MXPA99004557A - Pigments of chinacridone heterociclico-substitui - Google Patents

Abstract

The present invention relates to quinacridone pigments of formula (I), wherein X is O, SôNR, R is hydrogen, C 1 -C 6 alkyl, C 5 -C 7 cycloalkyl or C 7 -C 16 aralkyl; Y is C 1 -C 6 alkyl, C 1 alkoxy; -C6 or halogen, the dashed line represents an eventual double bond, R1 and R2 are independently hydrogen, C1-C6alkyl, C5-C7cycloalkyl, C6-C10 aryl, C7-C16 aralkyl, nitrile or carboxyl or an aester or amide thereof, or R1 and R2 together form a C5-C8 cycloaliphatic ring or a fused aromatic or heteroaromatic ring, R3 is hydrogen or C1-C6 alkyl, and m is 0.112. This invention also relates to the preparation and use of said quinacrid pigments

Description

s- t HETEROCICLIC-SUBSTITUTE QUINACRIDONE PIGMENTS BACKGROUND OF THE INVENTION This invention relates to novel heterocyclic-substituted quinacridone pigments which are useful for the coloring of plastics and other macromolecular materials, coating compositions and paints and inks for printing and for inkjet. The use of quinacridones as pigments is known. For example, W. Herbst and K. Hunger, Industrial Organic Pigments. 2nd ed. (New York: VCH Publishers, Inc., 1997), pages 454-474, and S.S. Labana and L.L. Labana, "Quinacridones", in Chemical Review, 67, 1-18 (1967). The substitution of rings of the quinacridones can produce pigments having different coloristic and physical properties, but the substituents of the commercially useful pigments are typically alkyl, alkoxy or halogen groups. For example, Herbst and Hunger, on pages 464-465. Quinacridones having more complex substituents are not generally used as commercial pigments by themselves, but are instead more commonly used as pigment additives to enhance the physical and coloristic properties of other quinacridone pigments. For example, US Patents 5,457,203, 5,453,151, 5,424,429, 5,368,641, 5,334,727, 5,286,863, . 264,032, 5,137,576, 5,229,515, 5,194,088, 5,145,524, 4,895,949, 4,844,742, 4,541,872, 4,478,968, 4,455,173, 4,439,240, 4,256,507 and 4,310,359. However, new substituted quinacridones that have adequately modified color and physical properties would still be desirable. It has now been seen that the introduction of certain heterocyclic substituents into quinacridones gives unusual properties, including colors not easily achieved with quinacridone.

COMPENDIUM OF THE INVENTION This invention relates to quinacxidine pigments having the formula (I) where X is O, S or NR; R is hydrogen, C ^ Cg alkyl (preferably methyl), C5-C7 cycloalkyl or C7-C16 aralkyl; is Cx-C6 alkyl (preferably methyl), CjL-Cg alkoxy (preferably methoxy) or halogen (preferably chlorine or fluorine); the dashed line represents an eventual double bond (ie, a single carbon-carbon bond or a carbon-carbon double bond); R1 and R2 are independently hydrogen, C1-Cg alkyl (preferably methyl), C5-C7 cycloalkyl, Cg-Cu-aryl, C7-C16 aralkyl, nitrile or carboxyl, or an ester or an amide thereof, or R1 and R2 form together a C5-C8 cycloaliphatic ring or a fused aromatic or heteroaromatic ring (preferably a ring of unsubstituted or substituted benzene in the ring); R3 is hydrogen or alkyl and m is 0 (ie, no Y is present, which means that no more substituents are present in the quinacridone ring than hydrogen), 1 or 2. This invention is further related to the preparation and use of said quinacridone pigments for the coloring of plastics and other macromolecular materials, coating compositions and paints and printing and inkjet inks. DETAILED DESCRIPTION OF THE INVENTION As used herein, the term "Cx-C6 alkyl" refers to straight or branched chain aliphatic hydrocarbon groups having from 1 to 6 carbon atoms, which is also referred to as lower alkyl. Examples of alkyl are Cg methyl, ethyl, propyl, butyl, pentyl, hexyl and their isomeric forms. 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 "C6-C10 aryl" refers to phenyl and 1- or 2-naphthyl, as well as to phenyl or naphthyl groups substituted with alkyl, alkoxy, halogen or cyano, as defined herein. The term "C7-C1S aralkyl" refers to alkyl substituted with C6-C10 aryl, such that the total number of carbon atoms is from 7 to 16. Examples of C7-C16 aralkyl are benzyl, phenethyl and naphthylmethyl. The term "alkoxy" refers to straight or branched chain alkyloxy groups having from 1 to 6 carbon atoms. They are examples of alkoxy methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy and their isomeric forms. Examples of halogen are fluorine, chlorine, bromine and iodine. As used herein, the term "carboxyl or an ester or amide thereof" refers to -COOH and the corresponding esters -COOR1 (wherein R1 is alkyl, cycloalkyl, aralkyl or aryl) and amides -COONR ^ R111 (in which where R11 and R i are independently hydrogen, alkyl, cycloalkyl, aralkyl or aryl). The dotted line in the heterocyclic substituent represents an eventual double bond, which means that the bond between the two carbon atoms is either a single carbon-carbon bond (for which hydrogen atoms are present in the carbon atoms at each end of the bond, even when R1 and R2 are not hydrogen) , or a carbon-carbon double bond (for which the hydrogen atoms are not present in the carbon atoms at each end of the bond, unless, of course, that R1 and R2 are hydrogen). Said carbon-carbon double bonds are topical of compounds in which R1 and R2 together form the aromatic ring used, but may also be present when R1 and R2 together form a fused cycloafumatic ring or do not form a ring. Suitable heterocyclic-substituted quinacridone pigments include compounds of formula (I) in which