MXPA97010432A - Compositions of organi pigments - Google Patents

Abstract

The present invention relates to a pigment composition consisting of an organic pigment treated with about 0.1 to about 20% by weight, based on the organic pigment, of a pigment derivative having the formula: wherein Q represents a rest of organic pigment, X is O or S, Het represents a heteroaromatic group bonded in a carbon atom of the ring to the linking group (thio) amidomethyl -CH2-NH-CX- and n is 1 to

Description

COMPOSITIONS OF ORGANIC PIGMENTS BACKGROUND OF THE INVENTION This invention relates to pigment compositions obtained by treating organic pigments with heteroarylamidomethyl and / or heteroarylthioamidomethyl pigment derivatives that impart improved rheological properties and dispersibility. Many types of organic pigments are known and each can be prepared by one or more known methods. Typically, however, the raw compounds initially formed are unsuitable for use as pigments and have to undergo one or more additional finishing steps to modify the particle size, the particle shape or the crystal structure to achieve a pigmentary quality , rheological properties and adequate dispersibility. Methods for improving the rheological properties are known. For example, the pigments can be treated with various additives, such as sulfonic acid and sulfonamide derivatives of various pigments. For example, US Patents 3,418,322, 3,446,641, 4,088,507, 4,310,359 and 5,368,641 and British Patents 1,544,839 and 2,009,205. Other pigment derivatives have also been described for use as pigment additives. For example, pyrazolylmethylquinacridone derivatives are described in U.S. Pat. 5,334,727. This patent, however, does not suggest the introduction of an amido or thioamido functionality between the heterocyclic ring and the methyl group, a critical feature of the present invention. Substituted benzamidomethylquinacridones and structurally related phthalimidomethyl- and sulfobenzimidomethylquinacridones are described in US Pat. 3,635,981, 4,197,404, 4,256,507, 4,439,240, 4,455,173, 4,478,968, 4,541,872, 4,844,742, 4,895,949, 5,194,088, 5,264,032, 5,286,863, 5,424. 429, 5,453,151 and 5,457,203. These patents, however, describe compounds in which the amide carbonyl groups are attached only to benzene rings and do not suggest binding to heterocycles, another critical feature of the present invention. It has now been surprisingly seen that pigment compositions having pigmentary quality and excellent rheological properties can be obtained by treating organic pigments with certain pigment derivatives bearing one or more heteroarylamidomethyl and / or heteroarylthioamidomethyl substituents wherein the carbonyl function of each linking group (uncle ) amidomethyl is attached to a ring carbon atom of the heteroaromatic group. These advantages are found even in comparison with the benzamido-methylquinacidones. COMPENDIUM OF THE INVENTION This invention relates to pigment compositions consisting of an organic pigment treated with about 0.1 to about 20% by weight (preferably 1 to 10% by weight), based on the organic pigment, a pigment derivative that has the formula where Q represents an organic pigment residue, X is O or S, Het represents a heteroaromatic group attached at a ring carbon atom to the linking group (thio) amidomethyl-CH2-NH-CX- and n is from 1 to 4. This invention also relates to processes for the preparation of said pigment compositions and to the use of said pigment compositions in the pigmentation of paints, plastics, fibers, inks and toners. DETAILED DESCRIPTION OF THE INVENTION Suitable organic pigments which can be treated by the process of the present invention include quinacridone pigments, phthalocyanine and perylene, as well as other known organic pigments. Mixtures, including solid solutions, of such pigments are also suitable. Quinacridone pigments are particularly suitable organic pigments. Quinacridones (which, as used herein, include unsubstituted quinacridone, quinacridone derivatives, and solid solutions thereof) can be prepared by any of several methods known in the art., but are preferably prepared by thermal ring closure of various precursors of 2,5-dianilinoterephthalic acid in the presence of polyphosphoric acid. For example, S.S. Labana and L.L. Labana, "Quinacridones", in Chemical Review, 67, 1-18 (1967) and US Patents. 3,157,659, 3,256,285, 3,257,405 and 3,317,539. Suitable quinacridone pigments may be unsubstituted or substituted (for example, with one or more alkyl, alkoxy, halogens such as chlorine or other substituents typical of quinacridone pigments). The metallic phthalocyanine pigments are also suitable organic pigments. Although copper phthalocyanines are preferred, other phthalocyanine pigments containing metals, such as those based on zinc, cobalt, iron, nickel and other metals of this type, can also be used. Suitable phthalocyanine pigments may be unsubstituted or partially substituted (for example, with one or more alkyl, alkoxy, halogens such as chlorine or other substituents typical of phthalocyanine pigments). The crude phthalocyanines can be prepared by any of several methods known in the art, but are preferably prepared by a reaction of phthalic anhydride, phthalonitrile or derivatives thereof with a metal donor, a nitrogen donor (such as urea or phthalonitrile itself) and an eventual catalyst, preferably in an organic solvent. For example, . Herbst and K. Hunger, Industrial Organic Pigments (New York: VCH Publishers, Inc., 1993), pages 418-427; H. Zollinger, Color Chemistry (VCH Verlagsgesellschaft, 1973), pages 101-104, and N.M. Bigelow and M.A. Perkins, "Phthalocyanine Pigments," in The