MXPA98000112A - 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 N-heteroarylamidomethyl pigment derivative having the formula: Q represents an organic pigment residue, NHet represents a nitrogen-containing heteroaromatic group bonded in a nitrogen atom of the ring to the carbonyl function of the amidomethyl linking group and is 1 to

Description

COMPOSITIONS OF ORGANIC PIGMENTS BACKGROUND OF THE INVENTION This invention relates to pigment compositions obtained by treating organic pigments with N-heteroarylamidomethyl pigment derivatives that impart excellent pigment properties and improved rheological properties. The chemistry employed in the manufacture of known organic pigments is generally simple. Typically, however, the raw compounds initially formed are unsuitable for use as pigments and must undergo one or more additional finishing steps to modify the particle size, particle shape or crystal structure and achieve 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 functionality between the pyrazole ring and the methyl group, a critical feature of the present invention. Substituted benzamidomethylquina-cridones and structurally related phthalimidomethyl- and sulfobenzimidome-tilquinacridones 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 carbonyl groups of the amide are attached to benzene rings on the ring carbon atoms and do not suggest compounds in which a carbonyl group of the amide is attached to a nitrogen atom. of the ring, another critical feature of the present invention. It has now surprisingly been found 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 heteroarylamido-methyl-lysubstituents, wherein the carbonyl function of each amidomethyl-linking group is bound in a nitrogen atom of the ring of a nitrogen-containing heteroaromatic group. COMPENDIUM OF THE DESCRIPTION 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 N-heteroaryl-amidomethyl pigment derivative (preferably a pyrazolyl-methomethyl pigment derivative) having the formula (I) where Q represents an organic pigment residue, NHet represents a nitrogen-containing heteroaromatic group attached at a ring nitrogen atom to the carbonyl function of the amidomethyl linking group -CH2-NH-CO- and n is from 1 to 4. This invention it is also related to the use of said pigment compositions in the pigmentation of paints, plastics, fibers, inks and teneres. 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 said 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 various methods known in the art, but are preferably prepared by thermally closing the ring 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, halogen substituents such as chlorine, or others typical of quinacridone pigments). The metallic phthalocyanine pigments are also suitable organic pigments. Although copper phthalocyanines are preferred, phthalocyanine pigments containing other 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, halogen substituents such as chlorine, or others typical of phthalocyanine pigments). The crude phthalocyanines can be prepared by any of various methods known in the art, but are preferably prepared by means of a reaction of phthalic anhydride, phthalonitrile or its derivatives with a metal donor, a nitrogen donor (such as urea or the same phthalonitrile) and an optional catalyst, preferably in an organic solvent. For example, W. 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. Perylenes, particularly 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, halogen substituents such as chlorine, or other typical of perylene pigments), including those substituted on nitrogen atoms of the imide 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, triphenoxazole), 1,4-diketopyrrolopyrroles, anthrapyrimidines, antanthroins, flavantrones, indatrones, isoindolines, isoindolinones, perinones, pyrantrones, thioindigos , 4,4'-diamino-1, 1'-diantraquinonyl and the azo compounds, as well as the substituted derivatives. The organic pigments can be treated according to the invention, for example by mixing crude organic pigments with N-heteroarylamide-domethyl dye derivatives in a strong mineral acid, by wet or dry mixing of crude organic pigments or finishes with N-pigment derivatives. heteroarylamidomethyl, or by adding N-heteroarylamidomethyl pigment derivatives during