CA2224619C - Organic pigment composition - Google Patents

Abstract

This invention relates to pigment compositions comprising an organic pigment treated with about 0.1 to about 20% by weight, based on the organic pigment, of an N-heteroarylamidomethyl pigment derivative having the formula (I)

Description

Mo-4630 ORGANIC PIGMENT COMPOSITIONS
BACKGROUND OF THE INVENTION

This invention relates to pigment compositions obtained by treating organic pigments with N-heteroarylamidomethyl pigment derivatives that impart excellent pigmentary and improved rheological properties.
The chemistry used in the manufacture of known organic pigments is generally straightforward. Typically, however, the initially formed crude compounds 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 to achieve suitable pigmentary quality, rheological properties, and dispersibility.
Methods to improve rheological properties are known. For example, pigments can be treated with various additives, such as sulfonic acid and sulfonamide derivatives of various pigments. E.g., U.S. 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 disclosed for use as pigment additives. For example, pyrazolylmethyl quinacridone derivatives are described in U.S. Patent 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 benzamidomethyl quinacridones and structurally related phthalimidomethyl and sulfobenzimidomethyl quinacridones are described in U.S. Patents 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, disclose compounds in which amide carbonyl groups are attached to benzene rings at ring carbon atoms and do not suggest -Mo-4630 .2 compounds in which an amide carbonyl group is att ached to a ring nitrogen atom, another critical feature of the present invention.
it has now surpris'rngly been found that pigment compositions having excellent pigmentary quality and rheological properties can be obtained by treating organic pigments with certain pigment derivatives bearing one or more heteroarylamidomethyl substrtuents in which the carbonyl function of each amidomethyl linking group is attached at a ring nitrogen atom of a nitrogen-containing heteroaromatic group.
SUMMARY OF THE INVENTION
This invention relates to pigment compositions comprising an organic pigment treated with about 0.1 to about 20% by weight (preferably 1 to 10% by weight), based on the organic pigment, of an N-heteroarylamidomethyl pigment derivative (preferably a pyrazolylamido-methyl pigment derivative) having the formula ({) Ct-NH-C-NHet (I) n wherein Q represents an organic pigment moiety, NHet represents a nitrogen-containing heteroaromatic group attached at a ring nitrogen atom to the carbonyl function of the amidomethyl -CH2-NH-CO- linking group, and n is from 1 to 4.
This invention further relates to the use of such pigment composi-tions in the pigmentation of paints, plastics, fibers, inks, and toners.

-2a-Thus, in a specific embodiment of the invention, there is provided a pigmented paint containing a pigment composition of the invention and a paint vehicle for the composition.
In still another specific embodiment of the invention, there is provided an ink containing as pigment, a pigment composition of the invention and an ink vehicle for the composition.
In a further specific embodiment of the invention, there is provided a toner containing as pigment, a pigment composition of the invention, and a toner vehicle for the composition.

lo DETAILED DESCRIPTION OF THE INVENTION
Suitable organic pigments that can be treated by the process of the present invention include quinacridone, phthalocyanine, and perylene pigments, as well as other known organic pigments. Mixtures, including solid solutions, of such pigments are also suitable.

Mo-4630 - 3 -Quinacridone pigments are particulariy suitable organic pigments.
Quinacridones (which, as used herein, includes unsubstituted quin-acridone, quinacridone derivatives, and solid solutions thereof) can be prepared by any of several methods known in the art but are preferably prepared by thermally ring-closing various 2,5-dianilinoterephthalic acid precursors in the presence of polyphosphoric acid. E.g., S.S. Labana and L.L. Labana, "Quinacridones" in Chemical Review, 67, 1-18 (1967), and U.S. Patents 3,157,659, 3,256,285, 3,257,405, and 3,317,539. Suitable quinacridone pigments can be unsubstituted or substituted (for example, with one or more alkyl, alkoxy, halogens such as chlorine, or other substituents typical of quinacridone pigments).
Metal phthalocyanine pigments are also suitable organic pigments.
Although copper phthalocyanines are preferred, other metal-containing phthalocyanine pigments, such as those based on zinc, cobalt, iron, nickel, and other such metals, may also be used. Suitable phthalocyanine pigments can be unsubstituted or partially substituted (for example, with one or more alkyl, alkoxy, halogens such as chlorine, or other substitu-ents typical of phthalocyanine pigments). 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 the phthalonitrile itself), and an optional catalyst, preferably in an organic solvent. E.g., W. Herbst and K. Hunger, Industrial Organic Pigments (New York: VCH Publishers, Inc., 1993), pages 418-427, H. Zollinger, Color Chemistry (VCH Verlagsgesselischaft, 1973), pages 101-104, and N.M. Bigelow and M.A. Perkins, "Phthalocyanine Pigments" in The Chemistry of Synthetic Dyes and Pigments, ed. H.A. Lubs (Malabar, Florida: Robert E. Krieger Publishing Company, 1955), pages 584-587;
see also U.S. Patents 4,158,572, 4,257,951, and 5,175,282 and British Patent 1,502,884.

