispersed, whereby a dispersion above-mentioned compound (E-13). was obtained. Next, 2 g of this compound was ground together with 8g of Then, a heat-sensitive recording material was produced in a 2.5 wt % poly(Vinyl alcohol) aqueous Solution in a paint the same manner as in Example 1 except for using this dis shaker for 45 minutes to be dispersed, whereby a dispersion persion of said compound in place of the dispersion of the 10 was obtained. compound obtained in Example 1, and was evaluated. The Then, a heat-sensitive recording material was produced in results obtained are summarized in Table 1. the same manner as in Example 1 except for using this dis persion of said compound in place of the dispersion of the EXAMPLE 13 compound obtained in Example 1, and was evaluated. The 15 results obtained are summarized in Table 1. To 19.5g of 2,4-toluene diisocyanate was added 155 g of toluene as a solvent, followed by adding thereto 3.2 g of EXAMPLE 1.5 2.2-bis(4-hydroxyphenyl)propane, and the reaction was car ried out at 80° C. for 12 hours. After completion of the To 40 g of 2,4-toluene diisocyanate was added 100 g of reaction, the reaction solution was cooled to -20° C. and the toluene as a solvent, followed by adding dropwise thereto a white solid precipitated was recovered by filtration and dis dilution of 4.28 g of aniline with 40 g of toluene, and the solved in chlorobenzene. Hexane was added to the resulting reaction was carried out at 5° C. for 1 hour. After completion solution and the crystals precipitated were recovered by fil of the reaction, the white solid precipitated was recovered by tration and then dried overnight in a vacuum to obtain 8.0 g of filtration, washed with hexane and then dried overnight in a a compound as white crystals. Subsequently, 50g of toluene 25 vacuum to obtain 12.2 g of a compound as white crystals. was added as a solvent to 4 g of the obtained compound, Subsequently, 40 g of methyl ethyl ketone was added as a followed by adding thereto 4 gofaniline, and the reaction was Solvent to 4 g of the obtained compound, followed by adding carried out at 25°C. for 24 hours. After completion of the thereto a dilution of 4.23g of phenol with 10g of methylethyl reaction, the crystals precipitated were recovered by filtra ketone, and the reaction was carried out at 90° C. for 3 hours. tion, washed with toluene and then dried overnight in a 30 Thereafter, the reaction solution was cooled at 5° C. for 6 vacuum to obtain 5.0 g of a compound as white crystals. days, and the crystals precipitated were recovered by filtra Analytical values of these white crystals were as follows. tion and dried overnight in a vacuum to obtain 2.58 g of a compound as white crystals. Analytical values of these white Result of IR measurement: crystals were as follows. Characteristic peaks appeared at 750cm, 840 cm, 1020 35 cm, 1500 cm, 1600 cm, 1720 cm and 3300 cm. Result of IR measurement: The structural formula of the major component of this Characteristic peaks appeared at 880 cm, 1000 cm, compound is presumed to be the structural formula of the 1040cm, 1440 cm7', 1720 cm, 1720cm and 3300cm'. above-mentioned compound (E-32). The structural formula of the major component of this Next, 2 g of this compound was ground together with 8g of 40 compound is presumed to be the structural formula of the a 2.5 wt % poly(Vinyl alcohol) aqueous Solution in a paint above-mentioned compound (E-1). shaker for 45 minutes to be dispersed, whereby a dispersion Next, 2 g of this compound was ground together with 8g of was obtained. a 2.5 wt % poly(Vinyl alcohol) aqueous Solution in a paint Then, a heat-sensitive recording material was produced in shaker for 45 minutes to be dispersed, whereby a dispersion the same manner as in Example 1 except for using this dis 45 was obtained. persion of said compound in place of the dispersion of the Then, a heat-sensitive recording material was produced in compound obtained in Example 1, and was evaluated. The the same manner as in Example 1 except for using this dis results obtained are summarized in Table 1. persion of said compound in place of the dispersion of the compound obtained in Example 1, and was evaluated. The EXAMPLE 1.4 50 results obtained are summarized in Table 1. To 30 g of 2,4-toluene diisocyanate was added 30 g of EXAMPLE 16 toluene as a solvent, followed by adding thereto 3.24 g of phenol, and the reaction was carried out at 100° C. for 1 hour To 30 g of 2,4-toluene diisocyanate was added 30 g of and 30 minutes. After completion of the reaction, the toluene 55 toluene as a solvent, followed by adding thereto 3.24 g of was removed by concentration and hexane was added to the phenol, and the reaction was carried out at 100° C. for 1 hour residue, and the white solid precipitated was recovered by and 30 minutes. After completion of the reaction, the toluene filtration, washed with hexane and then dried overnight in a was removed by concentration and hexane was added to the vacuum to obtain 6.9 g of a compound as white crystals. residue, and the white solid precipitated was recovered by Subsequently, toluene was added as a solvent to 1.5 g of the 60 filtration, washed with hexane and then dried overnight in a obtained compound, followed by adding thereto 1.44 g of vacuum to obtain 6.9 g of a compound as white crystals. 2-methoxy-5-N,N-diethylsulfamoylaniline, and the reaction Subsequently, toluene was added as a solvent to 5.4 g of the was carried out at 50° C. for 16 hours. The crystals precipi obtained compound, followed by adding thereto 0.9 g of tated were recovered by filtration, washed with hexane and water and then a small amount of dibutyltin dilaurate, and the then dried overnight in a vacuum to obtain 2.3 g of a com 65 reaction was carried out at ordinary temperature for 10 hours. pound as white crystals. Analytical values of these white The crystals precipitated were recovered by filtration, washed crystals were as follows. with hexane and then dried overnight in a vacuum to obtain US 7,635,662 B2 139 140 2.1 g of a compound as white crystals. Analytical values of g of methyl ethyl ketone was added thereto, and the reaction these white crystals were as follows. Result of IR measure was carried out at 90° C. for 6 hours. Thereafter, the reaction ment: Solution was poured into hexane, and the crystals precipitated Characteristic peaks appeared at 990 cm, 1030 cm', were recovered by filtration and dried overnight in a vacuum 1300 cm, 1480 cm, 1540 cm, 1720 cm and 3300 5 to obtain 3.7 g of a compound as white crystals. Analytical cm. values of these white crystals were as follows. The structural formula of the major component of this Result of IR measurement: compound is presumed to be the structural formula of the Characteristic peaks appeared at 880 cm, 1000 cm', above-mentioned compound (E-17). 1040 cm, 1500 cm, 1720 cm and 3300 cm. Next, 2 g of this compound was ground together with 8g of 10 The structural formula of the major component of this a 2.5 wt % poly(Vinyl alcohol) aqueous Solution in a paint compound is presumed to be the structural formula of the shaker for 45 minutes to be dispersed, whereby a dispersion above-mentioned compound (E-4). was obtained. Next, 2 g of this compound was ground together with 8g of Then, a heat-sensitive recording material was produced in a 2.5 wt % poly(Vinyl alcohol) aqueous Solution in a paint the same manner as in Example 1 except for using this dis- 15 shaker for 45 minutes to be dispersed, whereby a dispersion persion of said compound in place of the dispersion of the was obtained. compound obtained in Example 1, and was evaluated. The Then, a heat-sensitive recording material was produced in results obtained are summarized in Table 1. the same manner as in Example 1 except for using this dis persion of said compound in place of the dispersion of the EXAMPLE 17 2O compound obtained in Example 1, and was evaluated. The results obtained are summarized in Table 1. To 40 g of 2,4-toluene diisocyanate was added 100 g of toluene as a solvent, followed by adding dropwise thereto a EXAMPLE19 dilution of 4.28 g of aniline with 40 g of toluene, and the reaction was carried out at 5°C. for 1 hour. After completion 25 To 40 g of 2,4-toluene diisocyanate was added 100 g of of the reaction, the white solid precipitated was recovered by toluene as a solvent, followed by adding dropwise thereto a filtration, washed with hexane and then dried overnight in a dilution of 5.66 g of p-methoxy-aniline with 40 g of toluene, vacuum to obtain 12.2 g of a compound as white crystals. and the reaction was carried out at 10° C. for 1 hour. After Subsequently, 40 g of methyl ethyl ketone as a solvent and completion of the reaction, the whitish-purple solid precipi then 5 mg of dibutyltin laurate were added to 5 g of the 30 tated was recovered by filtration, washed with hexane and obtained compound. A dilution of 2.58g of p-methoxyphenol then dried overnight in a vacuum to obtain 13.4 g of a com with 10 g of methyl ethyl ketone was added thereto, and the pound as whitish-purple crystals. Subsequently, 65 g of reaction was carried out at 90° C. for 6 hours. Thereafter, the methyl ethyl ketone as a solvent and then 5 mg of dibutyltin reaction solution was poured into hexane, and the crystals laurate were added to 5g of the obtained compound. A dilu precipitated were recovered by filtration and dried overnight 35 tion of 2.37 g of phenol with 15 g of methyl ethyl ketone was in a vacuum to obtain 3.7 g of a compound as whitish-purple added thereto, and the reaction was carried out at 90° C. for 4 crystals. Analytical values of the whitish-purple crystals were hours. Thereafter, the reaction Solution was concentrated and as follows. then cooled at 5° C. for 1 day, and the crystals precipitated Result of IR measurement: 40 were recovered by filtration and dried overnight in a vacuum Characteristic peaks appeared at 840 cm, 1040 cm, to obtain 2.50 g of a compound as whitish-purple crystals. 1440 cm, 1720 cm and 3300 cm. Analytical values of these whitish-purple crystals were as The structural formula of the major component of this follows. compound is presumed to be the structural formula of the Result of IR measurement: above-mentioned compound (E-3). 45 Characteristic peaks appeared at 820 cm, 1030 cm', Next, 2 g of this compound was ground together with 8g of 1420 cm, 1730 cm and 3300 cm. a 2.5 wt % poly(Vinyl alcohol) aqueous Solution in a paint The structural formula of the major component of this shaker for 45 minutes to be dispersed, whereby a dispersion compound is presumed to be the structural formula of the was obtained. above-mentioned compound (E-6). Then, a heat-sensitive recording material was produced in 50 Next, 2 g of this compound was ground together with 8g of the same manner as in Example 1 except for using this dis a 2.5 wt % poly(Vinyl alcohol) aqueous Solution in a paint persion of said compound in place of the dispersion of the shaker for 45 minutes to be dispersed, whereby a dispersion compound obtained in Example 1, and was evaluated. The was obtained. results obtained are summarized in Table 1. Then, a heat-sensitive recording material was produced in 55 the same manner as in Example 1 except for using this dis EXAMPLE 1.8 persion of said compound in place of the dispersion of the compound obtained in Example 1, and was evaluated. The To 40 g of 2,4-toluene diisocyanate was added 100 g of results obtained are summarized in Table 1. toluene as a solvent, followed by adding dropwise thereto a dilution of 4.28 g of aniline with 40 g of toluene, and the 60 EXAMPLE 20 reaction was carried out at 5°C. for 1 hour. After completion of the reaction, the white solid precipitated was recovered by To 30 g of 2,4-toluene diisocyanate was added 30 g of filtration, washed with hexane and then dried overnight in a toluene as a solvent, followed by adding thereto 3.24 g of vacuum to obtain 12.2 g of a compound as white crystals. phenol, and the reaction was carried out at 100° C. for 1 hour Subsequently, 40 g of methyl ethyl ketone as a solvent and 65 and 30 minutes. After completion of the reaction, the toluene then 5 mg of dibutyltin laurate were added to 5 g of the was removed by concentration and hexane was added to the obtained compound. A dilution of 2.22 g of p-cresol with 10 residue, and the white solid precipitated was recovered by US 7,635,662 B2 141 142 filtration, washed with hexane and then dried overnight in a dry solids, and this recording material was evaluated. The vacuum to obtain 6.9 g of a compound as white crystals. results obtained are summarized in Table 1. Subsequently, 100 g of toluene was added as a solvent to 5.0 g of the obtained compound, followed by adding thereto 3.50 EXAMPLE 22 g of aniline, and the reaction was carried out at 25°C. for 3 hours. The crystals precipitated were recovered by filtration, To 30 g of 2,4-toluene duisocyanate was added 30 g of washed with hexane and then dried overnight in a vacuum to toluene as a solvent, followed by adding thereto 3.24 g of obtain 5.5 g of a compound as white crystals. Analytical phenol, and the reaction was carried out at 100° C. for 1 hour values of these white crystals were as follows. and 30 minutes. After completion of the reaction, the toluene 10 was removed by concentration and hexane was added to the Result of IR measurement: residue, and the white solid precipitated was recovered by Characteristic peaks appeared at 890 cm, 1000 cm', filtration, washed with hexane and then dried overnight in a 1030 cm, 1440 cm, 1720 cm and 3350 cm. vacuum to obtain 6.9 g of a compound as white crystals. The structural formula of the major component of this Subsequently, 100 g of toluene was added as a solvent to 5.0 compound is presumed to be the structural formula of the 15 g of the obtained compound, followed by adding thereto 3.58 above-mentioned compound (E-8). g of p-chloroaniline, and the reaction was carried out at 25°C. Next, 2 g of this compound was ground together with 8g of for 6 hours. The crystals precipitated were recovered by fil a 2.5 wt % poly(Vinyl alcohol) aqueous Solution in a paint tration, washed with hexane and then dried overnight in a shaker for 45 minutes to be dispersed, whereby a dispersion vacuum to obtain 7.0 g of a compound as whitish-purple was obtained. crystals. Analytical values of the whitish-purple crystals were as follows. Then, a heat-sensitive recording material was produced in the same manner as in Example 1 except for using this dis Result of IR measurement: persion of said compound in place of the dispersion of the Characteristic peaks appeared at 870 cm, 1030 cm', compound obtained in Example 1, and was evaluated. The 1390 cm, 1540 cm, 1720 cm and 3350 cm. results obtained are summarized in Table 1. 25 The structural formula of the major component of this compound is presumed to be the structural formula of the EXAMPLE 21 above-mentioned compound (E-11). Next, 2 g of this compound was ground together with 8g of To 30 g of 2,4-toluene diisocyanate was added 30 g of a 2.5 wt % poly(Vinyl alcohol) aqueous Solution in a paint toluene as a solvent, followed by adding thereto 3.24 g of shaker for 45 minutes to be dispersed, whereby a dispersion phenol, and the reaction was carried out at 100° C. for 1 hour was obtained. and 30 minutes. After completion of the reaction, the toluene Then, a heat-sensitive recording material was produced in was removed by concentration and hexane was added to the the same manner as in Example 1 except for using this dis residue, and the white solid precipitated was recovered by persion of said compound in place of the dispersion of the filtration, washed with hexane and then dried overnight in a compound obtained in Example 1, and using Crystal Violet vacuum to obtain 6.9 g of a compound as white crystals. lactone in place of 3-dibutyl-amino-6-methyl-7-anilinofluo Subsequently, 100 g of toluene was added as a solvent to 5.0 ran, and was evaluated. The results obtained are summarized g of the obtained compound, followed by adding thereto 3.00 in Table 1. g of p-toluidine, and the reaction was carried out at 25°C. for EXAMPLE 23 3 hours. The crystals precipitated were recovered by filtra tion, washed with hexane and then dried overnight in a To 10 g of diphenylmethane-4,4'-diisocyanate was added vacuum to obtain 5.5 g of a compound as white crystals. 120 g of methyl ethyl ketone as a solvent, followed by adding Analytical values of these white crystals were as follows. dropwise thereto a dilution of 3.72 g of aniline with 15 g of Result of IR measurement: 45 methyl ethylketone, and the reaction was carried out at 25°C. for 3 hours. After completion of the reaction, the white solid Characteristic peaks appeared at 870 cm, 1000 cm', precipitated was recovered by filtration, washed with hexane 1030 cm, 1460 cm, 1720 cm and 3350 cm. and then dried overnight in a vacuum to obtain 11.8g of a The structural formula of the major component of this compound as white crystals. Subsequently, 80 g of methyl compound is presumed to be the structural formula of the 50 ethyl ketone was added as a solvent to 5g of the obtained above-mentioned compound (E-10). compound, followed by adding thereto a dilution of 2.06 g of Next, 2 g of this compound was ground together with 8g of phenol with 15 g of methyl ethyl ketone, and the reaction was a 2.5 wt % poly(Vinyl alcohol) aqueous Solution in a paint carried out at 70° C. for 8 hours. Thereafter, the reaction shaker for 45 minutes to be dispersed, whereby a dispersion Solution was concentrated and then cooled, and the crystals was obtained. 55 precipitated were recovered by filtration and dried overnight Separately, 70g of 2.2-bis(4-hydroxyphenyl)-propane was in a vacuum to obtain 2.7 g of a compound as white crystals. ground together with 130 g of a 5.4 wt % poly(vinyl alcohol) Analytical values of these white crystals were as follows. aqueous solution in a sand grinder (mfl. by AIMEX CO., Result of IR measurement: LTD., vessel capacity 400 ml) at a number of revolution of Characteristic peaks appeared at 890 cm, 1030 cm, 2,000 rpm for 3 hours to be dispersed, whereby a dispersion 60 1420 cm, 1720 cm and 3300 cm. was obtained. The structural formula of the major component of this Then, a heat-sensitive recording material was produced in compound is presumed to be the structural formula of the the same manner as in Example 1 except for using the disper above-mentioned compound (E-15). sion of the compound obtained in Example 21, in place of the Next, 2 g of this compound was ground together with 8g of dispersion of the compound obtained in Example 1, and add 65 a 2.5 wt % poly(Vinyl alcohol) aqueous Solution in a paint ing the 2.2-bis(4-hydroxyphenyl)propane dispersion to the shaker for 45 minutes to be dispersed, whereby a dispersion coating liquid in a proportion of 10 parts by weight interms of was obtained. US 7,635,662 B2 143 144 Separately, 70g of 4-hydroxy-4-isopropoxy-diphenylsul vacuum to obtain 6.9 g of a compound as white crystals. fone was ground together with 130g of a 5.4 wt % poly(vinyl Subsequently, 30 g of toluene was added as a solvent to 2.0 g alcohol) aqueous solution in a sand grinder (mfl. by AIMEX of the obtained compound, followed by adding thereto 0.90 g CO.,LTD., vessel capacity 400 ml) at a number of revolution ofo-dianisidine, and the reaction was carried out at 50° C. for of 2,000 rpm for 3 hours to be dispersed, whereby a dispersion 6 hours. The crystals precipitated were recovered by filtra was obtained. tion, washed with hexane and then dried overnight in a Then, a heat-sensitive recording material was produced in vacuum to obtain 2.6 g of a compound as white crystals. the same manner as in Example 1 except for using the disper Analytical values of these white crystals were as follows. sion of the compound obtained in Example 23, in place of the Result of IR measurement: dispersion of the compound obtained in Example 1, and add 10 ing the 4-hydroxy-4-isopropoxydiphenyl Sulfone dispersion Characteristic peaks appeared at 820 cm, 1000 cm', to the coating liquid in a proportion of 10 parts by weight in 1030 cm, 1320 cm, 1590 cm, 1710 cm and 3300 terms of dry solids, and this recording material was evaluated. cm. The results obtained are summarized in Table 1. The structural formula of the major component of this 15 compound is presumed to be the structural formula of the EXAMPLE 24 above-mentioned compound (E-29). Next, 2 g of this compound was ground together with 8g of To 30 g of 2,4-toluene diisocyanate was added 30 g of a 2.5 wt % poly(Vinyl alcohol) aqueous Solution in a paint toluene as a solvent, followed by adding thereto 3.24 g of shaker for 45 minutes to be dispersed, whereby a dispersion phenol, and the reaction was carried out at 100° C. for 1 hour was obtained. and 30 minutes. After completion of the reaction, the toluene Then, a heat-sensitive recording material was produced in was removed by concentration and hexane was added to the the same manner as in Example 1 except for using this dis residue, and the white solid precipitated was recovered by persion of said compound in place of the dispersion of the filtration, washed with hexane and then dried overnight in a compound obtained in Example 1, and was evaluated. The vacuum to obtain 6.9 g of a compound as white crystals. 