3,458,517 United States Patent Office Patiented July 29, 1969 2 It is the primary object of this invention to provide a 3,458,517 V - phthalocyanine pigment which is truly non-focculating PYRIDYLENE ANDSUBSTITUTED PHENYL and non-crystallizing. The term "non-focculating' means ENE DERVATIVES OF PHTHALOCYANNE PGMENTS a pigment, which, on testing by the procedure in Exam James D. Stepp, Holland, Mich., assignor, by mesne as 5 ple II, will produce a coating that shows no difference signments to Chemetron Corporation, Chicago, Ill., a between the sprayed and poured portion of the test panel, corporation of Delaware while the term “non-crystallizing' means coloring matter No Drawing. Filed Feb. 18, 1966, Ser. No. 528,656 which will not crystallize from a 2% dispersion in xylene Int, C. C09 47/06 maintained at 70° C. for 24 hours, a crystallization test U.S. C, 260-270 8 Claims employed in the pigment art. IO It is an additional object to provide non-focculating phthalocyanine pigments without change in shade to the ABSTRACT OF THE DISCLOSURE green side. Another object is to provide a method of Phthalocyanine pigments having resistance to floccula manufacture for a non-crystallizing, non-flocculating tion and crystallization are provided by introducing at 5 phthalocyanine pigments. Phthalocyanines such as copper are manufactured com least one pyridine and one halo, sulfo or chlorosulfo Sub mercially be reacting urea, phthalic anhydride, a copper stituted phenylene or a substituted or unsubstituted sul Salt, and a molybdic catalyst at temperatures of about fonamido phenylene into a porphyrazine structure. 200° C. This yields a "crude” which usually is then given 20 a preliminary extraction with water or dilute acid to This invention relates to novel phthalocyanine colors give a “base.' of improved stability. More particularly, this invention The base, fairly pure copper phthalocyanine, must be relates to metal phthalocyanine compositions and com conditioned to pigmentary form which can be used in pounds which are non-flocculating and non-crystallizing decorative coatings. Various means of conditioning have in paint and other solvent systems. 25 been employed, namely, acid pasting or solution in sul Metal phthalocyanines, and especially copper, are furic acid, followed by dilution with water and isolation known to be exceptionally stable both chemically and of the insoluble pigment; salt grinding, in which the base physically. However, copper phthalocyanine has varying is Subjected to intense grinding action with hard inorganic crystal forms, two of which are used commercially. These Salts; Solvent treatments, which disperse the phthalocy 30 anine in organic solvents, followed by solvent removal. have been designated alpha, the unstable form and beta, It has been discovered that when a quinolinic group the stable configuration. The alpha form is characterized of the formula as a "red shade” pigment, the absorbance in the green NS region is more pronounced. The absorbance in the beta N C= or “green shade' has shifted to the red region. These forms can be changed from one to the other at will by 35 various chemical and physical treatments as illustrated -- by the following diagram: is fused into a tetraazoporphine group to form a benzaza phthalocyanine and combined with a substituted or an Beta Dissolved in Sulfuric Acid Alpha, 40 unsubstituted metal phthalocyanine, a phthalocyanine Heat Dilute with Water Contact pigment composition results which is non-flocculating and 225. organic 250 C. Solvents non-crystallizing. The quinolinic group can be present in Alpha Ball Mill Dry Inorganic Beta an independent tetraazoporphine structure or in the same tetraaZOporphine molecule comprising the substituted Sats phthalocyanine. Mixtures of benzaza phthalocyanine, 45 Substituted phthalocyanine, unsubstituted phthalocyanine Both crystalline forms are desirable as pigments, thus as Well as benzaza phthalocyanine further containing sub giving a range of shade. In commercial use, however, it stituents are employed wherein the substituted phthalic is necessary to maintain the initial crystal form. Various to quinolinic group mole ratio is in the range of about methods of treating the alpha form to stabilize it have 1.5-2.0 to 1. Correspondingly, the unsubstituted phthalic been tried. The addition of chlorine to the molecule and 50 to quinolinic mole ratio is in the range of about 5.30 to 1. the addition of phthalocyanine mono sulfonic acid, as in When the quinolinic group is fused into a tetraaZopor U.S. 3,024,247 leave nothing to be desired in crystal phine group to form an otherwise unsubstituted phthal stability. ocyanine and this benzaza phthalocyanine is combined The addition of phthalimidomethyl groups, diluting the With a molecularly independent substituted