Mo-4630 - 4 -Perylenes, particularly the diimides and dianhydrides of peryiene-3,4,9,10-tetracarboxylic acid, are also suitable organic pigments. Suitable perylene pigments can be unsubstituted or substituted (for example, w(dh one or more alkyl, alkoxy, halogens such as chlorine, or other substitu-ents typical of peryiene pigments), including those substituted at imide nitrogen atoms with chemically reasonable groups such as alkyl. Crude peryienes can be prepared by methods known in the art. E.g., W. Herbst and K. Hunger, Industrial Organic PiQments (New York: VCH Publishers, Inc., 1993), pages 9 and 467-475, H. Zollinger, Color Chemistry (VCH
Verlagsgessellschaft, 1973), pages 227-228 and 297-298, and M.A.
Perkins, "Pyridines and Pyridones" in The Chemistry of Synthetic Dyes and Pigments, ed. H.A. L'ubs (Malabar, Florida: Robert E. Kriet3er Publishing Company, 1955), pages 481-482.
Other suitable organic pigments include dioxazines (that is, triphenedioxazines), 1,4-diketopyrrolopyrroles, anthrapyrimidines, anthanthrones, flavanthrones, indanthrones, isoindolines, isoindolinones, perinones, pyranthrones, thioindigos, 4,4'-diamino-l,1'-dianthraquinonyl, 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 N-heteroarylamido-methyl pigment derivatives in a strong mineral acid, by wet or dry blending crude or finished organic pigments with N-heteroarylamido-methyl pigment derivatives, or by adding N-heteroarylamidomethyl pigment derivatives during pigment synthesis. It is also possible to treat organic pigments by conditioning in the presence of N-heteroarylamido-methyl pigment derivatives. Combinations of such methods are also suitable.
Suitable N-heteroarylamidomethyl pigment derivatives are compounds having the formu(a (I) Mo-4630 - 5 -O