Chemistry of Synthetic Dyes and Pigments, ed. HE HAS. Lubs (Malabar, Florida: Robert E. Krieger Publishing Company, 1955), pages 584-587; see also US Pat. 4,158,572, 4,257,951 and 5,175,282 and British Patent 1,502,884. The perylenes, particularly the diimides and dianhydrides of perylene-3, 4, 9, 10-tetracarboxylic acid, are also suitable organic pigments. Suitable perylene pigments may be unsubstituted or substituted (for example, with one or more alkyl, alkoxy, halogens such as chlorine or other typical perylene pigment substituents), including those which are substituted on the nitrogen atoms imida with chemically reasonable groups such as alkyl. The crude perylenes can be prepared by methods known in the art. For example, W. Herbst and K. Hunger, Industrial Organic Pigments (New York: VCH Publishers, Inc., 1993), pages 9 and 467-475; H. Zollinger, Color Chemistry (VCH Verlagsgesellschaft, 1973), pages 227-228 and 297-298, and M.A. Perkins, "Pyridines and Pyridones", in The Chemistry of Synthetic Dyes and Pigments, ed. HE HAS. Lubs (Malabar, Florida: Robert E. Krieger Publishing Company, 1955), pages 481-482. Other suitable organic pigments include dioxazines (ie, triphenoxazoles), 1,4-diketopyrropyrroles, anthrapyrimidine, antantrones, flavantrones, indantrones, isoindolines, isoindolinones, perinones, pyrantrones, thioindigos, 4, '-diamino-1, 1' - diantraquinonyl and azo compounds, as well as substituted derivatives. The organic pigments can be treated according to the invention, for example by mixing crude organic pigments with heteroarylamido-methyl and / or heteroarylthioamidomethyl pigment derivatives in a strong mineral acid, by wet or dry mixing of crude or finished organic pigments with the derivatives of pigment, or by adding the pigment derivatives during the pigment synthesis. It is also possible to treat organic pigments by conditioning in the presence of heteroarylamidomethyl and heteroarylthioamidomethyl pigment derivatives. The combinations of said methods are also suitable. Suitable heteroarylamidomethyl and heteroarylthioamidomethyl pigment derivatives are compounds having the formula (I) where Q represents an organic pigment residue, X represents 0 (for amidomethyl linking groups) or S (for thioamidomethyl linking groups), Het represents a heteroaromatic group attached at a carbon atom of the ring to the carbonyl or thiocarbonyl group of the group (tio) amidomethyl (i.e., -CH2-NH-CX-) and n is from 1 to 4 (preferably 1 or 2, more preferably 1). The remaining pigment Q can be derived essentially from any kind of organic pigments, including quinacridones, phthalocyanines, perylenes (particularly the imides, diimides, anhydrides and / or dianhydrides of 3, 4, 9, 10-tetracarboxylic acid), dioxazines (ie triphenyloxazines), 1,4-diketopyrrolopyrroles, anthrapyrimidines, antantrones, flavantrones, indantrones, isoindolines, isoindolinones, perinones, pyrantrones, thioindigos, 4,4'-diamino-1,1'-diantraquinonyl or azo compounds, as well as substituted derivatives thereof. Suitable derivatives include those having one or more substituents which are typical of said pigments, such as C ^ Cg alkyl groups, C ^ Cg alkoxy, C5-C cycloalkyl, C5-C7 cycloalkoxy, C6-C10 aryl, C6 aryloxy. -C10, C7-C16 aralkyl, C7-C16 aralkoxy, hydroxy, halogen, nitrile, carboxyl or its amides, sulfonyl (such as alkyl- and arylsulfonyl or sulfoxyl and its amides) or combinations thereof. The substituted derivatives of the remaining pigment Q may include, of course, those in which the ring nitrogen atoms are substituted with chemically reasonable groups, such as alkyl, cycloalkyl, aryl or aralkyl. It is also frequently desirable to use heteroarylamidomethyl and heteroarylthioamidomethyl pigment derivatives in which the pigment residue Q is the same type of pigment as the organic pigment being treated. However, it may often be desirable to use heteroarylamidomethyl and heteroarylthioamidomethyl pigment derivatives in which the pigment residue Q is a different type of pigment from the organic pigment being treated. Preferred pigment derivatives are those derived from quinacridones, phthalocyanines and perylenes. Suitable heteroaromatic Het groups are aromatic species containing one or more ring heteroatoms (selected from N, O and S) and which are attached at a ring carbon atom to the amidomethyl (thio) linking group (i.e., -CH2 -NH-CX-). Examples of suitable heteroaromatic Het groups include derivatives of pyrrole, imidazole, pyrazole, pyridine, pyrazine, pyrimidine, pyridazine, triazine, furan, thiophene, isoxazole, isothiazole and furazane or their derivatives, wherein one or more ring atoms are substituted with C 1 -C 6 alkoxy, C 5 -C 7 cycloalkyl, C 5 -C 7 cycloalkoxy, C 6 -C 10 aryl, C 6 -C 10 aryloxy, C 7 -C 16 aralkyl, C 7 -C 16 aralkoxy, hydroxy, halogen, nitrile, carboxyl or their amides groups, sulfonyl (such as alkyl- and arylsulfonyl or sulfoxyl and its amides) or combinations thereof. Although some of the above Het groups, such as furan, may exhibit a low degree of aromaticity, said compounds are to be considered as heteroaromatics for the purposes of this invention if not more than one hydrogen atom or substituent is attached to each atom of the invention. ring. As used herein, the term "C 1 -C 6 alkyl" refers to straight or branched chain aliphatic hydrocarbon groups having from 1 to 6 carbon atoms. Examples of alkyl are methyl, ethyl, propyl, butyl, pentyl, hexyl and their isomeric forms. The term "Cj ^ -C8 alkoxy" refers to straight or branched chain alkyloxy groups having from 1 to 6 carbon atoms. Examples of alkoxy methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy and its isomeric forms are examples. The