MXPA99011476A - Procedure for the preparation of perilene pigments highly cromati - Google Patents

Abstract

This invention relates to a process for preparing perylene pigment compositions by reacting (a) a perylene tetracarboxylic compound, (b) about 0.01 to about 20% by weight, relative to the perylene tetracarboxylic compound, of a non-pigmentary cyclic halide or imide of formula (I) wherein W is O or NR1 (where R1 is hydrogen, a metal or optionally substituted alkyl, cycloalkyl, aralkyl or aryl): R2, R3 and R4 are various combinations of substituents and / or fused rings, and the dashed line is an optional double bond representing R2-C = C-R3; ammonia or a primary alkyl-, aralkyl- or arylamine, optionally in the presence of (d) a solvent and / or (c) one or more dispersant

Description

PROCEDURE FOR THE PREPARATION OF HIGHLY CHROMATIC PERILENE PIGMENTS BACKGROUND OF THE INVENTION This invention relates to a process for preparing perylene pigment compositions in the presence of certain non-pigment cyclic anhydrides or imides. The perylenes, including the diimides of 3, 4, 9, 10-tetracarboxylic acid, can be prepared by methods known in the art. For example, . Herbst and K. Hunger, Industrial Organic Pigments, 2nd ed. (New York: VCH Publishers, Inc., 1997), pages 9 and 476-47; H. Zollinger, Color Chemistry (VCH Verlagsgesellschaft, 1991), pages 227-228 and 297-298, and M.A. Perkins,] b "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; see also US Pat. 4,431,806, 4,496,731, 4,797,162, 5,248,774, 5,264,034 and 5,466,807. The perylenes, as initially insulated in the process of the present invention, which are frequently remitted as crude perylenes, are generally unsuitable for use as pigments and, therefore, must be subjected to to one or more additional finishing steps that b modify the particle size, the particle shape and / or the structure of the crystal such that a good pigment quality is obtained. See, for example, K. Merkle and H. Schfer, "Surface Treatment of Organic Pigments," in Pigment Handbook, Vol. III (New York: John Wiley '^ 0 &Sons, Inc., 1973), page 157; R.B. McKay, "The Develop- ment of Organic Pigments with Particular Reference to Physical Form and Consequent Behavior in Use," in Rev.

Prog. Coloration, 10_, 25-32 (1979), and R.B. McKay, "Control of the application performance of classical organic pigments", in JOCCA, 89-93 (1989). The addition of determined perylene derivatives to the ring closure step has also been described. For example, U.S. Pat. No. 5,264,034 discloses the use of certain bisimides or perylene imide-anhydrides to improve the color and rheological properties of perylene pigments. U.S. Pat. 5,248,774 describes certain zwitterionic perylene bisimide derivatives for use as colorants or as surface modifying agents for known perylene pigments. U.S. Pat. No. 5,472,494 describes the use of certain perylene monoimide derivatives to modify the properties of the \ b organic pigments. These patents do not disclose, however, the non-pigment cyclic anhydrides and imides of the present invention. It has now been found that the presence of certain non-pigment cyclic anhydrides and imides during The chemical synthesis of perylene bisimides provides perylene pigment compositions that have improved transparency and color properties, even in the unfinished form that is initially isolated, and are especially suitable for use in metal paints. The non-pigment cyclic anhydrides and imides of the type used in the present invention are known. For example, US Pat. 4,992,204 and J.M. Chap-man, Jr. et al., J. Pharm. Sci., 78, 903-909 (1989). Said compounds have, however, been used in combination with organic pigments The non-pigmentary naphthalimide derivatives have been described in a journal article describing the computer design of additives to improve the pigment properties of Pigment Red 179, a N, N-disubstituted perylene pigment. P. Erk