United States Patent (19) (11) 3,947,471 Akamatsu Et Al

United States Patent (19) (11) 3,947,471 Akamatsu et al. (45) Mar. 30, 1976 54 BENZ (c) FLUORAN COMPOUNDS AND 56 References Cited RECORDING SHEET CONTAINING THEM UNITED STATES PATENTS Inventors: Takashi Akamatsu, Ashiya; Koichi 1,194,380 8/1916 Hagenbach......................... 260/335 Koga, Toyonaka; Mitsuru Kondo, 3,654,314 4/1972 Farber et al........................ 260/335 Kawanishi; Makoto Miyake, 3,669,711 6/1972 Kimura et al....................... 260/335 Nishinomiya; Hiroshi Twasaki, 3,691,203 9/1972 Koga et al........................... 260/335 Takatsuki; Masatoshi Matsuo, 3,849,164 l l 11974 Schwab et al....................... 260/335 Ibaragi; Seiji Hotta, Hirakata; Isao FOREIGN PATENTS OR APPLICATIONS Yuji, Takarazuka, Yukiaki to, 2,024,859 1/1970 Germany Minoo, all of Japan 73 Assignees: Sumitomo Chemical Company, Ltd., Primary Examiner-Norma S. Milestone Osaka; Kanzaki Paper Attorney, Agent, or Firm-Stevens, Davis, Miller & Manufacturing Co., Ltd., Tokyo, Mosher both of Japan (57) ABSTRACT 22 Filed: May 20, 1974 Novel benzcifluoran compounds such as 2 phenylamino-8-diethylamino-benzcifluoran, 2 21) Appl. No.: 471,698 (2',4',6'-trimethylphenylamino)-8-diethylamino Related U.S. Application Data benzcifluoran and N-8-diethylaminobenzcifluoran 63 Continuation of Ser. No. 188,541, Oct. 12, 1971, 2-yl)-N-6-diethylaminofluoran-2-yl)amine, which are abandoned. useful as a coloring material for record material sys tems such as pressure-sensitive copying paper or heat 30 Foreign Application Priority Data sensitive copying paper, wherein colored images Dec. 26, 1970 Japan.............................. 46-130387 formed by an electron-donoracceptor color-forming Dec. 26, 1970 Japan.............................. 46-30392 reaction between coloring material and acidic material. 52) U.S. Cl................................. 260/.335; 282/27.5 51 int. C.’........................................ C07D 311/84 58 Field of Search..................................... 260/335 9 Claims, No Drawings 3,947,471 2 (wherein R5 stands for hydrogen atom, a lower alkyl, a BENZ (C) FLUORAN COMPOUNDS AND lower acyl, a lower haloalkyl, a lower alkoxy, nitro, a RECORDING SHEET CONTAINING THEM halogen, a lower alkoxycarbonyl, a lower alkanesulfo nyl, benzenesulfonyl, toluenesulfonyl, a haloben This is a continuation of application Ser. No. 188,544 5 zenesulfonyl or methoxybenzenesulfonyl;Rs represents filed Oct. 12, 1971, and now abandoned. hydrogen, a lower alkyl, a lower alkoxy, a halogen, This invention relates to a chromogenic compounds nitro, amino, or an amino group substituted by at least for use in recording sheet which develops color images one lower alkyl group; n is an integer of 1 to 7; R, by an electro donor-acceptor color-forming reaction stands for hydrogen, a lower alkyl, a lower haloalkyl, between chromogenic material and acidic material 10 phenyl, a halophenyl, tolyl, methoxyphenyl or nitro which react upon contact to produce a color. phenyl; Rs represents hydrogen, a lower alkyl, a lower More particularly, the present invention relates to alkenyl, a lower alkynyl, a lower haloalkyl or a lower novel benzcifluorans represented by the following alkoxyalkyl; Rs represents hydrogen, a lower alkyl, a general formulas (I), which have never been disclosed lower alkoxy, a halogen or nitro; Rio stands for hydro in prior art references, methods for the preparation 15 gen, a lower alkyl, benzyl or phenyl; Y signifies hydro thereof and recording sheet containing the same as gen, a lower alkyl, a lower alkoxy, a halogen, nitro, chromogenic materials. amino or an amino substituted by at least one lower alkyl group; Z is hydrogen, a lower alkyl, a halogen, a 20 lower alkoxy, nitro, amino, an amino substituted by at least one lower alkyl group or a group of (I) - N = CH -- B wherein B represents hydrogen, a lower alkyl, phenyl unsubstituted or substituted by a lower alkyl, a lower 25 alkoxy, a halogen or nitro; m is an integer of 1 to 4; and R signifies a group of wherein R and Reach signify hydrogen, a lower alkyl, a lower alkoxyalkyl, a lower haloalkyl, benzyl, or a 30 benzyl substituted by a lower alkoxy, a lower alkyl, a halogen or nitro; Ra signifyies hydrogen, a lower alkyl, a lower alkoxyalkyl, a lower hydroxyalkyl, a lower haloalkyl, a lower cyanoalkyl, carbamoyl, a lower alke nyl, a lower alkynyl or a group of 35 -la-Gas -"2"-G- G-(Rs) 40 o -Ge (t). -SC-(Rs) -CH - CH = CH2- R7 , wherein R, R and m are as defined above, and Y, signifies hydrogen, a lower alkyl, a lower alkoxy, a (CH2CE CH3 R7 -COR8 , SO2Re halogen, nitro, amino or an amino substituted by at 50 least one lower alkyl group, and A signifies benzene or naphthalene nucleus. " " . , ', Throughout the present specification, the term -CO-Q g “lower" as is seen in "lower alkyl group' indicates that the number of carbon atoms is 1 to 4. 55 In the present specification, the present benz(c)-fluo rans are named and the position substituted in the benzcifluoran nucleus are numbered as follows: 60 or -CH2COORO 3,947,471 3 4. 