MXPA98006969A - Organic pigment compositions - Google Patents

Abstract

This invention relates to pigment compositions containing an organic pigment treated with a pigment derivative having the fórmula (I) (see fórmula) wherein Q represents an organic pigment moiety;X is O, S, or N-R1;Y is N-R2, O, or a direct bond;Z is-CO-, -Ar-, or chemically reasonable combinations thereof;Alk is C1-C5 alkylene, C2-C5 alkenylene, or C4-C5 alkadienulene, of substituted derivatives thereof;Ar is arylene;R1 is hydrogen, C1-C6 alkyl, C7-C16 aralkyl, or -CN;and R2 is hydrogen, C1-C6 alkyl, C5-C7 cycloalkyl, C7-C16 aralkyl, or C6-C10 aryl;with the provisos that (1) the cyclic moiety represented by the fórmula (see fórmula) must be a four-to seven-membered ring, (2) Z can contain a C=O group adjacent to the nitrogen atom of the Q-CH2-N moiety only if Y is N-R2 or O, and (3) X can be O only if Y is N-R2 or O.

Description

COMPOSITIONS OF ORGANIC PIGMENT BACKGROUND OF THE INVENTION This invention relates to pigment compositions obtained by treating organic pigments with cyclic derivatives of amidomethyl, thioamidomethyl and amidinomethyl pigments which impart improved rheological properties and dispersibility. Many types of organic pigments are known and each can be prepared by one or more known methods. Typically, however, the gross 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 in order to achieve pigment quality, rheological properties and adequate dispersibility. The methods for improving the rheological properties are known. For example, 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 disclosed in U.S. Pat. 5,334,727. Substituted benzamidomethylquinacridones and structurally related phthalimidomethyl- and sulfobenzimidomethylquinacridones are described in US Pat. 3,635,981, 4,197,404, 4,256,507, 4,439,240, 4,455,173, 4,478,968, 4,541,872, 4,844,742, 4,895,949, 5,194,088, 5,264,032, 5,286,863, 5,424. 429, 5,453,151 and 5,457,203. In U.S. Pat. No. 5,207,829 describes analogous compounds in which a methylene bridging group is bonded to a nitrogen atom of the lactam ring (i.e., (1-aza-2-oxocycloalkan-1-yl) methylquinacridones). These patents, however, do not describe the cyclic derivatives of amidomethyl, thioamidomethyl and amidino-methyl pigment of the present invention. It has now surprisingly been discovered 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 cyclic amidomethyl, thioamidomethyl or amidinomethyl substituents. Said advantages can be found even in comparison with the phthalimidomethylquinacridones. COMPENDIUM OF THE INVENTION This invention relates to pigment compositions consisting of an organic pigment treated with about 0.1 to about 20% by weight (preferably, 1 to 10% by weight), based on the organic pigment, of a pigment derivative having the formula (Ii) where: Q represents a remainder of organic pigment; X is O, S or N-R1; And it is N-R2 or a direct link; Z is -CO-, -Alk-, -Ar- or chemically reasonable combinations thereof (preferably, -CO-Alk- or -CO-Ar-); Alk is C1-C5 alkylene, C2-C5 alkenylene or C4-C5 alkylene diene or substituted derivatives thereof: Ar is arylene (preferably ortho-phenylene or a substituted derivative thereof); R is hydrogen, C 1 -C 3 alkyl, C 7 -C 1 aralkyl or -CN, and R is hydrogen, C 5 -C 7 cycloalkyl, C 7 -C 16 aralkyl or C 6 -C 10 aryl, with the provisos that: (1) the cyclic moiety represented by the formula it must be a ring of four to seven members (preferably a ring of five or six members), (2) Z may contain a group C = 0 adjacent to the nitrogen atom of the remainder Q-CH2-N only if Y is N- R2 or 0 and (3) 'X may be 0 only if Y is N-R2 or O. This invention is further related to processes for the preparation of said pigment compositions and to the use of said pigment compositions in the pigmentation of paints, plastics, fibers, inks and toners. DETAILED DESCRIPTION OF THE INVENTION Suitable organic pigments which can be treated by the process of the present invention include quinacridone pigments., phthalocyanine and perylene, as well as other known organic pigments. Also suitable are mixtures of said pigments, including solid solutions and even mixtures of different types of pigments. Quinacridone pigments are particularly suitable organic pigments. Quinacridones (which, as used herein, include unsubstituted quinacridone, quinacridone derivatives and solid solutions thereof) can be prepared by any of several methods known in the art, but are preferably prepared by thermally closing the ring of several 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 other typical quinacridone pigments). The phthalocyanine pigments are also suitable organic pigments. Although copper phthalocyanines are preferred, it is also possible to use phthalocyanine pigments free of metal and phthalocyanine pigments containing other metals, such as those based on zinc, cobalt, iron, nickel and other metals of this type. 