25 results obtained are summarized in Table 1. Subsequently, 30 g of toluene was added as a solvent to 2.0 g of the obtained compound, followed by adding thereto 0.41 g EXAMPLE 26 of p-phenylenediamine, and the reaction was carried out at 50° C. for 10 hours. The crystals precipitated were recovered To 30 g of 2,4-toluene diisocyanate was added 30 g of by filtration, washed with hexane and then dried overnight in 30 toluene as a solvent, followed by adding thereto 3.24 g of a vacuum to obtain 2.3 g of a compound as white crystals. phenol, and the reaction was carried out at 100° C. for 1 hour Analytical values of these white crystals were as follows. and 30 minutes. After completion of the reaction, the toluene was removed by concentration and hexane was added to the Result of IR measurement: residue, and the white solid precipitated was recovered by Characteristic peaks appeared at 840 cm, 1000 cm', 35 filtration, washed with hexane and then dried overnight in a 1200 cm, 1640 cm, 1720 cm and 3300 cm. vacuum to obtain 6.9 g of a compound as white crystals. The structural formula of the major component of this Subsequently, 30 g of dimethylformamide was added as a compound is presumed to be the structural formula of the solvent to 2.7 g of the obtained compound, followed by add above-mentioned compound (E-28). ing thereto 1.2 g of 4,4'-diaminobenzanilide and then 3 mg of Next, 2 g of this compound was ground together with 8g of 40 dibutyltin dilaurate, and the reaction was carried out at 25°C. a 2.5 wt % poly(Vinyl alcohol) aqueous Solution in a paint for 24 hours. Methanol was poured into the reaction solution, shaker for 45 minutes to be dispersed, whereby a dispersion and the crystals precipitated were recovered by filtration, was obtained. washed and then dried overnight in a vacuum to obtain 2.3g Separately, 70 g of bis(4-hydroxyphenyl) sulfone was of a compound as white crystals. ground together with 130 g of a 5.4 wt % poly(vinyl alcohol) 45 The structural formula of the major component of this aqueous solution in a sand grinder (mfl. by AIMEX Co., compound is presumed to be the structural formula of the LTD., vessel capacity 400 ml) at a number of revolution of above-mentioned compound (E-26). 2,000 rpm for 3 hours to be dispersed, whereby a dispersion Next, 2 g of this compound was ground together with 8g of was obtained. a 2.5 wt % poly(Vinyl alcohol) aqueous Solution in a paint Then, a heat-sensitive recording material was produced in 50 shaker for 45 minutes to be dispersed, whereby a dispersion the same manner as in Example 1 except for using the disper was obtained. sion of the compound obtained in Example 24, in place of the Then, a heat-sensitive recording material was produced in dispersion of the compound obtained in Example 1, and add the same manner as in Example 1 except for using this dis ing the bis(4-hydroxy-phenyl) sulfone dispersion to the coat persion of said compound in place of the dispersion of the ing liquid in a proportion of 10 parts by weight in terms of dry 55 compound obtained in Example 1, and was evaluated. The Solids, and this recording material was evaluated. The results results obtained are summarized in Table 1. obtained are summarized in Table 1. EXAMPLE 27 EXAMPLE 25 60 To 40 g of 2,4-toluene diisocyanate was added 100 g of To 30 g of 2,4-toluene diisocyanate was added 30 g of toluene as a solvent, followed by adding dropwise thereto a toluene as a solvent, followed by adding thereto 3.24 g of dilution of 4.28 g of aniline with 40 g of toluene, and the phenol, and the reaction was carried out at 100° C. for 1 hour reaction was carried out at 5° C. for 1 hour. After completion and 30 minutes. After completion of the reaction, the toluene of the reaction, the white solid precipitated was recovered by was removed by concentration and hexane was added to the 65 filtration, washed with hexane and then dried overnight in a residue, and the white solid precipitated was recovered by vacuum to obtain 12.2 g of a compound as white crystals. filtration, washed with hexane and then dried overnight in a Subsequently, 60 g of methyl ethyl ketone as a solvent and US 7,635,662 B2 145 146 then a small amount of dibutyltin dilaurate were added to 3g by filtration, washed with hexane and then dried overnight in of the obtained compound. Thereafter, a dilution of 1.4 g of a vacuum to obtain 13.0 g of a compound as white crystals. 4,4'-dihydroxydiphenyl sulfone (bisphenol S) with 10 g of Subsequently, 65 g of methyl ethyl ketone as a solvent and methyl ethyl ketone was added dropwise thereto at 90° C. then 5 mg of dibutyltin laurate were added to 5 g of the and the reaction was carried out for 16 hours. After comple obtained compound. A dilution of 2.28 g of phenol with 15 g. tion of the reaction, the resulting crystals were recovered by of methyl ethyl ketone was added thereto, and the reaction filtration, washed with methyl ethyl ketone and then dried was carried out at 90° C. for 4 hours. Thereafter, the reaction overnight in a vacuum to obtain 2.1 g of a compound as white solution was concentrated and then cooled at 5°C. for 1 day, crystals. after which the crystals precipitated were recovered by filtra The structural formula of the major component of this 10 tion and dried overnight in a vacuum to obtain 1.0 g of a compound is presumed to be the structural formula of the compound as white crystals. above-mentioned compound (E-33). The structural formula of the major component of this Next, 2 g of this compound was ground together with 8g of compound is presumed to be the structural formula of the a 2.5 wt % polylvinyl alcohol) aqueous solution in a paint above-mentioned compound (E-7). shaker for 45 minutes to be dispersed, whereby a dispersion 15 Next, 1 g of this compound was ground together with 4g of was obtained. a 2.5 wt % poly(Vinyl alcohol) aqueous Solution in a paint Then, a heat-sensitive recording material was produced in shaker for 45 minutes to be dispersed, whereby a dispersion the same manner as in Example 1 except for using this dis was obtained. persion of said compound in place of the dispersion of the Separately, 70g of an imino compound 1,3-diimino-4,5,6, compound obtained in Example 1, and was evaluated. The 7-tetrachloroisoindoline was ground together with 130 g of a results obtained are summarized in Table 1. 5.4 wt % poly(vinyl alcohol) aqueous solution in a sand grinder (mfl. by AIMEX CO.,LTD., vessel capacity 400 ml) EXAMPLE 28 at a number of revolution of 2,000 rpm for 3 hours to be dispersed, whereby a dispersion was obtained. To 40 g of 2,4-toluene diisocyanate was added 100 g of 25 toluene as a solvent, followed by adding dropwise thereto a Separately, 70g of an isocyanate compound 4,4',4'-triso dilution of 4.28 g of aniline with 40 g of toluene, and the cyanato-2,5-dimethoxytriphenylamine was ground together reaction was carried out at 5°C. for 1 hour. After completion with 130 g of a 5.4 wt % poly(vinyl alcohol) aqueous solution of the reaction, the white solid precipitated was recovered by in a sandgrinder (mfl. by AIMEXCO.,LTD., vessel capacity filtration, washed with hexane and then dried overnight in a 30 400 ml) at a number of revolution of 1,000 rpm for 1 hour to vacuum to obtain 12.2 g of a compound as white crystals. be dispersed, whereby a dispersion was obtained. Subsequently, 40 g of methyl ethyl ketone as a solvent and Separately, 70 g of 3,3'-diaminodiphenyl sulfone was then 5 mg of dibutyltin laurate were added to 5 g of the ground together with 130 g of a 5.4 wt % poly(vinyl alcohol) obtained compound. A dilution of 2.64 g of p-chlorophenol aqueous solution in a sand grinder (mfl. by AIMEX CO., with 10 g of methyl ethyl ketone was added thereto, and the 35 LTD., vessel capacity 400 ml) at a number of revolution of reaction was carried out at 90° C. for 5 hours. Thereafter, the 2,000 rpm for 3 hours to be dispersed, whereby a dispersion reaction solution was poured into hexane, and the crystals was obtained. precipitated were recovered by filtration and dried overnight Then, a heat-sensitive recording material was produced in in a vacuum to obtain 1.1 g of a compound as white crystals. the same manner as in Example 1 except for using the disper The structural formula of the major component of this 40 sion of the compound obtained in Example 29, in place of the compound is presumed to be the structural formula of the dispersion of the compound obtained in Example 1, and add above-mentioned compound (E-5). ing to the coating liquid the 1,3-diimino-4,5,6,7-tetrachlor Next, 1 g of this compound was ground together with 4g of oisoindoline dispersion in a proportion of 8 parts by weight in a 2.5 wt % poly(Vinyl alcohol) aqueous Solution in a paint terms of dry solids, the 4,4',4'-triisocyanato-2,5-dimethoxy shaker for 45 minutes to be dispersed, whereby a dispersion 45 tripheylamine dispersion in a proportion of 5.3 parts by was obtained. weight in terms of dry solids, and the 3,3'-diaminodiphenyl Then, 2 g of 1,3-bis(3-isocyanato-4-methyl-pheyl)urea Sulfone dispersion in a proportion of 5.3 parts by weight in was ground together with 8 g of a 2.5 wt % poly(vinyl alco terms of dry solids, and this recording material was evaluated. hol) aqueous Solution in a paint shaker for 45 minutes to be The results obtained are summarized in Table 1. dispersed, whereby a dispersion was obtained. 50 Subsequently, a heat-sensitive recording material was pro EXAMPLE 30 duced in the same manner as in Example 1 except for using the dispersion of the compound obtained in Example 28, in To 30 g of 2,4-toluene diisocyanate was added 30 g of place of the dispersion of the compound obtained in Example toluene as a solvent, followed by adding thereto 3.24 g of 1, and adding the 1,3-bis(3-isocyanato-4-methylphenyl)urea 55 phenol, and the reaction was carried out at 100° C. for 1 hour dispersion to the coating liquid in a proportion of 10 parts by and 30 minutes. After completion of the reaction, the toluene weight in terms of dry solids, and this recording material was was removed by concentration and hexane was added to the evaluated. The results obtained are summarized in Table 1. residue, and the white solid precipitated was recovered by filtration, washed with hexane and then dried overnight in a EXAMPLE 29 60 vacuum to obtain 6.9 g of a compound as white crystals. Subsequently, 30 g of toluene was added as a solvent to 2.0 g To 40 g of 2,4-toluene diisocyanate was added 100 g of of the obtained compound, followed by adding thereto 0.75g toluene as a solvent, followed by adding dropwise thereto a of 4,4'-diaminodiphenyl ether, and the reaction was carried dilution of 6.21 g of p-aminoaceto-phenone with a mixture of out at 50° C. for 16 hours. The crystals precipitated were 30 g of toluene and 30 g of methyl ethyl ketone, and the 65 recovered by filtration, washed with hexane and then dried reaction was carried out at 25°C. for 20 hours. After comple overnight in a vacuum to obtain 2.4 g of a compound as white tion of the reaction, the white solid precipitated was recovered crystals. US 7,635,662 B2 147 148 The structural formula of the major component of this Then, a heat-sensitive recording material was produced in compound is presumed to be the structural formula of the the same manner as in Example 1 except for using this dis above-mentioned compound (E-25). persion of said compound in place of the dispersion of the Next, 2 g of this compound was ground together with 8g of compound obtained in Example 1, and was evaluated. The a 2.5 wt % poly(Vinyl alcohol) aqueous Solution in a paint 5 results obtained are summarized in Table 1. shaker for 45 minutes to be dispersed, whereby a dispersion was obtained. EXAMPLE 33 Then, a heat-sensitive recording material was produced in the same manner as in Example 1 except for using this dis While stirring 150 g of 2,4-toluene diisocyanate at 50° C., persion of said compound in place of the dispersion of the 10 a solution of 17.2 g of 4,4'-diaminodiphenylmethane in 120 compound obtained in Example 1, and was evaluated. The ml of methyl ethyl ketone was added dropwise thereto over a results obtained are summarized in Table 1. period of 4 hours, and the reaction was continued at 50° C. for another 2 hours. After completion of the reaction, the reaction EXAMPLE 31 Solution was cooled to room temperature and then toluene 15 was added thereto, and the white solid precipitated was recov To 30 g of 2,4-toluene diisocyanate was added 30 g of ered by filtration, washed with toluene and then dried over toluene as a solvent, followed by adding thereto 3.24 g of night in a vacuum to obtain 43 g of a compound as white phenol, and the reaction was carried out at 100° C. for 1 hour crystals. Subsequently, 51.5g of phenol and 100 ml of methyl and 30 minutes. After completion of the reaction, the toluene ethyl ketone were added to 30g of the obtained compound, was removed by concentration and hexane was added to the followed by adding thereto 30 mg of triethylamine, and the residue, and the white solid precipitated was recovered by reaction was carried out at 50° C. for 20 hours. After comple filtration, washed with hexane and then dried overnight in a tion of the reaction, toluene was added to the reaction Solution vacuum to obtain 6.9 g of a compound as white crystals. and the crystals precipitated were recovered by filtration, Subsequently, 30 g of toluene was added as a solvent to 2.0 g washed with toluene and then dried overnight in a vacuum to of the obtained compound, followed by adding thereto 0.74g 25 obtain 38.5g of a compound as white crystals. of 4,4'-diaminodiphenylmethane and 10 g of methyl ethyl The structural formula of the major component of this ketone, and the reaction was carried out at 50° C. for 10 hours. compound is presumed to be the structural formula of the The crystals precipitated were recovered by filtration, washed above-mentioned compound (E-27). with hexane and then dried overnight in a vacuum to obtain Next, 2 g of this compound was ground together with 8g of 30 a 2.5 wt % poly(Vinyl alcohol) aqueous Solution in a paint 2.1 g of a compound as white crystals. shaker for 45 minutes to be dispersed, whereby a dispersion The structural formula of the major component of this was obtained. compound is presumed to be the structural formula of the Then, a heat-sensitive recording material was produced in above-mentioned compound (E-27). the same manner as in Example 1 except for using this dis Next, 2 g of this compound was ground together with 8g of 35 persion of said compound in place of the dispersion of the a 2.5 wt % poly(Vinyl alcohol) aqueous Solution in a paint compound obtained in Example 1, and was evaluated. The shaker for 45 minutes to be dispersed, whereby a dispersion results obtained are summarized in Table 1. was obtained. Then, a heat-sensitive recording material was produced in EXAMPLE 34 the same manner as in Example 1 except for using this dis 40 persion of said compound in place of the dispersion of the While stirring 31.5g of 2,4-toluene diisocyanate at 60°C., compound obtained in Example 1, and was evaluated. The a solution of 21.5g of 4,4'-diaminodiphenylsulfone in 120 ml results obtained are summarized in Table 1. of methyl ethyl ketone was added dropwise thereto over a period of 6 hours. Uninterruptedly, the reaction solution was EXAMPLE 32 45 cooled to 25°C., followed by adding thereto 17.1 g of phenol and then 30 mg of triethylamine, and the reaction was carried To 30 g of 2,4-toluene diisocyanate was added 30 g of out at 25°C. for 4 hours. After completion of the reaction, the toluene as a solvent, followed by adding thereto 3.24 g of methyl ethyl ketone was distilled off and the solid thus phenol, and the reaction was carried out at 100° C. for 1 hour obtained was ground and then dried overnight in a vacuum to and 30 minutes. After completion of the reaction, the toluene 50 obtain 70g of a compound as light-yellow powder. was removed by concentration and hexane was added to the The structural formula of the major component of this residue, and the white solid precipitated was recovered by compound is presumed to be the structural formula of the filtration, washed with hexane and then dried overnight in a above-mentioned compound (E-24). vacuum to obtain 6.9 g of a compound as white crystals. Next, 2 g of this compound was ground together with 8g of Subsequently, 30 g of toluene was added as a solvent to 1.5g 55 a 2.5 wt % poly(Vinyl alcohol) aqueous Solution in a paint of the obtained compound, followed by adding thereto 0.3 g shaker for 45 minutes to be dispersed, whereby a dispersion of ethylamine, and the reaction was carried out at 50° C. for 6 was obtained. hours. The crystals precipitated were recovered by filtration, Then, a heat-sensitive recording material was produced in washed with hexane and then dried overnight in a vacuum to the same manner as in Example 1 except for using this dis obtain 1.8g of a compound as white crystals. 60 persion of said compound in place of the dispersion of the The structural formula of the major component of this compound obtained in Example 1, and was evaluated. The compound is presumed to be the structural formula of the results obtained are summarized in Table 1. above-mentioned compound (E-44). Next, 1 g of this compound was ground together with 4g of COMPARATIVE EXAMPLE 1 a 2.5 wt % poly(Vinyl alcohol) aqueous Solution in a paint 65 shaker for 45 minutes to be dispersed, whereby a dispersion A heat-sensitive recording material was produced in the was obtained. same manner as in Example 1 except for using 2.2-bis(4- US 7,635,662 B2 149 150 hydroxyphenyl)propane in place of the urea-urethane com pound synthesized in Example 1, and was evaluated. The -continued results obtained are summarized in Table 1. (C-2) O COMPARATIVE EXAMPLE 2 5 O-C-N CH3 H To 10 g of 2,4-toluene diisocyanate was added 50 g of toluene as a solvent, followed by adding thereto 30 g of HN aniline, and the reaction was carried out at 25°C. for 3 hours. 10 YEO After completion of the reaction, the white solid precipitated V was recovered by filtration, washed with hexane and then O dried overnight in a vacuum to obtain 17 g of a compound as white crystals. The presumed structural formula of the major component 15 of this compound is the structural formula of the compound (C-1) shown below. Next, 2 g of this compound was ground together with 8g of COMPARATIVE EXAMPLE 4 a 2.5 wt % poly(Vinyl alcohol) aqueous Solution in a paint shaker for 45 minutes to be dispersed, whereby a dispersion A heat-sensitive recording material was produced in the was obtained. same manner as in Example 1 except for using 1,3-dipheny Then, a heat-sensitive recording material was produced in lurea in place of the urea-urethane compound synthesized in the same manner as in Example 1 except for using this dis Example 1, and was evaluated. The results obtained are sum persion of said compound in place of the dispersion of the 25 marized in Table 1. compound obtained in Example 1, and was evaluated. The 1. Sensitivity becomes higher with an increase of optical results obtained are summarized in Table 1. density (OD value). 2. Plasticizer resistance (print preservability) COMPARATIVE EXAMPLE 3 (3) --Substantially no fading. 30 O-A slight color tone change without blur and the like. To 10 g of 2,4-toluene diisocyanate was added 30 g of A-Marked fading. toluene as a solvent, followed by adding thereto 30 g of X-Complete loss of the color of print. phenol, and the reaction was carried out at 100° C. for 3 hours. 3. Heat resistance (print preservability at 60° C. and 80°C.) After completion of the reaction, the toluene was removed by (3) --Substantially no fading. concentration and hexane was added to the residue, and the 35 O-A slight color tone change without blur and the like. white solid precipitated was recovered by filtration, washed A-Marked fading. with hexane and then dried overnightina vacuum to obtain 15 X-Complete loss of the color of print. g of a compound as white crystals. 4. Heat resistance (the preservability of an original recording The presumed structural formula of the major component material surface at 80°C.) of this compound is the structural formula of the compound (9-Substantially no fog was caused. (C-2) shown below. O-Reading of a print portion was possible though there Next, 2 g of this compound was ground together with 8g of was a slight color tone change. a 2.5 wt % poly(Vinyl alcohol) aqueous Solution in a paint A-Reading of a print portion was difficult owing to fog. shaker for 45 minutes to be dispersed, whereby a dispersion X-Reading of a print portion was impossible owing to was obtained. 