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United States Patent Office 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.
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