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 several methods known in the art, but are preferably prepared by a reaction of italic anhydride, phthalonitrile or its derivatives with a metal donor, a nitrogen donor (such as urea or phthalonitrile itself) and an eventual catalyst, preferably in an organic solvent. For example, W. Herbst and K. Hunger, Industrial Organic Pi ments (New York: VCH Publishers, Inc., 1993), pages 418-427, H. Zollinger, Color Chemistry (VCH Verlagsgessellschaft, 1973), pages 101-104 , and NM Bigelow and M.A. Perkins, "Phthalocyanine Pigments," in The Chemistry of Synthetic Dyes and Pigments, ed. HE HAS. Lubs (Malabar, Florida: Robert E. Krieger Publisher-hing 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 the diimides and dianhydrides of perylene-3, 4, 9, 10-tetracarboxylic acid, are also suitable organic pigments. Suitable perylene pigments may be unsubstituted or substituted (for example, with one or more alkyl, alkoxy, halogen substituents such as chlorine or other typical perylene pigments), including those substituted on the imidate nitrogen atoms 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, triphenoxazines), 1,4-diketopyrropyrroles, anthrapyrimidines, antantrones, flavantrones, indatrones, isoindolines, isoindolinones, perinones, pyrantrones, thioindigos, 4,4'-diamino-1, 1 ' -diantraquinonyl and azo compounds, as well as substituted derivatives. The organic pigments can be treated according to the invention, for example by mixing crude organic pigments with cyclic amidomethyl, thioamidomethyl and / or amidinomethyl pigment derivatives in a strong mineral acid, wet or dry mixing the crude forms of finished organic pigments with the derivatives of pigment, by adding the pigment derivatives during the pigment synthesis, or by conditioning in the presence of cyclic derivatives of amidomethyl, thioamidomethyl and / or amidinomethyl pigment. Also suitable are combinations of said methods. Suitable cyclic derivatives of amidomethyl, thioamidomethyl amidinomethyl pigment are compounds having the where Q, X, Y and Z have the meanings given above. The remaining pigment Q can be derived essentially from any kind of organic pigments, including quinacridones, phthalocyanines, perylenes (particularly the imides, diimides, anhydrides and / or dianhydrides of perylene-3, 4, 9, 10-tetracarboxylic acid), dioxazines ( ie, triphenoxazines), 1,4-diketopyrrolopyrroles, anthrapyrimidines, antantrones, flavantrones, indantrones, isoindolones, isoindolinones, perinones, pyrantrones, thioindigos, 4,4'-diamino-1,1'-diantraquinonyl or azo compounds , as well as its substituted derivatives. Suitable derivatives include those having one or more substituents typical of such pigments, such as C1-C6 alkoxy, C5-C7 cycloalkyl, C3-C7 cycloalkoxy, C6-C10 aryl, C6-C10 aryloxy, C7-C16 aralkyl groups. , C7-C16 aralkoxy, hydroxy, halogen, nitrile, carboxyl or its amides, sulfonyl (such as alkyl- and arylsulfonyl or sulfoxyl and its amides) or combinations thereof. The substituted derivatives of the pigment residue Q can, of course, include those in which the ring nitrogen atoms are substituted with chemically reasonable groups such as alkyl, cycloalkyl, aryl or aralkyl. It is often desirable to use cyclic derivatives of amidomethyl, thioamidomethyl and amidinomethyl pigment in which the pigment residue Q is the same type of pigment as the organic pigment being treated. However, it can often be desirable to use cyclic derivatives of amidomethyl, thioamidomethyl and amidinomethyl pigment 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. The Alk groups may be C ^ C alkylene, Cj-C3 alkenylene or C4-C5 alkadienylene or substituted derivatives thereof, but their chain lengths must be selected to obtain rings of four to seven members. The term "alkylene" refers to straight or branched chain difunctional aliphatic hydrocarbon groups having from 1 to 5 carbon atoms Examples of C 1 -C 5 alkylene are methylene, ethylene, propylene, butylene and pentylene, each of which may be optionally substituted The term "C2-C5 alkenylene" refers to straight or branched chain difunctional aliphatic hydrocarbon groups having from 2 to 5 carbon atoms and a carbon-carbon double bond in the main chain. C5 include ethenylene (ie, vinylene), propenylene, butenylene and pentenylene, each of which may be optionally substituted.The term "C4-C3 alkadienylene" refers to straight or branched chain difunctional aliphatic hydrocarbon groups having the or 5 carbon atoms and two carbon-carbon double bonds in the main chain, examples of C4-C5 alkadienylene include butadienylene and pentadi enylene, each of which may be optionally substituted. The alkylene groups C ^^, alkenylene ^ - ^ and C4-C5 alkadienylene can be substituted with one or more substituents, such as C?