45 serious fog. Then, a heat-sensitive recording material was produced in the same manner as in Example 1 except for using this dis EXAMPLE 35 persion of said compound in place of the dispersion of the compound obtained in Example 1, and was evaluated. The so (1) Production of Upper Paper results obtained are summarized in Table 1. A solution prepared by dissolving 2.5 parts by weight of 3-diethylamino-7-chlorofluoran in 80 parts by weight of NIS SEKI HISOL N-296 (an oil, a trade name, mfcd. by Nippon (C-1) Sekiyu Kagaku K.K.) was emulsified in 100 parts by weight 55 of a 5% aqueous solution of pH 4.0 prepared by dissolving a styrene-maleic anhydride copolymer together with a small H H amount of sodium hydroxide. On the other hand, when a (O)--- CH3 mixture of 10 parts by weight of melamine, 25 parts by weight HN of a 37% aqueous formaldehyde solution and 65 parts by V 60 weight of water was adjusted to pH 9.0 with sodium hydrox CEO V ide and heated at 60°C., the mixture became transparent after NH 15 minutes and a melamine-formaldehyde precondensate was obtained. The precondensate was added to the emulsion obtained above, and the resulting mixture was continuously 65 stirred for 4 hours while maintaining the mixture at 60°C., and then was cooled to room temperature. The Solid content of the resulting microcapsule dispersion was 45%. US 7,635,662 B2 151 152 The thus obtained microcapsule dispersion was applied on Next, a dispersion was prepared by dispersing 2 g of this paper and dried to obtain upper paper. compound by grinding the compound together with 8 g of a 2.5 wt % aqueous solution of a poly(vinyl alcohol) (Goseran (2) Production of Under Paper L-3266, a trade name, mfcd. by The Nippon Synthetic Chemi At ordinary temperature, 15 g of a compound (the pre cal Industry Co., Ltd.) in a paint shaker for 6 hours. The Sumed structural formula of the major component of this temperature of the dispersion immediately after the dispers compound is the structural formula of the above-mentioned ing operation was 25°C. The diameter of dispersed particles compound (E-22)) synthesized in the same manner as in of the compound was about 0.6 um. Example 4 was ground together with 45 g of a 2 wt % poly Another dispersion was prepared by dispersing 70 g of (vinyl alcohol) aqueous solution in a paint shaker for 45 10 3-dibutylamino-6-methyl-7-anilinofluoran by grinding it minutes to be dispersed, whereby a dispersion was obtained. together with 130 g of a 8 wt % poly(vinyl alcohol) aqueous Separately, 60 g of calcium carbonate was mixed with 90 g solution in a sand grinder (mfl. by AIMEXCO.,LTD., vessel of water and dispersed with a stirrer to obtain a dispersion. capacity 400 ml) at a number of revolution of 2,000 rpm for 3 A coating liquid was prepared by mixing and stirring 40 hours. parts by weight of the dispersion of the aforesaid synthesized 15 A still another dispersion was prepared by dispersing 70 g compound, 125 parts by weight of the calcium carbonate of diphenyl sulfone by grinding it together with 130g of a 5.4 dispersion and 120 parts by weight of a 10 wt % poly(vinyl wt % poly(vinyl alcohol) aqueous Solution in a sand grinder alcohol) aqueous solution. (mfl. by AIMEX CO.,LTD., vessel capacity 400 ml) at a The coating liquid was applied on base paper with a basis number of revolution of 2,000 rpm for 3 hours. weight of 40 g/m by the use of a bar coater of rod number 10 Separately, 10 g of calcium carbonate was mixed with 30 g to obtain under paper. of water and dispersed by stirring by the use of a stirrer to The result of color density evaluation was so good that the obtain a dispersion. optical density was 0.7. A coating liquid was obtained by stirring and mixing the The result of evaluating the solvent resistance by the use of above-mentioned dispersions and other components in the hand cream was so good that reading of a print portion was 25 following proportions (dry basis); the dispersion of the possible. The results are summarized in Table 2. above-mentioned compound in terms of dry solids: 30 parts by weight, the 3-dibutylamino-6-methyl-7-anilinofluoran COMPARATIVE EXAMPLE 5 dispersion in terms of dry solids: 15 parts by weight, the diphenyl sulfone dispersion in terms of dry solids: 30 parts by A pressure-sensitive recording material was produced in 30 weight, the calcium carbonate dispersion in terms of dry the same manner as in Example 35 except for using activated Solids: 20 parts by weight, a Zinc Stearate dispersion (solid clay as developer in place of the urea-urethane compound, content: 16 wt %) in terms of dry solids: 10 parts by weight, and was evaluated. The results are summarized in Table 2. and a 15 wt % polylvinyl alcohol) in terms of dry solids: 7 1. Coloring density becomes higher with an increase of opti parts by weight. cal density (OD value). 35 The coating liquid was applied on base paper with a basis 2. Solvent resistance (hand cream) weight of 50 g/m by the use of a barcoater of rod number 10. (3) --Substantially no fading. After drying, Supercalendering was conducted to obtain a O-A slight color tone change without blur and the like. heat-sensitive recording material. The coating amount of the A-Marked fading. coating liquid was 4 g/m in terms of dry weight. X-Complete loss of the color of print. 40 The result of evaluating the sensitivity of the heat-sensitive recording material obtained was so good that the optical EXAMPLE 36 density was 1.2. The result of estimating the degree of a thermal color change of the original recording material Sur To 27.8g of 2,4-toluene diisocyanate was added 111 g of face (the heat resistance) was so good that the color change toluene as a solvent, followed by adding dropwise thereto a 45 was slight. The thermal fading of a printed portion was desir solution of 7.4 g of aniline in 37 g of toluene at room tem perature over a period of 1 hour, and the reaction was carried ably slight. These evaluation results are summarized in Table out for another 1 hour. The white solid precipitated was recov 3. ered by filtration, washed with hexane and then dried over EXAMPLE 37 night in a vacuum to obtain 20 g of white crystals. Subse 50 quently, 5g of the thus obtained compound was added to 50 mL of methanol, and the reaction was carried out at 60° C. for To 17 g of 2,4-toluene diisocyanate was added 40 g of 30 minutes, after which the excess methanol was removed by methyl ethyl ketone as a solvent, followed by adding drop the use of an evaporator, and toluene was added to the residue wise thereto 3.8g of methanol, and the reaction was carried to effect crystallization. The resulting white crystals were 55 out with stirring at 60° C. for 5 hours. Then, 9.9 g of 4,4'- recovered by filtration, washed with hexane and then dried diaminodiphenyl Sulfone was added thereto, and the reaction overnight in a vacuum to obtain 5.4 g of white crystals. The was carried out with stirring at 60° C. for 4 hours. After melting point of these white crystals was 196° C. completion of the reaction, the reaction solution was cooled Analytical values of these white crystals were as follows. to room temperature and poured into 800g of acetonitrile, and 60 the crystals precipitated were recovered by filtration, washed Result of IR measurement: with hexane and then dried overnightina vacuum to obtain 15 Characteristic peaks appeared at 1060 cm, 1250 cm', g of a compound as white crystals. 1600 cm, 1650 cm, 1670 cm, 1700 cm and 3300 The melting point of the white crystals was 169°C., and cm. their analytical values were as follows. Result of IR measure The structural formula of the major component of this 65 ment: compound is presumed to be the structural formula of the Characteristic peaks appeared at 1220 cm, 1550 cm, above-mentioned compound (S-1). 1590 cm, 1660 cm, 1740 cm and 3300 cm. US 7,635,662 B2 153 154 Result of mass spectrum measurement: Next, 3 g of the above urea-urethane compound and 2 g of M+H" was detected at m/z 661. the urethane compound were mixed to obtain a urea-urethane The structural formula of the major component of this composition. Subsequently, a dispersion was prepared by compound is presumed to be the structural formula of the dispersing 2 g of the urea-urethane composition by grinding above-mentioned compound (S-13). the composition together with 8 g of a 2.5 wt % aqueous Then, a heat-sensitive recording material was produced in solution of methyl cellulose in a paint shaker for 45 minutes. the same manner as in Example 36 except for using the Then, a heat-sensitive recording material was produced in compound obtained above, in place of the urea-urethane com the same manner as in Example 36 except for using the pound synthesized in Example 36, and was evaluated. The dispersion of the above composition in place of the dispersion results are summarized in Table 3. 10 of the compound obtained in Example 36, and was evaluated. The results are summarized in Table 3. EXAMPLE 38 EXAMPLE 38-2 In 100 mL of methyl acetate was dissolved 3.46 g of aniline, and the resulting Solution was stirred at room tem 15 A heat-sensitive recording material was produced in the perature. A solution of 10 g of trimethylolpropane adduct of same manner as in Example 38-1 except for using a urea toluene diisocyanate (Coronate L, a trade name, mfcd. by urethane composition obtained by mixing 4.5 g of the urea Nippon Polyurethane Industry Co., Ltd.; a 75% ethyl acetate urethane compound and 0.5 g of the urethane compound solution) in 50 mL of ethyl acetate was added dropwise obtained in Example 38-1, and was evaluated. The results are thereto over a period of 1 hour, and the reaction was carried summarized in Table 3. out for another 1 hour. The crystals formed were recovered by EXAMPLE 38-3 filtration and dried overnight in a vacuum to obtain 5.1 g of a compound as white crystals. The melting point of the white A heat-sensitive recording material was produced and crystals was 161° C., and their analytical values were as evaluated in the same manner as in Example 38-1, except that follows. 25 after completion of the reaction for synthesis of the urea Result of IR measurement: urethane compound in Example 38-1, 2.2 g of diphenylsul Characteristic peaks appeared at 1070 cm, 1220 cm', fone was added to the reaction and stirred before the precipi 1550 cm, 1600 cm, 1700 cm and 3300 cm. tation with toluene, then the crystals precipitated with toluene The structural formula of the major component of this 30 were recovered by filtration, washed with hexane and then compound is presumed to be the structural formula of the dried overnight in a vacuum to obtain 7.4 g of a urea-urethane above-mentioned compound (S-33). composition as white crystals. The results are summarized in Then, a heat-sensitive recording material was produced in Table 3. the same manner as in Example 36 except for using the EXAMPLE 39 compound obtained above, in place of the urea-urethane com 35 pound synthesized in Example 36, and was evaluated. The To 31.5g of 2,4-toluene diisocyanate was added dropwise results are summarized in Table 3. a solution of 21.5g of 4,4'-diaminodiphenylsulfone in 60 mL of MEK at 70° C. with stirring at 300 to 500 rpm over a period EXAMPLE 38-1 of 4 hours, and the reaction was carried out for another 4 hours 40 to obtain a white viscous slurry reaction mixture. Then, the To 10.4 g of 2,4-toluene diisocyanate was added 20 g of reaction mixture was cooled to 50° C., and 17.1 g of phenol methyl ethyl ketone as a solvent, followed by adding drop was poured into the reaction mixture to be dissolved therein, wise thereto a solution of 3.7 g of 4,4'-diaminodiphenylsul after which 0.015 g of triethylamine was added thereto as a fone in 30 g of methyl ethyl ketone, and the reaction was catalyst, and the reaction was carried out for 4 hours to obtain carried out at room temperature for 20 hours, after which 45 a yellow, transparent and Viscous reaction mixture. This reac methyl ethylketone was removed by evaporation, and toluene tion mixture was freed of the solvent and concentrated under was added to the residue. The white solid precipitated was reduced pressure to be solidified, after which the resulting recovered by filtration, washed with hexane and then dried Solid was ground and then dried overnight in a vacuum to overnight in a vacuum to obtain 8.8 g of white crystals. obtain about 70 g of a urea-urethane composition as light Subsequently, 4 g of the thus obtained compound was added 50 yellow powder. to 15 g of phenol and a small amount of dibutyl tin dilaurate. The melting point of the light-yellow powder was 160 The reaction was then carried out at 50° C. for 4 hours, after 180° C. In IR measurement for the powder, a wide peak which toluene was added to the residue to effect crystalliza formed by overlapping of characteristic peaks due to a urea tion. The resulting crystals were recovered by filtration, group and a urethane group, respectively, appeared at 1700 washed with hexane and then dried overnight in a vacuum to 55 cm. The content of the urea-urethane main constituent in obtain 5.2 g of a urea-urethane compound as white crystals. the urea-urethane composition was 68% as measured by liq To 10 g of 2,4-toluene diisocyanate was then added 30 g of uid chromatography. toluene as a solvent, followed by adding dropwise thereto 30 Then, a heat-sensitive recording material was produced in g of phenol, and the reaction was carried out at 100° C. for 3 the same manner as in Example 36 except for using the hours, after which toluene was removed by evaporation, and 60 above-mentioned composition in place of the urea-urethane hexane was added to the residue. The white solid precipitated compound synthesized in Example 36, and was evaluated. was recovered by filtration, washed with hexane and then The results are summarized in Table 3. dried overnight in a vacuum to obtain 15 g of a urethane compound as white crystals. EXAMPLE 40 The structural formula of the major component of this 65 compound is presumed to be the structural formula of the To 158.5g of 2,4-toluene diisocyanate was added 240 g of above-mentioned compound (C-2). methyl ethyl ketone as a solvent, and 107.5 g of 4,4'-diami US 7,635,662 B2 155 156 nodiphenyl sulfone was added thereto in the form of powder composition as white crystals. The melting point of the white at 30° C. with stirring at 400 rpm over a period of 8 hours. crystals was 169°C. In IR analysis on the crystals, character After 1 hour, 26 g of methyl ethyl ketone was added thereto istic peaks due to a urea-urethane compound appeared at and stirred for another 15 hours to obtain a white viscous 1660 cm and 1740 cm. The content of the urea-urethane slurry reaction mixture. Then, a solution of 89.5 g of phenol main constituent in the urea-urethane composition was 52% in 15.8g of methyl ethyl ketone was poured into the reaction as measured by liquid chromatography. mixture to be dissolved therein, after which 9.3 g of a 1 wt % Then, a heat-sensitive recording material was produced in solution of triethylamine in methyl ethyl ketone was added the same manner as in Example 36 except for using the thereto as a catalyst over a period of 2 hours, and the reaction above-mentioned composition in place of the urea-urethane was uninterruptedly carried out for 1 hour. Thereafter, the 10 compound synthesized in Example 36, and was evaluated. reaction mixture was cooled to 20° C. and continuously The results are summarized in Table 3. stirred for 3 hours to obtain a slurry containing slightly yellow crystals precipitated therein. The slurry was freed of the sol EXAMPLE 43 vent and concentrated under reduced pressure to be solidified, after which the resulting solid was ground and then dried 15 In 253 mL of toluene was dissolved 27.5g of 2,4-toluene overnight in a vacuum to obtain 355 g of a urea-urethane diisocyanate, followed by adding dropwise thereto a solution composition as slightly yellow powder. of 14.7 g of aniline in 85 mL of toluene at 40°C. with stirring The melting point of the slightly yellow powder was 130 at 200 rpm over a period of 30 minutes, and the reaction was 170° C. In IR measurement for the powder, a wide peak carried out for another 30 minutes. To the thus obtained white formed by overlapping of characteristic peaks due to a urea slurry were added 18.0 g of 2.2-bis(4-hydroxyphenyl)pro group and a urethane group, respectively, appeared at 1700 pane, 262 mL of toluene and 0.42 mg of triethylamine as cm. The content of the urea-urethane main constituent in catalyst, and the stirring rate was increased to 400 rpm. In the urea-urethane composition was 65% as measured by liq order to prevent the aggregation of particles in the slurry in the uid chromatography. initial reaction by controlling the reaction rate, the reaction Then, a heat-sensitive recording material was produced in 25 was carried out as follows while raising the reaction tempera the same manner as in Example 36 except for using the ture step-wise: 60° C. for 5h, 65° C. for 2h, 70° C. for 1 h, and above-mentioned composition in place of the urea-urethane 75°C. for 1 h. Then, 0.42 mg of triethylamine was added, and compound synthesized in Example 36, and was evaluated. the reaction was carried out at 80° C. for another 8 h. The The results obtained are summarized in Table 3. reaction mixture was cooled to room temperature and the 30 white crystals were recovered by filtration. The white crystals EXAMPLE 41 were dried overnight in a vacuum to obtain 59 g of a urea urethane composition as white crystals. The melting point of To 27.8g of 2,4-toluene diisocyanate was added 100 g of these white crystals was 170°C. In IR analysis on the crystals, toluene as a solvent, followed by adding dropwise thereto a a wide characteristic peak due to urea-urethane appeared at solution of 7.4 g of aniline in 37 g of toluene at room tem 35 1720 cm. The content of the urea-urethane main constituent perature over a period of 1 hour, and the reaction was carried in the urea-urethane composition was 81% as measured by out for another 1 hour. The white solid precipitated was recov liquid chromatography. ered by filtration, washed with hexane and then dried over Then, a heat-sensitive recording material was produced in night in a vacuum to obtain 20 g of white crystals. Subse the same manner as in Example 36 except for using the quently, 5g of the thus obtained compound was added to 50 40 mL of methanol, and the reaction was carried out at 60° C. for above-mentioned composition in place of the urea-urethane 30 minutes, after which the excess methanol was removed by compound synthesized in Example 36, and was evaluated. the use of an evaporator, and the residue was dried overnight The results are summarized in Table 3. in a vacuum to obtain 5.4 g of aurea-urethane composition as EXAMPLES44. TO 55 white crystals. The melting point of the white crystals was 45 196° C. In IR measurement for the crystals, characteristic peaks due to a urea-urethane compound appeared at 1670 Heat-sensitive recording materials were produced in the cm' and 1700 cm. The content of the urea-urethane main same manner as in Example 40 except for using 4,4'-dichlo constituent in the urea-urethane composition was 92% as rodiphenyl sulfone (Example 44), 4,4'-dihydroxydiphenyl measured by liquid chromatography. 50 sulfone (Example 45), 2,4'-dihydroxy-diphenyl sulfone (Ex Then, a heat-sensitive recording material was produced in ample 46), 4-(benzyloxy)phenol (Example 47), salicylanilide the same manner as in Example 36 except for using the (Example 48), 4,4'-diaminodiphenyl sulfone (Example 49), above-mentioned composition in place of the urea-urethane 4,4'-dichloro-benzophenone (Example 50), 4,4'-diamino compound synthesized in Example 36, and was evaluated. diphenylmethane (Example 51), 4,4'-dimethoxybenzophe The results are summarized in Table 3. 55 none (Example 52), diphenyl carbonate (Example 53), 4,4'- dimethoxydiphenyl sulfone (Example 54) or 4,4'- EXAMPLE 42 diallyloxydiphenylsulfone (Example 55) in place of diphenyl Sulfone, and the heat-sensitive recording materials were To 17 g of 2,4-toluene diisocyanate was added 40 g of evaluated. The results are summarized in Table 3. methyl ethyl ketone as a solvent, followed by adding drop 60 wise thereto 3.8g of methanol, and the reaction was carried COMPARATIVE EXAMPLE 6 out with stirring at 60° C. for 5 hours. Then, 9.9 g of 4,4'- diaminodiphenyl Sulfone was added thereto, and the reaction A heat-sensitive recording material was produced in the was carried out with stirring at 60° C. for 4 hours. After same manner as in Example 36 except for using 2.2-bis(4- completion of the reaction, the methyl ethyl ketone as solvent 65 hydroxyphenyl)propane in place of the urea-urethane com was removed by the use of an evaporator, and the residue was pound synthesized in Example 36, and was evaluated. The dried overnight in a vacuum to obtain 16 g of a urea-urethane results are summarized in Table 3. US 7,635,662 B2 157 158 COMPARATIVE EXAMPLE 7 added dropwise thereto over a period of 1 hour, and the reaction was uninterruptedly carried out at 50° C. for 5 hours. To 17.4 g of 2,4-toluene diisocyanate was added 5 ml of After completion of the reaction, the reaction mixture was methyl ethyl ketone as a solvent, followed by adding drop concentrated and then poured into hexane to effect crystalli wise thereto a solution of 3.2 g of methanol in 5 mL of methyl 5 zation. The solid precipitated was recovered by filtration, ethyl ketone, and the reaction was carried out with stirring at washed with hexane and then dried overnight in a vacuum to room temperature for 2 hours. Then, a solution of 7.3 g of obtain 4.9 g of brown crystals. Subsequently, 2 g of this n-butylamine in 100 mL of methyl ethyl ketone was added compound was added to 50 mL of dioxane and the resulting dropwise thereto at room temperature, and the resulting solu mixture was stirred at 80°C. A solution of 3.8g of octadecyl tion was stirred for 1 hour. The crystals precipitated were 10 isocyanate in 10 mL of dioxane and then 2 mg of dibutyltin recovered by filtration, washed with hexane and then dried laurate as catalyst were added thereto, and the reaction was overnight in a vacuum to obtain 27g of a compound as white uninterruptedly carried out at 80° C. for 20 hours. After crystals. completion of the reaction, the reaction mixture was cooled to The melting point of the white crystals was 156°C., and room temperature, and the crystals precipitated were recov their analytical values were as follows. 15 ered by filtration, washed with dioxane and then dried over Result of IR measurement: night in a vacuum to obtain 2.7 g of slightly pink crystals. Characteristic peaks appeared at 1240 cm, 1550 cm', Analytical values of the slightly pink crystals were as follows. 1640 cm, 1720 cm and 3300 cm. Result of IR measurement: The presumed structural formula of the major component Characteristic peaks appeared at 1230 cm, 1470 cm', of this compound is the formula (R-1) shown hereinafter. 1510 cm, 1570 cm, 1620 cm, 1700 cm, 2900 cm Then, a heat-sensitive recording material was produced in and 3300 cm. the same manner as in Example 36 except for using the The presumed structural formula of the major component compound obtained above, in place of the urea-urethane com of this compound is the formula (R-3) shown below. pound synthesized in Example 36, and was evaluated. The 25 A heat-sensitive recording material was produced in the results are summarized in Table 3. same manner as in Example 36 except for using the com pound obtained above, in place of the urea-urethane com COMPARATIVE EXAMPLE 8 pound synthesized in Example 36, and was evaluated. The results are summarized in Table 3.