the heterocyclic substituents are attached to the two external benzene rings. Preferred heterocyclic-substituted quinacridone pigments are those in which the heterocyclic substituents are located para to the nitrogen atoms of the quinacridone ring (i.e., in a substitution pattern 2.9) and which are represented by the formula (the) where X, Y, R1, R2 and the dashed line are as defined above. Particularly preferred heterocyclic-substituted quinacridone pigments include the compounds of the formula (Ib) where Y and m are defined as before; X is O, S or NH, and is alkyl C5-C7 cycloalkyl, Cs-C7 cycloalkoxy, C6-C10 aryl, C6-C6 aryloxy, C7-C16 aralkyl, C7-C aralkoxy? hydroxy, halogen or nitrile and n is (preferably 0), or any two adjacent groups (which requires n to be at least 2) form an aromatic ring fused in a polyaromatic system. The quinacridones of formula (Ib) correspond, therefore, to compounds of formula (la) in which R1 and R2 together form a fused benzene ring. The terms C ^ Cg alkyl, alkoxy C3-C7 cycloalkyl, C6-C10 aryl, C7-C16 aralkyl, hydroxy, halogen and nitrile have the same meanings as those given above. 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 aryloxy" refers to phenoxy and 1- or 2-naphthoxy, wherein the aryl portion may optionally be substituted as described above for "aryl". The term "C7-C16 aralkoxy" refers to C-L-Cg alkoxy substituted with C3-C10 aryl, such that the total number of carbon atoms is from 7 to 16. An example of a C7-C16 aralkoxy is benzyloxy. Preferred heterocyclic-substituted quinacridones of formula (Ib) are those in which the fused benzene rings of the heterocyclic group are unsubstituted (ie, not present, which means that no substituent other than hydrogen is present). Particularly preferred heterocyclic-substituted quinacridone pigments of formula (Ib) are those in which X is NH, O or S and m and n are both 0 (meaning that no Y groups are present). The heterocyclic-substituted quinacridone pigments prepared according to the invention can be used alone or in combination with other pigments, including mixtures and solid solutions with other heterocyclic-substituted quinacridone pigments of the invention or other pigments known in the art. As examples of other suitable pigments include unsubstituted or substituted quinacridones, quinacridonaquinones, diketo-pyrrolopyrroles, perylenes, phthalocyanines, dioxazines (ie triphenyloxazines), 1,4-diketopyrrolopyrroles, anthrapyrimidines, antantrones, flavantrones, indatrones, isoindolines, isoindolinones, perinones, pyrantrones, thioindigos, 4, 4'-diamino-1, 1'-diantraquinonyl and azo compounds. The heterocyclic-substituted quinacridone pigments of formula (I) can be prepared by any of several methods known in the art. In a preferred preparative method, quinacridones of formula (I) are prepared by condensation of carboxy-substituted quinacridones of formula (II) (II) where each Y is independently alkyl (preferably methyl), C ^ Cg (preferably methoxy) or halogen alkoxy (preferably chlorine or fluorine) and m is 0, 1 or 2 (preferably 0), with amines of formula (III) where X is O, S or NR (where R is hydrogen, C ^ Cg alkyl, C3-C7 cycloalkyl or C7-C16 aralkyl); the dashed line represents an eventual double bond, such that the bond between the two carbon atoms is a single carbon-carbon bond or a carbon-carbon double bond (ie, forming an amine of formula (R1) (XH) C = C (NH2) - (R2)), and R1 and R2 are independently hydrogen, alkylCG (preferably methyl), C5-C7 cycloalkyl, C6-C10 aryl, C7-C16 aralkyl, nitrile or a carboxylic ester or amide , or R1 and R2 together form a C5-C8 cycloaliphatic ring (ie, where R1 and R2 together are a C3-C6 aliphatic group which may contain a heteroatom, such as O, S or N, may be substituted and may be unsaturated ) or a fused aromatic or heteroaromatic ring (preferably, an unsubstituted or substituted benzene ring). The compounds of formula (III) having a double bond carbon-carbon in the position represented by the dashed line are typically aromatic amines in which R1 and R2 together form a fused aromatic ring (such as aminobenzenes, used to prepare compounds of formula (Ib)), but double bonds can be present in this location even when R1 and R2 do not form a fused (hetero) aromatic ring. Although R1 and R2 can not be free carboxylic acid groups (i.e., -COOH) or their salts when this method is used, corresponding esters and amides can often be used to prepare corresponding esters or amides of formula (I), thus providing an indirect route to free carboxylic acids. For example, esters can be hydrolysed by known methods to free carboxylic acids or their salts. The heterocyclic-substituted quinacridones of formula (I) wherein R3 is alkyl they can be prepared in an analogous manner using suitable N-alkylated precursors or intermediates. However, it is generally preferable to rent quinacridones of formula (I) in which R3 is hydrogen, using alkylation methods known in the art. For example, US Pat. 5,725,651. When the condensation method described above is used to prepare the preferred heterocyclic-substituted quinacridone pigments of formula (Ib), wherein the heterocyclic substituents contain fused aromatic rings, the preferred amines are anilines of the formula (Illa) where X, and n are defined as before. The fused aromatic rings can be substituted with up to four substituents, including ^ Cg alkyl, C ^ Cg alkoxy, C3-C7 cycloalkyl, C3-C7 cycloalkoxy, C6-C10 aryl, C6-C10 aryloxy, C7-C16 aralkyl, C7-aralkoxy C1S, hydroxy, halogen or nitrile, or may be fused with additional aromatic rings to form polyaromatic