-C6 alkyl groups, CL-Cg alkoxy, C3-C7 cycloalkyl, C5-C7 cycloalkoxy, aryl C3-C10, C6-C10 aryloxy, C7-C16 aralkyl, C7-C16 aralkoxy, hydroxy, halogen, nitrile, carboxyl or its amides, sulfonyl (such as alkyl- and arylsulfonyl or sulfoxyl and its amides) or combinations thereof. The Ar groups can be arylene groups, including the heteroarylene groups in which one or more carbon atoms of the ring of an arylene group are each substituted by an O, S or N in a chemically reasonable manner, provided that the overall size of the ring is from 4 to 7. Suitable arylene groups also include derivatives in which one or more ring atoms are substituted with C5-C7 alkoxy-cycloalkyl, C5-C7-cycloalkoxy, C6-C10-aryl., C6-C10 aryloxy, C7-C16 aralkyl, C7-C16 aralkoxy, hydroxy, halogen, nitrile, carboxyl or its amides, sulfonyl (such as alkyl- and arylsulfonyl or sulfoxyl and its amides) or combinations thereof. Preferred arylene groups are C6-C10 arylene groups, especially ortho-phenylene and naphthalene with various ortho and 1.8 substitution patterns. Preferred C6-C10 arylene groups also include substituted derivatives with the substituents described above and, less preferably, polyaromatic derivatives in which one or two pairs of the adjacent ring atoms of the C6-C10 arylene group are fused with additional aromatic rings (such as as benzene analogs or heteroaromatics thereof to form, for example, anthracenes, phenanthrenes and the like, which may themselves be substituted on the ring as described above or contain one or more ring heteroatoms selected from O, S and N. As used herein, the term "Cx-Cs alkyl" refers to straight or branched chain aliphatic hydrocarbon groups having from 1 to 6 carbon atoms Examples of alkyl methyl, ethyl, propyl, butyl, pentyl, hexyl and its isomeric forms The term "C1-C6 alkoxy" refers to straight or branched chain alkyloxy groups having from 1 to 6 carbon atoms. Examples of alkoxy methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy and its isomeric forms are examples. The term "C3-C7 cycloalkyl" refers to cycloaliphatic hydrocarbon groups having from 5 to 7 carbon atoms. Examples of C5-C7 cycloalkyl are cyclopentyl, cyclohexyl and cycloheptyl. The term "C5-C7 cycloalkoxy" refers to cycloalkyloxy groups having from 5 to 7 carbon atoms.

Examples of C5-C7 cycloalkoxy are cyclopentyloxy, cyclohexyloxy and cycloheptyloxy. The term "C6-C10 aryl" refers to phenyl and 1- or 2-naphthyl, as well as to phenyl and naphthyl groups substituted with alkyl, alkoxy, halogen and cyano, as defined herein. The term "C6-C10 aryloxy" refers to phenoxy and 1- or 2-naphthoxy, wherein the aryl portion may be optionally substituted as described above for "aryl". The term "C7-C16 aralkyl" refers to Cj-Cg alkyl substituted with C6-C10 aryl, such that the total number of carbon atoms is from 7 to 16. Examples of C7-C16 aralkyl are benzyl, phenethyl and naphthylmethyl. The term "C7-C15 aralkoxy" refers to Ci-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. The group Z can be -CO-, -Alq-, -Ar- or any chemically reasonable combination of these, provided that the cyclic moiety represented by the formula have a global ring size of four to seven (preferably 5 or 6) and as long as a group C = 0 is not adjacent to the nitrogen atom of the ring of the * residue Q-CH2-N, unless Y'sea N- R2 or 0. For example, the group Z can be -CO-Alq- (meaning the order of the groups -CO- and Alq that the -CO- is attached to the nitrogen atom of the ring of the residue Q-CH2-N) , -Alq-CO- (meaning that -CO- is not bonded to the nitrogen atom of the ring of the residue Q-CH2-N), -Alq-CO-Alq- (where, if Y is a direct bond, both groups Alk they can be methylene, ethylene or ethenylene or a substituted derivative thereof, but where, if Y is N-R2 or O, an Alq must be methylene or a substituted derivative thereof), -CO-Ar- (where -CO - is attached to the nitrogen atom of the ring of the radical Q-CH2-N), -Alq-CO- (where -CO- is not attached to the nitrogen atom of the ring of the radical Q-CH2-N), -Alk- CO-Ar- (where, if Y is a direct link and Ar has an ortho-substitution pattern, Alq it may be methylene, ethylene or ethenylene or a substituted derivative thereof, but where, if Y is N-R2 or 0 and Ar has an ortho-substitution pattern, or if Y is a direct bond and Ar has a meta or other pattern; substitution 1.3, Alq must be methylene or a substituted derivative thereof), -Alk-Ar-, -Ar-Alk- and -Alq-Ar-Alq- (where, if Y is a direct bond and Alk groups are attached to Ar in an ortho pattern, an Alk can be methylene, ethylene or ethenylene or a substituted derivative thereof, while the other Alk is methylene or a substituted derivative thereof, but where, if Y is N-R2 or 0 and the Alq groups are linked to Ar in an ortho pattern, or if Y is a direct link and the Alq groups are linked to Ar in a meta pattern or another 1.3, both groups Alk can be methylene or a substituted derivative thereof), as well as other combinations such as to provide rings of four to seven members with the -N- (C = X) -e and eventual groups. Although a group -CO- can be located adjacent to the group C = X (for example, in compounds of oxalate type), said arrangements are generally less preferred. In general, the preferred pigment derivatives of formula (1) are those in which Z is -CO-Alk- or -CO-Ar- (meaning that each -CO- is attached to the nitrogen atom of the ring of the remainder Q- CH2-N). The groups X and Y can be selected to obtain, for example, cyclic ureas, thioureas, guanidines, urethanes, thiourethanes, isoureas, thioamides