2-(N-methyl-3'-methyl-5'-chloro-anilino)-8-dime 1. These fluoran compounds represented by the gen thylamino-benzc) fluoran eral formula (I) are colorless and stable in air at ordi So far oil carbon paper was used for making out nary temperature, but, the compounds (I) change in documents and slips as office work materials. It has color from white to red, blue, green or black when they drawbacks that it is liable to stain clothes and hands are brought into contact with an acidic electron-accep and it is troublesome to insert the oil carbon paper tor explained in detail above. between documents and slips. W 2. These fluoran compounds (I) show all sorts of dark In order to eliminate the inefficiencies and defects of colors, for example, deep red, dark green, dark blue the oil carbon paper, pressure-sensitive copying paper green, dark greenish black, or black according to the or noncarbon paper, which is economic and handy, has O number, kind and position of substituents. recently made its debut in place of the oil carbon paper These various colors are due to the same benz complying with demand for speed-up of office works. cifluoran nucleus except the kind, number and posi Heretofore, leucoauramines, leucomethyleneblues, tion of substituents. The present benzc fluoran com phthalides and fluorans are well known as color precur pounds have almost the same color developing speed sors. They are colorless or nearly colorless compounds, 15 and the pressure-sensitive copying paper obtained by which may change to a certain coloring matter when mixing the present benzcifluoran compounds shows they are brought into contact with acidic electron no lag of the color developing time and changes the acceptor as explained below. color of the image. For example, 2-methyl-6-diethylamino-fluoran hav It is also possible to use the said compounds together ing the following formula (II) is one of the well-known with other color precursors such as C.V.L. (crystal color precursors which are colorless compounds under violet lactone), B.L.M.B. (benzoyl leucomethylene ordinary condition but change to red coloring matters . blue) or 2-methyl-6-diethylaminofluoran, etc. to obtain by opening their lactone ring when they are brought a special color such as blue-black or black image on the into contact with acidic electron-acceptor. paper without spoiling the other color precursers. 25 These are significant features of the present invention. 3. These benzcifluoran compounds are well soluble under colorless condition in a non-volatile non-polar (II) solvent used for preparing a recording sheet. Examples 30 of the non-polar solvent are as follows: - - - Chlorinated benzenes such as trichlorobenzenes and tetrachlorobenzenes; chlorinated biphenyls such as The pressure-sensitive copying paper is usually pre dichlorodiphenyls, trichlorodiphenyls, and tetra pared by coating a back side of one sheet of paper with chlorodiphenyls; alkylated benzenes; alkylated naph a color precursor such as a leucoauramine or a fluoran, 35 thalenes such as dimethylnaphthalene and dipropyl and coating a surface of another sheet of paper with an naphthalene; mineral oil; paraffin oil; olive oil; and acidic electron-acceptor such as kaolin, bentonite, tricresyl phosphate, etc. activated clay, acid clay, aluminum silicate, attapulgite, Such good solubility in the above solvents is probably metal oxides, metal chlorides, metal sulfates, organic caused by the naphthalene ring in the benz-clfluoran acids such as phenols, aliphatic acids or tannic acid, or 40 nucleus represented by the general formula (I). Good phenolic resins such as p-phenylphenol-formaldehyde solubility particularly in the aromatic solvents makes it resin, p-cyclohexylphenol-formaldehyde resin, etc. The easy to prepare the recording sheet and to obtain a pressure-sensitive copying paper is used by placing the deep image on the paper. coated papers upon one another so that the back side 4. The present fluoran compounds have no solubility of the first paper may be faced to the surface of the 45 and good stability in water, acids or alkalis. For exam second paper, and the back side of the second paper to ple, 2-(2',4'-dimethylphenylamino)-8-die the surface of the third paper and so on. By applying thylaminobenzcifluoran can be boiled with an alkali pressure or impact to the papers by means of a pencil, solution without being destroyed. a ball-point pen or a typewriter on the first paper, the 5. The present benzcifluoran compounds have good material on the back side and the electron-acceptor fastness to light, moisture and sublimation. substances on the surface of the papers are brought The obtained deep image on this recording sheet into contact with each other, whereby the colorless does not disappear or change in color by moisture or pressure-sensitive material moves to the electron droplets of water, or by exposure to sun-light or by acceptor layer and undergoes color development and heating.

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