term "C5-C7 cycloalkyl" refers to cycloaliphatic hydrocarbon groups having from 5 to 7 carbon atoms. Examples of C5-C7 cycloalkyl are cyclopentyl, cyclohexyl and cycloheptyl. The term "C5-C7 cycloalkoxy" refers to cycloalkyloxy groups having from 5 to 7 carbon atoms. Examples of C5-C7 cycloalkoxy are cyclopentyloxy, cyclohexyloxy and cycloheptyloxy. The term "C6-C10 aryl" refers to phenyl and 1- or 2-naphthyl, as well as to phenyl and naphthyl groups substituted with alkyl, alkoxy, halogen and cyano as defined herein. The term "C6-C10 aryloxy" refers to phenoxy and 1- or 2-naphthoxy, wherein the aryl portion may be optionally substituted as described above for "aryl". The term "C7-C16 aralkyl" refers to C ^ Cg alkyl substituted with C6-C10 aryl, such that the total number of carbon atoms is from 7 to 16. Examples of C7-C16 aralkyl are benzyl, phenethyl and naphthylmethyl. The term "C7-C16 aralkoxy" refers to a Cj-Cg alkoxy substituted with C6-C10 aryl, such that the total number of carbon atoms is from 7 to 16. An example of a C7-C16 aralkoxy is benzyloxy. Examples of halogen are fluorine, chlorine, bromine and iodine. Particularly preferred heteroaromatic hetero groups are the pyridine, furan and thiophene derivatives. It is suitable, but in general less preferred, that heteroaromatic Het groups include polyaromatic derivatives in which one or two pairs of adjacent ring atoms are fused to one or two aromatic rings (such as benzene or heteroaromatic analogs thereof) which can, they themselves, be substituted in the ring as described above or contain one or more ring heteroatoms selected from 0, S and N. Examples of such suitable polyaromatic Het groups include those based on indole, isoindole and indolazine (ie, benzoderivatives of pyrrole), carbazole (ie, a dibenzo derivative of pyrrole), indazole, benzimidazole, quinoline, isoquinoline and quinolazine (ie, benzoderivatives of pyridine), quinazoline, quinoxaline, cinnoline, purine, benzofuran and isobenzofuran (ie, benzene derivatives of furan), phenoxazine, benzothiazine, naphthothiophene and thianthrene, as well as their substituted derivatives in the ring. The linking group -CH2-NH-CX- can be an amidomethyl group (i.e., -CH2-NH-C0-) or a thioamidomethyl group (i.e., -CH2-NH-CS-). The heteroarylamidomethyl and heteroarylthioamidomethyl pigment derivatives used according to the invention can be prepared by known methods, for example by condensation of the pigment to be derivatized with a mixture of a heteroarylcarboxamide or heteroarylthiocarboxamide or derivatives thereof and formaldehyde or a functional equivalent (such as the polymeric form paraformaldehyde or a formaldehyde-producing compound, such as trioxane) or with a corresponding N-methylol derivative of a heteroarylcarboxamide or heteroarylthiocarbo-xamide in the presence of a dehydrating agent at a temperature of about 0 to about 200 ° C . Suitable dehydrating agents include sulfuric acid, oil, polyphosphoric acid, organic acids or their anhydrides and mixtures thereof. Oil is a particularly suitable condensing agent, especially for less reactive pigments. The degree of substitution in the pigment molecule can be affected by several factors, such as the amount of heteroaryl (thio) carboxamide, the reaction temperature and the duration of the reaction. The resultant heteroarylamidomethyl or heteroaryl thioamidomethyl pigment derivatives can be isolated by addition of the reaction mixture to a liquid in which the pigment derivative is completely or almost completely insoluble, preferably water or methanol or other lower aliphatic alcohols (such as ethanol, propanol or butanol), as well as their mixtures. It may also be advantageous to include various additives, such as surfactants, in the liquid. The pigment derivatives are then isolated (for example, by filtration or other known methods) and washed until free of residual acid. Particularly preferred pigment derivatives for the treatment of pigments according to the invention are nicotinamidomethyl- and thionicotinamidomethylqui-nacridones having the formula (II) where X is O or S and n is 1 or 2; 2-furamido-methyl-substituted quinacridones having the formula (III) : n ?: and the 2-thiophenecarboxamidomethylquinacridones having the formula (IV) The formulas (II), (III) and (IV) are not intended to indicate specific locations for the hetero-aryl (thio) amidomethyl groups, but rather to indicate that said groups are located at chemically reasonable positions of the quinacridone moiety. Various methods are known for the preparation of pigment compositions of the invention. In a preferred method, a crude organic pigment and a pigment derivative heteroarylamidomethyl and / or heteroarylthioamidomethyl in a strong mineral acid are dissolved ("turned into paste") or suspended ("swollen") and then precipitated. A sufficient amount of mineral acid, preferably concentrated acid, is added to ensure the formation of an acid solution or suspension in a reasonable amount of time. However, except for the requirement that the solution or suspension be acidic, the amount and concentration of the acid are generally not critical. For example, more dilute acid can be used if the stirring time is prolonged, but the use of more concentrated acids is preferred for commercial applications. Suitable mineral acids include sulfuric acid and polyphosphoric acid, with preference for sulfuric acid. It is particularly preferred to use at least 64% aqueous sulfuric acid in amounts of about 4 to about 15 parts by weight of acid relative to the total amount of crude organic pigment and pigment derivative. Although the rate of dissolution of the mixture of crude pigment and