To 10.0 g of 2,4-toluene diisocyanate was added 100 mL of 30 toluene, and the resulting mixture was stirred at 25° C. A solution of 15.5 g of stearylamine in 100 mL of toluene was (R-1) added thereto, and the reaction was uninterruptedly carried CH out at 25°C. for 22 hours. After completion of the reaction, C C the white solid precipitated was recovered by filtration, 35 HC-O1 YN N1 N-n-CH, washed with toluene and then dried overnight in a vacuum to H H H obtain 20.4 g of white crystals. Subsequently, 5 g of this (R-2) compound was added to 50 mL of methyl ethylketone and the O resulting mixture was stirred at 80°C. A solution of 8.6 g of I H H3C p-hydroxybenzylcarboxylic acid in 20 mL of methyl ethyl 40 ketone and then 5 mg of dibutyltin laurate as catalyst were --C a Y-C a added thereto, and the reaction was uninterruptedly carried int-C O NH Ol NH N-(CH2)CHH (CH2)17CH3 out at 80° C. for 12 hours. After completion of the reaction, (R-3) the reaction mixture was cooled to room temperature, and the O O crystals precipitated were recovered by filtration, washed 45 with methyl ethyl ketone and then dried over-night in a CH-5-N1 YO N1 YN- CH3 vacuum to obtain 5.6 g of white crystals. Analytical values of the white crystals were as follows. O Result of IR measurement: Characteristic peaks appeared at 1220 cm, 1520 cm, 50 1630 cm, 1710 cm, 2900 cm and 3300 cm. TABLE 3 Result of mass spectrum measurement: Heat resistance M+H" was detected at m/z 596. Preserva The presumed structural formula of the major component 55 Color bility of develop- Plasticizer original of this compound is the formula (R-2) shown hereinafter. ment resistance Print recording A heat-sensitive recording material was produced in the sensitivity (print preserva- material Total same manner as in Example 36 except for using the com of thermal preserva- bility at Surface at evalua pound obtained above, in place of the urea-urethane com paper bility) 60° C. 80° C. tion pound synthesized in Example 36, and was evaluated. The 60 Example 36 1.2 A (6) O O results are summarized in Table 3. Example 37 1.2 (3) (3) O (3) Example 38 1.1 O (3) O O-(9) COMPARATIVE EXAMPLE 9 Example 38-1 1.2 O (3) O O-(9) Example 38-2 1.2 (6) (6) (6) (6) Example 38-3 1.2 O (3) O O-(9) To 100 mL of dioxane was added 3.0 g of p-aminophenol 65 Example 39 1.2 (3) (3) O (3) and the resulting mixture was stirred at 50° C. A solution of Example 40 1.2 (3) (3) O (3) 5.4 g of toluenesulfonyl isocyanate in 30 mL of dioxane was US 7,635,662 B2 159 160 etsu Chemical Co., Ltd.) in a sand grinder (mfl. by AIMEX TABLE 3-continued CO.,LTD., vessel capacity 400 ml) at a number of revolution of 2,000 rpm for 3 hours. Heat resistance A still another dispersion was prepared by dispersing 70 g Preserva of diphenyl sulfone by grinding it together with 130 g of a 8 Color bility of wt % poly(vinyl alcohol) aqueous Solution in a sand grinder develop- Plasticizer original (mfl. by AIMEX CO.,LTD., vessel capacity 400 ml) at a ment resistance Print recording sensitivity (print preserva- material Total number of revolution of 2,000 rpm for 3 hours. of thermal preserva- bility at Surface at evalua Separately, 10 g of calcium carbonate was mixed with 30 g paper bility) 60° C. 80° C. tion 10 of water and dispersed by stirring by the use of a stirrer to Example 41 .2 A (6) O O obtain a dispersion. Example 42 .2 (3) (3) O (3) A coating liquid was obtained by stirring and mixing the Example 43 .2 O (3) O O-(9) above-mentioned dispersions and other components in the Example 44 .2 (6) (6) (6) (6) following proportions (dry basis); the dispersion of the Example 45 .2 O (3) (3) O-(9) 15 Example 46 3 O (3) O-(9) O-(9) above-mentioned compound in terms of dry solids: 20 parts Example 47 .2 (3) (3) O O-(9) by weight, the 3-dibutylamino-6-methyl-7-anilinofluoran Example 48 .2 (6) (6) (6) (6) dispersion in terms of dry solids: 10 parts by weight, the Example 49 .1 O (3) (3) O-(9) diphenyl sulfone dispersion in terms of dry solids: 25 parts by Example 50 .2 (3) (3) O O-(9) Example 51 .2 O-(9) (3) O-(9) O-(9) weight, the calcium carbonate dispersion in terms of dry Example 52 3 O (6) (6) O-(9 Solids: 40 parts by weight, a Zinc Stearate dispersion (solid Example 53 .2 (3) (3) (3) (3) content: 16 wt %) in terms of dry solids: 20 parts by weight, Example 54 .2 (3) (3) (3) (3) and a 15 wt % poly(vinyl alcohol) in terms of dry solids: 15 Example 55 .2 (3) (3) (3) (3) parts by weight. Comparative 3 X A-O X X Example 6 The coating liquid was applied on base paper with a basis Comparative O.3 X X A X 25 weight of 50 g/m by the use of a barcoater of rod number 10. Example 7 The coating amount of the coating liquid was 5g/m in terms Comparative O.3 X A X Example 8 of dry weight. After drying, Supercalendering was conducted Comparative 0.4 X A X to obtain a heat-sensitive recording material. Example 9 The result of evaluating the sensitivity of the heat-sensitive 30 recording material obtained was so good that the optical density was 1.3. The print preservability evaluated by the use 1. Sensitivity becomes higher with an increase of optical of vinyl chloride wrap films was good. The whiteness of the density (OD value). original recording material Surface was as good as 82. These 2. Plasticizer resistance (print preservability) results are summarized in Table 4. G-Substantially no fading. 35 O-A slight color tone change without blur and the like. EXAMPLES 57 TO 58 A-Marked fading. X-Complete loss of the color of print. Heat-sensitive recording materials were produced in the 3. Heat resistance (print preservability at 60° C.) same manner as in Example 56 except for using 3-diethy 40 lamino-6-methyl-7-anilinofluoran (Example 57) or 3.3-bis (3) --Substantially no fading. (p-dimethylaminophenyl)-6-dimethylamino-phthalide (Ex O-A slight color tone change without blur and the like. ample 58) in place of 3-dibutylamino-6-methyl-7- A-Marked fading. anilinofluoran, and were evaluated. The results are X-Complete loss of the color of print. summarized in Table 4. 4. Heat resistance (the preservability of an original recording 45 material surface at 80° C.) EXAMPLES 59 TO 61 (3)-Substantially no fog was caused. O-Reading of a print portion was possible though there Heat-sensitive recording materials were produced in the was a slight color tone change. same manner as in Example 56 except for using methyl cel 50 lulose (Metolose M-15, mfcd. by Shin-etsu Chemical Co., A-Reading of a print portion was difficult owing to fog. Ltd.) (Example 59), a polyoxyethylene alkyl ether sulfate X-Reading of a print portion was impossible owing to (Rebenol WX, mfcd. by Kao Corp.) (Example 60) or sodium serious fog. 2-ethylhexylsulfosuccinate (Neocol SWC, mfcd. by Dai-ichi Kogyo Seiyaku Co., Ltd.) in place of the hydroxypropylm EXAMPLE 56 55 ethyl cellulose used in Example 56 for dispersing 3-dibuty lamino-6-methyl-7-anilinofluoran, and the heat-sensitive A dispersion was prepared by dispersing 2 g of the com recording materials were evaluated. The results are Summa pound obtained in Example 3, by grinding this compound rized in Table 4. together with 8 g of a 2.5 wt % poly(vinyl alcohol) aqueous solution in a paint shaker for 6 hours. The temperature of the 60 EXAMPLE 62 dispersion immediately after the dispersing operation was 25°C. The diameter of dispersed particles of the compound Aurea-urethane compound developer dispersion, a 3-dibu was 0.6 um. tylamino-6-methyl-7-anilinofluoran dispersion, a diphenyl Another dispersion was prepared by dispersing 70 g of Sulfone dispersion and a calcium carbonate dispersion were 3-dibutylamino-6-methyl-7-anilinofluoran by grinding it 65 prepared in the same manner as in Example 56. together with 130g of a 5.4 wt % aqueous solution of hydrox On the other hand, a dispersion was prepared by dispersing ypropylmethyl cellulose (Metolose 60SH-03, mfcd. by Shin 70 g of 2.2-bis(4-hydroxyphenyl)propane by grinding it US 7,635,662 B2 161 162 together with 130g of a 5.4 wt % poly(vinyl alcohol) aqueous EXAMPLE 99 solution in a sandgrinder (mfl. by AIMEXCO.,LTD., vessel capacity 400 ml) at a number of revolution of 2,000 rpm for 3 hours. A heat-sensitive recording material was produced in the A coating liquid was obtained by stirring and mixing the same manner as in Example 62 except for adding a stilbene above-mentioned dispersions and other components in the type fluorescent dye (Kayahol 3BS, a trade name, mfcd. by following proportions (dry basis); the urea-urethane com Nippon Kayaku Co., Ltd.) to the coating liquid prepared in pound dispersion in terms of dry solids: 10 parts by weight, Example 62, in a proportion of 1 part by weight per 100 parts the 3-dibutylamino-6-methyl-7-anilinofluoran dispersion in by weight (in terms of dry solids) of the coating liquid, and terms of dry solids: 10 parts by weight, the diphenyl sulfone 10 was evaluated. The results are summarized in Table 4. dispersion in terms of dry solids: 20 parts by weight, the 2.2-bis(4-hydroxyphenyl)propane dispersion in terms of dry EXAMPLE 100 Solids: 10 parts by weight, the calcium carbonate dispersion in terms of dry solids: 20 parts by weight, a Zinc Stearate A dispersion was obtained by dispersing 70g of 1,1,3-tris dispersion (solid content: 16 wt %) in terms of dry solids: 10 15 parts by weight, and a 15 wt % poly(vinyl alcohol) in terms of (2-methyl-4-hydroxy-5-tert-butylphenyl)-butane by grind dry Solids: 10 parts by weight. A heat-sensitive recording ing this compound together with 130 g of a 5.4 wt % poly material was produced in the same manner as in Example 56 (vinyl alcohol) aqueous Solution in a sand grinder (mfl. by except for using the coating liquid obtained above, and was AIMEX CO.,LTD., vessel capacity 400 ml) at a number of evaluated. revolution of 2,000 rpm for 3 hours. The results are summarized in Table 4. Then, a heat-sensitive recording material was produced in the same manner as in Example 62 except for adding the EXAMPLES 63 TO 66 aforesaid 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl) 25 butane dispersion to the coating liquid prepared in Example Heat-sensitive recording materials were produced in the 62, in a proportion of 10 parts by weight per 100 parts by same manner as in Example 62 except for using 4-isopropy loxyphenyl-4'-hydroxyphenyl sulfone (D-8, a trade name, weight (in terms of dry solids) of the coating liquid, and was mfd. by Nippon Soda Co., Ltd.). (Example 63), bis(3-allyl evaluated. The results are summarized in Table 4. 4-hydroxyphenyl) sulfone (TG-SA, a trade name, mfcd. by Nippon Kayaku Co., Ltd.) (Example 64), 2,4'-dihydroxy 30 EXAMPLE 101 diphenyl sulfone (24BPS, a trade name, mfd. by Nicca Chemical Co., Ltd.) (Example 65) or a mixture composed A heat-sensitive recording material was produced in the mainly of 4,4'-oxybis-(ethyleneoxy-p-phenylenesulfonyl) same manner as in Example 100 except for using the urea diphenol (D-90, a trade name, mfcd. by Nippon Soda Co., Ltd.) 35 urethane compound obtained in Example 20, in place of the (Example 66) in place of 2.2-bis(4-hydroxyphenyl)propane, urea-urethane compound used in Example 100, and was and the heat-sensitive recording materials were evaluated. The results are summarized in Table 4. evaluated. The results are summarized in Table 4.

EXAMPLES 67 TO 96 EXAMPLES 102 TO 107 40 Heat-sensitive recording materials were produced in the Heat-sensitive recording materials were produced in the same manner as in each of Examples 62 to 66 except for using same manner as in Example 100 except for using 1,1,3-tris B-naphthylbenzyl ether (BON, a trade name, mfcd. by Ueno (2-methyl-4-hydroxy-5-cyclohexyl-phenyl)butane (Ad Fine Chemicals Industry Ltd.) (Examples 67 to 71), p-ben 45 karkls DH-43, mfcd. by Asahi Denka Kogyo K.K.) (Example Zylbiphenyl (PBBP, a trade name, mfcd. by Nippon Steel 102), 4-benzyloxy-4'-(2,3-epoxy-2-methylprop-1-yloxy) Chemical Co., Ltd.) (Examples 72 to 76), 1,2-di(m-meth diphenyl sulfone (NTZ-95, mfcd. by Nippon Soda Co., Ltd.), ylphenoxy)ethane (KS-235, a trade name, mfcd. by SANKO (Example 103), methylenebis(2-hydroxy-3-(benzotriazol-2- SHA CO., LTD.) (Examples 77 to 81), di-p-methylbenzyl yl)-5-tert-octylphenyl) (Example 104), 2-(2-hydroxy-5'-me oxalate (HS3520, a trade name, mfcd. by Dainippon Ink and 50 thylphenyl)-benzotriazole (Adkarkls DN-13, mfcd. by Asahi Chemicals, Inc.) (Examples 82 to 86), 1,2-diphenoxymeth Denka Kogyo K.K.) (Example 105), 1,3,5-tris(2,6-dimethyl ylbenzene (PMB-2, a trade name, mfcd. by Nicca Chemical 4-tert-butyl-3-hydroxybenzyl) isocyanurate (Adkarkls Co., Ltd.) (Examples 87 to 91) or m-terphenyl (mtp, a trade DH-48, mfcd. by Asahi Denka Kogyo K.K.) (Example 106) or name, mfcd. by Nippon Steel Chemical Co., Ltd.) (Examples sodium 2.2-methylenebis(4,6-di-tertbutylphenyl)-phosphate 92 to 96) in place of diphenyl sulfone, and the heat-sensitive 55 (Adkarkls F-85, mfcd. by Asahi Denka Kogyo K.K.) (Example recording materials were evaluated. The results are Summa 107) in place of 1,1,3-tris(2-methyl-4-hydroxy-5-tert-bu rized in Table 4. tylphenyl)butane, and the heat-sensitive recording materials EXAMPLES 97 TO 98 were evaluated. The results are summarized in Table 4. 60 Heat-sensitive recording materials were produced in the COMPARATIVE EXAMPLE 10 same manner as in Example 56 except for using a Stearamide emulsified product (Highmicron G-270, a trade name, mfcd. A heat-sensitive recording material was produced in the by Chukyo Yushi Co., Ltd.) (Example 97) or acetoactic same manner as in Example 56 except for using 2.2-bis(4- o-chloroanilide (mfl. by Mitsubishi Chemical Co., Ltd.) (Ex 65 hydroxyphenyl)propane in place of the urea-urethane com ample 98) in place of diphenyl sulfone, and were evaluated. pound used in Example 56, and was evaluated. The results are The results are summarized in Table 4. summarized in Table 4. US 7,635,662 B2 163 164 When the recording material showed no remarkable trace of TABLE 4 the rubbing, it was rated good in resistance to rubbing. Plasticizer resistance Sensitivity (print A cylinder (weight: 2 kg) having a Surface with a diameter of thermal preserva- Total of 5 cm was moved 50 times on one and the same portion with paper bility) Whiteness evaluation a length of 20 cm of the recording surface of each heat Example 56 3 (6) 82 (6) sensitive recording material produced, at a rate of 20 cm/sec. Example 57 3 (3) 81 (3) and then the recording material was allowed to stand at room Example 58 3 (3) 82 (3) 10 Example 59 3 (6) 82 (6) temperature for one week. After one week of the standing, Example 60 3 (6) 82 (6) whether a printed image could be read was visually judged. Example 61 3 (3) 82 (3) When the printed image could be sufficiently read, the record Example 62 3 O-(9) 81 O Example 63 3 O-(9 81 O ing material was rated good. Example 64 3 O-(9) 81 O 15 Example 65 3 O-(9) 81 O EXAMPLE 108 Example 66 .2 (3) 81 O Example 67 .4 O-(9 82 O-(3) Example 68 .4 O-(9) 83 O-(3) A heat-sensitive coating liquid was obtained in the same Example 69 .4 O-(9) 82 O-(3) manner as in Example 56. Then, the coating liquid was Example 70 3 O-(9) 82 O-(3) Example 71 .2 (6) 82 O-(3) applied on base paper with a basis weight of 50 g/m by the Example 72 3 O-(9) 82 O-(3) use of a bar coater of rod number 10. After drying, supercal Example 73 3 O-(9) 83 O-(3) endering was conducted to form a heat-sensitive color-pro Example 74 3 O-(9) 82 O-(3) Example 75 3 O-(9 82 O-(3) ducing layer on the Substrate. The coating amount of the Example 76 .2 (3) 82 O-(3) coating liquid was 5g/m in terms of dry weight. Example 77 3 O-(9) 83 O-(3) 25 Example 78 3 O-(9) 83 O-(3) Then, a dispersion was prepared by dispersing 40 g of Example 79 3 O-(9 82 O-(3) kaolin by grinding it together with 60 g of a 0.7% sodium Example 80 3 O-(9) 82 O-(3) hexametaphosphate aqueous solution in a sand grinder (mfc. Example 81 .2 (3) 82 O-(3) Example 82 3 O-(9 83 O-(3) by AIMEXCO.,LTD., vessel capacity 400 ml) at a number of Example 83 .4 O-(9 82 O-(3) 30 revolution of 2,000 rpm for 3 hours. Example 84 .4 O-(9) 82 O-(3) A coating liquid for forming a protective layer was Example 85 3 O-(9) 82 O-(3) Example 86 .2 (6) 82 O-(3) obtained by stirring and mixing this dispersion and other Example 87 3 O-(9 83 O-(3) components in the following proportions (dry basis); the Example 88 3 O-(9) 82 O-(3) kaolin dispersion in terms of dry solids: 20 parts by weight, a Example 89 3 O-(9) 82 O-(3) 35 Example 90 3 O-(9 82 O-(3) Zinc stearate dispersion (solid content: 16 wt %) in terms of Example 91 .2 (3) 82 O-(3) dry solids: 10 parts by weight, a carboxy-modified poly(vinyl Example 92 3 O-(9) 82 O-(3) alcohol) aqueous solution in terms of dry solids: 40 parts by Example 93 3 O-(9) 82 O-(3) weight, and a polyacrylamido-epichlorohydrin crosslinking Example 94 3 O-(9 82 O-(3) Example 95 3 O-(9) 82 O-(3) agent aqueous solution in terms of dry solids: 5 parts by Example 96 .2 (3) 82 O-(3) 40 weight. Example 97 3 O-(9) 83 (3) Example 98 .2 (6) 82 (6) The coating liquid for forming a protective layer was Example 99 3 O-(9) 85 O-(3) applied on the heat-sensitive color-producing layer by the use Example 100 3 (3) 82 (3) of a bar coater of rod number 5. After drying, supercalender Example 101 3 (3) 82 (3) Example 102 3 (6) 82 (6) 45 ing was conducted to obtain a heat-sensitive recording mate Example 103 3 (3) 82 (3) rial. The coating amount of the coating liquid for forming a Example 104 3 O-(9) 83 O-(3) protective layer was 2 g/m in terms of dry weight. Example 105 3 O-(9 82 O-(3) Example 106 3 O-(9 82 O-(3) The result of evaluating the sensitivity of the heat-sensitive Example 107 3 O-(9) 83 O-(3) recording material obtained was so good that the optical Comparative 3 X 78 X 50 Example 10 density was 1.3. The print preservability evaluated by the use of vinyl chlo ride wrap films was good. The surface of the heat-sensitive 1. Sensitivity becomes higher with an increase of optical recording material was strongly rubbed with a nail and density (OD value). whether color development had been caused in the rubbed 2. Plasticizer resistance (print preservability) 55 portion was visually judged to find that the trace of the rub (3) --Substantially no fading. bing was not remarkable, namely, the resistance to rubbing O-A slight color tone change without blur and the like. was good. Even after a long-term test for evaluating the resis A-Marked fading. tance to rubbing, a printed image could be sufficiently read, X-Complete loss of the color of print. 