systems. Heteroaromatic analogues of the compounds (Illa) can also be used to prepare heteroaromatic-substituted quinacridone pigments analogous to the compounds of formula (Ib). Preferred amines (III) are those that do not have groups (ie, where n is 0) and are represented by the formula (Illb) where X is "O, S or NR (where R is hydrogen or alkyl (^ Cg). Preferred amines of formula (Illb) include 1,2-phenylenediamine (ie, where X is NH 2), 2-aminophenol ( that is, where X is OH) and 2-aminobenzenethiol (ie, where X is SH). "Replaced ring-substituted compounds include 2,3-diaminotoluene and 3,4-diaminotoluene, which are isomeric amines of formula (Illa) wherein X is NB ^, W is methyl and n is 1. Suitable amines (III) also include heteroaromatic amines, such as 2,3-diaminopyridine and 4,5-diaminopyrimidine (ie, where X is NH2 and R1 and R2 together are fused heteroaromatic rings); aliphatic amines, such as 2-aminoethanol (ie, where X is OH) and 2-aminoethanethiol (ie, where X is SH), and cycloaliphatic amines, such as 1 , 2-diaminocyclohexane, 2-aminocyclohexanol and l-amino-2-thiocyclohexane (ie, where R1 and R2 together are 1,4-butylene to form a cyclohexane ring and X is, r specifically, NH2, OH and SH). The heterocyclic-substituted quinacridone pigments of formula (I) are preferably prepared by condensation of a carboxy-substituted quinacridone of formula (II) with an excess of an amine of formula (III) in the presence of a dehydrating agent. Suitable dehydrating agents include sulfuric acid and other mineral acids, sulfonic acids such as acid methanesulfonic acid and p-toluenesulfonic acid, phosphoric acid and monoesters and acid diesters thereof, polyphosphoric acid, boric acid, organic acids and Lewis acids such as FeCl3 and A1C13. When using acids that are not liquid, such as boric acid, FeCl3 or AlCl3, the condensation reaction is usually carried out in an inert solvent. In a preferred method, a carboxy-substituted quinacridone of formula (II) is condensed with at least two molar equivalents of an amine of formula (III) in polyphosphoric acid, at an elevated temperature (eg, 30 to 200 ° C). Although, in general, it is less preferred, it is possible to use trichloromethyl-substituted quinacridones in place of carboxy-substituted quinacridones, but condensation with the amines of formula (III) must be carried out under pressure. For example, German Patent Application Publication 2,619,547. The resulting heterocyclic-substituted quinacridone pigment of formula (I) is then isolated by pouring the reaction mixture into a liquid in which the pigment is substantially insoluble, preferably water, an organic water-soluble liquid (including partially water-soluble) or mixtures thereof, and then picked up. Suitable liquids include water and mixtures of water and 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 the style known in the art. Other organic liquids can be used, but are, in general, less preferred. The carboxy-substituted quinacridone precursors (II) can be prepared by methods known in the art. In a preferred method, the compounds of formula (II) are prepared by ring closure of carboxy-substituted derivatives of the 2,5-dianilinoterephthalic acid of formula (IV). where Z is ORa (where Ra is hydrogen or alkyl (preferably methyl, ethyl or butyl and, more preferably, methyl)) or NRbRc (wherein Rb and Rc are independently hydrogen or CL-C alkyl); each Y is independently alkyl alkoxy halogen, carboxyl or an ester or an amide thereof, or a sulfonyl group, and m is 0, 1 or 2. Compare U.S. Pat. 3,752,817 and 3,873,548. Preferred carboxy-substituted derivatives of 2,5-dianilinoterephthalic acid are free acids and esters of formula (IVa) where Ra is hydrogen or alkyl and Y and m are defined as before. Particularly preferred carboxy substituted derivatives of 2,5-dianilinoterephthalic acid are the esters of formula (IVa) wherein Ra is methyl or ethyl (preferably methyl) and m is 0 (meaning that no Y group is present). Other methods of preparing the compounds of formula (II) can, of course, also be used. For example, U.S. Pat. No. 3,726,874 describes the preparation of carboxy-substituted quinacridones by acid hydrolysis of the corresponding trifluoromethyl-substituted quinacridones. It is sometimes desirable to isolate quinacridones carboxy-substituted of formula (II) before carrying out the condensation reaction with amines of formula (III), especially if by-products or other impurities are formed during the reaction of the ring closure. However, it is often possible, and sometimes preferred, to carry out the condensation reaction without first isolating the carboxy-substituted quinacridones. The desirability or need for an isolation step can easily be determined. Carboxy-substituted derivatives of 2,5-dianilinoterephthalic acid of formula (IV) can be prepared by known methods, such as the condensation of succinylsuccinic compounds of formula (V) where Z is ORa (where R is hydrogen or C ^ Cg alkyl (preferably methyl, ethyl or butyl and, more preferably, methyl)) or NRbRc (where Rb and Rc are independently hydrogen or alkyl) with aminobenzoic acids of formula (VI) HOOC ^ AX where each Y is independently alkyl C ± -C6 alkoxy, halogen, carboxyl or an ester or amide thereof, or a sulfonyl group, and m is 0, 1 or 2. It is also possible to use analogous aminobenzoic esters or aminobenzonitriles for the condensation of succinylsuccinic compounds of formula (V) , but further reactions are required to obtain the -COOH group. The succinylsuccinic compounds of formula (V) can be prepared by methods known in the art.