pigment derivative in acid can be increased by heating the mixture (eg, to about 50 ° C), it is generally preferable to dissolve the mixture in acid at 35 ° C or less to minimize sulfonation (when sulfuric acid is used) or degradation of the pigment or pigment derivative. After completion of the acid treatment, the pigment composition is precipitated by adding the strongly acid solution to a liquid in which the pigment and the pigment derivative are completely or almost completely insoluble, preferably water or methanol or other lower aliphatic alcohols (such as as ethanol, propanol or butanol), as well as their mixtures. When sulfuric acid or oil is used in the preparation of the heteroarylamidomethyl or heteroarylthioamidomethyl pigment derivatives or of the final pigment compositions, the pigment residue may be sulfonated. Said sulfonated derivatives may be isolated as free acid, ammonium salt or metal salt (including, for example, alkali metal salts such as sodium or potassium salts, alkaline earth metal salts such as calcium or barium salts and salts thereof. Group III metals such as aluminum). In a second preferred method, an organic pigment is mixed with a suitable heteroarylamidomethyl and / or heteroaryl thioamidomethyl pigment derivative using wet or dry mix variants. The dry mix variant consists of (a) dry blending an organic pigment with about 0.1 to about 20% by weight (preferably 1 to 10% by weight), based on the organic pigment, of a derivative of pigment of formula (I) and (b) collecting the pigment composition. The wet mix variant consists of (a) treating an organic pigment with (1) about 0.1 to about 20% by weight (preferably 1 to 10% by weight), based on the organic pigment, of a pigment derivative of formula (I) and (2) about 5 to about 20% by weight (preferably 5 to 15% by weight), based on the organic pigment, of a liquid in which the organic pigment is substantially insoluble, thereby forming a suspension of the pigment composition treated in the liquid, and (b) collecting the pigment composition. The liquid used for the wet mixture is a liquid in which the organic pigment is substantially insoluble, preferably water, a water-miscible solvent such as methanol or other lower aliphatic alcohols, or mixtures thereof. It is desirable, but not necessary, that the pigment derivative heteroarylamidomethyl or heteroarylthioamidomethyl be at least partially insoluble in the liquid. Suitable liquids include water and / or organic liquids miscible in water, including for example, lower aliphatic alcohols, such as methanol; ketones and ketoalcohols, such as acetone, methyl ethyl ketone and diacetone alcohol; amides, such as dimethylformamide and dimethylacetamide; ethers, such as tetrahydrofuran and dioxane; alkylene glycols and triols, such as ethylene glycol and glycerol, and other organic liquids of this type known in the art. Other organic liquids may be used, but are generally less preferred. The temperature at which the mixing is carried out is not critical in general, but is normally maintained between about 5 ° C and about 60 ° C (preferably, below the boiling point of the liquid). In a third preferred method, which is particularly useful for preparing quinacridone pigment compositions, a suitable pigment heteroarylamidomethyl and / or heteroarylthioamidomethyl derivative is added during or even before the synthesis of the organic pigment being treated, in such a way that the reaction and the treatment processes can take place in situ, at least in part, as the organic pigment is formed. For example, when preparing quinacridone pigments, a preferred preparatory method consists of (a) heating, at a temperature of about 80 ° C to about 145 ° C (preferably 100 ° C to 130 ° C), a consistent reaction mixture. in (i) 2, 5-dianilinoterephthalic acid, 2,5-dianilino-6,13-dihydroterephthalic acid, 2,5-dianilino-3,6-dioxo-1,4-cyclohexadiene-1,4-dicarboxylic acid or derivative thereof having one or more substituents on at least one aniline ring; a salt or ester of said acid or derivative thereof; or a mixture thereof, (ii) about 0.1 to about 15 weight percent (preferably 0.1 to 10 weight percent), based on component (a) (i), of a a suitable heteroarylamidomethyl and / or heteroarylthioamidomethyl pigment derivative, (iii) about 3 to about 20 parts by weight (preferably, 3 to 10 parts by weight), per part of component (a) (i), of a dehydrating agent (preferably, polyphosphoric acid), with the proviso that, if both the component (a) (i) and the component (a) (ii) is a 2, 5-dianilino-6, 13-dihydroterephthalic acid or derivative thereof, the step of reaction (a) further includes an oxidation step (which converts the dihydroquinacridone intermediate initially formed into the corresponding quinacridone); (b) drowning the reaction mixture of step (a) by adding said reaction mixture at about 3 to about 15 parts by weight (preferably, 5 to 10 parts by weight), on the part of component (a) (i), of a liquid in which the quinacridone pigment is substantially insoluble, and (c) isolating the quinacridone pigment. Each of the above methods can be carried out in the presence of one or more additional pigment derivatives known in the art, particularly sulfonic acid and sulfonamide derivatives. Regardless of which of the above methods is employed, the resulting pigment composition is collected by methods known in the art, preferably filtration followed by a washing step to remove residual acid. Other collection methods known in the art, such as centrifugation or even simple decanting, are suitable, but less preferred in general. The pigment composition is then dried for use or for further handling prior use. The