the pigment synthesis. It is also possible to treat organic pigments by conditioning in the presence of N-heteroarylamidomethyl pigment derivatives. Also suitable are combinations of said methods. Suitable N-heteroarylamidomethyl pigment derivatives are compounds of formula (I) where Q represents an organic pigment residue, NHet represents a nitrogen-containing heteroaromatic group attached at a ring nitrogen atom to the carbonyl function of the amidomethyl linking group (i.e., -CH2-NH-C0-) and n is from 1 to 4. The preferred N-heteroarylamidomethyl pigment derivatives are those containing one to two (preferably one) N-heteroarylamide-domethyl groups attached to the remainder of Q pigment. Pigment residue Q can be derived essentially from any kind of organic pigments, including quinacridones, phthalocyanines, perylenes (particularly the imides, diimides, anhydrides and / or dianhydrides of perylene-3, 4, 9, 10-tetracarboxylic acid), dioxazines ( that is, triphenoxazines), 1,4-diketopyrrolopyrroles, anthrapyrimidines, antantrones, flavantrans, indantrones, isoindolines, isoindolinones, perinones, pyrantrones, thioindigos, 4,4'-diamino-1,1'-diantraquinonyl or azo compounds, as well as their substituted derivatives. Suitable derivatives include those having one or more substituents typical of said pigments, such as Ci-Cg alkyl, 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. , C7-C16 aralkyl, C7-C16 aralkoxy, hydroxy, halogen, nitrile, carboxyl or their amides, sulfonyl groups (such as alkyl- and arylsulfonyl or sulfoxyl and their amides) or combinations thereof. The substituted derivatives of the pigment residue Q can, of course, include those in which the nitrogen atoms of the ring are substituted with chemically reasonable groups, such as alkyl, cycloalkyl, aryl or aralkyl. It is often desirable to use N-heteroarylamidomethyl 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 N-heteroarylamidomethylated pigment derivatives in which the pigment residue Q is a type of pigment different from the organic pigment being treated. Preferred pigment derivatives are those derived from quinacridones, phthalocyanines and perylenes. Suitable NHet heteroaromatic groups are nitrogen-containing aromatic species in which the ring nitrogen atom that is bonded to the amidomethyl linking group can not be quaternary (ie, tetravalent). Preferred nitrogen-containing NHet heteroaromatic groups include pyrrolyl, imidazolyl and pyrazolyl groups or derivatives thereof in which one or more ring carbon atoms are substituted with Ci-Cg alkyl, C5-C7 alkoxycycloalkyl, C5-C7 cycloalkoxy , C6-C10 aryl, C6-C10 aryloxy, C7-C16 aralkyl, C7-C16 aralkoxy, hydroxy, halogen, nitrile, carboxyl or its amides, sulfonyl groups (such as alkyl- and arylsulfonyl or sulfoxyl and its amides) or combinations of these. As used herein, the term "C-L-Cg 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-Cg alkoxy" refers to straight or branched chain alkyloxy groups having from 1 to 6 carbon atoms. Examples of alkoxy are 0 -, - Cg methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy and their isomeric forms. 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 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 alkyl substituted with C6-C10 aryl, such that the total number of carbon atoms is from 7 to 16. Examples of C7-C16 aralkyl benzyl are, phenethyl and naphthylmethyl. The term "C7-C16 aralkoxy" refers to 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. A particularly preferred heteroatomatic NHet group is the 3,5-dimethylpyrazolyl group bound to the amidomethyl linking group in nitrogen 1. Suitably, but less preferable in general, the heteroaromatic NHet groups include polyaromatic pyrrolyl, imidazolyl or pyrazolyl derivatives in which one or two pairs of adjacent carbon atoms of the ring are fused with aromatic rings (such as benzene or heteroaromatic analogs thereof) which may themselves be substituted in the ring as described above or, less preferably, may contain one or more ring heteroatoms selected from O, S and N. Examples of such suitable polyaromatic NHet groups include indolyl and isoindolyl (ie, benzoderivatives of pyrrole), carbazolyl (ie, a dibenzo derivative of pyrrole), indazolyl and benzimidazolyl, as well as derivatives thereof substituted in the ring.