For example, W. Herbst and K. Hunger, Industrial Organic Pigments, 2nd ed. (New York: VCH Publishers, Inc., 1993), page 456; H. Zollínger, Color Chemistry (VCH Verlagsgessellschaft, 1991), page 239; F.F. Ehrich, "Quinacridone Pigments", in Pigment Handbook. Vol. I, edited by P.A. Lewis (John Wiley &Sons, 1988), page 604, and US Pat. 5,367,096. For example, the preferred dialkyl succinylsuccinates of formula (Va) where Ra is alkyl they can be prepared by cyclization of the corresponding dialkyl succinates. The dimethyl and diethyl succinylsuccinates (especially the dimethyl succinylsuccinate) are particularly suitable and marketed, for example, by Hoechst AG, DSM Chemie Linz and Aldrich Chemical. Succinyl succinic acid (as free acid or metal salts) and their amides are generally less preferred. The aminobenzoic acids of formula (VI) can be prepared by known methods, but can also be purchased commercially. The selection of Y and m depends, of course, on the particular heterocyclic-substituted quinacridone derivatives that must be prepared last. For example, quinacridones (I) having no Y substituents would ultimately derive from the unsubstituted aminobenzoic acid, where the Y groups are absent (ie, where tn is 0). The p-aminobenzoic acids are used to prepare the preferred compounds of formula (I) of the invention. In a preferred method for preparing carboxy-substituted derivatives of 2,5-dianilinoterephthalic acid of formula (IV), a succinylsuccinic compound of formula (V) is condensed with an aminobenzoic acid of formula (VI) in an alcohol solvent (such as methanol) or ethanol) in the presence of an acid catalyst (such as hydrochloric, sulfuric or acetic acid), preferably at the boiling point of the solvent. The resulting intermediate is oxidized and hydrolyzed, for example, using aromatic nitro compounds (such as nitrobenzene), chloro-naphthyl, anthraquinone-2-acid sulfonic acid or a salt thereof, anthraquinone-2,7-disulfonic acid or a salt thereof, air or other gases containing oxygen, halogens or electrolytic oxidation together with a base (such as alkali metal hydroxide). The acidification of the basic solution produces the carboxy-substituted derivative of 2,5-dianilinoterephthalic acid (IV). If the trifluoromethyl method of US Pat. 3,726,874 (mentioned above), compounds of formula (VII) are used where Y and m are defined as above, in place of the aminobenzoic acids of formula (VI) and the resultant trifluoromethyl-substituted quinacridones are hydrolyzed into acid to obtain carboxy-substituted quinacridones. It is possible, although generally less preferred, to introduce the heterocyclic group before ring closure by reaction of the carboxy-substituted derivatives of 2,5-dianilinoterephthalic acid of formula (IV) with amines of formula (III) to produce heterocyclic derivatives. substituted 2, 5-dianilinoterephthalic acid of formula (VIII) where X, Y, Z, R1, R2 and m are defined as before. The compounds of formula (VIII) can then be closed in the ring in the usual manner to form heterocyclic-substituted quinacridones of formula (I) of the invention. For example, preferred heterocyclic-substituted quinacridone pigments of formula (Ib) can be prepared from the corresponding compounds of formula (IX) where X, Y, Ra and m are defined as before. Regardless of the method used to prepare the heterocyclic-substituted quinacridones of the invention, the resultant pigments are generally conditioned and surface treated to obtain better pigment properties. Although many suitable methods of conditioning are known to those skilled in the art, the most commonly used methods include dissolving or suspending the crude pigment in strong mineral acids, followed by precipitation, treating with a solvent other than a strong acid and / or grinding the pigment. stupid. Conditioning with a strong acid, although possible, is not generally necessary for the heterocyclic-substituted quinacridones according to the invention. However, if conditioning with a strong acid is used in combination with other conditioning methods, the acid treatment is generally carried out before the other methods. Conditioning with a strong acid involves treatment with aqueous mineral acid (preferably sulfuric acid) in a process known as "acid pasting" (in which an acid solution containing protonated pigment is formed) or "acid swelling" (wherein a protonated pigment suspension is formed). A sufficient amount of mineral acid, preferably concentrated acid, is added to ensure the formation of an acid solution or suspension in a reasonable amount of time. However, except for the requirement that the solution or suspension be acidic, the amount and concentration of acid are not critical, in general. For example, more dilute acid may be used if the stirring time is prolonged, but the use of more concentrated acids is preferred for commercial applications. Suitable mineral acids include sulfuric acid and polyphosphoric acid, with sulfuric acid being preferred. It is particularly preferred to use at least 64% aqueous sulfuric acid in amounts of about 4 to about 15 parts by weight of acid relative to the amount of pigment. Although the rate of dissolution of the pigment in acid can be increased by heating the mixture (e.g., at about 50 ° C), it is generally preferred to dissolve the pigment in acid at 35 ° C or less to minimize sulfonation (when sulfuric acid is used) ) or the degradation of the pigment. After completing the acid treatment, the pigment is precipitated by adding the strongly acid solution to a liquid in which the pigments 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 of these. It