pigment compositions according to the invention can be obtained by conditioning organic pigments in the presence of a pigment derivative heteroarylamidomethyl and / or heteroarylthioamidomethyl, making it in place of or in addition to the preparative methods described above. It is, of course, possible to include one or more additional pigment derivatives known in the art, particularly sulfonic acid and the sulfonamide derivatives. The conditioning can be carried out using any of several methods known in the art., such as solvent treatment or grinding in combination with solvent treatment. The final particle size of the pigment can be controlled by varying the post-treatment method. For example, the pigments can be made more transparent by reducing the particle size or more opaque by increasing the particle size. Suitable methods of grinding include dry milling methods such as grinding sand, grinding balls and the like, with or without additives, or wet grinding methods, such as kneading with salts, grinding pearls and the like. in water or organic solvents, with or without additives. The dyeing strength and transparency of the pigment can also be affected by the solvent treatment carried out by heating a dispersion of the pigment composition, often in the presence of additives, in a suitable solvent. Suitable solvents include organic solvents, such as alcohols, esters, ketones and aliphatic and aromatic hydrocarbons and their derivatives, and inorganic solvents such as water. Suitable additives include compositions that reduce or prevent flocculation, increase the stability of the dispersion and reduce the viscosity of the coating, such as polymeric dispersants (or surfactants). For example, US Patents 4,455,173, 4,758,665, 4,844,742, 4,895,948 and 4,895,949. During or after the eventual conditioning step, it is often desirable to use various other eventual components that provide better properties. Examples of such optional components include fatty acids having at least 12 carbon atoms, such as stearic acid or behenic acid or amides, esters or corresponding salts, such as magnesium stearate, zinc stearate, aluminum stearate or aluminum behenate. magnesium; quaternary ammonium compounds, such as tri [(C 1 -C 4 alkyl) benzyl] ammonium salts; plasticizers, such as epoxidized soybean oil; waxes, such as polyethylene wax; resin acids, such as abietic acid, rosin soap, hydrogenated or dimerized rosin; C12-C18 paraffinisulfonic acids; alkylphenols; alcohols, such as stearyl alcohol; amines, such as laurylamine or stearylamine, and aliphatic 1,2-diols, such as dodecane-1,2-diol. Said additives can be incorporated in amounts ranging between 0.05 and 20% by weight (preferably, between 1 and 10% by weight), based on the amount of pigment. Due to their stability against light and their migratory properties, the pigment compositions according to the present invention are suitable for many different pigment applications. For example, the pigment compositions according to the invention can be used as a colorant (or as one of two or more colorants) for pigment systems which are very stable to light. Examples thereof include blends pigmented with other materials, pigment formulations, paints, printing inks, colored paper or colored macromolecular materials. It is understood that the term "mixtures with other materials" includes, for example, mixtures with inorganic white pigments, such as titanium dioxide or cement, or other inorganic pigments. Examples of pigment formulations include pastes washed with organic liquids or pastes and dispersions with water, dispersants and, where appropriate, preservatives. Examples of paints in which the pigment compositions of the invention may be used include, for example, physical or oxidative drying lacquers, hot enamels, reactive paints, two-component paints, solvent-based or water-based paints, emulsion paints for waterproof coatings and tempers. Paints for printing include those known for use in printing on paper, textiles and tin. Suitable macromolecular substances include those of natural origin, such as gum; those obtained by chemical modification, such as acetylcellulose, cellulose butyrate or viscose; or those produced synthetically, such as polymers, polyaddition products and polycondensates. Examples of synthetically produced macromolecular substances include plastic materials, such as polyvinyl chloride, polyvinyl acetate and polyvinyl propionate; polyolefins, such as polyethylene and polypropylene; high molecular weight polyamides; polymers and copolymers of acrylates, methacrylates, acrylonitrile, acrylamide, butadiene or styrene; polyurethanes, and polycarbonates. The pigmented materials with the pigment compositions of the present invention can have any desired shape. The pigment compositions prepared according to this invention are highly water resistant, oil resistant, acid resistant, lime resistant, alkali resistant, solvent resistant, overcoat stable, over spray stable, sublimation stable, heat resistant. and resistant to vulcanization and still provide a very good dyeing performance and are easily dispersible (for example, in plastic materials). The following examples still illustrate the details for the preparation and use of the compositions of this invention. The invention, set forth in the foregoing description, is not limited in spirit or scope by these examples. Those skilled in the art will readily understand that known variations of the conditions and procedures of the following preparatory procedures for preparing these compositions can be used. Unless otherwise indicated, all temperatures are degrees Celsius and all percentages are percentages by weight.