60 namely, the resistance to rubbing was good. These evaluation 3. Whiteness becomes higher with an increase of its numeral results are summarized in Table 5. value. Whiteness is sufficient in practice when its numeral value is 80 or more. EXAMPLES 109 TO 110 The Surface of each heat-sensitive recording material was 65 Heat-sensitive recording materials were produced in the strongly rubbed with a nail, and whether color development same manner as in Example 108 except for using a poly(vinyl had been caused in the rubbed portion was visually judged. alcohol) (Example 109) or an acrylic copolymer (Example US 7,635,662 B2 165 166 110) in place of the carboxy-modified poly(vinyl alcohol), 3. Resistance to rubbing and were evaluated. The results are summarized in Table 5. G-A trace of rubbing shows no development of a black color. EXAMPLES 111 TO 113 O-A trace of rubbing shows slight color development but is not remarkable. Heat-sensitive recording materials were produced in the A-A trace of rubbing shows color development to a limited same manner as in Example 108 except for using aluminum extent and is remarkable. hydroxide (Example 111), a crosslinkable poly(methyl meth X-A trace of rubbing shows development of a black color acrylate) resin (Example 112) or silica dioxide (Example and is remarkable. 113) in place of kaolin, and were evaluated. The results are 10 4. Accumulation of traces of rubbing summarized in Table 5. (3) --A good result is obtained without difficulty in reading a printed image. EXAMPLE 114 O-Traces of rubbing show slight color development but a printed image can be sufficiently read. A coating liquid for intermediate layer was obtained by 15 stirring and mixing a 33 wt % calcined kaolin dispersion and A-Traces of rubbing show color development, so that a a 50 wt % styrene/butadiene based latex aqueous dispersion printed image is difficult to read. in proportions (dry basis) of 100 parts by weight and 12 parts X-Traces of rubbing show development of a black color, so by weight, respectively. that a printed image cannot be read. Then, a back coating liquid was obtained by stirring and EXAMPLE 115 mixing a 20 wt % acrylic emulsion and a 10 wt % silica fine powder dispersion (Fineseal SP-10) in proportions (dry basis) A dispersion was prepared by dispersing 2 g of the com of 100 parts by weight and 7 parts by weight, respectively. pound obtained in Example 3, by grinding this compound The aforesaid coating liquid for intermediate layer was together with 8 g of a 2.5 wt % aqueous solution of a poly applied on one side of base paper (50 g/m) in an amount of 10 25 (vinyl alcohol) (Gosenol KL-05, mfcd. by The Nippon Syn g/min terms of solids and dried, and the heat-sensitive coat thetic Chemical Industry Co., Ltd.) in a paint shaker for 6 ing liquid prepared in Example 108 was applied on the same hours. The temperature of the dispersion immediately after side in an amount of 5 g/m in terms of solids and dried, after the dispersing operation was 25°C. and the pH of the disper which the coating liquid for protective layer prepared in sion was 8. The diameter of dispersed particles of the com Example 108 was applied on the same side in an amount of 2 30 pound was 0.6 um. g/min terms of solids and dried. Then, the aforesaid back Another dispersion was prepared by dispersing 70 g of coating liquid was applied on the uncoated side in an amount 3-dibutylamino-6-methyl-7-anilinofluoran by grinding it of 1 g/min terms of solids and dried, and calendaring was together with 130g of a 5.4 wt % poly(vinyl alcohol) aqueous conducted to obtain a heat-sensitive recording material, solution in a sand grinder (mfl. by AIMEX Co., LTD., vessel which was evaluated. The results are summarized in Table 5. 35 capacity 400 ml) at a number of revolution of 2,000 rpm for 3 hours. COMPARATIVE EXAMPLE 11 A still another dispersion was prepared by dispersing 70 g of diphenyl sulfone by grinding it together with 130g of a 5.4 A heat-sensitive recording material was produced in the wt % aqueous solution of a poly(vinyl alcohol) (Gosenol same manner as in Example 108 except that no coating liquid 40 KL-05, mfcd. by The Nippon Synthetic Chemical Industry for forming a protective layer was applied on the heat-sensi Co., Ltd.) in a sand grinder (mfl. by AIMEX CO., LTD.; tive color-producing layer, and the recording material was vessel capacity 400 ml) at a number of revolution of 2,000 evaluated. The results are summarized in Table 5. rpm for 3 hours. 45 Separately, 10 g of calcium carbonate was mixed with 30 g TABLE 5 of water and dispersed by stirring by the use of a stirrer to Plasticizer obtain a dispersion. resistance Accumu A coating liquid was obtained by stirring and mixing the Sensitivity (print lation of of thermal preserva- Resistance traces of Total above-mentioned dispersions and other components in the paper bility) to rubbing rubbing evaluation 50 following proportions (dry basis); the dispersion of the above-mentioned compound in terms of dry solids: 30 parts Example 108 1.3 (6) (6) (6) (6) by weight, the 3-dibutylamino-6-methyl-7-anilinofluoran Example 109 1.3 (3) (3) (3) (3) Example 110 1.3 (3) O-(3) (3) O-(3) dispersion in terms of dry solids: 15 parts by weight, the Example 111 1.3 (6) (6) (6) (6) diphenyl sulfone dispersion in terms of dry solids: 30 parts by Example 112 1.3 (6) O-(3) (6) O-(3) 55 weight, the calcium carbonate dispersion in terms of dry Example 113 1.3 (3) (3) (3) (3) Solids: 20 parts by weight, a Zinc Stearate dispersion (solid Example 114 1.4 (3) (3) (3) (3) Comparative 1.3 A- X- X X content: 16 wt %) in terms of dry solids: 10 parts by weight, Example 11 and a 15 wt % poly(vinyl alcohol) in terms of dry solids: 7 parts by weight. The pH of the coating liquid was 8.2. 60 Then, the coating liquid was applied on the Surface of 1. Sensitivity becomes higher with an increase of optical woodfree paper with a basis weight of 50 g/m in an amount density (OD value). of 5 g/min terms of dry weight and dried, after which super 2. Plasticizer resistance (print preservability) calendering was conducted to produce a heat-sensitive (3) --Substantially no fading. recording material. O-A slight color tone change without blur and the like. 65 The result of evaluating the color development sensitivity A-Marked fading. of the heat-sensitive recording material obtained was so good X-Complete loss of the color of print. that the optical density was 1.3. The print preservability US 7,635,662 B2 167 168 evaluated by the use of vinyl chloride wrap films was so good EXAMPLES 12O TO 124 that no fading occurred. The results are summarized in Table 6. Heat-sensitive recording materials were produced in the same manner as in Example 115 except for using a polycar EXAMPLE 116 boxylic acid ammonium salt (Dispersant 5027, mfcd. by Sun nopco Co., Ltd.) (Example 120), a water-soluble low-mo A dispersion was prepared by dispersing 2 g of the same lecular weight copolymer (Discort N14, mfcd. by Dai-ichi urea-urethane compound as used in Example 115 and 2 g of Kogyo Seiyaku Co., Ltd.) (Example 121), Sodium 2-ethyl diphenyl Sulfone by grinding them together with 16 g of a 2.5 hexylsulfosuccinate (Neocol SWC, mfcd. by Dai-ichi Kogyo wt % aqueous solution of a modified poly(vinyl alcohol) 10 Seiyaku Co., Ltd.) (Example 122), hydroxypropylmethylcel (Gosenol KL-05, mfcd. by The Nippon Synthetic Chemical lulose (Metolose 60SH-03, mfcd. by Shin-etsu Chemical Co., Industry Co., Ltd.) in a paint shaker for 6 hours. Ltd.) (Example 123), or sodium condensed naphthalene-Sul Then, a heat-sensitive recording material was produced in fonate (Roma D. mfcd. by Sunnopco Co., Ltd.) (Example 124) the same manner as in Example 115 except for adding the in place of the poly(vinyl alcohol) (Gosenol KL-05, mfd. by aforesaid co-dispersion in a proportion of 60 parts by weight 15 The Nippon Synthetic Chemical Industry Co., Ltd.) used as a in terms of dry solids, in place of the dispersion of the urea dispersing agent for the urea-urethane compound in Example urethane compound used in Example 115 and the diphenyl 115, and the heat-sensitive recording materials were evalu Sulfone dispersion, and the recording material was evaluated. ated. The results are summarized in Table 6. The results are summarized in Table 6. EXAMPLES 125 TO 130 EXAMPLE 117 A dispersion was prepared by dispersing 2 g of the com Heat-sensitive recording materials were produced in the pound obtained in Example 10 and 2 g of diphenyl sulfone by same manner as in Example 115 except for using methyl cellulose (Metolose SM-15, mfcd. by Shin-etsu Chemical Co., grinding them together with 16 g of a 2.5 wt % aqueous 25 Ltd.) (Example 125), a water-soluble low-molecular weight solution of a modified poly(vinyl alcohol) (Goseran L-3266, copolymer (Discort N14, mfcd. by Dai-ichi Kogyo Seiyaku mfd. by The Nippon Synthetic Chemical Industry Co., Ltd.) Co., Ltd.) (Example 126), sodium 2-ethylhexylsulfosucci in a paint shaker for 6 hours. nate (Neocol SWC, mfcd. by Dai-ichi Kogyo Seiyaku Co., Then, a heat-sensitive recording material was produced in Ltd.) (Example 127), hydroxypropylmethyl cellulose (Meto the same manner as in Example 115 except for adding the 30 lose 60SH-03, mfcd. by Shin-etsu Chemical Co., Ltd.) (Ex aforesaid co-dispersion of the aforesaid compound and ample 128), Sodium condensed naphthalenesulfonate (Roma dipheny Sulfone in a proportion of 60 parts by weight interms D, mfcd. by Sunnopco Co., Ltd.) (Example 129) or a polycar of dry solids, in place of the dispersion of the urea-urethane boxylic acid ammonium salt (Dispersant 5027, mfcd. by Sun compound used in Example 115 and the diphenyl sulfone nopco Co., Ltd.) (Example 130) in place of the poly(vinyl dispersion, and the recording material was evaluated. The 35 alcohol) (Gosenol KL-05, mfcd. by The Nippon Synthetic results are summarized in Table 6. Chemical Industry Co., Ltd.) used as a dispersing agent for diphenyl sulfone in Example 115, and the heat-sensitive EXAMPLE 1.18 recording materials were evaluated. The results are Summa rized in Table 6. A dispersion was prepared by dispersing 2 g of the com 40 pound obtained in Example 20 and 2 g of dimethylbenzyl oxalate by grinding them together with 16 g of a 2.5 wt % EXAMPLES 131 TO 133 aqueous solution of a modified poly(vinyl alcohol) (Goseran L-3266, mfcd. by The Nippon Synthetic Chemical Industry Heat-sensitive recording materials were produced in the Co., Ltd.) in a paint shaker for 6 hours. 45 same manner as in Example 119 except for using methyl Then, a heat-sensitive recording material was produced in cellulose (Metolose SM-15, mfcd. by Shin-etsu Chemical Co., the same manner as in Example 115 except for adding the Ltd.) (Example 131), hydroxy-propylmethyl cellulose (Me aforesaid co-dispersion of the aforesaid compound and dim tolose 60SH-03, mfcd. by Shin-etsu Chemical Co., Ltd.) (Ex ethylbenzyl oxalate in a proportion of 60 parts by weight in ample 132) or a modified poly(vinyl alcohol) (Goseran terms of dry solids, in place of the dispersion of the urea 50 L-3266, mfcd. by The Nippon Synthetic Chemical Industry urethane compound used in Example 115 and the diphenyl Co., Ltd.) (Example 133) in place of the poly(vinyl alcohol) Sulfone dispersion, and the recording material was evaluated. (Gosenol KL-05, mfcd. by The Nippon Synthetic Chemical The results are summarized in Table 6. Industry Co., Ltd.) used as a dispersing agent for diphenyl sulfone in Example 119, and the heat-sensitive recording EXAMPLE 119 55 materials were evaluated. The results are Summarized in Table 6. A dispersion was prepared by dispersing 2 g of the com pound obtained in Example 37, by grinding this compound EXAMPLE 134 together with 8 g of a 2.5 wt % aqueous solution of methyl cellulose (Metolose SM-15, mfcd. by Shin-etsu Chemical Co., 60 A heat-sensitive recording material was produced in the Ltd.) in a paint shaker for 6 hours. same manner as in Example 131 except for using a modified Then, a heat-sensitive recording material was produced in poly(vinyl alcohol) (Goseran L-3266, mfcd. by The Nippon the same manner as in Example 115 except for using the Synthetic Chemical Industry Co., Ltd.) in place of the methyl dispersion of the aforesaid compound in place of the disper cellulose (Metolose SM-15, mfcd. by Shin-etsu Chemical Co., sion of the urea-urethane compound used in Example 3, and 65 Ltd.) used as a dispersing agent for the urea-urethane com the recording material was evaluated. The results obtained are pound in Example 131, and the recording material was evalu summarized in Table 6. ated. The results are summarized in Table 6. US 7,635,662 B2 169 170 EXAMPLES 135 AND 136 sion thus obtained, a heat-sensitive recording sheet was pro duced in the same manner as in Example 115, and was evalu Heat-sensitive recording materials were produced in the ated. The results are summarized in Table 6. same manner as in Example 121 except for using methyl cellulose (Metolose SM-15, mfcd. by Shin-etsu Chemical Co., COMPARATIVE EXAMPLE 16 Ltd.) (Example 135) or hydroxypropylmethyl cellulose (Me tolose 60SH-03, mfcd. by Shin-etsu Chemical Co., Ltd.) (Ex The same urea-urethane compound as used in Example ample 136) in place of the poly(vinyl alcohol) (Gosenol 115 was dispersed in the same manner as in Example 115. In KL-05, mfcd. by The Nippon Synthetic Chemical Industry this case, the pH of the dispersion medium used for the Co., Ltd.) used as a dispersing agent for diphenyl Sulfone in 10 dispersing operation was adjusted to 4. Except for using the Example 121, and the heat-sensitive recording materials were dispersion thus obtained, aheat-sensitive recording sheet was evaluated. The results are summarized in Table 6. produced in the same manner as in Example 115, and was evaluated. The results are summarized in Table 6. EXAMPLES 137 AND 138 15 COMPARATIVE EXAMPLE 17 Heat-sensitive recording materials were produced in the same manner as in Example 123 except for using methyl The same urea-urethane compound as used in Example cellulose (Metolose SM-15, mfcd. by Shin-etsu Chemical Co., 115 was dispersed in the same manner as in Example 115. In Ltd.) (Example 137) or hydroxypropylmethyl cellulose (Me this case, the pH of the dispersion medium used for the tolose 60SH-03, mfcd. by Shin-etsu Chemical Co., Ltd.) (Ex dispersing operation was adjusted to 11. Except for using the ample 138) in place of the poly(vinyl alcohol) (Gosenol dispersion thus obtained, aheat-sensitive recording sheet was KL-05, mfcd. by The Nippon Synthetic Chemical Industry produced in the same manner as in Example 115, and was Co., Ltd.) used as a dispersing agent for diphenyl Sulfone in evaluated. The results are summarized in Table 6. Example 123, and the heat-sensitive recording materials were evaluated. The results are summarized in Table 6. 25 COMPARATIVE EXAMPLE 1.8 EXAMPLES 139 AND 140 The pH of the coating liquid prepared in Example 115 was adjusted to-4.0 with 1 N-sulfuric acid. Except for using the Heat-sensitive recording materials were produced in the coating liquid thus adjusted, a heat-sensitive recording sheet same manner as in Example 136 except for using hydroxypro 30 was produced in the same manner as in Example 115, and was pylmethyl cellulose (Metolose 60SH-03, mfcd. by Shin-etsu evaluated. The results are summarized in Table 6. Chemical Co., Ltd.) (Example 139) or a mixed dispersing agent of hydroxypropylmethyl cellulose (Metolose 60SH-03, COMPARATIVE EXAMPLE 19 mfd. by Shin-etsu Chemical Co., Ltd.) and sodium 2-ethyl hexylsulfosuccinate (Neocol SWC, mfcd. by Dai-ichi Kogyo 35 The pH of the coating liquid prepared in Example 115 was Seiyaku Co., Ltd.) (weight ratio: 1/1) (Example 140) in place adjusted to 12.5 with 1 N-sodium hydroxide. Except for using of the poly(vinyl alcohol) used as a dispersing agent for the coating liquid thus adjusted, a heat-sensitive recording 3-dibutylamino-6-methyl-7-anilinofluoran in Example 136, sheet was produced in the same manner as in Example 115, and the heat-sensitive recording materials were evaluated. and was evaluated. The results are summarized in Table 6. The results are summarized in Table 6. 40 TABLE 6 COMPARATIVE EXAMPLE 12 Plasticizer Plasticizer resistance resistance A heat-sensitive recording sheet was produced in the same (print (preservability of manner as in Example 115 except for using 2.2-bis(4-hydrox 45 Sensitivity of preserva- original recording Total yphenyl)propane in place of the urea-urethane compound thermal paper bility) material Surface) evaluation used in Example 115, and was evaluated. The results are Example 115 3 (6) O-(9 O-(3) summarized in Table 6. Example 116 .4 (6) O-(9 O-(3) Example 117 3 O-(9) (3) O-(3) COMPARATIVE EXAMPLES 13 AND 14 50 Example 118 3 O (3) O-(3) Example 119 3 O-(9 (6) O-(3) Example 120 3 (6) (6) (6) The same urea-urethane compound as used in Example Example 121 3 (3) (3) (3) 115 was dispersed in the same manner as in Example 115 Example 122 .2 (3) (3) (3) except for changing the dispersion time, and the average Example 123 3 (6) O-(9 O-(3) 55 Example 124 .2 (6) O-(9 O-(3) particle sizes of the resulting dispersions were measured and Example 125 3 (3) (3) (3) found to be 0.04 um (Comparative Example 10) and 6.5 um Example 126 3 (3) (3) (3) (Comparative Example 11). Heat-sensitive recording sheets Example 127 3 (6) (6) (6) were produced in the same manner as in Example 115 except Example 128 3 (3) O-(9) O-(3) Example 129 3 (3) O-(9) O-(3) for using each of the above-mentioned dispersions, and were Example 130 3 (3) O-(9) O-(3) evaluated. The results are summarized in Table 6. 60 Example 131 3 (6) (6) (6) Example 132 3 (3) (3) (3) COMPARATIVE EXAMPLE 1.5 Example 133 .4 (3) (3) (3) Example 134 .4 (3) (3) (3) Example 135 3 (6) (6) (6) The same urea-urethane compound as used in Example Example 136 3 (3) (3) (3) 115 was dispersed in the same manner as in Example 115. In 65 Example 137 3 (3) (3) (3) this case, the dispersion temperature was maintained at 65°C. Example 138 3 (3) (3) (3) during the dispersing operation. Except for using the disper US 7,635,662 B2 171 172 COMPARATIVE EXAMPLES 20 AND 21 TABLE 6-continued Heat-sensitive recording materials were produced in the Plasticizer Plasticizer resistance resistance same manner as in Example 141 except for using woodfree (print (preservability of paper with a surface pH of 2.8 (Comparative Example 20) or Sensitivity of preserva- original recording Total woodfree paper with a surface pH of 9.5 (Comparative thermal paper bility) material Surface) evaluation Example 21) in place of the wood free paper with a surface pH Example 139 1.3 (6) (6) (6) of 3.2, and were evaluated. The results are summarized in Example 140 1.4 (3) (3) (3) Table 7. Comparative 1.3 X O X 10 Example 12 TABLE 7 Comparative 1.3 O X X Example 13 Plasticizer Plasticizer Comparative 0.7 A O X resistance resistance Example 14 (print (preservability of Comparative O.8 A A X 15 Example 15 Sensitivity of preserva- original recording Total Comparative 1.O A X X thermal paper bility) material Surface) evaluation Example 16 Example 141 1.3 (3) O-(9) O-(3) Comparative O.8 A A X Example 142 1.3 (3) (3) (3) Example 17 Example 13 1.3 (3) (3) (3) Comparative 1.1 A X X Comparative 1.3 A X X Example 18 Example 20 Comparative O.9 X A X Comparative 1.O A A X Example 19 Example 21