and amidines, as well as the corresponding N-carbonyl derivatives in which Z contains an adjacent C = 0 group to the nitrogen atom of the residue Q-CH2-N and Y is N-R2 or 0. However, the groups X, Y and Z can not be selected so as to provide compounds in which Y is a direct bond and Z contains a group C = 0 adjacent to the nitrogen atom of the residue Q-CH2-N (for example, imides such as succinimide and phthalimide) or wherein Y is a direct bond, Z is Alk and X is 0 (for example, lactams such as caprolactam). The cyclic derivatives of amidomethyl, thioamidomethyl and amidinomethyl pigment 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 appropriate cyclic residue represented by the formula 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 the cyclic moiety in the presence of a dehydrating agent at a temperature of from about 0 to about 200. ° C. Suitable dehydrating agents include sulfuric acid, fuming sulfuric acid, polyphosphoric acid, organic acids or their anhydrides and mixtures thereof. Fuming sulfuric acid is a particularly suitable condensing agent, especially for less reactive pigments. The degree of substitution on the pigment molecule can be affected by various factors, such as the amount of the cyclic moiety, the temperature of the reaction and the duration of the reaction. The resultant cyclic amidomethyl, thioamidomethyl and amidinomethyl 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 may also be advantageous to include various additives, such as surfactants, in the liquid. The pigment derivatives are then isolated (for example, by filtration or other known methods) and washed until free of residual acid. Particularly preferred pigment derivatives for treating pigments according to the invention are (1-methyl-2,4-imidazolidinadione-3-yl) methylquinacridones of formula (II) and (l-ethyl-2-benzimidazolidonyl) methylquinacridone of formula (III) in which the formulas are not intended to indicate the specific locations for the cyclic amidomethyl groups, but rather to indicate that said groups are located at chemically reasonable positions of the quinacridone moiety. Various methods are known for preparing the pigment compositions of the invention. In a preferred method, a crude organic pigment and a suitable cyclic derivative of amidomethyl, thioamidomethyl and / or amidinomethyl pigment are dissolved ("packed") or suspended. ("swell") in a strong mineral acid and then precipitate. A sufficient amount of mineral acid, preferably concentrated acid, is added to ensure the formation of an acid solution or suspension in a reasonable amount of time. However, with the exception of 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 may be used if the agitation time is prolonged, but is preferred. the use of more concentrated acids for commercial applications Suitable sulfuric acid and polyphosphoric acid are included as suitable mineral acids, with sulfuric acid being preferred It is particularly preferred to use at least 64% sulfuric acid in amounts of about 4 to about 15 parts by weight of acid in relation to the total amount of crude organic pigment and 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 to minimize sulfonation (when sulfuric acid is used) ri-co) or pigment degradation or pigment derivative. After completion of the acid treatment, the pigment composition is precipitated by adding the strongly acid solution to a liquid in which the pigment and the pigment derivative are completely or almost completely insoluble, preferably water or methanol or other lower aliphatic alcohol (such as ethanol, propanol or butanol), as well as their mixtures. When sulfuric acid or fuming sulfuric acid is used in the preparation of the cyclic derivatives of amidomethyl, thioamidomethyl and amidinomethyl pigment or of the final pigment compositions, the remaining pigment may be sulfonated. Said sulfonated derivatives may be isolated as the free acid, as an ammonium salt or as a metal salt (including, for example, alkali metal salts such as sodium or potassium salts, alkaline earth metal salts such as calcium salts or barium and salts of Group III metals such as aluminum). In a second preferred method, an organic pigment is mixed with a suitable cyclic derivative of amidomethyl, thioamidomethyl and / or amidinomethyl pigment 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 Pigment derivative of formula (I) and (b) Collect 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 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 pigment Organic 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 the wet mixture is a liquid in which the organic pigment is substantially insoluble, preferably water, a water-miscible solvent such as methanol or other lower aliphatic alcohol, or mixtures thereof. It is desirable, but not necessary, that the cyclic derivative of amidomethyl, thioamidomethyl and amidinomethyl pigment 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 employed, but are generally less preferred. The temperature at which the wet mixture is carried out is not critical in general, but