Q CH2 NH-C-NHet (I) n in which Q represents an organic pigment moiety; NHet represents a nitrogen-containing heteroaromatic group attached at a ring nitrogen atom to the carbonyl function of the amidomethyl (i.e., -CH2-NH-CO-) linking group; and n is from 1 to 4. Preferred N-heteroarylamidomethyl pigment derivatives are those containing from one or two (preferably one) N-heteroarylamidomethyl groups attached to pigment moiety Q.
Pigment moiety Q can be derived from essentially any class 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, triphene-dioxazines), 1,4-diketopyrrolopyrroles, anthrapyrimidines, anthanthrones, flavanthrones, indanthrones, isoindolines, isoindolinones, perinones, pyranthrones, thioindigos, 4,4'-diamino-l,1'-dianthraquinonyl, or azo compounds, as well as substituted derivatives thereof. Suitable deriva-tives include those having one or more substituents that are typical of such pigments, such as C1-C6 alkyl, Cl-C6 alkoxy, C5-C7 cycloalkyl, C5-C7 cycloalkoxy, Cs-C10 aryl, C6'C10 aryloxy, CTC16 aralkyl, C7-C16 aralkoxy, hydroxy, halogen, nitrile, carboxyl or amides thereof, sulfonyl groups (such as alkyl- and arylsulfonyl or sulfoxyl and amides thereof) or combinations thereof. Substituted derivatives of pigment moiety Q can, of course, include those in which ring nitrogen atoms 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 pigment moiety Q is the same pigment type as the organic pigment being treated. However, it can often be desirable to use N-heteroaryl-amidomethyl pigment derivatives in which the pigment moiety Q is a different pigment type from the organic pigment being treated. Preferred Mo-4630 - 6 -pigment derivatives are those derived from quinacridones, phthalo-cyanines, and perylenes.
Suitable heteroaromatic NHet groups are nitrogen-containing aromatic species in which the ring nitrogen atom that is attached to the amidomethyl linking group cannot be quaternary (i.e., tetravalent).
Preferred nitrogen-containing heteroaromatic NHet groups include pyrrolyl, imidazolyl, and pyrazolyl groups or derivatives thereof in which one or more ring carbon atoms are substituted with Ci-C6 alkyl, Cl-Cs alkoxy, C5-C7 cycloalkyl, C5-C7 cycloalkoxy, C6-C10 aryl, Cs-CjO
aryloxy, C7-C16 aralkyl, C7-C16 aralkoxy, hydroxy, halogen, nitrile, carboxyl or amides thereof, sulfonyl groups (such as alkyl- and arylsulfonyl or sulfoxyl and amides thereof) or combinations thereof.
As used herein, the term "Ci-C6 alkyl" refers to straight or branched chain aliphatic hydrocarbon groups having from 1 to 6 carbon atoms. Examples of Ci-C6 alkyl are methyl, ethyl, propyl, butyl, pentyl, hexyl, and the isomeric forms thereof. The term "Ci-Cs alkoxy" refers to straight or branched chain alkyl oxy groups having from 1 to 6 carbon atoms. Examples of Ci-C6 alkoxy are methoxy, ethoxy, propoxy, butoxy, pentytoxy, hexyloxy, and the isomeric forms thereof. The term "C5-C7 cycloalkyl" refers to cycloaliphatic hydrocarbons groups having from 5 to 7 carbon atoms. Examples of C5-C7 cycloalkyl are cyclopentyl, cyclo-hexyl, and cycloheptyl. The term "C5-C7 cycloalkoxy" refers to cycloalkyl oxy groups having from 5 to 7 carbon atoms. Examples of C5-C7 cyclo-alkoxy are cyclopentyloxy, cyclohexyloxy, and cycloheptytoxy. The term "C6-Cio aryl" refers to phenyl and 1- or 2-naphthyl, as well as to phenyl and naphthyl groups substituted with alkyl, alkoxy, halogen, cyano, as defined herein. The term "C6-C l0 aryloxy" refers to phenoxy and 1- or 2-naphthoxy, in which the aryl portion can optionally be substituted as described above for "aryl" The term "C7-C16 aralkyl" refers to Ci-Cs alkyl substituted with C6-Cjp aryl such that the total number of carbon Mo-4630 - 7 -atoms is from 7 to 16. Examples of C7-C16 aralkyl are benzyl, phenethyl, and naphthyimethyl. The term "C7-C16 aralkoxy" refers to Ci-Cs alkoxy substituted with C6-Clo aryl such that the total number of carbon atoms is from 7 to 16. An example of C7-C16 aralkoxy is benzyloxy. Examples of halogen are fluorine, chlorine, bromine, and iodine. A particularly preferred heteroaromatic NHet group is the 3,5-dimethylpyrazolyl group attached to the amidomethyl linking group at the 1-nitrogen.
Suitable, but generally less preferred, heteroaromatic NHet groups include polyaromatic pyrrolyl, imidazolyi, or pyrazolyl derivatives in which one or two pairs of adjacent ring carbon atoms are fused with aromatic rings (such as benzene or heteroaromatic analogs thereof) that can themselves be ring-substituted as described above or, less preferably, that can contain one or more ring heteroatoms selected from 0, S, and N. Examples of suitable such polyaromatic NHet groups include indolyl and isoindolyl (i.e., benzo derivatives of pyrrole), carbazolyl (i.e., a dibenzo derivative of pyrrole), indazolyl, and benzimidazolyl, as well as ring-substituted derivatives thereof.
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-hetero-arylcarboxamide (such as pyrazolyl-l-carboxamide) or derivative thereof and formaldehyde or a functional equivalent (such as the polymeric form paraformaidehyde or a formaldehyde-producing compound such as trioxane) or with a corresponding N-methylol derivative of a N-hetero-arylcarboxamide in the presence of a dehydrating agent at a temperature of about 0 to about 200 C. Suitable dehydrating agents include sulfuric acid, oleum, polyphosphoric acid, organic acids or their anhydrides, and mixtures thereof. Oleum is a particularly suitabte condensing agent, especially for the less reactive pigments. The degree of N-heteroaryl-amidomethyl substitution on the pigment molecule can be affected by Mo-4630 - 8 -various factors, such as the quantity of N-heteroarylcarboxamide, the reaction temperature, and length of reaction. The resultant N-heteroaryl-amidomethyl pigment derivatives can be isolated by adding 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 can 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-heteroarylamidomethyl pigment derivatives for use in treating pigrrients according to the invention include (a) pyrazolylamidomethylquinacridones having the formula (II) Rr ) CH2 NH-C-N ~ (II) ~ N N CH3 0 H -n in which R is Ci-C6 alkyl, Cj-C6 alkoxy, halogen, or sulfoxyl (or an amide thereof) attached to a quinacridone ring carbon atom; 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) pyrazolylamidomethyl copper phthalocyanines having the formula (III) Mo-4630 - 9 -II
CuPc CHZ NH-C-N' ~ (III) I's N CH3 n in which CuPc represents a copper phthalocyanine moiety; each R
independently represents CI-C6 alkyl, halogen, or sulfoxyl (or an amide thereof) attached to a phthalocyanine ring carbon atom; 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 copper phthalocyanine moiety is not substituted with R groups); and (c) pyrazolylamidomethylperyienes having the formula (N) \ / O \
Rt I CF{2 NH-C-N (IV) / I \ N CH3 \ / n in which each R independently represents halogen, carboxamido, or sulfonamido attached to a perylene ring carbon atom; 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 perylene moiety is not substituted with R groups).

Mo-4630 - 10 -Formulas (II), (III), and (IV) are not intended to indicate specific locations for the R groups and pyrazolylamidomethyl groups but rather to indicate that such groups are located in chemically reasonable positions of each pigment moiety.
Several methods for preparing the pigment compositions of the invention are known. In one preferred method, a crude organic pigment and a suitable N-heteroarylamidomethyl pigment derivative are dissolved ("pasted") or suspended {"swelled") in a strong mineral acid and then precipitated. A sufficient amount of mineral acid, preferably concentrated acid, is added to insure formation of an acidic solution or suspension within a reasonable amount of time. However, except for the requirement that the solution or suspension be acidic, the amount and concentration of acid is generally not critical. For example, more dilute acid may be used if the stirring time is extended, but use of the 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 warming the mixture (for example, to about 50 C), it is generally preferable to dissolve the mixture in acid at or below 35 C to minimize sulfonation (when using sulfuric acid) or degradation of the pigment or pigment derivative. After the acid treatment is completed, the pigment composition is precipitated by adding the strongly acidic solution to a liquid in which the pigment and pigment derivative are 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.