or unsubsti pigment with aluminum benzoates and blending with 55 tuted phthalocyanine the quinolinic containing phthal phthalocyanine Sulfonic acids are the subject of other ocyanine should be in a mole percentage range of about patents such as U.S. 3,024,247. All these treatments while 5-40 while the substituted or unsubstituted phthalocy generally successful in maintaining crystal stability, shift anine will be in a range of about 95-60 mole percent. the shade of the pigment much greener with the exception Where the quinonlinic group is present in the same of the benzoate treatment, which is costly and adds ex 60 traneous substance to the formulation. tetraazoporphine structure with a substituted phthalic Another problem in formulation of paints with copper group new compositions of matter are involved corre phthalocyanine is the phenomenon of flocculation. Floc sponding to the formula: culation is described as loose electrostatic binding of pig (I) ment particles in the vehicle. This occurs quickly after N-6"R-N the dispersion of the pigment and causes a progressive 65 loss in color value. Flocculation can be broken up by NY mechanical action such as that applied by spraying. How K N -/ r ever, lower degrees of work Such as brushing the paint, \-c/ Nc fail to defocculate the pigment. Again, the methods de 70 scribed above are used to prevent flocculation, and have -6 Y the same drawbacks. N-R-/ 3,458,517 3 4 where R, R, R'' and R' independently represent pyri pigment is boiled with a 10% sulfuric acid solution for dylene, phenylene, substituted phenylene such as halo two hours. The acid slurry is filtered, by vacuum on a substituted phenylene, sulfo substituted phenylene, chloro Buchner funnel, the insoluble cake washed with water sulfo Substituted phenylene, aliphatic and aromatic sub to remove the acid, and dried. stituted and unsubstituted sulfonamido substituted phen Sixteen parts of the resulting product and 34 parts of ylene, X is a complex forming metal such as copper, 5 monochloro copper phthalocyanine are added to 220 nickel and zinc, where at least one of R, R', R'' and parts of 97% sulfuric acid solution. The resulting solu R' is pyridylene and at least one of the remaining R, tion is stirred and heated at 75 C. for 4 hours and then R", R'' and R' is substituted phenylene as aforesaid placed into 2000 parts of cold water. The pigment is iso and in all instances only one sulfo or chlorosulfo sub 10 lated by filtering the slurry and washing with water to stituted phenylene is present. The aliphatic and aromatic remove the residual acid and salts. substituted sulfonamido derivatives which can be em Example II ployed are the mono and dilower alkyl sulfonamido such as mono and dimethyl, ethyl, propyl, isopropyl and butyl The pigment of Example I is dried, incorporated into and combinations thereof. The aromatic substituted de 15 a standard paint formulation and tested for flocculation rivatives are represented by phenyl, tolyl, xylyl, and ben by the following method. Two and one-half parts of the Zyl. Combinations of the aliphatic and aromatic sub pigment, 25 parts anatase titanium dioxide and 50 parts stituted sulfonamido derivatives can also be employed. of blown castor oil, are ground six passes on a three The novel compositions of the present invention can roll mill. Thirty-five parts of the color base so produced, be produced by including a minor percentage of quino 20 175 parts of clear nitrocellulose lacquer, and 25 parts linic compound with a substituted and an unsubstituted of lacquer thinner are mixed thoroughly to produce the phthalic compound in the initial reaction which includes test lacquer. A tin coated steel panel is sprayed with two urea, a complexing metal salt such as copper, Zinc or double coats of the lacquer and allowed to air dry. The nickel chloride and ammonium molybdate oxide cata remaining lacquer is allowed to stand 30 minutes and yist. It will be recognized that any quinolinic and sub 25 hand mixed to uniformity and then poured over a por stituted phthalic compound which will form the indi tion of the dry sprayed panel. The panel is air dried for cated tetraazoporphine structure under the previously in ten minutes and then forced dried at 85°C. for twenty dicated conditions are operable such as quinolinic acid minutes. The strength of the sprayed coating is com and substituted and unsubstituted phthalic acids as well pared spectrophotometrically with the poured coating. as the anhydrides, imides, amides, diamides and esters 30 The strengths of the two portions are identical. When thereof. The substituted phthalic compounds will corre the same test is performed using 50 parts of monochloro spond to the substituents indicated in conjunction with phthalocyanine and none of the product of Example