is normally maintained between about 5 ° C and about 60 ° C (preferably below the boiling point of the liquid). In a third preferred method, which is particularly useful for preparing quinacridone pigment compositions, a suitable cyclic derivative of amidomethyl, thioamidomethyl and / or amidinomethyl pigment is added during or even before the synthesis of the organic pigment being treated, in such a way that the reaction and the treatment processes can take place in situ, at least in part, as the pigment is formed. For example, when preparing quinacridone pigments, a preferred preparatory method consists of (a) heating, at a temperature of from about 80 ° C to about 145 ° C (preferably, from 100 ° C to 130 ° C), a mixture of reaction consisting of (i) 2, 5-dianilinoterephthalic acid, 2,5-dianilino-3,6-dihydroterephonic acid, 2,5-dianilino-3,6-dioxo-l, 4-cyclohexadiene-l, 4- acid dicarboxylic 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 of these; (i) about 0.1 to about 15 weight percent (preferably 0.1 to 10 weight percent), based on component (a) (i), of a suitable cyclic derivative of amidomethyl pigment , thioamidomethyl and / or amidinomethyl; (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 component (a) (ii) is a 2,5-dianilino-3,6-dihydroterephthalic acid or derivative thereof, the reaction step (a) additionally consists of 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 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 the quinacridone pigment is substantially insoluble, and (c) isolating the quinacridone pigment. Each of the above methods can be carried out in the presence of one or more additional pigment derivatives known in the art, particularly sulfonic acid and sulfonamide derivatives. Regardless of which of the above methods is employed, the resulting pigment composition is collected by methods known in the art, preferably filtration followed by a washing step to remove residual acid. Other collection methods known in the art, such as centrifugation, or even simple decanting, are suitable, but generally less preferred. The pigment composition is then dried for use or for further handling before use. The pigment compositions according to the invention can be obtained by conditioning organic pigments in the presence of a cyclic derivative of amidomethyl, thioamidomethyl and / or amidinomethyl pigment, carried out in place, or in addition, of 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. The conditioning can be carried out using any of the various methods known in the art., such as solvent treatment or grinding in combination with solvent treatment. The final particle size of the pigment can be controlled by varying the post-treatment method. For example, the pigments can be made more transparent by reducing the particle size, or more opaque by increasing the particle size. Suitable grinding methods include dry grinding methods, such as grinding sand, grinding balls and the like, with or without additives, or wet grinding methods, such as salt kneading, pearl grinding and similar in water or organic solvents, with or without additives. The dyeing 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, esters, ketones and aliphatic and aromatic hydrocarbons and derivatives thereof, and inorganic solvents, such as water. Suitable additives include compositions which decrease or prevent flocculation, which increase the stability of the dispersion and which reduce the viscosity of the coating, such as polymeric dispersants (or surfactants). For example, US Patents 4,455,173, 4,758,665, 4,844,742, 4,895,948 and 4,895,949. During or after the eventual conditioning step, it is often desirable to use various other eventual components that provide better properties. Examples of such optional components include fatty acids having at least 12 carbon atoms, such as stearic acid or behenic acid, or the corresponding amides, esters or salts, such as magnesium stearate, zinc stearate, aluminum stearate or magnesium behenate; quaternary ammonium compounds, such as tri [(C 1 -C 4 alkyl) benzyl] ammonium salts; plasticizers, such as epoxidized soybean oil; waxes, such as polyethylene wax; resin acids, such as abietic acid, rosin soap, hydrogenated or dimerized rosin; C12-C18-disulfonic paraffin acids; alkylphenols; alcohols, such as stearyl alcohol; amines, such as laurylamine or stearylamine, and 1,2-aliphatic diols, such as dodecane-1,2-diol. Said additives can be incorporated in amounts ranging from about 0.05 to 20% by weight (preferably, from 1 to 10% by weight), based on the amount of pigment. Due to their light stability and migratory properties, the pigment compositions according to the present invention are suitable for many different pigment applications. For example, the pigment compositions according to the invention can be used as a colorant (or as one of two or more colorants) for pigment systems 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 pulps washed with organic liquids or pastes and dispersions with water, dispersants and, where appropriate, preservatives. Examples of paints in which the pigment compositions of the invention may be used include, for example, physical or oxidative drying lacquers, hot enamels, reactive paints, two-component paints, solvent or water-based paints, emulsion paints for watertight coatings and tempera paints. Printing inks include those known for use in printing on paper, fabrics and tinplate. 