1. Sensitivity becomes higher with an increase of optical 1. Sensitivity becomes higher with an increase of optical density (OD value). 25 density (OD value). 2. Plasticizer resistance (print preservability) 2. Plasticizer resistance (print preservability) (3) --Substantially no fading. (3) --Substantially no fading. O-A slight color tone change without blur and the like. O-A slight color tone change without blur and the like. A-Marked fading. A-Marked fading. 30 X-Complete loss of the color of print. X-Complete loss of the color of print. 3. Plasticizer resistance (the preservability of an original 3. Plasticizer resistance (the preservability of an original recording material Surface) recording material Surface) (9-The original recording material Surface is hardly col (3) --The original recording material Surface is hardly col 35 ored. ored. O-The original recording material surface is very slightly O-The original recording material surface is very slightly colored though there was a Subtle color tone change. colored though there was a Subtle color tone change. A-The original recording material Surface is markedly col A-The original recording material Surface is markedly col ored. ored. 40 X-The original recording material Surface is so seriously X-The original recording material Surface is so seriously colored that reading of a print was difficult. colored that reading of a print was difficult. EXAMPLE 1.44 EXAMPLE 141 45 A) Preparation of a Coating Liquid for Magnetic Recording The coating liquid prepared in Example 115 was applied on Layer woodfree paper with a surface pH of 3.2 in an amount of 5 A coating liquid for magnetic recording layer was prepared g/min terms of dry weight and dried, after which supercal by subjecting 100 parts by weight of barium ferrite (coercive endering was conducted to produce aheat-sensitive recording force: 2700), 25 parts by weight of sodium polyacrylate (a 20 material. 50 wt % aqueous solution), 100 parts by weight of a poly(vi The result of evaluating the color development sensitivity nylidene chloride) (a 49 wt % dispersion), 15 parts by weight of the heat-sensitive recording material obtained was so good of carbon black (a 36 wt % dispersion), 10 parts by weight of that the optical density was 1.3. The print preservability paraffin wax (a 20 wt % dispersion in methyl cellulose) and evaluated by the use of vinyl chloride wrap films was so good 100 parts by weight of water to dispersion in a ball mill for 10 that no fading occurred. The preservability or the original 55 hours. recording material Surface was so good that the Surface was B) Preparation of a Coating Liquid for Heat-sensitive Record hardly colored. The results are summarized in Table 7. ing Layer A coating liquid for heat-sensitive recording layer was EXAMPLES 142 AND 143 60 obtained in the same manner as in Example 56. Next, the coating liquid for magnetic recording layer pre Heat-sensitive recording materials were produced in the pared in A) was applied on one side of woodfree paper with a same manner as in Example 141 except for using woodfree basis weight of 150 g/m in an amount of 30 g/m in terms of paper with a surface pH of 5 (Example 142) or wood free dry weight to obtain a magnetic recording layer. Then, the paper with a surface pH of 6.8 (Example 143) in place of the 65 coating liquid for heat-sensitive recording layer prepared in woodfree paper with a surface pH of 3.2, and were evaluated. B) was applied on the other side of the substrate having the The results are summarized in Table 7. aforesaid magnetic recording layer, in an amount of 6 g/min US 7,635,662 B2 173 174 terms of dry weight and dried, after which Supercalendering was conducted to obtain a heat-sensitive magnetic recording TABLE 8 material. Plasticizer The result of evaluating the color development sensitivity resistance (print of the heat-sensitive magnetic recording material obtained Sensitivity of preserva- Total was so good that the optical density was 1.3. The print pre thermal paper bility) evaluation servability evaluated by the use of vinyl chloride wrap films Example 144 1.3 (6) (6) was so good that no fading occurred. The results are Summa Example 145 1.2 (3) (3) rized in Table 8. 10 Example 146 1.3 (3) (3) Comparative 1.3 X X Example 22 EXAMPLE 145 1. Sensitivity becomes higher with an increase of optical C) Preparation of a Coating Liquid for Protective Layer 15 density (OD value). Twenty parts by weight of zinc stearate, 20 parts by weight 2. Plasticizer resistance (print preservability) of a 5 wt % methyl cellulose aqueous solution and 60 parts by (3) --Substantially no fading. weight of water were mixed and Subjected to dispersion in a O-A slight color tone change without blur and the like. sand grinder for 2 hours. Then, 20 parts by weight of a 10 wt A-Marked fading. % carboxy-modified poly(vinyl alcohol) aqueous solution, X-Complete loss of the color of print. 1.5 parts by weight of silica, 6.5 parts by weight of a 12.5 wt EXAMPLE 1.47 % polyamidoepichlorohydrin aqueous solution and 15.0 parts by weight of water were mixed and then subjected to A) Preparation of a Coating Liquid for Heat-sensitive dispersion in a sand grinder for 2 hours. 25 Recording Layer Subsequently, 0.7 part by weight of the zinc stearate dis A coating liquid for heat-sensitive recording layer was persion obtained above, 45.0 parts by weight of the silica obtained in the same manner as in Example 56. dispersion obtained above and 11.3 parts by weight of water The coating liquid for heat-sensitive recording layer pre pared in A) was applied on the surface of woodfree paper with were mixed to prepare a coating liquid for protective layer. A 30 heat-sensitive magnetic recording material was produced in a basis weight of 150 g/m in an amount of 7 g/m in terms of the same manner as in Example 144 except for forming a dry weight and dried, and Supercalendering was conducted to protective layer by applying the aforesaid coating liquid for produce a sheet coated with a heat-sensitive recording layer. protective layer on the heat-sensitive recording layer of the B) Production of a Release Sheet heat-sensitive magnetic recording material of Example 144 in 35 A mold release agent consisting of oily dimethyl silicone an amount of 3 g/m in terms of dry weight, followed by was applied on base paper with a basis weight of 40 g/m in an amount of 1 g/m by the use of a gravure coater to form a drying, and was evaluated. The results are Summarized in release layer. Then, an adhesive layer component consisting Table 8. of 100 parts by weight of chlorinated rubber, 20 parts by 40 weight of ester gum and 120 parts by weight of dibutyl phtha EXAMPLE 1.46 late was applied on the release layer in an amount of 10 g/m. C) Production of a Label for Heat-sensitive Recording D) Preparation of a Coating Liquid for Intermediate Layer The uncoated surface of the sheet coated with a heat A coating liquid for intermediate layer was prepared which sensitive recording layer which had been produced in the was composed of 80 parts by weight (in terms of dry solids) 45 above item A) and the surface coated with an adhesive layer of of a 48% dispersion of polystyrene fine particles and 20 parts the release sheet produced in the above item B) were stuck together so that they might face each other, whereby a label by weight (in terms of dry solids) of a 40% styrene-acrylic for heat-sensitive recording was produced. ester copolymer emulsion. The result of evaluating the color development sensitivity A heat-sensitive magnetic recording material was pro 50 of the obtained label for heat-sensitive recording was so good duced in the same manner as in Example 145 except for that the optical density was 1.3. The print preservability forming an intermediate layer by applying the aforesaid coat evaluated by the use of vinyl chloride wrap films was so good ing liquid between the heat-sensitive recording layer and that no fading occurred. The results are summarized in Table Substrate of the heat-sensitive magnetic recording material of 9. Example 145 in an amount of 8 g/min terms of dry weight, 55 followed by drying, and was evaluated. The results are sum EXAMPLE 1.48 marized in Table 8. D) Preparation of a Coating Liquid for Back Coating Layer COMPARATIVE EXAMPLE 22 60 A coating liquid for back coating layer was prepared by mixing 100 parts by weight of a styrene-maleic acid copoly mer with 50 parts by weight of kaolin. A label for heat A heat-sensitive recording sheet was produced in the same sensitive recording was produced in the same manner as in manner as in Example 144 except for using 2.2-bis(4-hydrox Example 147 except for forming a back coating layer by yphenyl)propane in place of the urea-urethane compound 65 applying the aforesaid coating liquid on the side reverse to the used in Example 144, and was evaluated. The results are side coated with a heat-sensitive recording layer of the label summarized in Table 8. for heat-sensitive recording of Example 147 in an amount of US 7,635,662 B2 175 176 1 g/min terms of dry weight, followed by drying, and the 1. Sensitivity becomes higher with an increase of optical label was evaluated. The results are summarized in Table 9. density (OD value). 2. Plasticizer resistance (print preservability) EXAMPLE 149 (3) --Substantially no fading. O-A slight color tone change without blur and the like. E) Preparation of a Coating Liquid for Intermediate Layer A-Marked fading. A coating liquid for intermediate layer was prepared which X-Complete loss of the color of print. was composed of 80 parts by weight (in terms of dry solids) of a 48% dispersion of polystyrene fine particles and 20 parts EXAMPLE 1.51 by weight (in terms of dry solids) of a 40% styrene-acrylic 10 ester copolymer emulsion. The coating materials for heat-sensitive color-producing A label for heat-sensitive recording was produced in the layers and intermediate layers described below were applied same manner as in Example 148 except for forming an inter on one side of a commercial poly(ethylene terephthalate) film mediate layer by applying the aforesaid coating liquid 15 of 75um in thickness (Lumilar E, a trade name, Toray Indus between the heat-sensitive recording layer and substrate of tries, Inc.) so that the following multiple layers might be the label for heat-sensitive recording of Example 148 in an amount of 8 g/min terms of dry weight, followed by drying, formed on the substrate in the following order: a cyan color and the label was evaluated. The results are summarized in development heat-sensitive recording layer, an intermediate Table 9. layer, a magenta color development heat-sensitive recording layer, an intermediate layer, a yellow color development heat EXAMPLE 150 sensitive recording layer, and an intermediate layer. The application was carried out by bar coating so that the coating F) Preparation of a Coating Liquid for Protective Layer amounts of each heat-sensitive recording layer and each inter Twenty parts by weight of zinc stearate, 20 parts by weight 25 mediate layer after drying might be 6.5 g/m and 2.0 g/m. of a 5 wt % methyl cellulose aqueous solution and 60 parts by respectively, whereby a multi-color heat-sensitive recording weight of water were mixed and then subjected to dispersion material was obtained. in a sand grinder for 2 hours. Then, 20 parts by weight of a 10 Preparation of a Coating Material for Cyan Color Develop wt % carboxy-modified poly(vinyl alcohol) aqueous solu ment Heat-sensitive Recording Layer tion, 1.5 parts by weight of silica, 6.5 parts by weight of a 12.5 30 wt % polyamidoepichlorohydrin aqueous solution and 15.0 Liquid A (a Heat-sensitive Color Development Dye Disper parts by weight of water were mixed and then subjected to sion) dispersion in a sand grinder for 2 hours. Twenty parts by weight of 3,3-bis(p-dimethylaminophe Subsequently, 0.7 part by weight of the zinc stearate dis nyl)-6-dimethylaminophthalide, 20 parts by weight of a 10% persion obtained above, 45.0 parts by weight of the silica 35 poly(vinyl alcohol) aqueous solution and 10 parts by weight dispersion obtained above and 11.3 parts by weight of water of water were mixed and then subjected to dispersion and were mixed to prepare a coating liquid for protective layer. A grinding in a sand grinder (mfl. by AIMEX CO., LTD.) to label for heat-sensitive recording was produced in the same prepare a dispersion having an average particle size of 0.7 um. manner as in Example 149 except for forming a protective 40 Liquid B (a Developer Dispersion) layer by applying the aforesaid coating liquid on the heat A urea-urethane compound was synthesized in the same sensitive recording layer of the label for heat-sensitive record ing of Example 149 in an amount of 3 g/m in terms of dry manner as in Example 3, and a dispersion was prepared by weight, followed by drying, and the label was evaluated. The dispersing 30g of this compound by grinding it together with results are summarized in Table 9. 120 g of a 2.5 wt % poly(vinyl alcohol) aqueous solution in a 45 sand grinder for 3 hours. The temperature of the dispersion COMPARATIVE EXAMPLE 23 immediately after the dispersing operation was 25°C. The diameter of dispersed particles of the compound was 0.6 um. A heat-sensitive recording sheet was produced in the same A coating material for cyan color development heat-sensi manner as in Example 147 except for using 2.2-bis(4-hydrox 50 tive color-producing layer was prepared by mixing 30 parts yphenyl)propane in place of the urea-urethane compound by weight of the liquid A, 120 parts by weight of the liquid B, used in Example 147, and was evaluated. The results are 52 parts by weight of a 60% calcium carbonate slurry, 40 parts summarized in Table 9. by weight of a 10% poly(vinyl alcohol) aqueous solution, 28 parts by weight of a SBR latex (L-1537, a trade name, ASAHI TABLE 9 55 Chemical Industry, Co., Ltd.: solid content 50%), 11 parts by weight of stearamide (Celozol A-877, a trade name, mfcd. by Plasticizer resistance Chukyo Yushi Co., Ltd.; solid content 26.5%) and 82 parts by (print weight of water. Sensitivity of preserva- Total thermal paper bility) evaluation Preparation of a Coating Material for Magenta Color Devel 60 opment Heat-sensitive Recording Layer Example 147 1.3 O-(3) O-(9) Example 148 1.3 O-(3) O-(9) Liquid A (a Heat-sensitive Color Development Dye Disper Example 149 1.4 O-(3) (3) sion) Example 150 1.3 (6) (6) Comparative 1.3 X X Twenty parts by weight of 4-N-(2-(2,4-di-tertamylphe Example 23 65 noxy)butyryl)piperaZinobenzenediaZonium hexafluorophos phate, 20 parts by weight of a 10% poly(vinyl alcohol) aque ous solution and 10 parts by weight of water were mixed and US 7,635,662 B2 177 178 then Subjected to dispersion and grinding in a sand grinder to thane acrylate emulsion (EM90, a trade name, mfcd. by prepare a dispersion having an average particle size of 0.7 um. Arakawa Chemical Industries Ltd.: solid content 40%), 5 Liquid B (a Coupler Dispersion) parts by weight of a polysiloxane (SM7025, a trade name, Fifty parts by weight of 1-(2-octylphenyl)-3-methyl-5- mfd. by Dow Corning Toray Silicone Co., Ltd.: solid content pyrazolone, 50 parts by weight of 1,2,3-triphenylguanidine, 33%) and 40 parts by weight of water. 50 parts by weight of a 10% poly(vinyl alcohol) aqueous EXAMPLE 152 solution and 25 parts by weight of water were mixed and then Subjected to dispersion and grinding in a sand grinder to prepare a dispersion having an average particle size of 1.0Lum. An example of the production of a two-color heat-sensitive A coating material for magenta color development heat 10 recording material is described below. sensitive color-producing layer was prepared by mixing 30 (A) Dye precursor for high-temperature color-producing parts by weight of the liquid A, 90 parts by weight of the liquid layer: 3-(4-dibutylamino-2'-hydroxyphenyl)-3-(5'-anilino B, 52 parts by weight of a 60% calcium carbonate slurry, 40 4'-methyl-2'-methoxy-phenyl)phthalide. parts by weight of a 10% poly(vinyl alcohol) aqueous solu (B) Dye precursor for low-temperature color-producing tion, 28 parts by weight of a SBR latex (L-1537, a trade name, 15 layer: 3-diethylamino-7-chlorofluoran. ASAHI Chemical Industry, Co., Ltd.: solid content 50%), 11 (C) Developer: the urea-urethane compound synthesized parts by weight of stearamide (Celozol A-877, a trade name, in Example 151. mfd. by Chukyo Yushi Co., Ltd.: solid content 26.5%) and 82 (D) Sensitizer: diphenyl sulfone. parts by weight of water. Forty grams of each of the above-mentioned organic com pounds (A) to (D) was mixed with 40 g of a 10% poly(vinyl Preparation of a Coating Material for Yellow Color Develop alcohol) solution (degree of polymerization 500, and degree ment Heat-sensitive Recording Layer of saponification 90%) and 20 g of water, and each of the thus Liquid A (a Heat-sensitive Color Development Dye Disper obtained compositions was subjected to dispersion in a ver sion) tical sand mill (a sand grinder manufactured by AIMEXCO. Twenty parts by weight of 2,5-dibutoxy-4-tolylthioben 25 LTD.) so that the particle size might be 1 lum. From the ZenebenzenediaZonium hexafluorophosphate, 20 parts by dispersions thus obtained, liquids (A) to (D) corresponding to weight of a 10% poly(vinyl alcohol) aqueous solution and 10 the compound (A) to (D) were prepared. parts by weight of water were mixed and then subjected to On the other hand, 40 g of light calcium carbonate (Bril dispersion and grinding in a sand grinder to prepare a disper 30 liant 15, mfcd. by Siraishi Industry Co., Ltd.; average particle sion having an average particle size of 0.7 um. size 0.15um) and 60 g of a 0.7% sodium hexametaphosphate Liquid B (a Coupler Dispersion) solution were mixed, and the resulting composition was sub Fifty parts by weight of 2-chloro-5-(3-(2,4-di-tertpentyl) jected to dispersion in a Cowles dispersing machine. phenoxypropylamino)acetanilide, 50 parts by weight of 1.2, Separately, a 21% zinc Stearate dispersion was prepared as 3-triphenylguanidine, 50 parts by weight of a 10% poly(vinyl 35 a lubricant dispersion, liquid (F), and a 10% poly(vinyl alco alcohol) aqueous solution and 25 parts by weight of water hol (NM11, mfcd. by The Nippon Synthetic Chemical Indus were mixed and then Subjected to dispersion and grinding in try Co., Ltd.) was prepared as a adhesive solution, liquid (G). a sand grinder to prepare a dispersion having an average Preparation of a Coating Liquid (I) for High-temperature particle size of 1.0 Lum. Color Development Heat-sensitive Layer A coating material for yellow color development heat 40 A coating liquid for high-temperature color development sensitive color-producing layer was prepared by mixing 30 heat-sensitive layer was prepared by blending the above parts by weight of the liquid A, 90 parts by weight of the liquid mentioned liquids (A), (C), (D) and (G) so that their weight B, 52 parts by weight of a 60% calcium carbonate slurry, 40 ratio after drying might be as follows: (A):(C): (E):(G)=20: parts by weight of a 10% poly(vinyl alcohol) aqueous solu 40:25:15. tion, 28 parts by weight of a SBR latex (L-1537, a trade name, 45 ASAHI Chemical Industry, Co., Ltd.: solid content 50%), 11 Formation of a High-temperature Color Development Heat parts by weight of stearamide (Celozol A-877, a trade name, sensitive Layer mfd. by Chukyo Yushi Co., Ltd.: solid content 26.5%) and 82 A high-temperature color development heat-sensitive layer parts by weight of water. was formed by applying the aforesaid coating liquid (I) for 50 Preparation of a Coating Material (Solid Content: 15%) for high-temperature color development heat-sensitive layer on Intermediate Layer woodfree paper (neutral paper) with a basis weight of 60 g/m A coating material for intermediate layer was prepared by in an amount of 8 g/m (dry) by means of a Mayer bar. mixing 42 parts by weight of a 60% kaolinite clay (average Preparation of a Coating Liquid (II) for Low-temperature particle size: 0.6 um) dispersion, 200 parts by weight of a 55 Color Development Heat-sensitive Layer carboxylic acid-modified poly(vinyl alcohol) aqueous solu A coating liquid for low-temperature color development tion (Gosenol T-330, a trade name, mfcd. by The Nippon heat-sensitive layer was prepared by blending the above Synthetic Chemical Industry Co., Ltd.: solid content 40%), mentioned liquids (B), (C), (D), (E), (F) and (G) so that their 100 parts by weight of an acrylic emulsion (SC-2250, a trade weight ratio after drying might be as follows: (B):(C):(D): name, mfcd. by Nippon Shokubai Co., Ltd.: solid content 60 (E):(F):(G)=10:20:20:20:10:10. 