is also possible to condition the raw pigment using a solvent other than a strong acid. Suitable solvents include organic acids, such as formic or acetic acid; alcohols, such as methanol, ethanol or ethylene glycol; ethers, such as dioxane, tetrahydrofuran, monoethyl or diethyl ether of ethylene glycol or oligo- and polyglycol ethers; ketones, such as acetone or methyl ethyl ketone; aromatics, such as toluene, xylene, chlorobenzene, nitrobenzene or chloronaphthalene; ~~ esters, such as methyl benzoate, dimethyl phthalate or methyl salicylate; amides, such as formamide, dimethylformamide or N-methylpyrrolidone, and sulfoxides, such as dimethyl sulfoxide. The pigment thus obtained is collected by methods known in the art, preferably by filtration, followed by washing to remove residual acid. Other collection methods known in the art, such as centrifugation or even simple decanting, are suitable, although generally less preferred. The pigment is then dried for use or for further conditioning, for example by grinding. Crushing can, of course, be used in place of acid or solvent treatment. Suitable grinding methods include dry grinding methods, such as grinding with sand, grinding with balls and the like, and wet grinding methods, such as salt kneading, grinding with beads and the like in water or organic liquids (such as alcohols or ethers), with or without additives The grinding may be carried out using additives, such as inorganic salts (especially for dry milling) and surfactants or dispersants, particularly various sulfonamide, carboxamide and aminoalkyl derivatives known to be phthalocyanines or quinacridones (especially for wet milling). Suitable grinding liquids for wet milling include organic liquids, such as alcohols, esters, ethers, ketones and aliphatic or aromatic hydrocarbons and their derivatives, and inorganic liquids, such as water. After completion of the grinding step, an eventual treatment with solvents, generally at temperatures between about 10 ° C and about 200 ° C, can also be used. The eventual treatment with solvents is preferably carried out at elevated temperatures, such as 60 ° C to 145 ° C. Suitable solvents for the eventual treatment with solvents include water; inorganic acids, such as sulfuric or phosphoric acid, adjusted to an adequate strength; organic acids, such as formic or acetic acid, and various organic solvents, such as alcohols (e.g., methanol, ethanol or ethylene glycol), cyclic or open chain ethers (e.g., dioxane, tetrahydrofuran, monoalkyl or dialkyl ethers of ethylene glycol and oligo- and polyglycol ethers), ketones (for example, acetone or methyl ethyl ketone), aromatics (for example, toluene, xylene, chlorobenzene, nitrobenzene or chloronaphthalene), esters (for example, methyl benzoate, dimethyl phthalate, dimethyl succinate or methyl salicylate) and amides (for example, formamide, dimethylformamide or N-methylpyrrolidone). It is often advantageous to use mixtures of these solvents. The pigments of this invention are highly resistant to water, resistant to oils, resistant to acids, resistant to lime, resistant to alkalis, resistant to solvents, stable to overcoat, stable to over-spray, stable to sublimation, heat-resistant and resistant to vulcanization and still give a very good dyeing performance and are easily dispersible (for example, in plastic materials). Due to their stability against light and their migratory properties, the pigments according to the present invention are suitable for many different pigment applications. For example, the pigments prepared according to the invention can be used as a colorant (or as one of two or more colorants) for light-stable pigment systems. The pigments of the present invention are particularly suitable for use with macromolecular materials, especially macromolecular synthetically produced substances. Examples of synthetic 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. Other suitable macromolecular substances include those of natural origin, such as rubber; those obtained by chemical modification, such as acetylcellulose, cellulose butyrate or viscose; or those produced synthetically, such as polymers, polyaddition products and polycondensates. The materials pigmented with the pigments of the invention can have any desired shape. The pigments of the present invention are also suitable for blends pigmented with other materials, pigment formulations, paints, printing ink and colored paper. It is understood that the term "mixtures with other materials" includes, for example, mixtures with inorganic white pigments, such as titanium dioxide (rutile) or cement, or other inorganic pigments. Examples of pigment formulations include pastes washed with organic liquids or pastes and dispersions with water, dispersants and, if appropriate, preservatives. Examples of paints in which the pigments of this invention may be used include, for example, physical or oxidative drying lacquers, hot enamels, reactive paints, two-component paints, solvent or water-based paints, paints in emulsion for coatings resistant to weathering and tempes. Printing inks include those known for use in printing on paper, fabrics and tinplate. The following examples still illustrate the details for the preparation and use of the compounds of this invention. The invention, set forth in the foregoing description, is not limited in its 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 preparative procedures for preparing these compounds can be used. Unless otherwise indicated, all temperatures are degrees Celsius and all percentages are percentages by weight.