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 may have any desired shape or 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, resistant heat and vulcanization resistant and still give a very good dyeing performance and are easily dispersible (for example, in plastic materials). The following examples further illustrate the details for the preparation and use of the compositions of this invention. The invention, which is established in the foregoing description, is not limited either in spirit i or in scope by these examples. Those skilled in the art will readily understand that known variations of the conditions and procedures of the following preparatory procedures for preparing these compositions can be used. Unless otherwise indicated, all temperatures are degrees Celsius and all percentages are percentages by weight. EXAMPLES Preparation of Cyclic Amidomethylquinacridone Derivatives Cyclic amidomethylquinacridone derivatives used according to the invention were prepared as follows. (1-methyl -2,4-imidazolidinadion-3-yl) methylquinacridone To 220 g of 100% sulfuric acid at 10 ° C was added 3.0 g (0.10 mol) of paraformaldehyde, followed by slow addition of 11.4 g (0.10 mol) of 1-methylhydantoin, while the temperature was maintained below 25 ° C. The reaction mixture was stirred for two hours at a temperature lower than 30 ° C and then cooled to 10 ° C. 31.3 g (0.10 mol) of quinacridone were slowly added to this mixture at a temperature maintained below 15 ° C. The mixture was stirred for 19 hours at a temperature below 30 ° C and for three hours at 60-65 ° C. After cooling to room temperature, the reaction mixture was slowly poured into 2 kg of ice water, while maintaining a temperature below 15 ° C. The resulting suspension was stirred for 30 minutes, after which the solid was isolated by filtration and washed with water. The wet cake of the filter press was resuspended with water and heated for thirty minutes at 60 ° C, after which the solid was isolated by filtration and washed with water. The wet cake was dried from the filter press to give 37.6 g of (1-methyl-2,4-imidazolidinadione-3-yl) methylquinacridone. (l-Ethyl-2-benzimidazolidonyl) methylquinacridone To 210 g of 100% sulfuric acid at 8 ° C was added 3.0 g "(0.10 mole) of paraformaldehyde. The mixture was stirred for ten minutes, after which 16.2 g (0.25 g) were added slowly. , 10 mol) of 1-ethylbenzimidazolidone while maintaining the temperature below 25 ° C. The reaction mixture was stirred for two hours at room temperature and then cooled to 5 ° C. 31 were slowly added to this mixture. 2 g (0.10 mol) of quinacridone The mixture was stirred for one hour at a temperature below 10 ° C and for one hour at 60 ° C. After cooling to room temperature, the reaction mixture was slowly poured into the mixture. 2 kg of ice water The resulting suspension was stirred for 30 minutes, after which the solid was isolated by filtration and washed with water, the wet cake of the filter press was resuspended with water and heated for thirty minutes to 60 ° C, after which the solid was isolated by filtration and washed with water. Eight wet cake of the filter press to give 37.8 g of 1- (ethyl-2-benzimidazolidonyl) methylquinacridone. Examples 1-5 The preparation and the study of the pigment compositions are described in Examples 1-5. Differences in shade and chromaticity were measured for the pigments prepared according to the Examples using a Spectral Sensor of Applied Color Systems (Hunt Associated Laboratories, Fairfax, Virginia). Solvent-based paint tests Solvent-based paint tests were carried out using a generic alkyd melamine paint system. 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-binding ratio of 4:33 and a total solids content of 37%. The pigment-to-binder ratio 1:10 was reduced by the addition of 2.3% AROPLAZ alkyd resin "1453 -X-50 and 6.5% RESIMENE * 717 melamine resin (Monsanto Company), which gave a total solids content of 40% Mass mass and transparency measurements were made using films applied at 152 μm and 38 μm wet film thickness, respectively, and exposed at room temperature for 30 minutes and at 121 ° C C for 30 minutes Dye paints were prepared with subtone with the dispersion described above having a pigment-to-binder ratio of 4:33 adding 31% of a dispersion prepared from 30% alkyd resin AROPLAZ® 1453 -X-50, 20% xylene, 5% NUOSPERSE® 657 (Hüls America) and 50% Ti02 pigment TI-PURE® R-960 (DuPont), 21% AROPLAz alkyd resin "1453 -X-50, and 7% RESIMENE® 717 melamine resin, which gave a pigment-to-binder ratio of 1: 2, a content or total in solids of 50% and a ratio Ti02-a-pígmento of 90:10. Color measurements were made using films applied at a wet film thickness of 76 μm and