N-heteroarylamidomethyl pigment derivatives used according to the invention can be prepared by known methods, for example by condensing the pigment to be derivatized with a mixture of an N-heteroaryl carboxamide (such as pyrazolyl-1-carboxamide) or derivative of the same 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 an N-heteroarylcarboxamide 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 N-heteroarylamidomethyl substitution on the pigment molecule can be affected by several factors, such as the amount of N-heteroarylcarboxamide, the reaction temperature and the duration of the reaction. The resulting N-heteroarylamidomethyl 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 mixtures thereof. 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 N-heteroarylamidometrical pigment derivatives for use in the treatment of pigments according to the invention include (a) pyrazolyl amidomethylquinacridones of formula (II) where R is C1-C6 alkyl, Cj-C6 alkoxy, halogen or sulfoxyl (or an amide thereof) attached to a carbon atom of the quinacridone ring, n is from 1 to 4 (preferably, 1 or 2) and r is zero to 9 (preferably, zero to 4, more preferably zero to 2 and, most preferably, zero, where a value of zero indicates that the quinacridone moiety is not substituted with R groups); (b) Copper pyrazolyl amidyl phthalocyanines of formula (III) where CuPc represents a phthalocyanine copper moiety; each R independently represents Cj-Cg alkyl, halogen or sulfoxyl (or an amide thereof) attached to a carbon atom of the phthalocyanine ring, n is from 1 to 4 (preferably, 1 or 2) and s is zero to 15 (preferably , zero to 8, more preferably zero to 4 and, most preferably, zero, where a value of zero indicates that the phthalocyanine copper residue is not substituted with groups R), and (c) pyrazolylmidomethylperylenes of formula (IV) wherein each R independently represents halogen, carboxamido or sulfonamido bonded to a carbon atom of the perylene ring, n is from 1 to 4 (preferably, 1 or 2) and t is zero to 7 (preferably, zero to 4 and, more preferably, , zero, where a value of zero indicates that the rest of perylene is not substituted with groups R). The formulas (II), (III) and (IV) are not intended to indicate specific locations for the R groups and the pyrazolylmidomethyl groups, but rather to indicate that said groups are located at chemically reasonable positions of each pigment residue. Various methods are known for the preparation of pigment compositions of the invention. In a preferred method, a crude organic pigment and a suitable N-heteroarylamidomethyl pigment derivative in a strong mineral acid are dissolved ("pulped") 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. Nevertheless, except for the requirement that the solution or suspension be acidic, the amount and concentration of the acid are not critical in general. 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 sulfuric acid being preferred. 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 N-heteroarylamidomethyl pigment derivative. Although the dissolution rate of the mixture of crude pigment and pigment derivative in acid can be increased by heating the mixture (for example to about 50 ° C), it is generally preferable to dissolve the mixture in acid at 35 ° C or less so that sulfonation (when sulfuric acid is used) or degradation of the pigment or pigment derivative are minimal. 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 mixtures thereof. When sulfuric acid or oil is used in the preparation of the N-heteroarylamido-methyl pigment derivatives or the final pigment compositions, the pigment residue may be sulphonated. Said sulfonated derivatives can be isolated as free acid, ammonium salt or metal salt (including, for example, alkali metal salts such as sodium and potassium salts, alkaline earth metal salts such as calcium or barium salts and metal salts of the Group III as aluminum). In a second preferred method, an organic pigment is mixed with a suitable N-heteroarylamidomethyl 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 N-heteroarylamidomethyl pigment derivative 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, a N-heteroarylamidomethyl 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, thus forming a suspension of the pigment composition treated in the liquid, and (b) collecting the pigment composition. The liquid used for wet mixing 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 preferable that the N-heteroarylamidomethyl pigment derivative 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 less preferred in general. The temperature at which the wet mixing is carried out is not critical in general, but is usually 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 N-heteroarylamidomethyl pigment derivative is added during, or even before, the synthesis of the organic pigment being treated, in such a manner that the reaction and the treatment processes may take place in situ, at least in part, as the organic pigment is formed. For example, when preparing quinacridone pigments, a preferred method of preparation is to (a) heat, at a temperature from about 80 ° C to about 145 ° C (preferably 100 ° C to 130 ° C), a reaction mixture. consisting of (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 a 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 one 0.1 to 10 percent by weight), based on the component (a) (i), of a suitable N-heteroarylamidomethyl 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 the component (a) (i) or the component (a) (ii) is a 2, 5-dianilino-6, 13-dihydroterephthalic acid or derivative thereof, the reaction step (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 used, 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 are suitable, such as centrifugation or even simple decanting, but, in general, are less preferred. The pigment composition is then dried for use or for subsequent manipulation prior use. The pigment compositions according to the invention can be obtained by conditioning organic pigments in the presence of a N-heteroarylamidomethyl pigment derivative, carrying it out in place of or in addition to the preparation methods described above. It