40%), 33 parts by weight of a dimethylolurea solution (J-001, a trade name, mfcd. by Showa Denko K.K., solid content Production of a Two-color Heat-sensitive Recording Material 30%), 13 parts by weight of a 40% zinc stearate dispersion The coating liquid (II) for low-temperature color develop (Highmicron F-930, a trade name, mfcd. by Chukyo Yushi Co., ment heat-sensitive layer was applied on the above-men Ltd.; average particle size 0.9 um), 70 parts by weight of 65 tioned high-temperature color development heat-sensitive heavy calcium carbonate (NS-100, a trade name, mfcd. by layer in an amount of 5 g/m (dry). Then, the Bekk smooth Nitto Funka Kogyo Co., Ltd.), 25 parts by weight of a ure ness (JIS-P8119) of the heat-sensitive recording surface was US 7,635,662 B2 179 180 adjusted to 150 seconds by Smoothing treatment by means of A-Marked fading. a Supercalender, whereby a two-color heat-sensitive record X-Complete loss of the color of print. ing material was obtained. EXAMPLE 153 COMPARATIVE EXAMPLE 24 5 A multicolor heat-sensitive recording material was pro A urea-urethane compound was synthesized in the same duced in the same manner as in Example 151 except for using manner as in Example 3, and a dispersion was prepared by 2.2-bis(4-hydroxyphenyl)propane in place of the urea-ure dispersing 2 g of this compound by grinding it together with thane compound synthesized in Example 151, and was evalu 10 8 g of a 2.5 wt % poly(Vinyl alcohol) aqueous solution in a ated. The results are summarized in Table 10. paint shaker for 6 hours. The temperature of the dispersion immediately after the dispersing operation was 25°C. The COMPARATIVE EXAMPLE 25 diameter of dispersed particles of the compound was 0.6 um. Another dispersion was prepared by dispersing 70 g of A two-color heat-sensitive recording material was pro- 15 3-dibutylamino-6-methyl-7-anilinofluoran by grinding it duced in the same manner as in Example 152 except for using 2.2-bis(4-hydroxyphenyl)propane in place of the urea-ure together with 130g of a 5.4 wt % poly(vinyl alcohol) aqueous thane compound used in Example 152, and was evaluated. solution in a sand grinder (mfl. by AIMEXCO.,LTD., vessel The results are summarized in Table 10. capacity 400 ml) at a number of revolution of 2,000 rpm for 3 hours. Evaluation of the Multicolor Heat-sensitive Recording Mate- 20 rials A still another dispersion was prepared by dispersing 70 g The multicolor heat-sensitive recording materials obtained of diphenyl sulfone by grinding it together with 130g of a 5.4 in Examples 151 and 152 and Comparative Examples 21 and wt % poly(vinyl alcohol) aqueous Solution in a sand grinder 22 were Subjected to printing by the use of a commercial (mfl. by AIMEX CO.,LTD., vessel capacity 400 ml) at a thermal printer (NC-1, a trade name, mfcd. by Fuji Photo Film 25 number of revolution of 2,000 rpm for 3 hours. Co., Ltd.), and the quality of image and the image preserv Separately, 10 g of calcium carbonate was mixed with 30 g ability were evaluated by the following methods. of water and dispersed by stirring by the use of a stirrer to obtain a dispersion. For 5 sheets of each recording material, the definition, 30 On the other hand, an aluminum hydroxide dispersion was contrast, density nonuniformity of image, and the like were prepared by treating a mixture of 60 parts by weight of alu visually judged and they were evaluated in the 5 grades (O: minum hydroxide and 40 parts by weight of a 12.5 wt % good, O-A: Somewhat good, A. mediocre, A-X: somewhat poly(vinyl alcohol) aqueous Solution for 2 hours by the use of bad, X: bad) a sand grinder to disperse aluminum hydroxide so that the 35 average particle size might be about 1 um. Each recording material was held between vinyl chloride A coating liquid was obtained by stirring and mixing the wrap films or in a vinyl chloride file, and a load of 300 g/cm above-mentioned dispersions and other components in the was applied thereto from above. After standing at 40°C. for following proportions (dry basis); the dispersion of the 24 hours, the coloring density of the printed portion and the above-mentioned compound in terms of dry solids: 20 parts non-printed portion (the original recording material Surface) 40 by weight, the 3-dibutylamino-6-methyl-7-anilinofluoran was visually estimated. When there was only a slight decrease dispersion in terms of dry solids: 10 parts by weight, the in printing density, the image preservability was rated good. diphenyl sulfone dispersion in terms of dry solids: 25 parts by The results are as shown in Table 10. That is, the recording weight, the calcium carbonate dispersion in terms of dry materials of Examples 151 and 152 were good in quality of solids: 40 parts by weight, the aluminum hydroxide disper image and exhibited an excellent image preservability, while sion in terms of dry solids: 13 parts by weight, a Zinc Stearate the recording materials of Comparative Examples 21 and 22 dispersion (solid content: 16 wt %) in terms of dry solids: 20 were inferior to the recording materials of Examples 151 and parts by weight, and a 15 wt % polylvinyl alcohol) in terms of 152. dry solids: 15 parts by weight. Subsequently, this coating liquid for heat-sensitive record TABLE 10 50 ing layer was applied on aluminized paper at a rate of 50 Quality of Image Total m/min by the use of a gravure coater (200 mesh; plate depth image preservability evaluation 20LL). The paper thus treated was dried at 80°C. for 3 seconds Example 151 O (3) (3) to obtain a heat-sensitive recording layer of 2 L in thickness. Example 152 O (3) (3) 55 Then, a clear coating liquid consisting of an aqueous disper Comparative A A-X X sion of acrylic resin (composed mainly of methyl methacry Example 24 late units, 2-ethylhexyl acrylate units and styrene units, and Comparative X X X having a glass transition point of about 40°C.) was applied on Example 25 the coated surface of the paper to a thickness of 8L by the use 60 of a roll coater and dried at 80° C. for 10 seconds to obtain 1. Quality of image metallized paper for laser marking according to the present O-Good. invention. A-Mediocre. The metallized paper was irradiated with laser beams from X-Bad. a carbon dioxide laser. A clear mark could be obtained and the 2. Print preservability 65 color developability was good. A plasticizer resistance test (3) --Substantially no fading. was carried out by holding the metallized paper between vinyl O-A slight color tone change without blur and the like. chloride wrap films, to find that the plasticizer resistance was US 7,635,662 B2 181 182 So good that no fading took place in a printed portion. The position and a recording material which are excellent in results are summarized in Table 11. image preservability and color development sensitivity. EXAMPLE 154 What is claimed is: 5 1. A color-producing composition comprising a developer A urea-urethane compound was synthesized in the same and a colorless or light-colored dye precursor, manner as in Example 10, and a dispersion was prepared by wherein the colorless or light-colored dye precursor is a dispersing 2 g of this compound by grinding it together with leuco dye and develops color upon contact with said 8 g of a 2.5 wt % poly(Vinyl alcohol) aqueous solution in a developer, paint shaker for 6 hours. 10 wherein said developer is a urea-urethane composition Then, metallized paper for laser marking was produced in obtained by reacting a polyisocyanate compound with a the same manner as in Example 153 except for using the hydroxy compound and an amino compound, which is dispersion of the aforesaid compound in place of the disper characterized by comprising 50 wt % or more of a urea sion of the compound obtained in Example 153, and using urethane compound having at least one urea group and at diphenyl Sulfone in place of aluminum hydroxide, and was 15 evaluated. The results are summarized in Table 11. least one urethane group in a total number of 2 to 10 in the molecular structure and having a molecular weight COMPARATIVE EXAMPLE 26 of 5,000 or less, or wherein said developer is a urea-urethane composition Metallized paper for laser marking was produced in the obtained by reacting a polyisocyanate compound with a same manner as in Example 153 except for using 2.2-bis(4- phenol compound and an amino compound, which is hydroxyphenyl)propane in place of the urea-urethane com characterized by comprising 50 wt % or more of a urea pound synthesized in Example 153, and was evaluated. The urethane compound having at least one urea group and at results are summarized in Table 11. least one urethane group in a total number of 2 to 10 in 25 the molecular structure and having a molecular weight An article for laser marking was irradiated with laser of 5,000 or less, beams in a dose of 0.6 J/cm from a carbon dioxide laser or wherein said developer is a urea-urethane composition (Unimark, mfcd. by USHIOINC.) by using a stencil capable of obtained by reacting a polyisocyanate compound with permitting appearance of figures. When a clear mark was an alcohol compound and an amino compound, which is 30 characterized by comprising 50 wt % or more of a urea obtained and the coloring density was high, the color devel urethane compound having at least one urea group and at opment sensitivity was rated good. least one urethane group in a total number of 2 to 10 in the molecular structure and having a molecular weight Three vinyl chloride wrap films were placed on each of the of 5,000 or less. top and under Surfaces of the marked article for laser marking, 35 2. A color-producing composition comprising a developer and the resulting assembly was allowed to stand under a load and a colorless or light-colored dye precursor, wherein the of 300 kg/cm at 40°C. for 24 hours. After the standing, the colorless or light-colored dye precursor is a leuco dye and density of the printed portion was visually estimated. When develops color upon contact with said developer, there was only a slight decrease in printing density, the print wherein said developer is a urea-urethane compound rep preservability was rated good. 40 resented by the following formula (I):

TABLE 11 (I) O O Plasticizer resistance X-O-C-N-Yo-N-C-N-Z Marking (print preserva- Total 45 H H H sensitivity bility) evaluation wherein Yo is a group selected from the group consisting of Example 153 (6) (6) (6) tolylene group, Xylylene group, naphthylene group, hexam Example 154 O-(3) (3) (3) ethylene group and -(p-CH2-(p-group wherein -qp- is a phe Comparative O X X Example 26 50 nylene group; or said developer is aurea-urethane compound represented by the following formula (II): 1. Marking sensitivity (3-Good color developability. A clear mark can be (II) obtained. O-Somewhat insufficient color development without a 55 O O O problem about visibility. X-Low color developability and unclear print. 2. Plasticizer resistance (print preservability) or said developer is aurea-urethane compound represented (3)-substantially no fading. 60 by the following formula (III): O-A slight color tone change without blur and the like. X-Complete loss of the color of print. (III) INDUSTRIAL APPLICABILITY 65 Employment of a specific urea-urethane compound makes it possible to provide at a low price a color-producing com US 7,635,662 B2 183 184 wherein C. is a residue other than amino groups of an amine dipropylene glycol, 1,4-butanediol. 1.5-pentanediol, compound selected from the group consisting of 1,6-hexanediol. 1,6-hexane glycol, 1.9-nonanediol, 4,4'-diamino-3,3'-diethyldiphenylmethane, 4,4'-diami acryl polyols, fluorocarbon polyols, polybutadiene nobenzanilide, 3.5-diaminochlorobenzene, diamino polyols, polyhydroxy polyols, trimethylolpropane, tri diphenyl ether, 3,3'-dichloro-4,4-diaminodiphenyl methylolethane, hexanetriol, phosphoric acid, neopen methane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, tylglycol, pentaerythritol, methylpentanediol, ethylene 3,3'-dimethyl-4,4-diaminobiphenyl, dianisidine, bis4 diamine, C.-methylglucoside, Sorbitol, and Sucrose, (m-aminophenoxy)phenylsulfone, bis4-(p-aminophe and n is an integer of 2 or more depending on the Valence noxy)phenylsulfone, bis3-methyl-4-(p-aminophe number of B; noxy)phenylsulfone, 3,3'-dimethoxy-4,4'- 10 or said developer is aurea-urethane compound represented diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, by the following formula (VII): 2,2'-dichloro-4,4'-diamino-5,5-dimethoxybiphenyl, 2.2.5.5-tetrachloro-4,4'-diaminobiphenyl.o-tolidine Sulfone, 2,4'-diaminobiphenyl, 2,2'-diaminobiphenyl, (VII) 4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diaminobiphe 15 O O nyl, 3,3'-dichloro-4,4'diaminobiphenyl, 2,2'-dimethyl 4,4'-diaminobiphenyl, 4,4'-thiodianiline, 2,2'-dithiodi aniline, 4,4'-dithiodianiline, 4,4'-diaminodiphenylether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, wherein said X is anhydroxy compound bound through the 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenyl hydroxy group, wherein said hydroxy compound is at methane, bis(3-amino-4-chlorophenyl)sulfone, bis(3,4- least one selected from the group consisting of phenol, diaminophenyl)sulfone, 4,4'-diaminodiphenyl Sulfone, cresol, Xylenol, p-ethylphenol, o-isopropylphenol, 3,3'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl resorcinol, p-tert-butylphenol, p-tert-octylphenol, 2-cy Sulfone, 3,3'-diaminodiphenylmethane, 4,4'-diamino clohexylphenol, 2-allylphenol, 4-indanol, thymol, diphenylamine, 4,4'-ethylenedianiline, 4,4'-diamino-2, 25 2-naphthol, p-nitrophenol, o-chlorophenol, p-chlo 2'-dimethyldibenzyl, 3,3'-diaminobenzophenone, 4,4'- rophenol. 2.2-bis(4-hydroxyphenyl)-propane, 2.2-bis diaminobenzophenone, 1,4-bis(4-aminophenoxy) (hydroxyphenyl)butane, 2.2-bis(hydroxy-phenyl)pen benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3- tane, 2.2-bis(hydroxyphenyl)heptane, catechol, aminophenoxy)benzene, 9.9-bis(4-aminophenyl) 3-methylcatechol, 3-methoxycatechol, pyrogallol, hyd fluorene, 2.2-bis(4-aminophenoxy-phenyl)propane, 30 roquinone, methylhydroquinone, 4-phenylphenol, p.p'- 4,4'-bis(4-aminophenoxy)diphenyl, 3,3'-dichlorobenzi biphenol, 4-cumylphenol, butyl bis(4-hydroxyphenyl) dine, o-phenylenediamine, m-phenylenediamine, acetate, benzyl bis(4-hydroxyphenyl)acetate, bis(4- p-phenylenediamine, hydroxyphenyl)sulfone, bis(3-methyl-4- and n is an integer of 2 or more depending on the Valence hydroxyphenyl)sulfone, bis(3,5-dimethyl-4- number of C.; 35 hydroxyphenyl)sulfone, 4-hydroxyphenyl-4- or said developer is aurea-urethane compound represented methylphenyl sulfone, 3-chloro-4-hydroxyphenyl-4- by the following formula (IV): methylphenyl Sulfone, 3,4-dihydroxyphenyl-4- methylphenyl Sulfone, 4-isopropyloxyphenyl-4'- hydroxyphenyl sulfone, bis(2-allyl-4-hydroxyphenyl) (IV) 40 Sulfone, 4-hydroxyphenyl-4'-benzyloxyphenyl Sulfone, 4-isopropylphenyl-4-hydroxyphenyl Sulfone, 4hydroxy-4-isopropoxydiphenyl sulfone, bis(2-me thyl-3-tert-butyl-4-hydroxyphenyl)sulfide, 4,4'-dihy droxydiphenyl ether, 4,4'-thiodiphenol, 4,4'-dihydroxy 45 benzophenone, 2.2-bis(4-hydroxyphenyl) wherein B is a residue other than hydroxyl groups of a hexafluoropropane, 4,4'-dihydroxydiphenylmethane, hydroxy compound selected from the group consisting of 3,3'-dihydroxydiphenylamine, bis(4-hydroxy-3-meth 2.2-bis(4-hydroxyphenyl)propane, 2.2-bis(hydroxyphe ylphenyl)sulfide, bis(4-(2-hydroxy)phenyl)sulfone, nyl)butane, 2.2-bis(hydroxyphenyl)pentane, 2.2-bis 2,4-dihydroxybenzophenone, 2.2',4,4-tetrahydroxy (hydroxyphenyl)heptane, catechol, 3-methylcatechol, 50 benzophenone, phenyl salicylate, salicylanilide, methyl 3-methoxycatechol, pyrogallol, hydroquinone, methyl 4-hydroxybenzoate, benzyl 4-hydroxybenzoate, (4'- hydroquinone, p.p'-biphenol, butyl bis(4-hydroxyphe chlorobenzyl)4-hydroxybenzoate, ethyl 12-bis(4-hy nyl)acetate, benzyl bis(4-hydroxyphenyl)acetate, bis(4- droxybenzoate), penty1 1.5-bis(4-hydroxybenzoate), hydroxyphenyl)sulfone, bis(3-methyl-4- hexyl 1,6-bis(4-hydroxybenzoate), dimethyl 3-hydrox hydroxyphenyl)sulfone, bis(3,5-dimethyl-4- 55 yphthalate, Stearyl gallate, lauryl gallate, methylgallate, hydroxyphenyl)sulfone, 3,4-dihydroxyphenyl-4- 4-methoxyphenol, 4-(benzyloxy)phenol, 4-hydroxy methylphenyl sulfone, bis(2-allyl-4-hydroxyphenyl) benzaldehyde, 4-n-octyloxysalicylic acid, 4-n-butylox sulfone, bis(2-methyl-3-tert-butyl-4-hydroxyphenyl) ysalicylic acid, 4-n-pentyloxysalicylic acid, 3-n-dode sulfide, 4,4'-dihydroxydiphenylether, 4,4'-thiodiphenol, cyloxysalicylic acid, 3-n-octanoyloxysalicylicacid.4-in 4,4'-dihydroxybenzophenone, 2.2-bis(4-hydroxyphe 60 octyloxycarbonylaminosalicylicacid.-4-n-octanoyloxy nyl)hexafluoropropane, 4,4'-dihydroxyldiphenyl carbonylaminosalicylic acid, methanol, ethanol, methane, 3,3'-dihydroxydiphenylamine, bis(4-hydroxy propanol, butanol, pentanol, hexanol, heptanol, octanol, 3-methylphenyl)sulfide, polypropylene glycols, isopropanol, isobutanol, isoheptanol, 2-ethyl-1-hex polytetramethylene ether glycols, polyether ester poly anol. 1-decanol. 