Mo-4630 - 11 -When using sulfuric acid or oleum in the preparation of the N-heteroarylamidomethyl pigment derivatives or of the ultimate pigment compositions, the pigment moiety can be sulfonated. Such sulfonated derivatives can be isolated as the free acid, an ammonium salt, or a metal salt (including, for example, alkali metal salts such as those of sodium or potassium, alkaline earth metal salts such as those of calcium or barium, and Group III metal salts such as those of aluminum).
In a second preferred method, an organic pigment is blended with a suitable N-heteroarylamidomethyl pigment derivative using wet or dry blending variants. The dry blending variant comprises (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 an N-Fieteroarylamido-methyl pigment derivative of formula (I); and (b) collecting the pigment composition. The wet blending variant comprises (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 an 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, thereby forming a suspension of the treated pigment composition in the liquid; and (b) coltecting the pigment composition. The liquid used for wet blending 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 for the N-heteroarylamido-methyl pigment derivative to be at least partly insoluble in the liquid.
Suitable liquids include water and/or water-miscible organic liquids;
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 dimethyl-acetamide; ethers, such as tetrahydrofuran and dioxane; alkylene glycols Mo-4630 - 12 -and triols, such as ethylene glycol and glycerol; and other such organic liquids known in the art. Other organic liquids can be used but are generally less preferred. The temperature at which wet blending is carried out is generally not critical 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-heteroaryl-amidomethyl pigment derivative is added during or even before synthesis of the organic pigment being treated such 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 preparative method comprises (a) heating, at a temperature of about 80 C to about 145 C (preferably 100 C to 130 C), a reaction mixture comprising (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 in 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 percent by weight (preferably 0.1 to 10 percent by weight), based on 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 either component (a)(i) or component (a)(ii) is a 2,5-dianifino-6,13-dihydroterephthalic acid or derivative thereof, reaction step (a) additionally comprises an oxidation step (which converts the initially formed dihydroquinacridone intermediate to the corresponding quinacridone); (b) drowning the reaction mixture from step (a) by adding said reaction mixture to about 3 to about 15 parts by weight (preferably 5 to 10 parts by weight), per part of component (a)(i), of a liquid in which Mo-4630 - 13 -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 resuftant 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 decantation, are suitable but generally less preferred. The pigment composition is then dried for use or for further manipulation before use.
Pigment composi#ions according to the invention can be obtained by conditioning organic pigments in the presence of N-heteroarylamido-methyl pigment derivative, carried out either instead 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 sulfonamide derivatives. 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. Final particle size of the pigment can be controlled by varying the method of aftertreatment. For example, pigments can be made more transparent by reducing the particle size or more opaque by increasing the particle size.
Suitable milling methods include dry-milling methods such as sand-milling, ball-milling, and the like, with or without additives, or wet-milling methods such as salt-kneading, bead-milling, and the like in water or organic solvents, with or without additives.
Tinctorial strength and transparency of the pigment can also be affected by 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, Mo-4630 - 14 -esters, ketones, and aliphatic and aromatic hydrocarbons and derivatives thereof, and inorganic solvents, such as water. Suitable additives include compositions that lessen or avoid flocculation, increase dispersion stability, and reduce coating viscosity, such as polymeric dispersants (or surfactants). E.g., U.S. Patents 4,455,173, 4,758,665, 4,844,742, 4,895,948, and 4,895,949.
During or after the optional conditioning step it is often desirable to use various other optional ingredients that provide improved properties.
Examples of such optional ingredients include fatty acids having at least 12 carbon atoms, such as stearic acid or behenic acid, or corresponding amides, esters, or salts, such as magnesium stearate, zinc stearate, aluminum stearate, or magnesium behenate; quatemary ammonium compounds, such as tri[(Cl-C4 alkyl)benzyl]ammonium salts; plasticizers, such as epoxidized soya bean oil; waxes, such as polyethylene wax;
resin acids, such as abietic acid, rosin soap, hydrogenated or dimerized rosin; C12-C,$-paraffin-disulfonic acids; alkylphenols; alcohols, such as stearyl alcohol; amines, such as laurylamine or stearylamine; and aliphatic 1,2-diols, such as dodecane-1,2-diol. Such additives can be incorporated in amounts ranging from about 0.05 to 20% by weight (preferably 1 to 10% by weight), based on the amount of pigment.
Because of their light stability and migration properties, the pigment compositions according to the present invention are suitable for many different pigment applications. For example, pigment compositions according to the invention can be used as the colorant (or as one of two or more colorants) for very lightfast pigmented systems. Examples include pigmented mixtures with other materials, pigment formulations, paints, printing ink, colored paper, or colored macromolecular materials.
The term "mixtures with other materials" is understood to include, for example, mixtures with inorganic white pigments, such as titanium dioxide or cement, or other inorganic pigments. Examples of pigment Mo-4630 - 15 -formulations include flushed pastes with organic liquids or pastes and dispersions with water, dispersants, and, where appropriate, preserva-tives. Examples of paints in which pigment compositions of the invention can be used include, for example, physically or oxidatively drying lacquers, stoving enamels, reactive paints, two-component paints, solvent- or water-based paints, emulsion paints for weatherproof coatings, and distempers. Printing inks include those known for use in paper, textile, and tinplate printing. Suitable macromolecular substances include those of a natural origin, such as rubber; those obtained by chemical modification, such as acetyl cellulose, cellulose butyrate, or viscose; or those produced synthetically, such as polymers, polyaddition products, and polycondensates. Examples of synthetically produced macro-molecular 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 materials pigmented with the pigment compositions of the present invention can have any desired shape or form.
The pigment compositions prepared according to this invention are highly water-resistant, oil-resistant, acid-resistant, lime-resistant, alkaii-resistant, solvent-resistant, fast to over-lacquering, fast to over-spraying, fast to sublimation, heat-resistant, and resistant to vulcanizing, yet give a very good tinctorial yield and are readily dispersible (for example, in plastic materials).
The following examples further illustrate details for the preparation and use of the compositions of this invention. The invention, which is set forth in the foregoing disclosure, is not to be {imited either 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 Mo-4630 - 16 -preparative procedures can be used to prepare these compositions.
Unless otherwise noted, all temperatures are degrees Celsius and all percentages are percentages by weight.
EXAMPLES
Preparation of pvrazolyiamidomethyl pigment derivatives Pyrazolylamidomethyl derivatives of quinacridone, phthalocyanine, and peryiene were prepared as follows:

3, 5-DimethylpyrazolylamidomethvlQuinacridone N N CH
' 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 acidic mixture was stirred for an additional 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 extemal 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 tempera-ture and stir for 18 hours. The reaction mixture was then held at 60 C for three hours. After being cooled to 30 C, the reaction mixture was slowly poured into 2 kg of iced water over a period of 10 minutes. The resultant slurry was stirred for 30 minutes, after which the solid was isolated by filtration and washed with water. The wet presscake was reslurried with water and heated to 60 C, after which the solid was isolated by filtration and washed with water. The wet presscake was dried in an oven at 60 C

Mo-4630 - 17 -to give 41.5 g of 3,5-dimethylpyrazolylamidomethylquinacridone (90%
yield).
Method B (general method for the preparation of pyrazolylmethyl-quinacridones 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 acidic mixture was stirred for an additional 15 minutes, after which 13.92 g (0.10 mol) of 3,5-dimethylpyrazolyl-l-carboxamide was added over a period of 15 minutes while the temperature was maintained below 40 C with extemal cooling.
The resultant mixture was stirred for an additional 5 minutes, after which 3.0 g (0.10 mol) of paraformaldehyde was added over a period of 15 minutes while the temperature was maintained below 40 C. The reaction mixture was heated at 60 C for five hours. After being cooled to 30 C, the reaction mixture was slowly poured into 1 kg of iced water over a period of 10 minutes. The resultant slurry was stirred for 30 minutes, after which the solid was isolated by filtration and washed with water. The wet presscake was reslurried with water and heated to 60 C, after which the solid was isolated by filtration and washed with water. The wet presscake was dried in an oven at 60 C to give 41.9 g of 3,5-dimethylpyrazolyi-amidomethylquinacridone (90% yield).
Di(3.5-dimethylcyrazolylamidomethyl)Quinacridone H 0 Cti3 \ I \ ~ ~/ CH2 NH-C-N' 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.
The acidic mixture was stirred for an additional 10 minutes, after which 27.83 g (0.20 mol) of 3,5-dimethylpyrazolyi-l-carboxamide was added = CA 02224619 1997-12-11 Mo-4630 - 18 -over a period of 30 minutes. The reaction mixture was stirred for two hours at room temperature, then cooled to 5 C with extemal cooling. To this mixture was added 31.2 g(0.10 mol) of quinacridone over a period of minutes at a temperature of 5-10 C. The mixture was stirred for two 5 hours at 5-10 C, then allowed to warm to room temperature and stir for 18 hours. The reaction mixture was then held at 60 C for three hours.
After being cooled to 30 C, the reaction mixture was slowly poured into 2 kg of iced water over a period of 10 minutes. The resultant slurry was stirred for 30 minutes, after which the solid was isolated by fiftration and 10 washed with water. The wet presscake was reslurried with water and heated to 60 C, after which the solid was isolated by filtration and washed with water. The wet presscake was dried in an oven at 60 C to give 50.8 g of di(3,5-dimethylpyrazolylamidomethyl)quinacridone.
3.5-Dimethylgyrazolylamidomethyi copper ahthalocyanine O
II
CuPc-CHZ NH-C-N' To 410 g of 96% sulfuric acid at 6 C was added 8.3 g of 3,5-dimethylpyrazolyl-l-carboxamide. The acidic mixture was stirred for 25 minutes, after which 1.8 g of paraformaldehyde was added. The resultant mixture was stirred for 1.5 hours while the temperature was maintained below 25 C. To the reaction mixture was then added 29.1 g of copper phthalocyanine 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 being cooled to 25 C, the reaction mixture was slowly poured into 2 kg of iced water. The resultant slurry was stirred for 1.5 hours, after which the solid was isolated by filtration and washed with water. The wet presscake was reslurried with water and heated for Mo-4630 - 19 -30 minutes at 60 C, after which the solid was isolated by filtration and washed with water. The wet presscake was dried in an oven at 60 C to give 28.4 g of 3,5-dimethylpyrazolylamidomethyl copper phthalocyanine.
(3, 5-Dimethylpyrazolylamidomethyl)-N. N'-dimethylperylenetetracarboxvlic acid diimide CH2 NH-C-N' / I \ N CH3 To 600 g of 101% sulfuric acid at 6 C was added 13.9 g of 3,5-dimethylpyrazolyl-l-carboxamide. The acidic mixture was stirred for 10 minutes, after which 3.0 g of paraformaldehyde was added while the temperature was maintained below 10 C. The reaction mixture was stirred for 30 minutes at 20-25 C, after which 41.8 g of N,N'-dimethyl-perylenetetracarboxylic acid diimide was slowly added. The reaction mixture was stirred for five hours at 20-25 C and then for four hours at 110-115 C. After being cooled to 24 C, the reaction mixture was slowly poured into 3 kg of iced water while maintaining a temperature below 10 C. The resultant slurry was stirred for 1.5 hours, after which the solid was isolated by filtration and washed with water. The wet presscake was reslurried with water and heated for 30 minutes at 60 C, after which the solid was isolated by filtration and washed with water. The wet presscake Mo-4630 - 20 -was dried in an oven at 60 C to give 39.6 g of (3,5-dimethylpyrazolyl-amidomethyl)-N,N'-dimethylperylenetetracarboxylic acid diimide.
Examples 1-6 The preparation and testing of pigment composifions are described in Examples 1-6.
Differences in hue and chroma for pigments prepared according to the Examples were measured using an Applied Color System Spectral Sensor (Hunt Associated Laboratories, Fairfax, Virginia).
Water-based paint tests Water-based paints tests were carried out using a waterbome base coat/solvent-bome clear coat system. Aqueous dispersions were prepared using a mixture of 12.4% AROLON 559-G4-70 acrylic resin (Reichhold Chemicals, Inc.), 3.2% SOLSPERSE 27000 hyperdispersant (Zeneca, Inc.), 1.6% 2-amino-2-methyl-l-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 drawn for viscosity determinations.) The pigment-to-binder ratio was then reduced to 10:40 with additional AROLON
559-G4-70 acrylic resin (total amount 26%) and 25% CYMEL 325 melamine/formaidehyde resin (Cytec Industries), which gave a total solids content of 50%. Masstone and transparency measurements were made using films applied at 76 pm and 38 pm wet film thickness, respectively, and allowed to stand at room temperature for fifteen minutes and at 100 C for five minutes. Clear coats containing a mixture of 80% of AROPLAZ 1453-X-50 alkyd resin and 20% CYMEL 325 melamine/