is, of course, possible to include one or more additional pigment derivatives known in the art, particularly sulfonic acid and sulfonamide derivatives. The conditioning can be carried out using any of various methods known in the art, such as solvent treatment or milling 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 derivatives thereof and inorganic solvents, such as water. Suitable additives include compositions that decrease or prevent flocculation, which 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 several 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 their corresponding amides, esters or salts, such as magnesium stearate, zinc stearate, aluminum stearate or magnesium behenate; quaternary ammonium compounds, such as tri [(C, -C4) benzyl] ammonium salts; plasticizers, such as epoxidized soybean oil; waxes, such as polyethylene wax; rosin acids, such as abietic acid, rosin soap, hydrogenated or dimerized rosin; paraffin acids (C12-C18) disulfonic; 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 from about 0.05 to about 20% by weight (preferably 1 to 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 pigmented systems which are very stable to light. Examples include pigmented blends with other materials, pigment formulations, paints, printing ink, 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 can be used include, for example, physical or oxidative drying lacquers, hot enamels, reactive paints, two-component paints, solvent or water-based paints, emulsion paints for waterproof coatings and tempers. Printing inks include those known for use in printing on paper, fabrics 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, which is set forth in the foregoing description, should not be limited in spirit or scope by these examples. Those skilled in the art will readily understand that known variations of the conditions and processes of the following preparatory procedures can be used to prepare these compositions. Unless otherwise indicated, all temperatures are degrees Celsius and all percentages are percentages by weight. EXAMPLES Preparation of pyrazolyl-imidamethyl pigment derivatives Pirazolylamidomethyl derivatives of quinacridone, phthalocyanine and perylene were prepared as follows: 3,5-Dimethylpyrazolyl-amidomethylquinacridone Method A. To 210 g of 100% sulfuric acid was added 3.0 g (0.10 mol) of paraformaldehyde with stirring over a period of 15 minutes at about 25 ° C. The acid mixture was stirred for a further 10 minutes, after which 13.92 g (0.10 mol) of 3,5-dimethylpyrazolyl-1-carboxamide was added over a period of 10 minutes. The reaction mixture was stirred for two hours at room temperature, then cooled to 5 ° C with external cooling. 31.2 g (0.10 mol) of quinacridone were added to this mixture over a period of 10 minutes at a temperature of 5-10 ° C. The mixture was stirred for two hours at 5-10 ° C and then allowed to warm to room temperature and stirred for 18 hours. The reaction mixture was then kept at 60 ° C for three hours. After cooling to 30 ° C, the reaction mixture was slowly poured into 2 kg of ice water over a period of 10 minutes. 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 to 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 41.5 g of 3,5-dimethylpyrazolylmidomethylguinacridone (90% yield). Method B (general method for the preparation of pyrazolylmethylquinacridones described in U.S. Patent 5,334,727). To 200 g of 96% sulfuric acid was added 31.2 g (0.10 mol) of quinacridone with stirring over a period of 15 minutes at about 35 ° C. The acid mixture was stirred for a further 15 minutes, after which 13.92 g (0.10 mol) of 3,5-dimethyl-pyrazolyl-1-carboxamide was added over a period of 15 minutes, while that the temperature was maintained below 40 ° C with external cooling. The resulting mixture was stirred for a further 5 minutes, after which 3.0 g (0.10 mol) of paraformaldehyde was added over a period of 15 minutes, while maintaining the temperature below 40 °. C. The reaction mixture was heated at 60 ° C for five hours. After cooling to 30 ° C, the reaction mixture was slowly poured into 1 kg of ice water over a period of 10 minutes. 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 to 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 41.9 g of 3,5-dimethylpyrazolylmidomethylquinacridone (90% yield). Di (3,5-dimethylpyrazolylmidomethyl) quinacridone To 260 g of 100% sulfuric acid was added 63.0 g (0.20 mol) of paraformaldehyde with stirring over a period of 15 minutes at about 25 ° C. 27.83 g (0.20 mol) of 3,5-dimethylpyrazolyl-1-carboxamide was added over a period of 30 minutes. The mixture was stirred for a further 10 minutes. The reaction mixture was stirred for two hours at room temperature and then cooled to 5 ° C with external cooling. To this mixture was added 31.2 g (0.10 mol) of quinacridone over a period of 10 minutes at a temperature of 5-10 ° C. The mixture was stirred for two hours at 5-10 ° C, then allowed to warm to room temperature and stirred for 18 hours. The reaction mixture was then kept at 60 ° C for three hours. After cooling to 30 ° C, the reaction mixture was slowly poured over 2 kg of ice water over a period of 10 minutes. 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 to 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 50.8 g of di (3,5-dimethylpyrazolylamidomethyl) quinacridone. 3, 5-Dimethylpyrazolylmidomethylphthalocyanine copper To 410 g of 96% sulfuric acid 6 ° C was added 8.3 g of 3,5-dimethylpyrazolyl-1-carboxamide. The acid mixture was stirred for 25 minutes, after which 1.8 g of paraformaldehyde was added. The resulting mixture was stirred for 1.5 hours while maintaining the temperature below 25 ° C. 29.1 g of copper phthalocyanine were then added to the reaction mixture over a period of 10 minutes. The reaction mixture was stirred for fifteen minutes at a temperature below 35 ° C and then heated for five hours at 50-55 ° C. After cooling to 25 ° C, the reaction mixture was slowly poured into 2 kg of ice water. The resulting suspension was stirred for 1.5 hours, 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 28.4 g of 3,5-dimethylpyrazolylmidomethylphthalocyanine copper.