et al., Eur. Coat. J., H), 906-920 (1997). The article describes naphthalamides as poor growth inhibitors compared to LOS derived from perylene and does not disclose their incorporation during pigment synthesis. Moreover, cyclic anhydrides and non-pigment imides of the type used in the present invention are not described. COMPENDIUM OF THE INVENTION This invention relates to a process for preparing perylene pigment compositions, consisting of the reaction of (a) a perylene tetracarboxylic compound; (b) about 0.01 to about one % by weight (preferably 5 to 15% by weight), relative to the perylene tetracarboxylic compound, of a cyclic anhydride or non-pigment imide having the formula (I) where W is O or NR1; R 1 is hydrogen, a metal, C 1 -C 6 alkyl, C 5 -C 8 cycloalkyl, C 7 -C 6 aralkyl, C 6 -C 6 aryl or -Alk-X; R 2 and R 3 are independently hydrogen, C 1 -C 7 alkyl, C 7 -C 6 aralkyl or C 6 -C 6 aryl, or R 2 and R 3 together are fused rings (preferably fused cycloalkane or aromatic rings); the dotted line is an eventual double bond representing R2-C = C-R3 (including a formal double bond of any fumary ring formed by R2 and R3 taken together); Alk is Ci-Cis alkylene or C5-Ce cycloalkylene, and X is (i) an anionic group selected from -S03", -C00", -P03 =, -PO (ORx) 0 ~ (where Rx is L Ci alkyl C? -C6), -0-P03 = and -0-PO (ORy) 0 ~ (where Ry is Ci-Ce alkyl), each such anionic group being electrically balanced with a stoichiometric amount of a cation (preferably a hydrogen and a 1 metal ion and / or ammonium); (ii) a cationic group having the formula -NRRbRc + (wherein Ra, Rb and Rc are independently hydrogen, Ci-Cß alkyl, C7-C16 aralkyl or C6-C? aryl), each of said cationic groups being electrically equilibrated with a stoichiometric amount of an anion (preferably halide, sulfate, phosphate, nitrate, mesylate or tosylate, or, less preferably, hydroxide); B (iii) NRdRe, where Rd is hydrogen, C? -C6 alkyl, C7-C6 aralkyl, C6-C? Aryl, C2-C6 alkanoyl, C7-Cn aroyl or sulfonyl and Re is hydrogen, C 1 -C 6 alkyl, C 7 -C 6 aralkyl or C 1 -C 6 aryl, (iv) OR f, where R f is hydrogen, C 6 -C 6 alkyl or C 6 -C 0 aryl; (v) COORg, wherein Rg is C?-C6 alkyl, C7-Ci6 aralkyl or Cß-Cio ar aryl; (vi) sulfonyl; or (vii) C6-C6 aryl, and (c) ammonia or a primary amine of formula RA-NH2, where RA is C6-C6 alkyl, C7-Cie aralkyl or C6-C6 aryl; optionally in the presence of (d) a solvent and / or (e) one or more additives. The invention also relates to perylene pigment compositions prepared in this way. DETAILED DESCRIPTION OF THE INVENTION Among the perylene tetracarboxylic compounds that can be used for the preparation of the perylene pigment compositions of the present invention are various cyclic carboxylic acids, carboxylic esters, carboxamides, cyclic anhydrides and / or cyclic imides of the formula (II) where E1 and E_ "are independently OR or NR 'R" and E2 and E4 are independently OR, or E1 and E2 together are O or NA1 and E3 and E4 together are O or NA2; each R is independently hydrogen (ie, for free acid groups), a metal cation or an ammonium cation (ie, for salts), Ci-Cß alkyl (ie, for alkyl esters), C7-C16 aralkyl ( that is, for aralkyl esters) or C6-C? 0 aryl (ie, for aryl esters); each R 'and R "are independently hydrogen, Ci-Cd alkyl or C7-C16 aralkyl; AJ and A2 are independently (but, preferably, identically) hydrogen, a metal, alkyl Ci-Cß or substituted Ci-Ce alkyl, cycloalkyl C5-C8 or substituted C5-C8 cycloalkyl, C7-C16 aralkyl or substituted C7-C6-aralkyl or aryl Cβ-Cι or substituted Cß-Cι aryl; B is C? -C6 alkyl, C? -C6 alkoxy, a sulfonyl, amino, ammonium, hydroxy, nitro or halogen group, and p is zero or an integer from 1 to 8. The preferred perylene tetracarboxylic compounds of the component (a ) are perylenenetetracarboxylic perylene and / or ester acids, and salts thereof, wherein the groups E1, E2, E3 and E4 are independently OH or their salt forms or C? -Cd alkoxy (preferably tetracarboxylic acids or their salts, wherein E1, E2, E3 and E4 are identically OH or a corresponding salt form); bis-anhydrides, wherein E1 and E2 together and E3 and E4 together are oxygen atoms, and bisimides, wherein E1 and E2 and E3 and E4 together are independently NH or substituted nitrogen atoms (preferably, symmetric bisimides in which both nitrogen atoms have the same substitute-te). The preferred perylene tetracarboxylic compounds do not have aromatic ring substituents B (that is, p is zero), but substituted perylene tetracarboxylic compounds are also suitable in which at least one of the eight carbon atoms of the aromatic ring substitutable co-perylene has at least one group B (ie, where p is not zero). Some of the perylene tetracarboxylic compounds used as component (a) may themselves be pigments, but it is not necessary for the compounds to be pigments, insofar as the final perylene pigment composition is pigmentary. When used to describe the perylene tetracarboxylic compounds of component (a), the term "Ci-Cβ alkyl" refers to straight or branched chain aliphatic hydrocarbon groups having from 1 to 6 carbon atoms. Examples of C6-C6 alkyl are methyl, ethyl, propyl, butyl, pentyl, hexyl and their isomeric forms. The term "C5-C8 cycloalkyl" refers to cycloaliphatic hydrocarbon groups having from 5 to 8 carbon atoms. Examples of C5-C8 cycloalkyl are cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl. The term "aryl O, -Cu / 'refers to phenyl and 1- or 2-naphthyl The term" C7-C6 aralkyl "refers to C?-C6 alkyl substituted with C ar-C? Aryl, or such that the total number of carbon atoms is from 7 to 16. Examples of C 7 -C 6 aralkyl benzyl, phenethyl and naphthylmethyl are examples.The substituted alkyl groups are those in which one or more carbon atoms are substituted with alkoxy , halogen, hydroxy (including the oxo tautomeric forms), alkoxycarbonyl, aryloxy-carbonyl, cyano and nitro, as defined herein The substituted aryl and aralkyl groups are those in which one or more carbon atoms are substituted with alkyl, alkoxy , halogen, hydroxy (including the oxo tautomeric forms), alkoxycarbonyl, aryloxycarbonyl, cyano and nitro, as defined herein The term "C6-C6 alkoxy" refers to straight or branched chain alkyloxy groups having from 1 to 6 carbon atoms are examples of C?-C6 alkoxymethyl, ethoxy, pr opoxy, butoxy, pentyloxy, hexyloxy and their isomeric forms. The term "sulfonyl group" refers to -SO2-R1 groups, such as alkylsulfonyl (wherein R1 is alkyl; for example, methylsulfonyl or ethanesulfonyl), arylsulfonyl (wherein R1 is aryl, for example, phenylsulonyl, 1- or 2-naphthylsulfonyl and substituted forms, such as toluenesulfonyl), sulfoxyl and the corresponding esters (wherein R1 is OH, alkoxy, cycloalkoxy, aralkoxy, aryloxy) and sulfonamides (wherein R1 is -NR "L1R11, wherein R11 and R111 are independently hydrogen, alkyl, cycloalkyl, aralkyl or aryl.) The terms" amino "and" ammonium "refer, respectively , to -NR1VRV and -NR1VRVRV1 +, wherein Riv, Rv and RV1 are independently hydrogen, C?-C6 alkyl or C7-C ?6 aralkyl and each ammonium group is electrically balanced with a stoichiometric amount of an anion. "halogen" includes fluorine, chlorine, bromine and iodine It is possible to use salt forms of the tetracarboxylic perylene compounds if at least one of the groups E1, E2, E3 and E4 of the formula (II) represents a carboxylate anion or a are carboxylic salts ad equate those in which each carboxylate anion is electrically balanced with 1 / n molar equivalents of an n-valent cation Mn + (such as Li +, Na +, K +, Mg ++, Ca ++, Bal +, Al +++, Fe ++ or Fe +++) or an ammonium ion having the formula RIRIIRIIIRIVN + (where R1, R11, R111 and RIV are independently hydrogen, C? -C6 alkyl, C? -C6 hydroxyalkyl or C? 6 aralkyl). In general, the free acids in which at least one of E1, E2, E3 and E4 is OH are initially added to the reaction mixture, but