EXAMPLES Solvent-based paints were tested using a generic alkyd melamine paint system. Pigment dispersions were prepared using a mixture of 30% alkyd resin AROPLAZ * 1453 -X-50 (Reichold Chemicals, Inc.), 58% xylene and 12% pigment, which gave a pigment-to-binder ratio of 12:30 and a total solids content of 42%. The pigment-to-binder ratio was reduced to 2:10 by the addition of 16.6% AROPLAZ * 1453-X-50 alkyd resin and 6.6% RESIMENE * 717 melamine resin (Monsanto Company), that gave a total solids content of 40%. Measurements of mass tone and transparency were made using films applied at a wet film thickness of 152 μm and 38 μm, respectively, and exposed to room temperature for 30 minutes and at 121 ° C for 30 minutes. Paintings with low-tone dye were prepared from the dispersion described above, which had a pigment-to-binder ratio of 12:30, adding 40% of a dispersion prepared from 30% alkyd resin AROPLAZ * 1453 -X-50, 19.5% xylene, 0.5 NUOSPERSE * 657 (Hüls America) and 50% Ti02 pigment TI-PURE * R-960 (DuPont); 52% AROPLAZ * 1453-X-50 alkyd resin and 8% RESIMENE * 717 melamine resin, which gave a pigment-to-binder ratio of 1: 2, a total solids content of 50% and a Ti02-a-pigment ratio of 90:10. Color measurements were made using films applied at a wet film thickness of 76 μm and exposed to room temperature for 30 minutes and at 121 ° C for 30 minutes. Metal paints were prepared from the dispersion described above, which had a pigment-to-binder ratio of 12:30, using an aluminum paste (available as 5251 AR, from Siberline Manufacturing Co., Inc.), AROPLAZ * 1453-X-50 alkyd resin and RESIMENE * 717 melamine resin, in amounts that gave a pigment-to-binder ratio of 1: 9, an aluminum-to-pigment ratio of 20:80 and a total solids content of 43%. Color measurements were made using a film applied at a wet film thickness of 76 μm and exposed at room temperature for 30 minutes and at 121 ° C for 30 minutes. Example 1 Preparation of 2, 5-p-dicarboxy anilinote reftalic acid To 400 g of methanol were added, with stirring, 62.3 g (0.27 mol) of dimethyl succinylsuccinate, 97.2 g (0.71 mol) of p-aminobenzoic acid (Aldrich Chemical Co., Milwaukee, Wisconsin) and 1.3 g of concentrated sulfuric acid.