Diimide of (3,5-dimethylpyrazolyalidomethyl) -N, N '-dimethylperylenetetracarboxylic acid To 600 g of 101% sulfuric acid at 6 ° C was added 13.9 g of 3,5-dimethylpyrazolyl-1-carboxamide. The acid mixture was stirred for 10 minutes, after which 3.0 g of paraformaldehyde was added, while maintaining the temperature below 10 ° C. The reaction mixture was stirred for 30 minutes at 20-25 ° C, after which 41.8 g of N, N'-dimethylperylenetetracarboxylic acid diimide were slowly added. The reaction mixture was stirred for five hours at 20-25 ° C and then for four hours at 110-115 ° C. After cooling to 24 ° C, the reaction mixture was slowly poured into 3 kg of ice water, while maintaining a temperature below 10 ° C. The resulting suspension was stirred for 1.5 hours, 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 39.6 g of (3,5-dimethylpyrazolyl-amidomethyl) -N, N'-dimethylperylenetetracarboxylic acid diimide. Examples 1-6 The preparation and the study of pigment compositions are described in Examples 1-6. 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). Studies with water-based paints Studies with water-based paints were carried out 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%. (At this point, samples of some of the dispersion concentrates were taken for viscosity determinations). 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 solids content of 50%. Measurements of mass tone and transparency were made 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% alkyd resin AROPLAZ® 1453-X-50 and 20% melamine / formaldehyde resin CYMEL® 325 at a total solids level of 57% were then applied to the base coat. a wet film thickness of 76 μm, left to stand 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 TINT-AYD® white dispersion% CW-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. The color measurements were made using films applied at 38 μm thickness of wet film 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 with a pigment-to-binder ratio of 18:12, using a water-dispersible aluminum pigment (which can be obtained as HYDRO PASTE® 8726 from Silberline Manufacturing Co., Inc. ), acrylic resin AROLON® 559-G4-70 and melamine / formaldehyde resin CYMEL® 325 in amounts that provided a pigment-to-binder ratio of 1: 2, an aluminum-to-pigment ratio of 20:80 and a total solids content of 43%. Color measurements were made using films applied at 38 μm wet film thickness and baked as described above. Transparent layers were then applied and baked as described above. The viscosity was measured on dispersion samples (taken before reducing the pigment-aligant ratio from 18:12 to 10:40) using a RheoStress RS100 Haake rheometer equipped with a temperature control (Fission Instruments, Paramus, New Jersey). The viscosities were determined as shear stress (mPa-s) at a cutting speed of 4 sec "1 and at a temperature of 25 ° C. Studies with solvent-based paints Studies were carried out with solvent-based paints using a generic system of Alkyd melamine paint Pigment dispersions were prepared using a 33% blend of AROPLAZ® 1453-X-50 alkyd resin (Reichhold Chemicals, Inc.), 63% xylene and 4% pigment, which gave a pigment-to-binder ratio of 4:33 and a total solids content of 37% The pigment-to-binder ratio 1:10 was reduced by the addition of a 2.3% alkyd resin AROPLAZ® 1453-X- 50 and 6.5% RESIMENE® 717 melamine resin (Monsanto Company), which gave a total solids content of 40% Mass mass measurements and transparency were made using films applied at 152 μm and 38 μm. μm of wet film thickness, respectively, and subjected to flash at temperature environment for 30 minutes and at 121 ° C for 30 minutes. Superfine printing paints were prepared with the dispersion described above, with a pigment-to-binder ratio of 4:33 adding 31% of a dispersion prepared with 30% AROPLAZ® 1453-X-50 alkyd resin, 20% xylene, 5% NUOSPERSE® 657 (Hüls America) and 50% Ti02 pigment TI-PURE® R-960 (DuPont); 21% AROPLAZ® 1453-X-50 alkyd resin and 7% RESIMENE® 717 melamine resin, which gave a pigment-to-binder ratio of 1: 2, a total solids content of 50% and a Ti02-a-pigment ratio of 90:10. Color measurements were made using films applied at 76 μm wet film thickness and flashed at room temperature for 30 minutes and at 121 ° C for 30 minutes. Metal paints were prepared from the dispersion described above, with a pigment-to-binder ratio of 4:33 using an aluminum paste (which can be obtained as 5251 AR from Silberline Manufacturing Co., Inc.), AROPLAZ alkyd resin ® 1453-X-50 and RESIMENE® 717 melamine resin in amounts that give a pigment-to-binder ratio of 1: 9, an aluminum-to-pigment ratio of 20:80 and a total solids content of 41%. Color measurements were made using films applied at 76 μm wet film thickness and flashed at room temperature for 30 minutes and at 