I, the phenylene substituents described in the general For the poured portion of the panel has considerably less mula I, the non-nuclear carbon atoms of which form color value. a part of the tetraazoporphine structure. Similarly, the Example III unsubstituted phthalic compounds will form the unsub Following the procedure outlined in Example I, 195 stituted phenylene moiety and likewise the quinolinic parts of phthalic anhydride, 43 parts of 4-chlorophthalic compound will form a pyridylene moiety. anhydride, 21 parts of quinolinic acid, 400 parts of urea, A preferred manner of synthesizing the compositions 43 parts of copper chloride and 1 part of molybdic oxide of the present invention is to react quinolinic acid or 40 are charged into 100 parts of trichlorobenzene and heated quinolinic anhydride with phthalic anhydride in a minor to 200 C. for three hours. The crude pigment is iso molar amount which is about 0.04 to about 0.20 and lated by filtering off the trichlorobenzene followed by substantially less than stoichiometric so as to result in washing with isopropyl alcohol and dilute sulfuric acid a mixture of compounds wherein the usual phthalocya at 70° C. A mixture of copper phthalocyanine com nine is produced completely composed of phthalic groups 45 pounds results having the following structure: while a minor amount of the mixture will be composed of quinolinic or benzaza substituted phthalocyanines as Cl well as phthalocyanines containing substituted phthalic groups. The quinolinic and the substituted phthalic groups will be present in the mixture in the same tetraazopor 50 phine structure as well as joined to separate phthalo N=e 9=N cyanine molecules. The novel phthalocyanines indicated in the foregoing general formula I will be present in this N-Cu-NY -- mixture. g/ Yg An alternative to synthesizing the compositions in a N mixture is to first form a copper phthalocyanine con taining two phthalic acid groups and two quinolinic acid |- - groups by mixing equimolecular portions of phthalic an hydride and quinolinic acid with urea, copper chloride and ammonium molybdate. The resulting product is then 60 and formula admixed with a substituted or unsubstituted phthalo (C6H4)3.14 av. (C6H3Cl)0.55ay. (CNH3)0.31 ava (CN)6Cu cyanine preferably in an acid solution. A range of values is: The following examples are presented to disclose the Moles invention more fully. It should be understood, however, Phthalic acid residue groups ------3.00-3.28 that the examples are not intended to limit the invention Quinolinic acid residue group ------0.36-0.26 in any way. All parts indicated in the examples are by Chlorophthalic residue group ------0.64-0.46 weight. The product of this example when treated with sul Example I furic acid and acid pasted pursuant to Example I and A mixture comprising 21.2 parts of quinolinic acid, 70 Subsequently mixed into a paint formulation as described 56.2 parts of phthalic anhydride, 120 parts of urea, 12 in Example II results in a composition having comparable parts of copper chloride, and 0.3 part of ammonium flocculation resistant properties. molybdate is heated in an electrically heated oven at 160 The following example indicates a method for prepar 170° C. for two hours. After the reaction is completed ing the novel 4-chloro-phthalo monobenzaza copper it is cooled to the temperature of about 30° C., the crude 75 phthalocyanine alone. 3,458,517 5 6 Example IV Example I. A mixture of compounds is recovered having Following the procedure outlined in Example I, 184 the following formula:
parts of phthalic anhydride, 91.25 parts of 4-chloro SOE phthalic anhydride, 74.5 parts of quinolinic anhydride, 485 parts of urea, 52.25 parts or cuprous chloride, 1.2 parts of molybdic oxide and 1210 parts of trichloroben zene are heated at 200° C. for three hours. The crude NEC N pigment is isolated by filtering and washing with isopro panol. The resulting solid is boiled in dilute sulfuric acid s Y -- O N-Cu-N for one hour, filtered on a Buchner funnel, washed free Cl C/ of acid and dissolved salts and dried at 70° C. The de Yg NN sired 4-chloro-phthalo monobenzaza copper phthalo cyanine is obtained. N-6 - Example V Following the procedure outlined in Example I, 195 5 parts of phthalic anhydride, 57.5 parts of 4-sulfophthalic and formula acid, 21 parts of quinolinic acid, 400 parts of urea, 43 parts of cuprous chloride and one part of molybdic oxide are charged into 1000 parts of trichlorobenzene and heat 20 Moles ed to 200° C. for three hours. The crude pigment is iso Phthalic acid residue groups ------3.00.3.60 lated by filtering on a Buchner funnel followed by wash 4-sulfo phthalic acid residue group ------0.29-0.12 ing the solids cake with isopropanol. A mixture of com Chlorophthalic acid residue group ------0.35-0.14 