formaldehyde resin at a total solids level of 57% were then applied over the base coat at a 76 pm wet film thickness allowed to stand at room temperature for fifteen minutes and at 121 C for fifteen minutes.
Undertone tint paints were prepared from the reduced aqueous dispersions described above having a pigment-to-binder ratio of 10:40 by = CA 02224619 1997-12-11 Mo-4630 - 21 -adding additional AROLON 559-G4-70 acrylic resin, CYMEL 325 melamine/formaldehyde resin, and 35% TINT-AYD CW-5003 white dispersion (Daniel Products Company), which gave a pigment-to-binder ratio of 1:1.1, a total solids content of 55%, and a Ti02-to-pigment ratio of 90:10. Color measurements were made using films applied at 38 pm wet film thickness and allowed to stand at room temperature for fifteen minutes and at 100 C for five minutes. Clear coats were then applied and baked as described above.
Metallic paints were prepared from the dispersion described above having a pigment-to-binder ratio of 18:12 using a water-dispersible aluminum pigment (available as HYDRO PASTE 8726 from Silberiine Manufacturing Co., Inc.), AROLON 559-G4-70 acrylic resin, and CYMEL 325 melamine/formaidehyde resin in quantities 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 pm wet film thickness and baked as described above.
Clear coats were then applied and baked as described above.
Viscosity was measured on dispersion samples (taken before reducing the pigment-to-binder ratio from 18:12 to 10:40) using a Haake RheoStress RS100 rheometer fitted with a temperature control (Fision Instruments, Paramus, New Jersey). Viscosities were determined as shear stress (mPa-s) at a shear rate of 4 sec 1 at a temperature of 25 C.
Solvent-based aaint tests Solvent-based paint tests were carried out using a generic alkyd melamine paint system. Pigment dispersions were prepared using a mixture of 33% 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 was reduced 1:10 by addition of 2.3% AROPLAZ 1453-X-50 alkyd resin and 6.5% RESIMENE 717 melamine resin (Monsanto Company), which Mo-4630 - 22 -gave a total solids content of 40%. Masstone and transparency measure-ments were made using films applied at 152 pm and 38 pm wet film thickness, respectively, and flashed at room temperature for 30 minutes and at 121 C for 30 minutes.
Undertone tint paints were prepared from the dispersion described above having a pigment-to-binder ratio of 4:33 by adding 31% of a dispersion prepared from 30% AROPLAe 1453-X-50 alkyd resin, 20%
xylene, 5% NUOSPERSE 657 (Huls America), and 50% TI-PURE
R-960 Ti02 pigment (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-to-pigment ratio of 90:10. Color measurements were made using films applied at 76 pm wet film thickness and flashed at room temperature for 30 minutes and at 121 C for 30 minutes.
Metallic paints were prepared from the dispersion described above having a pigment-to-binder ratio of 4:33 using an aluminum paste (avail-able as 5251 AR from Silberline Manufacturing Co., Inc.), AROPIA.4 1453-X-50 alkyd resin, and RESIMENE 717 melamine resin in quantities that provided a pigment-to-binder ratio of 1:9, an aluminum-to-pigment ratio of 20:80, and a total solids content of 41 %. Color measure-ments were made using films applied at 76 pm wet film thickness and flashed at room temperature for 30 minutes and at 121 C for 30 minutes.
Example 1 (comparison) 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 at 88 C was added 68.2 g of 2,5-di(4-methylanilino)terephthalic acid over a period of 35 minutes, the temperature being maintained below 120 C by adjustment of the addition rate. The reaction mixture was heated at Mo-4630 - 23 -123 C for two hours. The melt was cooled to 93 C and then slowly poured into 494 g of methanol, the temperature being maintained below 64 C by external cooling and adjustment of melt addition rate. The slurry was heated at reflux for one hour, cooled to below 60 C, diluted with water, collected by filtration, and washed with water until acid free. The resultant presscake was reslurried in water. After adjustment of the pH to greater than 7, 5.5 g of 50% sodium hydroxide was added and the resultant slurry was heated at 90 C for one hour. The slurry was cooled, filtered, and washed with water until alkaline free, then reslurried in water.
After adjustment of the pH to 9.5, the slurry was heated at 143 C for two hours in a closed system (e.g., a pressure reactor), and cooled to 40 C.
After the slurry was acidified to 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 slurry was stirred for three hours. The wet cake was dried in an oven at 60 C to give approximately 60 g of 2,9-dimethylquinacri-done as a magenta pigment.
Example 2 2,9-Dimethylquinacridone prepared according to the method of comparison Example 1 was dry-blended with 10% by weight of 3,5-dimethylpyrazolylamidomethylquinacridone.
A water-based paint prepared as described above exhibited a more transparent masstone and increased metallic blueness and brightness compared to a paint prepared using the comparison 2,9-dimethyiquinacridone pigment of Example 1.
The viscosity of a dispersion concentrate (sampled as described above) was compared with a comparison dispersion concentrate of the comparison 2,9-dimethylquinacridone pigment of Example 1 and with a comparison dispersion concentrate of 2,9-dimethylquinacridone dry-blended with 10% by weight of 3,5-dimethylpyrazolylmethylquinacridone Mo-4630 - 24 -(prepared according to U.S. Patent 5,334,727). Test results are shown in the Table below.
Example 3 2,9-Dimethylquinacridone prepared according to the method of comparison Example 1 was dry-blended with 10% by weight of di(3,5-dimethylpyrazolylamidomethyl)quinacridone.
A water-based paint prepared as described above exhibited a more transparent masstone and increased metallic blueness and brightness compared to a paint prepared using the comparison 2,9-dimethylquinacridone pigment of Example 1.
The viscosity of a dispersion concentrate (sampled as desc(bed above) was compa'red with a comparison dispersion cohcentrate of the comparison 2,9-dimethylquinacridone pigment of Example 1 and with a comparison dispersion concentrate of 2,9-dimethylquinacridone dry-blended with 10% by weight of 3,5-dimethylpyrazolylmethylquinacridone (prepared according to U.S. Patent 5,334,727). Test results are shown in the Table below.