exposed at room temperature for 30 minutes and at 121 ° C for 30 minutes. Metal paints were prepared with the dispersion described above, which had a pigment-aligating ratio of 4:33, using an aluminum paste (available as 5251 AR from Silberline Manufacturing Co., Inc.), AROPLAZ 1453 -X alkyd resin -50 and RESIMENE8 melamine resin in amounts that gave a pigment-to-binder ratio of 1: 9, an aluminum-to-pigment ratio of 2 =: 80 and a total solids content of 41%. Color measurements were made using films applied at a wet film thickness of 76 μm and exposed at room temperature for 30 minutes and at 121 ° C for 30 minutes. Water-based paint tests Water-based paint tests were carried out using a water-based basecoat / solvent-based clearcoat system. Aqueous dispersions were prepared using a mixture of 12.4% acrylic resin AR0L0NF 559-G4-70 (Reichhold Chemicals, Inc.), 3.2% hyperdispersant SOLSPERSE 27000 (Zeneca, Inc.), 1.6% 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 AR0L0N9 559-G4-70 acrylic resin (total amount, 26%) and 25% of CYMEL® 325 melamine / formaldehyde resin (Cytec Industries), which gave a total solids content of 50%. Measurements of mass tone and transparency were made using films applied at a wet film thickness of 76 μm and 38 μm, respectively, and allowed to stand at room temperature for fifteen minutes and at 100 ° C for five minutes. Transparent layers were then applied containing a mixture of 80% alkyd resin AROPLAZ8 1453-X-50 and 20% melamine / formaldehyde resin CYMEL * 325 at a total solids level of 57% over the basecoat, a wet film thickness of 76 μm, allowed to stand at room temperature for fifteen minutes and at 121 ° C for fifteen minutes. Dye paints with subtone were prepared with the reduced aqueous dispersions described above, which had a pigment-to-binder ratio of 10:40, by adding additional acrylic resin AROLON 559-G4-70, melamine / formaldehyde resin CYMEL 325 and a % white dispersion TINT-AYDβ 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. Color measurements were made using films applied at a wet film thickness of 38 μm and allowed to stand at room temperature for fifteen minutes and at 100 ° C for five minutes. Transparent layers were then applied and baked as described above. Metal paints were prepared with the dispersion described above, which had a pigment-to-binder ratio of 18:12, using a water-dispersible aluminum pigment (available as HYDRO PASTE8 8726, from Silberline Manufacturing Co., Inc.), resin acrylic AROLON8 559-G4-70 and melamine / formaldehyde resin CYMEL9 325 in amounts that gave 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 a wet film thickness of 38 μm and baked as described above. Transparent layers were then applied and baked as described above. The viscosity was measured in samples of the dispersion (taken before reducing the pigment-aligante ratio) using a Haake RheoStress RS100 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. Example 1 (comparative) Pigmented 2,9-dimethylquinacridone was prepared in the absence of pigment derivative. according to the invention: 300 g of polyphosphoric acid (phosphoric acid) 112%) heated to 88 ° C were added 68.2 g of 2,5-di (4-methylanilino) terephthalic acid over a period of 35 minutes, keeping the temperature below 120 ° C by adjusting the addition speed. The reaction mixture was heated at 123 ° C for two hours. The melt was cooled to 93 ° C and then slowly poured into 526 g of methanol, keeping the temperature below 64 ° C by external cooling and adjusting the speed of addition of the melt. The suspension was heated at reflux for one hour, cooled to below 60 ° C, diluted with water, collected by filtration and washed with water until free of acid. The cake of the resulting filter press was resuspended in water. After adjusting the pH to more than 7, 5.5 g of 50% sodium hydroxide was added and the resulting suspension was heated at 90 ° C for one hour. The suspension was cooled, it was filtered and washed with water until it was free of alkalines 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 can be dried or used as such for specific applications. Here, 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 Dry 2, 9-dimethylquinacridone prepared according to the method of Comparative Example 1 was mixed with 10% by weight of (l-methyl-2,4-imidazolidinadion-3-yl) methylquinacridone. A water-based paint prepared as described above exhibited a reduced viscosity as compared to a paint prepared using the comparative pigment of Example 1. EXAMPLE 3 Dry 2,9-dimethylquinacridone prepared according to the method of Comparative Example 1 was mixed with a 10% by weight of (l-ethyl-2-benzimidazolidonyl) methylquinacridone. A water-based paint prepared as described above exhibited a reduced viscosity as compared to a paint prepared according to the comparative pigment of Example 1. Example 4 (comparative) The method described in Examples 2 and 3 was repeated, except for the fact that the 2,9-dimethylquinacridone of Example 1 was mixed dry with 10% by weight of phthalimidomethylquinacridone (which was prepared by