pounds result having the following formula: Quinolinic acid residue group ------0.36-0.14 25 The product of this example when treated pursuant to Example I and mixed into a standard paint formulation SOH as outlined in Example II results in a composition hav ing comparable focculating resistant qualities. The following example indicates a method for prepar 30 ing the novel 4-chloro-phthalo-4-sulfo-phthalo mono benzaza copper phthalocyanine alone. Example VIII Following the procedure outlined in Example I, 74 35 parts of phthalic anhydride, 74.5 parts of quinolinic an hydride, 98.0 parts of 4-sulfo-phthalic anhydride, 91.25 parts of 4-chlorophthalic anhydride, 485 parts of urea, 52.25 parts of cuprous chloride, 1.2 parts of molybdic oxide and 1210 parts of trichlorobenzene were heated 40 to 200 C. The desired product 4-chlorophthalo-4-sulfo phthalo monobenzaza copper phthalocyanine is isolated, and formula purified and treated as indicated in Example I. (C6H4)3.14 av. (C6H3SO3H)0.55ay. (C5NH3)0.31ay.(CN)6Cu Example IX A range of values is: 45 As outlined in Example I, 195 parts of phthalic an Phthalic acid residue groups ------3.00-3.50 hydride, 57.4 parts of 4-sulfonamidophthalic acid, 21 4-sulfo phthalic acid residue group ------0.64-0.32 parts of quinolinic acid, 400 parts of urea, 43 parts of Quinolinic acid residue group ------0.36-0.18 cuprous chloride and one part of molybdic oxide are add ed to 1000 parts of trichlorobenzene and heated to 200 After a dilute sulfuric acid treatment at 70° C. the C. for three hours. A mixture of copper phthalocyanine product is washed freely of acid and then dried. The 50 product is acid pasted by the method of Example I and compounds results having the following formula struc results in a product having comparable flocculation resist ture: ant properties. The following example indicates a method for prepar so.NH, ing the novel 4-sulfo-phthalo monobenzaza copper 55 phthalocyanine alone. Example VI N=. e Following the procedure outlined in Example I, 148 Y parts of phthalic anhydride, 98 parts of 4-sulfo-phthalic 60 N-- anhydride, 74.5 parts of quinolinic anhydride, 485 parts C4 NC of urea, 52.25 parts of cuprous chloride, 1.2 parts of molybdic oxide, 1210 parts of trichlorobenzene are heat ed to 200° C. for three hours. The isolation and purifica tion of the desired product is the same as indicated in 65 Example I and the desired 4-sulfo-phthalo monoben Zaza copper phthalocyanine is obtained. and formula Example VII Following the procedure outlined in Example I, 195 70 parts of phthalic anhydride, 25.8 parts of 4-sulfophthalic A range of values is: acid, 23.7 parts of 4-chlorophthalic anhydride, 21 parts Moles of quinolinic acid, 400 parts of urea, 43 parts of copper Phthalic acid residue groups ------3.00-3.50 chloride and one part of molybdic oxide are charged into 4-sulfonamide phthalic acid residue group -...- 0.64–0.32 1000 parts of trichlorobenzene and treated as outlined in 75 Quinolinic acid residue group ------0.36-0.18 3,458,517 7 8 The product ofthis example is isolated, acid pasted and of halo substituted phenylene, sulfo substituted phenyl mixed into a paint formulation as described in Examples ene, chlorosulfo substituted phenylene, alkyl and aro I and II resulting in a composition having comparable matic substituted and unsubstituted sulfonamido substi flocculation resistant properties. tuted phenylene and X is a complex forming metal, As previously indicated, the compounds of Examples wherein at least one of said R, R', R'' and R' is pyridyl IV, VI, and VIII are useful as pigments when employed ene, at least one of the remaining of said R, R, R'' and in a mixture. When employed alone these compounds R' is a substituted phenylene as aforesaid and in all in have pigment properties and can be employed in standard stances at least one Sulfo Substituted phenylene, chloro paint and ink formulations. sulfo substituted phenylene or alkyl and aromatic substi Referring to all of the compounds disclosed in the 10 tuted and unsubstituted sulfonamido substituted phenyl examples it will be noted that certain isomeric positions ene is present provided that in the instance of said sulfo are indicated for the pyridylene, phenylene and substi and chlorosulfo substituted phenylene only one said sulfo tuted phenylene groups in the tetraazoporphine structure. or chlorosulfo substituted phenylene is present. It will be recognized that any combination of isomeric 2. A mixture of compounds defined in claim 1 wherein positions are possible for these groups and the structures 5 said phenylene is present in a mole average of about 3.00 therein shown are representative only. to about 3.60, said pyridylene is present in a mole average In the foregoing examples, quinolinic acid or the an of about .40 to about .10 