Table Viscosities of concentrated dispersions of the pigment compositions of Examples 2 and 3 Dispersion Shear stress concentrate (mPa-s ) Example 1 (comp) 7200 Comparison additive(l) 6400 Example 2 3000 Example 3 3000 (1) 3,5-dimethylpyrazolylmethylquinacridone (U.S. Patent 5,334,727) Mo-4630 - 25 -Examale 4 2,9-Dimethylquinacridone (60 g) was prepared according. to the method of comparison Example 1 except that 6.8 g of 3,5-dimethyl-pyrazolylamidomethylquinacridone (10% by weight based on the 2,5-di(4-methylanilino)terephthalic acid) was added 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 deeper, brighter, more transparent masstone and increased metallic blueness and brightness compared to a paint prepared using the comparison 2,9-dimethylquinacridone pigment of Example 1.
Example 5 Monochlorol copper phthalocyanine chlorine content of about 5.7%
by weight) was dry-blended with 10% by weight of 3,5-dimethylpyrazolyl-amidomethyl copper phthalocyanine.
A water-based paint prepared as described above exhibited a brighter, redder tint and increased metallic redness and brightness compared to a water-based paint prepared using monochloro copper phthalocyanine that was not treated with 3,5-dimethylpyrazolylamido-methyl copper phthalocyanine.
A solvent-based alkyd paint prepared as described above exhibited a greener tint and increased metallic greenness compared to a solvent-based paint prepared using monochloro copper phthalocyanine that was not treated with 3,5-dimethylpyrazolylamidomethyl copper phthalocyanine.
Example 6 N,N'-Dimethylperylenetetracarboxylic acid diimide was dry-blended with 10% by weight of (3,5-dimethylpyrazolylamidomethyl)-N,N'-dimethyl-perylenetetracarboxylic acid diimide. A water-based paint prepared as described above exhibited a slightly lighter, slightly more opaque mass-tone and blue tint and increased metallic yellowness compared to a Mo-4630 - 26 -water-based paint prepared using N,N'-dimethylperylenetetracarboxylic acid diimide that was not treated with (3,5-dimethylpyrazolylamidomethyl)-N,N'-dimethylperylenetetracarboxylic acid diimide.