121 ° C for 30 minutes. Example 1 (comparative) Pigmentary 2,9-dimethylquinacridone was prepared in the absence of an N-heteroarylamidomethyl pigment derivative according to the invention. To 300 g of polyphosphoric acid (112% phosphoric acid) heated to 88 ° C was added 68.2 g of 2,5-di (4-methylanilino) terephthalic acid over a period of 35 minutes, maintaining the temperature by below 120 ° C by adjusting the rate of addition. The reaction mixture was heated at 123 ° C for two hours. The melt was cooled to 93 ° C and then poured slowly into 494 g of methanol, keeping the temperature below 64 ° C by external cooling and adjusting the rate 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 resulting cake was resuspended from the filter press 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 it was free of alkalies and 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 as a magenta pigment. EXAMPLE 2 2,9-dimethylquinacridone prepared according to the method of Comparative Example 1 was admixed with 10% by weight of 3,5-dimethylpyrazolylamidomethylquinacridone. A water-based paint prepared as described above exhibited a more transparent dough tone and a greater metallic blue tone and gloss compared to a paint prepared using the 2,9-dimethylquina-cridone pigment of Example 1. The viscosity of a concentrate of the dispersion (sampled as described above) was compared with a comparative dispersion concentrate of the comparative 2,9-dimethylquinacridone pigment of Example 1 and with a comparative dispersion concentrate of 2,9-dimethylqui-nacridone mixed in dry with 10% by weight of 3,5-dimethylpyrazolylmethylquinacridone (prepared according to U.S. Patent 5,334,727). The results of the test are shown in the following Table. EXAMPLE 3 2,9-Dimethylquinacridone prepared according to the method of Comparative Example 1 was admixed with 10% by weight of di (3,5-dimethylpyrazolylmidomethyl) quinacridone. A water-based paint prepared as described above exhibited a more transparent dough tone and a greater metallic blue tone and gloss compared to a paint prepared using the dye pigment., 9-dimethyliso-nacridone of Example 1. The viscosity of a concentrate of the dispersion (sampled as described above) was compared with a comparative dispersion concentrate of the comparative 2,9-dimethylquinacridone pigment of Example 1 and with a concentrate. of comparative dispersion of 2,9-dimethylquinacridone mixed dry with 10% by weight of 3,5-dimethylpyrazolylmethylquinacridone (prepared according to US Patent 5,334,727). The results of the test are shown in the following Table. Table Viscosities of concentrated dispersions of the pigment compositions of Examples 2 and 3 Dispersion Concentrate Cutting tension (mPa-s) Example 1 (comparative) 7200 Comparative additive (1) 6400 Example 2 3000 Example 3 3000 ', o-Dimethylazoleimetiquinacridone (U.S. Patent 5,334,727). Example 4 2, 9-dimethylquinacridone (60 g) was prepared according to the method of Comparative Example 1, except for the addition of 6.8 g of 3,5-dimethylpyrazolyl-amidomethylquinacridone (10 wt.% Based on 2: 5 acid). di (4-methylanilino) terephthalic) to the polyphosphoric acid before adding the 2,5-di (4-methylanilino) terephthalic acid. A water-based paint prepared as described above exhibited a much more intense, brighter and more transparent mass tone and a greater metallic blue hue and gloss compared to a paint prepared using the pigment of 2,9-dimethylquina-cridone. Comparative Example 1. Example 5 Copper monochlorophthalocyanine was mixed dry (chlorine content of about 5.7% by weight) with 10% by weight of 3,5-dimethylpyrazolylmidomethylphthalocyanine copper. A water-based paint prepared as described above exhibited a brighter and more red dye and a greater metallic red tone and gloss compared to a water-based paint prepared using copper monochlorophthalocyanine that was not treated with 3, 5-dimethylpyrazolyl- copper amidomethylphthalocyanine. An alkyd paint based on solvents prepared as described above exhibited a greener tint and a higher metallic green tone compared to a solvent based paint prepared using copper monochlorophthalocyanine which was not treated with 3,5-dimethyl-pyrazolylmidomethylphthalocyanine copper. EXAMPLE 6 N, N'-dimethylperylenetetracarboxylic acid diimide was mixed dry with 10% by weight of (3,5-dimethylpyrazolyazolidomethyl) -N, N "-dimethylperylenetetracarboxylic acid diimide A water-based paint prepared as described above. described above exhibited a slightly lighter and slightly more opaque dye and dye blue and a greater metallic yellow tone compared to a water-based paint prepared using N, N'-dimethylperylenetetracarboxylic acid diimide which was not treated with diimide (3, 5-dimethylpyrazolyl-amidemethyl) -N, N'-dimethylperylenetetracarboxylic acid.