EXAMPLES Preparation of heteroarylamidomethylquinacridone and heteroarylthioamidomethylquinacridone derivatives Nicotinamidomethylquinacridone To 219 g of 100% sulfuric acid was slowly added, with stirring, 15.2 g (0.10 mol) of N-hydroxy-methylnicotinamide at a temperature below 25 ° C. 31.2 g (0.10 mol) of quinacridone were slowly added to the acid mixture. The reaction mixture was stirred for one hour at a temperature below 10 ° C, allowed to warm to room temperature and stirred for 18 hours. After maintaining it at 60-65 ° C for three hours, the reaction mixture was cooled to 35 ° C and poured slowly into two liters of ice water. The resulting suspension was stirred for 30 minutes, while heating to 15 ° C. The solid was isolated by filtration and washed with water. The wet cake of the filter press was resuspended with water and heated at 60 ° C for 30 minutes, after which the solid was isolated by filtration and washed with water. The wet cake was dried from the filter press in an oven at 60 ° C to obtain 31.7 g of nicotinamidomethylquinacridone. Di (nicotinamidomethyl) quinacridone The method described above for the preparation of nicotinamidomethylquinacridone was repeated, except for the use of 260 g of 100% sulfuric acid and 30.0 g (0.20 mol) of N-hydroxymethylnicotinamide. Di (nicotinamidomethyl) quinacridone (24.7 g) was thus obtained. Tionicotinamidomilquinacridona To 210 g of 100% sulfuric acid were added 14.1 g (0.10 mol) of thionicotinamide over a period of 15 minutes, at a temperature below 15 ° C. The acid mixture was stirred for a further 10 minutes, after which 3 g (0.10 mol) of paraformaldehyde was added, while maintaining a temperature below 15 ° C. The reaction mixture was allowed to warm to room temperature, kept at 20-25 ° C for two hours and cooled to 10 ° C. 31.2 g (0.10 mol) of quinacridone were added to this mixture, while maintaining the temperature below 15 ° C. The mixture was allowed to warm to room temperature and then maintained at 60-65 ° C for two hours. After stirring at room temperature for 18 hours, the reaction mixture was slowly poured into two liters of ice water. The resulting suspension was allowed to warm to 20 ° C and was then stirred for one hour, after which the solid was isolated by filtration and washed with water. The wet cake of the filter press was resuspended with water and heated for 30 minutes at 60 ° C, after which the solid was again isolated by filtration and washed with water. The wet cake was dried from the filter press in an oven at 60 ° C to obtain 34.8 g of thionicotinamidomethylquinacridone. 2-Furamidomethylquinacridone To 200 g of 96% sulfuric acid at a temperature below 25 ° C was added 25 g (0.08 mol) of quinacridone. The acid mixture was stirred for 30 minutes, after which 9 g (0.08 mol) of 2-furamide (prepared by the method described in J. Amer. Chem. Soc., 75, 2370-2372 (1953) was added. )), while maintaining the temperature below 35 ° C. The resulting mixture was stirred for a further 30 minutes, after which 2.4 g (0.08 mol) of paraformaldehyde was added slowly.

The reaction mixture was heated at 60-65 ° C for five hours. The mixture was allowed to cool to room temperature, stirred at room temperature for 18 hours and poured slowly into two liters of ice water. The resulting suspension was stirred for 30 minutes, after which the solid was isolated by filtration and washed with water. The wet cake of the filter press was resuspended with water and heated for 30 minutes at 60 ° C, after which the solid was isolated by filtration and washed with water. The wet cake of the filter press was dried in an oven at 60 ° C to obtain 31.2 g of 2-furamidomethylquinacridone. 2-Thiophenecarboxamidomethylquinacridone To 210 g of 100% sulfuric acid was added 12 g (0.09 mol) of 2-thiophenecarboxamide at a temperature below 15 ° C. The acid mixture was stirred for 15 minutes, after which 2.7 g was slowly added. (0.09 mol) of paraformaldehyde. The reaction mixture was stirred for 15 minutes at a temperature lower than 10 ° C, allowed to stir at room temperature for two hours and cooled again to 10 ° C. After adding 28.1 g (0.09 mol) of quinacridone, the reaction mixture was maintained at 60 ° C for two hours. The mixture was then allowed to cool to room temperature, stirred at room temperature for 18 hours and poured slowly into two liters of ice water while maintaining a temperature below 15 ° C. The resulting suspension was stirred for one hour, after which the solid was isolated by filtration and washed with water. The wet cake of the filter press was resuspended with water and heated for 30 minutes at 60 ° C, after which the solid was again isolated by filtration and washed with water. The wet cake was dried from the filter press in an oven at 60 ° C to obtain 39.3 g of 2-thiophenecarboxamidomethylquinacridone. Examples 1-12 Examples 1-12 describe the preparation and testing of pigment compositions. The differences in hue and chromaticity for the pigments prepared according to the Examples were measured using an Applied Color System Spectral Sensor (Hunt Associated Laboratories, Fairfax, Virginia). Testing with water-based paints Tests were carried