Claims (18)

1. A pigment composition comprising an organic pigment treated with about 0.1 to about 20% by weight, based on the organic pigment, of an N-heteroarylamidomethyl pigment derivative having the formula wherein Q represents an organic pigment moiety, NHet represents a nitrogen-containing heteroaromatic group attached at a ring nitrogen atom to the carbonyl function of the amidomethyl linking group, and n is from 1 to 4.

2. A pigment composition according to Claim 1 wherein the organic pigment is treated with 1 to 10% by weight of the N-heteroaryl-amidomethyl pigment derivative.

3. A pigment composition according to Claim 1 or 2 wherein the N-heteroarylamidomethyl pigment derivative is a pyrazolylamidomethyl pigment derivative.

4. A pigment composition according to Claim 1 or 2 wherein the N-heteroarylamidomethyl pigment derivative is (a) a pyrazolylamidomethylquinacridone having the formula wherein R is C1-C6 alkyl, C1-C6 alkoxy, halogen, or sulfoxyl (or an amide thereof) attached to a quinacridone ring carbon atom; n is from 1 to 4, and r is zero to 4;
(b) a pyrazolylamidomethyl copper phthalocyanine having the formula wherein CuPc represents a copper phthalocyanine moiety; each R
independently represents C1-C6 alkyl, halogen, or sulfoxyl (or amides thereof) attached to a phthalocyanine ring carbon atom; n is from 1 to 4; and s is zero to 8; or (c) a pyrazolylamidomethylperylene having the formula wherein each R independently represents halogen, carboxamido, or sulfonamido attached to a perylene ring carbon atom; n is from 1 to 4;
and t is zero to 4.

5. A pigment composition according to Claim 1 or 2 wherein the N-heteroarylamidomethyl pigment derivative is a pyrazolylamidomethyl-quinacridone having the formula wherein n is from 1 to 4.

6. A pigment composition according to Claim 5 wherein the organic pigment is a quinacridone.

7. A pigment composition according to Claim 1 or 2 wherein the N-heteroarylamidomethyl pigment derivative is a pyrazolylamidomethyl copper phthalocyanine having the formula wherein CuPc represents a copper phthalocyanine moiety.

8. A pigment composition according to Claim 7 wherein the organic pigment is a copper phthalocyanine.

9. A pigment composition according to Claim 1 or 2 wherein the N-heteroarylamidomethyl pigment derivative is a pyrazolylamidomethyl-perylene having the formula wherein n is from 1 to 4.

10. A pigment composition according to Claim 9 wherein the organic pigment is a perylene.

11. A pigment composition according to Claim 1 wherein the organic pigment is treated by (a) mixing a crude organic pigment with an N-heteroarylamidomethyl pigment derivative as defined in claim 1, 3, 4, 5, 7 or 9, in a strong mineral acid, (b) wet or dry blending a crude or finished organic pigment with an N-heteroarylamidomethyl pigment derivative as defined in claim 1, 3, 4, 5, 7 or 9, (c) adding an N-heteroarylamidomethyl pigment derivative as defined in claim 1, 3, 4, 5, 7 or 9, during synthesis of the organic pigment, (d) conditioning an organic pigment in the presence of an N-heteroarylamidomethyl pigment derivative as defined in claim 1, 3, 4, 5, 7 or 9 or (e) a combination of one or more of methods (a) (b) (c) and (d).

12. A pigmented paint containing a pigment composition according to any one of Claims 1 to 10.

13. A pigmented paint according to claim 12, comprising a paint vehicle for said composition.

14. A pigmented plastic comprising a plastic containing a pigment composition according to any one of Claims 1 to 10.

15. An ink containing as pigment a pigment composition according to any one of Claims 1 to 10.

16. An ink according to claim 15, comprising an ink vehicle for said composition.

17. A toner containing as pigment a pigment composition according to any one of Claims 1 to 10.

18. A toner according to claim 17, comprising a toner vehicle for said composition.