2-pentanol, 3-hexanol, tert-butanol, ols, polycarbonate polyols, polycaprolactone diols, phe 65 tert-amyl alcohol, methyl Cellosolve, butyl Cellosolve, nolic polyols, ethylene glycol, diethylene glycol, 1.3- methyl Carbitol, allyl alcohol, 2-methyl-2-propen-1-ol. propanediol. 1.2-propanediol, propylene glycol, benzyl alcohol, 4-pyridinemethanol, phenyl Cellosolve, US 7,635,662 B2 185 186 furfuryl alcohol, cyclohexanol, cyclohexylmethanol, p-aminobenzoate, dodecyl p-aminobenzoate, benzyl cyclopentanol, 2-chloroethanol. 1-chloro-3-hydrox p-aminobenzoate, o-aminobenzophenone, m-ammoac ypropane, glycerin, glycerol, polypropylene glycol, etophenone, p-aminoacetophenone, m-aminobenza polytetramethylene ether glycol, polyether ester polyol, mide, o-aminobenzamide, p-aminobenzamide, polycarbonate polyol, polycaprolactone diol, phenolic p-amino-N-methylbenzamide, 3-amino-4-methylben polyol, ethylene glycol, diethylene glycol, 1,3-pro Zamide, 3-amino-4-methoxybenzamide, 3-amino-4- panediol. 1.2-propanediol, propylene glycol, dipropy chlorobenzamide, p-(N-phenylcarbamoyl)aniline, lene glycol, 1,4-butanediol. 1.5-pentanediol, 1.6-hex p-N-(4-chlorophenyl)-carbamoylaniline, p-N-(4- anediol, 1.6-hexane glycol, 1.9-nonanediol, acryl aminophenyl)carbamoylaniline, 2-methoxy-5-(N-phe polyol, fluorocarbon polyol, polybutadiene polyol, 10 nylcarbamoyl)aniline, 2-methoxy-5-N-(2-methyl-3- polyhydroxy polyol, trimethylolpropane, trimethylole chlorophenyl)carbamoylaniline, 2-methoxy-5-N-(2'- thane, hexanetriol, phosphoric acid, neopentylglycol, chlorophenyl)carbamoyl-aniline, 5-acetylamino-2- pentaerythritol, methylpentanediol, C.-methylglucoside, methoxyaniline, 4-acetylaminoaniline, 4(N-methyl-N- Sorbitol, and Sucrose; acetylamino)aniline, 2,5-diethoxy-4-(N-benzoylamino) said Y is an isocyanato compound bound through the iso 15 aniline, 2,5-dimethoxy-4-(N-benzoylamino)aniline, cyanato group, wherein said isocyanate having at least 2-methoxy-4-(N-benzoylamino)-5-methylaniline, two isocyanate groups is at least one selected from the 4-sulfamoylaniline, 3-sulfamoylaniline, 2-(N-ethyl-N- group consisting of p-phenylene diisocyanate, 2.5- phenylaminosulfonyl)aniline, 4-dimethylaminosulfo dimethoxybenzene-1,4-diisocyanate, 2,4-toluene diiso nylaniline, 4-diethylaminosulfonylaniline, Sulfathiaz cyanate, 2,6-toluene diisocyanate, diphenylmethane ole, 4-aminodiphenyl sulfone, 2-chloro-5-N- diisocyanate, o-tolidine diisocyanate, diphenyl ether phenylsulfamoylaniline, 2-methoxy-5-N,N- diisocyanate, 1.5-naphthylene diisocyanate, dianisidine diethylsulfamoylaniline, 2,5-dimethoxy-4-N- diisocyanate, 9-ethylcarbazole-3,6-diisocyanate, 3,3'- phenysulfamoylaniline, 2-methoxy-5- dimethyl-4,4'-diphenylmethane diisocyanate, hexam benzylsulfonylaniline, 2-phenoxysulfonylaniline, 2-(2- ethylene diisocyanate, isophorone diisocyanate, triph 25 chlorophenoxy)Sulfonylaniline, 3-anilinosulfonyl-4- enylmethane triisocyanate, tris(4-phenylisocyanate) methylaniline, bis4-(m-aminophenoxy)phenyl thiophosphate, 4,4',4'-triisocyanato-2,5-dimethoxyt Sulfone, bis4-(p-aminophenoxy)phenylsulfone, bis3 riphenylamine, 4,4',4'-triisocyanatotriphenylamine, methyl-4-(p-aminophenoxy)phenylsulfone, 3,3'- m-xylylene diisocyanate, lysine diisocyanate, dimer dimethoxy-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'- acid diisocyanate, isopropylidene bis-4-cyclohexyliso 30 diaminobiphenyl, 2,2'-dichloro-4,4'-diamino-5,5'- cyanate, dicyclohexylmethane diisocyanate, methylcy dimethoxybiphenyl, 2,2'.5,5'-tetrachloro-4,4'- clohexane diisocyanate, N,N'-(4,4'-dimethyl-3,3'- diaminobiphenyl, o-tolidine sulfone, 2,4'- diphenyldiisocyanato)urethodione, 4,4',4'-trimethyl-3, diaminobiphenyl, 2,2'-diaminobiphenyl, 4,4'- 3',3'-triisocyanato-2,4,6-triphenylcyanurate, Water diaminobiphenyl, 2,2'-dichloro-4,4'-diaminobiphenyl, adduct of toluene diisocyanate, water adduct of diphe 35 3,3'-dichloro-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'- nylmethane diisocyanate, 1,3-bis(3-isocyanato-4-meth diaminobiphenyl, 4,4'-thiodianiline, 2,2'-dithiodi ylphenyl)urea, trimethyloipropane adduct of toluene aniline, 4,4'-dithiodianiline, 4,4'-diaminodiphenyl ether, diisocyanate, and an amine adduct of toluene diisocyan 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, ate; and 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenyl said Z is an amino compound bound through the amino 40 methane, bis(3-amino-4-chlorophenyl)sulfone, bis(3,4- group, wherein said amino compound is at least one diaminophenyl)sulfone, 4,4'-diaminodiphenyl Sulfone, Selected from the group consisting of aniline, o-tolui 3,3'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl dine, m-toluidine, p-toluidine, o-anisidine, p-anisidine, Sulfone, 3,3'-diaminodiphenylmethane, 4.4-diamino p-phenetidine, N,N-dimethylaniline, N,N-diethyla diphenylamine, 4,4'-ethylenedianiline, 4,4'-diamino-2, niline, N,N-dimethyl-p-phenylenediamine, N,N-di 45 2'-dimethyldibenzyl, 3,3'-diaminobenzophenone, 4,4'- ethyl-p-phenylene-diamine, 2,4-dimethoxyaniline, 2.5- diaminobenzophenone, 1,4-bis(4-aminophenoxy) dimethoxyaniline, 3,4-dimethoxyaniline, benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3- p-aminoacetanilide, p-aminobenzoic acid, o-aminophe aminophenoxy)benzene, 9.9-bis(4-aminophenyl) nol, m-aminophenol, p-aminophenol. 2.3-Xylidine, 2,4- fluorene, 2.2-bis(4-aminophenoxy-phenyl)propane, Xylidine, 3,4-Xylidine, 2,6-Xylidine, 4-aminobenzoni 50 4,4'-bis(4-aminophenoxy)diphenyl, 3.3',4,4-tetraami trile, anthranilic acid, p-cresidine, 2,5-dichloroaniline, nodiphenyl ether, 3.3',4,4-tetraaminodiphenyl sulfone, 2,6-dichloroaniline, 3,4-dichloroaniline, 3,5-dichloroa 3.3',4,4-tetraaminobenzophenone, 3-aminobenzoni niline, 2,4,5-trichloroaniline, C.-naphthylamine, ami trile, 4-phenoxyaniline, 3-phenoxyaniline, 4,4'-methyl noanthracene, o-ethylaniline, o-chloroaniline, m-chlo enebis-o-toluidine, 4,4'-(p-phenyleneisopropylidene)- roaniline, p-chloroaniline, N-methylaniline, 55 bis-(2,6-Xylidine), o-chloro-p-nitroaniline, o-nitro-p- N-ethylaniline, N-propylaniline, N-butylaniline, N.N- chloroaniline, 2,6-dichloro-4-nitroaniline, 5-chloro-2- diglycidylaniline, N,N-diglycidyl-o-toluidine, nitroaniline, 2-amino-4-chlorophenol, o-nitroaniline, acetoacetic acid anilide, trimethylphenyl-ammonium m-nitroaniline, p-nitroaniline, 2-methyl-4-nitroaniline, bromide, 4,4'-diamino-3,3'-diethyldiphenylmethane, m-nitro-p-toluidine, 2-amino-5-nitrobenzonitrile, 4,4'-diaminobenzanilide, 3,5-diaminochlorobenzene, 60 Metol. 2,4-diaminophenol, N-(B-hydroxyethyl)-o-ami diaminodiphenyl ether, 3,3'-dichloro-4,4'-diamino nophenol Sulfate, Sulfanilic acid, metanilic acid, diphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenyl 2-amino-5-methylbenzenesulfonic acid, 2-amino-5- methane, tolidine base, o-phenylenediamine, m-phe chloro-4-methylbenzenesulfoniz acid, 4-amino-2-chlo nylenediamine, p-phenylenediamine, 2-chloro-p- rotoluene-5-Sulfonic acid, p-fluoroaniline, o-fluoroa phenylenediamine, dianisidine, methyl 65 niline, 3-chloro-4-fluoroaniline, 2,4-difluoroaniline, p-aminobenzoate, ethyl p-aminobenzoate, n-propyl 2,3,4-trifluoroaniline, m-aminobenzotrifluoride, p-aminobenzoate, isopropyl p-aminobenzoate, butyl m-toluylenediamine, 2-aminothiophenol, 2-amino-3- US 7,635,662 B2 187 188 bromo-5-nitrobenzonitrile, diphenylamine, p-amino or said X independently represents a monovalent aliphatic diphenylamine, octylated diphenylamine, 2-methyl-4- compound residue selected from the group consisting of methoxydiphenylamine, N,N-diphenyl-p- R—, A-(OR)m-, an allyl group, a methallyl group, a cyclo phenylenediamine, dianisidine, 3,3'-dichlorobenzidine, hexyl group, and a benzyl group, wherein R- represents an 4,4'-diaminostilbene-2,2'-disulfonic acid, benzylethyla alkyl group having 1 to 10 carbon atoms, A- represents an niline, 1.8-naphthalenediarnine, Sodium naphthionate, alkyl group having 1 to 4 carbon atoms or a phenyl group, R Tobias acid, sodium 1-amino-8-naphthol-3,6-disul represents an ethylene group or a propylene group, and m is fonate, 7-amino-4-hydroxy-2-naphthalene Sulfonic an integer of 1 or 2, acid, 6-phenylamino-1-naphthol-3-sulfonic acid, 1,4- said Y independently represents a divalent aromatic com diaminoanthraquinone, 1,4-diamino-2,3-dichloroan 10 thraquinone, 3-amino-1,2,4-triazole, 2-aminopyridine, pound residue selected from the group consisting of -d-. 3-aminopyridine, 4-aminopyridine, C.-amino-e-capro -dd-e-dd- and a naphthylene group, lactam, acetoguanamne, 2,4-diamino-6-2'-methylimi wherein said -dd- represents a phenylene group and said dazolyl-(1)ethyl-S-triazine, 2,3-diaminopyridine, 2.5- phenylene group can independently have a Substituent diaminopyridine, 2,3,5-triaminopyridine, 1-amino-4- 15 Selected from the group consisting of an alkyl group methylpiperazine, 1-(2-aminoethyl)piperazine, bis having 1 to 4 carbon atoms and an alkoxy group having (aminopropyl)piperazine, N-(3-aminopropyl) 1 to 4 carbon atoms, morpholine, methylamine, ethylamine, dimethylamine, diethylamine, Stearylamine, allylamine, diallylamine, said -e- represents a single bond or a group selected from isopropylamine, diisopropylamine, 2-ethyihexylamine, the group consisting of a methylene group and a ure ethanolamine, 3-(2-ethylhexyloxy)propyiamine, thodione group, 3-ethoxypropylamine, diisobutylamine, 3-(diethy or said Y independently represents a divalent aliphatic com lamino)propylamine, di-2-ethylhexylamine, 3-(dibuty pound residue selected from the group consisting of a hex lamino)propylamine, t-butylamine, propylamine, amethylene group, a methylene biscyclohexyl group, an iso 3-(methylamino)propylamine, 3-(dimethylamino)pro 25 propylidene biscyclohexyl group, a methylcyclohexylene pylamine, 3-methoxypropylamine, methylhydrazine, group and a Xylylene group, 1-methylbutylamine, methanediamine, 1,4-diaminobu said C. represents a divalent aromatic compound residue tane, cyclohexanemethylamine, cyclohexylamine, selected from the group consisting of -dd- and -d-e-d-. 4-methylcyclohexylamine, 2-bromoethylamine, wherein said -dd- represents a phenylene group and said 2-methoxyethylamine, 2-ethoxymethylamine, 30 2-amino-1-propanol, 2-aminobutanol, 3-amino-1,2- phenylene group can independently have a Substituent propanediol. 1,3-diamino-2-hydroxypropane, 2-amino selected from the group consisting of an alkyl group ethanethiol, ethylenediamine, diethylenetriamine, and having 1 to 4 carbon atoms, an alkoxy group having 1 to hexamethylenediamine. 4 carbon atoms, and a chlor group, 3. A color-producing composition comprising a developer 35 said -e- represents a single bond or a group selected from and a colorless or light-colored dye precursor, the group consisting of —SO , —O— —(S)m-, —(CH)m-, -CO , —CONH and any one selected wherein the colorless or light-colored dye precursor is a from the group consisting of groups represented by the leuco dye and develops color upon contact with said developer, formulas (a): 40 wherein said developer is a urea-urethane compound rep resented by the formula (III): (a) (III) 45 CO

50 th wherein -o-O--O-o- said X independently represents a monovalent aromatic CH3 compound residue selected from the group consisting of d-, d-e-dd- and a naphthyl group, t t 76. wherein said db - represents a phenyl group, and -dd- repre 55 sents a phenylene group, and these phenyl and phe --O----O-o-CH3 CH3 N-4 nylenegroups can eachindependently have a substituent Selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, an allyl group, an alkoxy group having 1 to 4 carbon atoms, an alkoxycarbonyl 60 group having 1 to 4 carbon atoms, a cyclohexyl group, a hydroxyl group, a nitro group, and a chlor group, said-e- represents a single bond or a group selected from the group consisting of SO. , —O— —S—, —CH2—, - CO-, -CONH-, -CH(COOR) , and 65 —CRR , wherein R, R and Rs each represent an wherein m is an integer of 1 or 2. alkyl group having 1 to 4 carbon atoms, and said n is an integer of 2. US 7,635,662 B2 189 190 said leuco dye is represented by the formula (i): wherein said X independently represents a monovalent aromatic compound residue selected from the group consisting of do-, d-e-dd- and a naphthyl group, wherein said db - represents a phenyl group, and -dd- repre sents a phenylene group, and these phenyl and phe nylene groups can each independently have a substituent Selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, an allyl group, an alkoxy group having 1 to 4 carbon atoms, an alkoxycarbonyl group having 1 to 4 carbon atoms, a cyclohexyl group, a hydroxyl group, a nitro group, a carboxyl group, and a halogen atom, said -e- represents a single bond or a group selected from the group consisting of —SO , —O— —(S)m-, 15 —(CH-)m-, —CO—, —CONH —NH , —CH (COOR)— —C(CF)—, and —CRR , wherein wherein Y and Y each independently represent an alkyl R. R. and Reach represent an alkyl group having 1 to group having 1 to 8 carbon atoms or an alkoxyalkyl group 4 carbon atoms, and m is an integer of 1 or 2, having 1 to 8 carbonatoms;Y represents a hydrogenatom, an or said X independently represents a monovalent aliphatic alkyl group having 1 to 8 carbon atoms or an alkoxy group compound residue selected from the group consisting of R-. having 1 to 8 carbonatoms; and YsandYeachindependently A-(OR)m-, an allyl group, a methallyl group, a cyclohexyl represent a hydrogen atom, a halogen atom, an alkyl group group, and a benzyl group, wherein R- represents an alkyl having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 group having 1 to 10 carbon atoms, A- represents an alkyl carbon atoms. group having 1 to 4 carbon atoms or a phenyl group, 4. A color-producing composition according to claim 3, 25 R-represents an ethylene group or a propylene group, and m wherein said urea-urethane compound has a molecular is an integer of 1 or 2. weight of 5000 or less. said Y independently represents a divalent aromatic com 5. A color-producing composition comprising a developer pound residue selected from the group consisting of -d-. and a colorless or light-colored dye precursor, -dd-e-dd- and a naphthylene group, wherein the colorless or light-colored dye precursor is a 30 wherein said -dd- represents a phenylene group and said leuco dye and develops color upon contact with said phenylene group can independently have a substituent developer, Selected from the group consisting of an alkyl group wherein said developer is a urea-urethane compound rep having 1 to 4 carbon atoms and an alkoxy group having resented by any of the following formulas (I) to (VII): 1 to 4 carbon atoms,

(I) (II)

(V) O O 21D-O----O-- 21 2 O O 2D-O----O- 21 2

or aurea-urethane compound represented by the following said -e- represents a single bond or a group selected from formula (VII): the group consisting of a methylene group and a ure 60 thodione group, or said Y independently represents a divalent aliphatic com pound residue selected from the group consisting of a hex (VII) amethylene group, a methylene biscyclohexyl group, an iso propylidene biscyclohexyl group, a methylcyclohexylene 65 group and a Xylylene group, said Yo represents a divalent residue selected from the group consisting of a tolylene group, a xylylene group, a naphthyl US 7,635,662 B2 191 192 enegroup, a hexamethylene group, and -dd-CH2-dd- wherein —(CH-)m-, —CO —NH , —CH(COOR)—, -dd- represents a phenylene group or a tolylene group, —C(CF)—, and —CRR , wherein R, R and R said Zindependently represents a monovalent aromatic com each represent an alkyl group having 1 to 4 carbonatoms pound residue selected from the group consisting of do-, di-e- and m is an integer of 1 or 2. d- and a naphthyl group, 5 or said B represents a divalent aliphatic compound residue wherein said db - represents a phenyl group, and -dd- repre selected from the group consisting of -R- and -R-O-R- sents a phenylene group, and these phenyl and phe wherein -R- represents a divalent group of a chain Saturated nylenegroups can eachindependently have a substituent hydrocarbon having 1 to 10 carbonatoms and -R-represents Selected from the group consisting of an alkyl group an ethylene group or a propylene group, having 1 to 4 carbon atoms, an alkoxy group having 1 to 10 4 carbon atoms, an alkoxycarbonyl group having 1 to 4 said Y represents a single bond or a group selected from the carbon atoms, a hydroxyl group, a nitro group, a nitrile group consisting of—SO , —O— —(S)m-, -(CH)m-, group, a carbamoyl group, a Sulfamoyl group, a carboxyl —CO—, —CONH , and any one selected from the group group, an amino group, a Sulfo group and a halogen consisting of groups represented by the formulas (a): atom, 15 said -e- represents a single bond or a group selected from the group consisting of —SO , —O— —(S)m-, (a) —(CH2)m-, CO , CONH , and NH , wherein m is an integer of 1 or 2. said C. represents a divalent aromatic compound residue selected from the group consisting of -dd-and-d-e-d-. wherein said -dd- represents a phenylene group and said CO phenylene group can independently have a substituent CH Selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 25 4 carbon atoms, and a chlor group, CH3 said -e- represents a single bond or a group selected from the group consisting of —SO. , —O— —(S)m-, t t 76. —(CH-)m-, —CO , —CONH and any one selected from the group consisting of groups represented by the 30 --O---o-O-o-CH3 CH3 N-4 formulas (a):

35

O

CO 40 wherein m is an integer of 1 or 2. CH said 6 represents a single bond or a group selected from the group consisting of —SO —O— —(S)m-, -(CH2)m-, —CO— —NH , —CH(COOR)— —C(CF)—, and CH3 —CRR , wherein R. R. and Rs each represent an alkyl 45 group having 1 to 4 carbon atoms and m is an integer of 1 or t t 76. 2. --O---o-O-o-CH CH N-4 said

50

| 55 each independently represents a benzene ring which is optionally Substituted with at least one group selected from the group consisting of an alkyl group having 1 to 4 carbon wherein m is an integer of 1 or 2. atoms, an alkoxy group having 1 to 4 carbon atoms, a nitro said B represents a divalent aromatic compound residue group, a hydroxyl group, a carboxyl group, a nitrile group, a selected from the group consisting of -dd-and-d-e-d-. 60 wherein said -dd- represents a phenylene group and said carbamoyl group, a Sulfo group and a halogen atom, phenylene group can independently have a substituent and said n is an integer of 2. Selected from the group consisting of an alkyl group 6. A color-producing composition comprising a developer having 1 to 4 carbon atoms, an alkoxy group having 1 to and a colorless or light-colored dye precursor, 4 carbon atoms, and an allyl group, 65 wherein the colorless or light-colored dye precursor is a said -e- represents a single bond or a group selected from leuco dye and develops color upon contact with said the group consisting of —SO , —O— —(S)m-, developer,