out with water-based paints using a waterborne basecoat / solvent-borne clearcoat system. Aqueous dispersions were prepared using a mixture of 12.4% acrylic resin AROLON® 559-G4-70 (Reichhold Chemicals, Inc.), 3.2% SOLSPERSE® 27000 hyperdispersant (Zeneca, Inc.), 1 , 6% of 2-amino-2-methyl-1-propanol (Angus Chemical) and 18% pigment, which gave a pigment-to-binder ratio of 18:12 and a total solids content of 30%. The pigment-to-binder ratio was then reduced to 10:40 with additional acrylic resin AROLON® 559-G4-70 (total amount 26%) and 25% melamine / formaldehyde resin CYMEL® 325 (Cytec Industries), which gave a total content in 50% solids. Measurements of mass tone and transparency were performed using films applied at 76 μm and 38 μm wet film thickness, respectively and allowed to stand at room temperature for fifteen minutes and at 100 ° C for five minutes. Transparent layers containing a mixture of 80% AROPLAZ® 1453-X-50 alkyd resin and 20% CYMEL® 325 melamine / formaldehyde resin were then applied at a total solids level of 57%, the base layer at a wet film thickness of 76 μm, at rest at room temperature for fifteen minutes and at 121 ° C for fifteen minutes. Surface printing paints were prepared with the reduced aqueous dispersions described above having a pigment-to-binder ratio of 10:40 by adding additional AROLON® 559-G4-70 acrylic resin, melamine / formaldehyde resin CYMEL® 325 and a % white dispersion TINT-AYD® C -5003 (Daniel Products Company), which gave a pigment-to-binder ratio of 1: 1.1, a total solids content of 55% and a Ti02-a-pigment ratio of 90:10. Color measurements were made using films applied at a wet film thickness of 38 μm and allowed to stand at room temperature for fifteen minutes and at 100 ° C for five minutes. Transparent layers were then applied and baked as described above. Metal paints were prepared from the dispersion described above, which had a pigment-to-binder ratio of 18:12, using a water dispersible aluminum pigment (available as HYDRO PASTE® 8726 from Silberline Manufacturing Co., Inc.) , AROLON® 559-G4-70 acrylic resin and CYMEL® 325 melamine / formaldehyde resin in amounts that provided a pigment-to-binder ratio of 1: 2, an aluminum-to-pigment ratio of 20:80 and a total content in solids of 43%. The color measurements were made using films applied at a wet film thickness of 38 um and baked as described above. Transparent layers were then applied and baked as described above. Example 1 (comparative) Pigmented 2,9-dimethylquinacridone was prepared in the absence of a heteroarylamide-methylamic or heteroarylthioamidomethyl pigment derivative according to the invention. To 300 g of polyphosphoric acid (phosphoric acid 112%) heated to 88 ° C was added 68.2 g of 2,5-di (4-methylanilino) terephthalic acid over a period of 35 minutes, keeping the temperature below 120 ° C by adjusting the addition speed. The reaction mixture was heated at 123 ° C for two hours. The melt was cooled to 93 ° C and then slowly poured into 494 g of methanol, keeping the temperature below 64 ° C by external cooling and adjusting the speed of addition of the melt. The suspension was heated at reflux for one hour, cooled to less than 60 ° C, diluted with water, collected by filtration and washed with water until free of acid. The cake of the resulting filter press was resuspended in water. After adjusting the pH to more than 7, 5.5 g of 50% sodium hydroxide was added and the resulting suspension was heated at 90 ° C for one hour. The suspension was cooled, filtered and washed with water until free of alkali and then resuspended in water. After adjusting the pH to 9.5, the suspension was heated at 143 ° C for two hours in a closed system (for example, a pressure reactor) and cooled to 40 ° C. After acidifying the suspension at pH 3.3, an emulsion of 2.2 g of an anionic surfactant, 30 g of a petroleum distillate and 80 g of water was added and the suspension was stirred for three hours. The wet cake was dried in an oven at 60 ° C to obtain approximately 60 g of 2,9-dimethylquinacridone in the form of a magenta pigment. EXAMPLE 2 2,9-Dimethylquinacridone prepared according to the method of Comparative Example 1 was admixed with 10% by weight of nicotinamidomethylquinacridone. A water-based paint prepared as described above exhibited a lower viscosity and a blue tint compared to a paint prepared using the comparative pigment of 2,9-dimethylquinacridone from Example 1. Example 3 (comparative) Example 2 was repeated , except for the use of 10% by weight of phthalimidomethylquinacridone. A water-based paint prepared as described above exhibited a slightly lighter shade of dough and a slightly lower metallic gloss compared to a paint prepared using the pigment of Example 2 of the invention. EXAMPLE 4 2,9-dimethylquinacridone prepared according to the method of Comparative Example 1 was admixed with 10% by weight of di (nicotinamidomethyl) quinacridone. A water-based paint prepared as described above exhibited a greater metallic blue hue and a higher gloss compared to a paint prepared using the comparative pigment of 2,9-dimethylquinacridone of Example 1. Example 5 Dry mixed 2.9 -dimethylquinacridone