The reaction was heated slowly to 95-100 ° C and maintained at that temperature for five hours. After cooling the reaction mixture to room temperature, 68.7 g of sodium 3-nitrobenzenesulfonate, 200 g of 45% aqueous potassium hydroxide and 50 g of water with stirring were added slowly. The resulting mixture was slowly heated to 90-95 ° C and maintained at that temperature for four hours. The reaction mixture was cooled to room temperature and added to 400 g of water. The total volume of the mixture was adjusted to 2,300 ml with water. Concentrated sulfuric acid was slowly added to produce a solid, which was collected by filtration and washed with water. The wet cake of the filter press was dried in an oven to obtain 108.6 g (91.2% of theory) of 2,5-p-dicarboxyanoylinoterephthalic acid. Example 2 Preparation of 2,3-dicarboxyquinacridone To 500 g of polyphosphoric acid (117.6% phosphoric acid) heated to 80 ° C was added 50 g of 2,5-p-dicarboxyanoylinoterephthalic acid over a period of 20 minutes, while maintaining the temperature at the same time. below 90 ° C. The reaction mixture was then heated at 125 ° C for three hours. The melt was cooled to 80 ° C, then slowly added to 1 kg of water and stirred for one hour. The solid was collected by filtration and washed with water. The wet cake of the filter press was dried in an oven at 60 ° C, to obtain 42.5 g of 2,3-dicarboxyquinacridone. Example 3 Preparation of 2,9-di (2-benzothiazolyl) quinacri dona (Method A) To 200 g of polyphosphoric acid (118.1% phosphoric acid) heated to 60 ° C was added 8.82 g of 2-aminothiophenol over a period of five minutes. After heating the mixture to 85 ° C, 10 g of 2,9-dicarboxyquinacridone was added over a period of ten minutes. The reaction mixture was heated at 175-180 ° C for three hours. The melt was cooled to 80 ° C and then slowly added to 500 g of ice water and stirred for 30 minutes. The solid was collected by filtration and washed with water. The cake of the filter press was dried in an oven at 60 ° C to obtain 14.3 g of 2,9-di (2-benzo-thiazolyl) uinacridone. Example 4 Preparation of 2,9-di (2-benzothiazolyl) quinacri dona (Method B) 2,9-Di (2-benzothiazolyl) quinacridone was prepared without isolation of the intermediate 2,9-dicarboxyquinacridone. na To 240 g of polyphosphoric acid (117.5% phosphoric acid) heated to 80 ° C was added 30 g of 2,5-p-dicarboxyanoylinoterephthalic acid over a period of ten minutes, while maintaining the temperature at the same time. below 100 ° C. The reaction mixture was heated at 125 ° C for three hours. After cooling the reaction mixture to 90 ° C, 26.4 g of 2-aminothiophenol was added over a period of ten minutes, while maintaining the temperature at 100 ° C. The reaction mixture was heated at 175-180 ° C for three hours. The melt was cooled to 90 ° C and then slowly added to 361 g of methanol over a period of 15 minutes, while maintaining a temperature below 65 ° C. The suspension was heated at reflux for one hour, cooled to below 60 ° C and diluted with water, after which the solid was collected by filtration and washed with water until acid-free. The wet cake of the filter press was dried in an oven at 60 ° C to obtain 33.4 g (84% of theory) of 2,9-di (2-benzothiazole) quinacridone. Example 5 Preparation of Crido 2,9-di (2-benzimidazolyl) cin To 300 g of polyphosphoric acid (117.5% phosphoric acid) heated to 80 ° C was added 30 g of 2,5-p-dicarboxyanoylinoterephthalic acid over a period of ten minutes, while maintaining a lower temperature at 100 ° C. The reaction mixture was heated at 125 ° C for three hours. After cooling the reaction mixture to 90 ° C, 19.4 g of 1,2-phenylenediamine was added over a period of ten minutes, while maintaining the temperature at 110 ° C. The reaction mixture was heated at 175-180 ° C for three hours. The melt was cooled to 130 ° C and then slowly added to 420 g of methanol over 15 minutes while maintaining a temperature below 65 ° C. The suspension was heated at reflux for one hour, cooled to less than 60 ° C and diluted with water, after which the solid was collected by filtration and washed with water until acid-free. The wet cake of the filter press was dried in an oven at 60 ° C to obtain 34.2 g (98% of theory) of 2,9-di (2-benzimidazolyl) quinacridone. Examples 6-8 Pigments according to the invention were prepared by grinding to reduce the particle size (Example 6) and autoclaving to induce growth of the particles (Examples 7 and 8). The conditioned pigments were then evaluated in the paint systems described above.

Example 6 2,9-di (2-benzothiazolyl) quinacridone (18 g) was resuspended in 153 g of water with 1.8 g of DYSPERBYK7 183 (BYK-Chemie USA, Wallingford, CT). The suspension was triturated for eight hours using an Eiger mill containing glass beads at 3,500 rpm. The slurry was discharged, filtered and washed. The filter cake was resuspended in 250 g of water, adjusted to pH 4.5 and maintained at 50 ° C. An aqueous emulsion containing 1.08 g of an anionic sulfosuccinate surfactant and 9.0 g of petroleum distillate was added and the mixture was stirred at 50 ° C for three hours. The solid component of the resulting suspension was collected by filtration and washed with water. The wet cake was dried from the filter press at 60 ° C overnight to obtain 18.9 g of pigment. A solvent based alkyd metal paint prepared as described above exhibited a very high brownish hue. Example 7 The filter cake of crude 2,9-di (2-benzothiazolyl) quinacridone (225 g, corresponding to 36.0 g of pigment with 100% strength) was resuspended in 300 g of water and the pH adjusted to 9.8. The suspension was heated at 140-145 ° C for four hours in a laboratory Parr reactor. After allowing the suspension to cool to room temperature, a solution of 3.0 g of rosin of wood dissolved in 25 g of water at pH 9.0 and stirred at 50 ° C for 30 minutes. A solution of 6.0 g of calcium chloride dihydrate dissolved in 30 g of water was then added and the mixture was then stirred at 50 ° C for one hour. The solid component of the resulting suspension was collected by filtration and washed with water. The wet filter cake was dried at 60 ° C overnight to obtain 41.4 g of a green camouflage pigment. An alkyd metal solvent-based paint prepared as described above exhibited a very high greenish-golden hue. EXAMPLE 8 The filter cake of crude 2,9-di (2-benzimidazolyl) quinacridone (105 g, corresponding to 26.8% pigment with 100% strength) was resuspended in 275 g of water and the pH was adjusted to 9.0. The suspension was heated at 140-145 ° C for four hours in a laboratory Parr reactor. After allowing the suspension to cool to room temperature, a solution of 2.5 g of wood rosin dissolved in 25 g of water at pH 9.0 was added and stirred at 50 ° C for 30 minutes. A solution of 5.0 g of calcium chloride dihydrate dissolved in 25 g of water was then added and the mixture was then stirred at 50 ° C for one hour. The solid component of the resulting suspension was collected by filtration and washed with water. The wet cake was dried from the filter press at 60 ° C overnight to obtain 29.4 g of a pigment red tile. An alkyd metal solvent-based paint prepared as described above exhibited a very high red tile pitch.