Claims (15)

1. 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, of a N-heteroarylamidomethyl pigment derivative having the formula where Q represents an organic pigment residue, NHet represents a nitrogen-containing heteroaromatic group attached at a nitrogen atom of the ring to the carbonyl function of the amidomethyl linking group and n - is from 1 to 4.
2. 2. A pigment composition according to Claim 1, wherein the organic pigment is treated with 1 to 10% by weight of the N-heteroarylamidomethyl pigment derivative.
3. 3. A pigment composition according to Claim 1, wherein the N-heteroarylamidomethyl pigment derivative is a pyrazolyl-dimethyl pigment derivative. . A pigment composition according to Claim 1, wherein the N-heteroarylamidomethyl pigment derivative is (a) a pyrazolylmidomethylquinacridone having the formula where R is Cj-Cg alkyl, Cj-Cg alkoxy, halogen or sulfoxy (or an amide thereof) attached to a carbon atom of the quinacridone ring, n is from 1 to 4 and r is zero to four; (b) a copper pyrazolyl amidomethylphthalocyanine having the formula where CuPc represents a phthalocyanine copper moiety, each R independently represents Cj-Cg alkyl, halogen or sulfoxyl (or its amides) bonded to a carbon atom of the phthalocyanine ring, n is from 1 to 4 and s is zero to 8; or (c) a pyrazolylmidomethylperylene having the formula wherein each R independently represents halogen, carboxamide or sulfonamide bonded to a carbon atom of the perylene ring, n is from 1 to 4 and t is zero to
4. 4.
5. 5. A pigment composition according to Claim 1, wherein the N-heteroarylamidomethyl pigment derivative is a pyrazolylmidomethylquinacridone having the formula where n is from 1 to 4.
6. 6. A pigment composition according to Claim 5, wherein the organic pigment is a quinacridone.
7. 7. A pigment composition according to Claim 1, wherein the N-hetero-arylamidomethyl pigment derivative is a copper pyrazolylmidomethylphthalocyanine having the formula where CuPc represents a phthalocyanine copper moiety.
8. 8. A pigment composition according to Claim 7, wherein the organic pigment is a copper phthalocyanine.
9. 9. A pigment composition according to claim 1, wherein the N-heteroarylamidomethyl pigment derivative is a pyrazolylmidomethylperylene having the formula where n is from 1 to 4
10. 10. A pigment composition according to Claim 9, wherein the organic pigment is a perylene.
11. 11. A pigment composition according to Claim 1, wherein the organic pigment is treated (a) by mixing a crude organic pigment with a N-heteroarylamidomethyl pigment derivative in a strong mineral acid, (b) wet or dry mixing a crude organic pigment or finished with a pigment derivative N-heteroarylamidomethyl, (c) adding an N-heteroarylamidomethyl pigment derivative during the synthesis of the organic pigment, (d) conditioning an organic pigment in the presence of a pigment derivative N-heteroarylamine dometyl, or (e) a combination of one or more of methods (a), (b), (c) and (d).
12. 12. A pigmented paint containing a pigment composition according to claim 1.
13. 13. A pigmented plastic containing a pigment composition according to claim 1.
14. 14. An ink containing as pigment a pigment composition according to claim 1. A toner containing as pigment a pigment composition according to Claim 1.