prepared according to the method of Comparative Example 1 with 10% by weight of thionicotinamidomethylquinacridone. A water-based paint prepared as described above exhibited a lower viscosity as compared to a paint prepared using the comparative pigment of 2,9-dimethylquinonacridone from Example 1. Example 6 Example 5 was repeated, except for the use of 5% by weight of thionicotinamidomethylquina-cridone. A water-based paint prepared as described above exhibited viscosity and color properties comparable to a paint prepared using the comparative pigment of 2,9-dimethylquinacridone of Example 1. Example 7 Dry 2,9-dimethylquinacridone prepared according to the method was mixed dry. of Comparative Example 1 with 10% by weight of 2-furamidomethylquinacridone. A water-based paint prepared as described above exhibited a lower viscosity as compared to a paint prepared using the comparative pigment of 2,9-dimethylqui-nacridone from Example 1. Example 8 Example 7 was repeated, except for the use of 5% by weight of 2-furamidomethylquinacridone. A water-based paint prepared as described above exhibited a reduced viscosity as compared to a paint prepared using the comparative pigment of 2,9-dimethylquinacridone of Example 1. Example 9 2 was prepared, 9-dimethylquinacridone pigment exactly as described in Comparative Example 1, except for the inclusion of 3.4 g of 2-furamidomethylqui-nacridone (5% by weight in relation to 2,5-di (4-methylanilino) acid) terephthalic) in the reaction of the ring closure. A water-based paint prepared as described above exhibited a more intense, brighter and more transparent mass tone and a greater metallic blue tone and gloss compared to a paint prepared using the comparative pigment of 2,9-dimethylquinacridone from Example 1. Example 10 (comparative) Example 9 was repeated, except for the use of 10% by weight of phthalimidomethylquinacridone. A water-based paint prepared as described above exhibited a lighter mass tone and dramatically lower metallic dye and gloss compared to a paint prepared using the pigment of Example 9 of the invention. EXAMPLE 11 2,9-Dimethylquinacridone prepared according to the method of Comparative Example 1 was admixed with 10% by weight of 2-thiophenecarboxamidomethylquinacridone. A water-based paint prepared as described above exhibited a lower viscosity as compared to a paint prepared using the comparative pigment of 2,9-dimethylqui-nacridone from Example 1. Example 12 Example 11 was repeated, except for the use of 5% by weight of 2-thiophenecarboxamidomethyl-quinacridone. A water-based paint prepared as described above exhibited a lower viscosity compared to a paint prepared using the comparative pigment of 2,9-dimethylquinacridone from Example 1.

Claims (10)

CLAIMS 1. A pigment composition consisting of an organic pigment treated with about 0.1 to about 20% by weight, based on the organic pigment, has the formula where Q represents an organic pigment residue, X is O or S, Het represents a heteroaromatic group attached at a carbon atom of the ring to the linking group (thio) amidomethyl -CH2-NH-CX- and n is 1 a. 2. A pigment composition according to Claim 1, wherein the organic pigment is treated with 1 to 10% by weight of the pigment derivative. 3. A pigment composition according to
1. Claim 1, wherein Het is a pyrrole, imidazole, pyrazole, pyridine, pyrazine, pyrimidine, pyridazine, triazine, furan, thiophene, isoxazole, isothiazole or furazan or derivative thereof wherein one or more ring atoms are substituted with Cj alkyl -Cg, C ^ Cg alkoxy, C5-C7 cycloalkyl, C5-C7 cycloalkoxy, C6-C10 aryl, C6-C10 aryloxy, C7-C16 aralkyl, C7-C16 aralkoxy, hydroxy, halogen, nitrile, carboxyl or an amide thereof , sulfonyl or combinations of these. 4. A pigment composition according to Claim 1, wherein the pigment derivative is (a) a nicotinamidomethylquinacridone or thionicoti namidomethylquinacridone of the formula where X is O or S and n is l or 2; (b) a 2-furamidomethyl-substituted quinacridone of the formula (c) a 2-thio-enecarboxamidomethylquinacridone of formula 5. A pigment composition according to Claim 4", wherein the organic pigment is a quinacridone 6. A pigment composition according to Claim 1, wherein the organic pigment is treated (a) by mixing a crude organic pigment with a pigment derivative heteroarylamidomethyl and / or heteroarylthioamidomethyl in a strong mineral acid, (b) wet or dry mixing a raw or finished organic pigment with a heteroarylamidomethyl and / or heteroarylthioamidomethyl pigment derivative, (c) adding a heteroaryl amidomethyl and / or heteroarylthioamidomethyl pigment derivative during the synthesis of the organic pigment, (d) by conditioning an organic pigment in the presence of a heteroarylamido methyl and / or heteroarylthioamidomethyl pigment derivative, or (e) a combination of one or more of the methods (a), (b), (c) and (d) 7. A pigmented paint containing a pigment composition according to Claim 1. 8. A pigmented plastic containing a pigment composition according to Claim 1. 9. An ink containing as pigment a pigment composition according to Claim 1. 10. A toner containing as pigment a pigment composition according to Claim 1.