Claims (8)

1. Claims A quinacridone pigment that has the formula where X is O, S or NR; R is hydrogen, alkyl C3-C7 cycloalkyl or C7-C16 aralkyl; And it's rent or halogen; the dashed line represents an eventual double bond; R1 and R2 are independently hydrogen, C ^ Cg alkyl, C5-C7 cycloalkyl, C6-C10 aryl, C7-C16 aralkyl, nitrile or carboxyl or an ester or amide thereof, or R1 and R2 together form a C5-Ca cycloaliphatic ring or a fused aromatic or heteroaromatic ring; R3 is hydrogen or alkyl and m is 0, 1 or 2
2. 2. A quinacridone pigment according to Claim 1, which has the formula where X is 0, S or NR; R is hydrogen, alkyl C5-C7 cycloalkyl or C7-C16 aralkyl; And it's rent alkoxy or halogen; the dashed line represents an eventual double bond; R1 and R2 are independently hydrogen, alkyl C3-C7 cycloalkyl, C6-C10 aryl, C7-C16 alkyl, nitrile or carboxyl or an ester or amide thereof, or R1 and R2 together form a C3-C8 cycloaliphatic ring or a fused aromatic or heteroaromatic ring, and m is 0, 1 or 23.
3. A quinacridone pigment according to Claim 1, which has the formula where X is O, S or NR; Y is C 1 -C 6 alkyl, C 1 Cg alkoxy or halogen; W is alkyl C3-C7-cycloalkyl, C5-C7-cycloalkoxy, C6-C10-aryl, C6-C6-aryloxy, C7-C16-aralkyl, C7-C16-aralkoxy, hydroxy, halogen or nitrile and n is 0 or 4, or any two W adjacent ones form a fused aromatic ring, and m is 0, 1 or 2.
4. 4. A quinacridone pigment according to Claim 1, which has the formula where X is O, S or NH.
5. 5. A process for preparing a quinacridone pigment having the formula where X is 0, S or NR; R is hydrogen, alkyl C3-C7 cycloalkyl or C7-Clfi aralkyl; And it's Ci-Cg alkyl, alkoxy or halogen; the dashed line represents an eventual double bond; R1 and R2 are independently hydrogen, alkyl C5-C7 cycloalkyl, C6-C10 aryl, C7-C1S aralkyl, nitrile or a carboxylic ester or amide, or R1 and R2 together form a C5-C8 cycloaliphatic ring or a fused aromatic or heteroaromatic ring, and is 0, 1 or 2 , consisting of the condensation of (1) a carboxy-substituted quinacridone of formula where Y is C1-C6 alkyl, alkoxy or halogen no and m is 0, 1 or 2, with (2) an amine of formula where X is O, b O JNIK; R is hydrogen, alkyl C5-C7 cycloalkyl or C7-C16 aralkyl; the dashed line represents an eventual double bond; R1 and R2 are independently hydrogen, C1-C6 alkyl, C5-C7 cycloalkyl, C6-C10 aryl, C7-C16 aralkyl, nitrile or a carboxylic amide ester, or R1 and R2 together form a C5-C8 cycloaliphatic ring or a fused aromatic or heteroaromatic ring.
6. 6. A pigmented macromolecular substance containing, as a pigment, a quinacridone pigment according to Claim 1.
7. 7. A pigmented coating composition containing, as a pigment, a quinacridone pigment according to Claim 1.
8. 8. A pigmented inkjet ink or printing ink containing, as a pigment, a quinacridone pigment according to Claim 1. SUMMARY OF THE INVENTION This invention relates to quinacridone pigments of formula (I) where X is O, S or NR; R is hydrogen, alkyl C3-C7 cycloalkyl or C7-C16 aralkyl; And it's rent alkoxy d-Cg or halogen; the dashed line represents an eventual double bond; R1 and R2 are independently hydrogen, alkyl C5-C7 cycloalkyl, C6-C10 aryl, C7-C16 aralkyl, nitrile or carboxyl or an ester or amide thereof, or R1 and R2 together form a C5-Ca cycloaliphatic ring or a fused aromatic or heteroaromatic ring; R3 is hydrogen or alkyl and m is 0, 1 or 2. This invention also relates to the preparation and use of said quinacridone pigments.