the method described in US Patent 3,275,637). A water-based paint prepared as described above exhibited a higher viscosity than paints prepared using (l-methyl-2,4-imidazolidinadion-3-yl) methylquinacridone (Example 2) and (l-ethyl-2-benzimidazole) lidonyl) methylquinacridone (Example 3) according to the invention. Example 5 (comparative) The method described in Examples 2 and 3 was repeated, except for the fact that portions separately of the 2,9-dimethylquinacridone of Example 1 were mixed dry with 5% and 10% by weight , respectively, of (l-aza-2-oxocyclohept-1-yl) methylquinacridone (which is described generically in US Patent 5,207,829, but which was prepared by the method described above for (l-ethyl- 2-benzimidazolidonyl) methylquinacridone using caprolactam in place of 1-ethylbenzimidazolidone). The water-based and solvent-based paints prepared as described above were compared with these comparative mixtures with the water-based paints prepared with the pigment mixtures according to the invention, which contained 5% by weight of (l-methyl-2) , 4-imidazolidin-dion-3-yl) methylquinacridone, and solvent-based paints prepared with the pigment mixtures according to the invention, containing 5% and 10% by weight of (l-methyl-2,4-imidazolidinedione) -3-yl) methylquinacridone. Although the viscosities of the corresponding pairs of paint samples were comparable, the water-based paint prepared using the pigment mixture containing 5% by weight of the additive according to the invention was slightly more transparent and exhibited a slightly greater metallic color strength. that the corresponding water-based comparative paint and the solvent-based paint prepared using the pigment mixture containing 10% by weight of the additive according to the invention exhibited a slightly more intense dough tone and a metallic color strength slightly greater than the corresponding solvent-based comparative paint.

Claims (11)

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 pigment derivative having the formula where: Q represents a remainder of organic pigment; X is 0, S or N-R1; And it is N-R2 or a direct link; Z is -CO-, -Alq-, -Ar- or chemically reasonable combinations thereof; Alk is Cx-C3 alkylene, C2-C5 alkenylene or C4-C5 alkylene diene or substituted derivatives thereof: Ar is arylene; R1 is hydrogen, C1-C6 alkyl, C7-C16 aralkyl or CN; R 2 is hydrogen, C 1 Cg alkyl, C 5 -C 7 cycloalkyl, C 7 -C 1 aralkyl or C 6 -C 10 aryl, with the provisos that: (1) the cyclic moiety represented by the formula must be a ring of four to seven members (2) Z may contain a group C = 0 adjacent to the nitrogen atom of the remainder Q-CH2-N only if Y is N-R2 or O and (3) X may be O only if Y is N-R2 or O.
2. 2. A pigment composition according to Claim 1, wherein the organic pigment is treated with 1 to 10% by weight of the pigment derivative.
3. 3. A pigment composition according to Claim 1, wherein the cyclic moiety represented by the formula It is a ring of five or six members.
4. 4. A pigment composition according to Claim 1, wherein the pigment derivative has the formula where Q represents an organic pigment residue, Z is -CO-Alk- (where Alk is methylene or ethylene or a substituted derivative thereof) or -CO-Ar- (where Ar is ortho-phenylene or a substituted derivative thereof) and R2 is hydrogen or alkyl v_? _g.
5. 5 . A pigment composition according to Claim 1, wherein the pigment derivative has the formula or
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 organic pigment is treated with the pigment derivative (a) by mixing a crude organic pigment with the" pigment derivative in a strong mineral acid, (b) wet mixing or dry a crude organic pigment or finished with the pigment derivative, (c) adding the pigment derivative during the synthesis of the organic pigment, (d) conditioning an organic pigment in the presence of the pigment derivative or (e) a combination of one or more of methods (a), (b), (c) and (d).
8. 8. A pigmented paint containing a pigment composition according to Claim 1.
9. 9. A pigmented plastic containing a pigment composition according to Claim 1.
10. 10. An ink containing as a pigment a pigment composition according to Claim 1. 11 A toner containing as pigment a pigment composition according to Claim 1. SUMMARY OF THE INVENTION This invention relates to a pigment composition containing an organic pigment treated with a pigment derivative having the formula (I) (i; QC rN X where: Q represents an organic pigment residue, - X is O, S or N-R1, Y is N-R2 or a direct bond, Z is -CO-, -Alq-, -Ar- or chemically reasonable combinations thereof: Alk is C ^ -C-C, C, -C, C- or C4-C5-alkenylene alkylene, or substituted derivatives thereof: Ar is arylene, R1 is hydrogen, C7-C16 is aralkyl or CN; R2 is hydrogen, C3-C7 cycloalkyl, C7-C16 aralkyl or C6-C1 aryl (), with the provisos that: (1) the cyclic moiety represented by the formula IZ - X must be a ring of four to seven members (2) Z may contain a group C = 0 adjacent to the nitrogen atom of the remainder Q-CH2-N only if Y is N-R2 or O and (3) X may be 0 only if Y is N-R2 or 0.