and said substituted phenylene hydride in addition to the mono substituted phthalic acids is mono substituted and present in a mole average of about are reacted to produce a tetraazoporphine structure con .70 to about .25. taining a pyridylene group and corresponding mono sub 20 3. The compound as defined in claim 1 wherein R is stituted phenylene groups which are fused into the tetra pyridylene, one of said R', R'' and R' is monohalosub aZoporphine structure through adjacent carbon atoms. In stituted phenylene, another is alkyl substituted sulfon the manner indicated therein other mono, di or trihalo amido substituted phenylene and the other is phenylene. Substituted phenylenes in addition to the chloro such as 4. The compound as defined in claim 1 wherein R is the bromo and the iodo can be formed by employing 25 pyridylene one of said R, R'' and R' is monosulfosub mono, di or tribromo or mono, di or triiodo phthalic stituted phenylene and the others are phenylene. acid. Similarly, any chlorosulfo substituted phthalic acid 5. The compound as defined in claim 1 wherein R is can be substituted for the 4-sulfo phthalic acid to yield pyridylene, one of said R, R'' and R' is monohalosub the corresponding chloro substituted phenylene moiety in stituted phenylene, another is monosulfosubstituted phen the tetraazoporphine structure. A substituted sulfon 30 ylene and the remaining is phenylene. amido Substituted phenylene can likewise be fused into 6. The compound as defined in claim 1 wherein R is such a structure in addition to the pyridylene moiety pyridylene, one of said R, R'' and R' is monosulfon formed from the quinolinic acid by employing a substi amido and the others are phenylene. tuted sulfonamidophthalic acid such as the mono or di 7. The compound of claim 1 wherein R is pyridylene, alkyl and aromatic derivatives thereof. As indicated in 35 one of said R', R'' and R' is monochlorosubstituted Example VII mixtures of the various substituted phthalic phenylene another is monochlorosulfo substituted phenyl acids in combination with the unsubstituted phthalic acids ene and the other is phenylene. can be employed to yield phthalocyanines with tetraazo 8. The compound as defined in claim 1 wherein R is porphine structures composed of mixtures of the corre pyridylene, R’ is monosulfosubstituted phenylene, R' is sponding unsubstituted phenylene, substituted and pyridyl 40 monochlorosubstituted phenylene and R' is phenylene. ene moieties resulting in compounds corresponding to the previously disclosed general Formula I. Correspondingly, References Cited tetraazoporphine structures having two or three like sub UNITED STATES PATENTS stituted phenylene moieties in addition to one or more 2,459,771 1/1949 Fox ------260-270 pyridylene groups can also be employed with the excep 45 2,765,308 10/1956 Campbell ------260-270 tion of the sulfo and chlorosulfo substituted phenylene in 3,024,247 3/1962 Moser and Stepp --- 260-314.5 which instances only a single such group should be con 3,063,779 11/1962 Rosch ------260-314.5 X densed on the tetraazoporphine structure. 3.366,641 1/1968 Zwahlen ------260-296 Others may readily adapt the invention for use under various conditions of service by employing one or more 50 FOREIGN PATENTS of the novel features disclosed or equivalents thereof. 696,590 9/1940 Germany. I claim: OTHER REFERENCES 1. A compound having the formula: Yokote et al.: Chem. Abstr., vol. 55, Col. 24019, -R- 55 (1961). N=C CSN Yokote et al.: Chem. Abstr., vol. 61, Col. 15895 (1964). Y ey Yokote et al.: Chem. Abstr., vol. 62, Col. 14859-60 (1965). N--NYo R v 60 ALEXMAZEL, Primary Examiner D. A. DAUS, Assistant Examiner wherein R, R', R' and R' are independently selected from the group consisting of pyridylene, phenylene, and 65 U.S. C.X.R. Substituted phenylene selected from the group consisting 106-288; 260-296, 314.5, 546 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3, 458,517 July 29, 1969 James D. Stepp It is certified that error appears in the above identified patent and that said Letters Patent are hereby corrected as shown below: Column 4, line 61, that portion of the formula reading (Cs NH3)0.31av4 should read - - (CSNH3)0.31av. -- . Column 6, line 20 should read - - A range of values is : - - ; lines 21 to 24 should be indented; in the formula appearing in Example IX, that portion of the formula appearing at the right side reading C C-21 should read C C SN same column 6, line 69, that portion of the formula reading Column 7, line 47, 'instances' should read -- instance - - ; in the formula appearing in claim 1, that portion of the formula reading - C C (N should read (N N-4 N/ Signed and sealed this 5th day of May 1970.
(SEAL) Attest: EDWARD M. FLETCHER, JR. WILLIAM E. SCHUYLER, JR. Attesting Officer Commissioner of Patents