are converted into the corresponding amine salts by an acid-base reaction in situ with the ammonia or the primary amine of component (c). Suitable imide salts of formula (II) are the perylenes in which at least one of A1 or A2 represents 1 / n molar equivalents of an n-valent cation Mn + (such as Li +, Na +, K, Mg +, Ca ++, Ba ++, Al +++ , Fe ++ or Fe +++). Said salts are formed whenever exposed to the imides of formula (II) wherein A1 and / or A2 is hydrogen to strongly basic media, either under the reaction conditions used to prepare the perylene imide or by addition of a strong base. The perylene tetracarboxylic compounds described above, some of which are crude or conditioned perylene pigments and some of which are peplen pigment precursors, can be prepared by any of several methods known in the art. For example, W. Herbst and K. Hunger, Industrial Organic Pigments, 2nd ed. (New York: VCH Publishers, Inc., 1997), pages 476-479; H. Zollinger, Color Chemistry (VCH Verlagsgesellschaft, 1991), pages 227-228; M.A. Perkins, "Pyridmes and Pyridones", in The Chemistry of Synthetic Dyes and Pigments, ed. HE HAS. Lubs (Malabar, Florida: Robert E. Kpeger Publishing Company, 1955), pages 481-482, and F. Graser, "Perylenes", in Pigment Handbook, 2nd edition, Vol. III (New York: John Wiley &Sons, Inc., 1988), pages 653-6 8. A critical feature of the invention is the use of cyclic anhydrides or non-pigment imides of formula (I). The term "non-pigmentary" means that the compounds are substantially colorless or are significantly less highly colored and lack good pigment properties compared to the perylene t tracarboxylic compounds and the perylene pigment compositions with which they are used. That is to say, that the appropriate cyclic anhydrides or imides of formula (I) would not themselves have a practical utility as pigments. The term "substantially colorless" does not mean that the cyclic anhydrides or imides should be completely devoid of color in the visible region, but instead, only means that the compounds do not have a significant coloration in comparison with the pigments of perylene with which they are used. For example, the preferred cyclic anhydrides or imides of formula (I) will exhibit minor molar absorbencies (preferably at least about one order of magnitude smaller) than those of the perylene precursors and the perylene pigment compositions with which they are used. When used to describe the non-pigment cyclic anhydrides or imides of component (b) (by incorporating the compounds described below), the terms "C? -Cd alkyl", "C5-C8 cycloalkyl", "C6-C? 0 aryl", "C7-C16 aralkyl", "C? -C6 alkoxy", "sulfonyl group", "amino" , "ammonium" and "halogen", have the same meanings as those previously given for the tetracarboxylic perylene compounds. The term "C? -C? 8 alkylene" refers to straight or branched chain aliphatic hydrocarbon groups of 1 to 18 carbon atoms and with two binding sites. Examples of C 1 -C 8 alkylene are methylene, ethylene, propylene, butylene, pentylene, hexylene and longer hydrocarbon chains, including both straight and branched chain groups. The term "cycloalkylene C, -Cp" refers to cycloaliphatic hydrocarbon groups having from 5 to 8 carbon atoms and two binding sites. Examples of C5-C8 cycloalkylene include 1,3-cyclopentylene, 1,4-cyclohexylene and the like. The term "C2-C6 alkanoyl" refers to straight or branched chain alkanoyl groups having from 2 to 6 carbon atoms. Examples of C2-C6 alkanoyl are acetyl, propanoyl, butanoyl, pentanoyl, hexanoyl and their isomeric forms. The term "C-Cn aroyl" refers to benzoyl and 1- or 2-uaftoilc, wherein the aryl portion may be optionally substituted as described above for "aplo". The term "fused rings" refers to groups that together form fused hydrocarbon rings, including cycloalkane rings and, more preferably, aromatic ring systems such as benzene or 1,2- or 2,3-naphthalene. Each of the fused ring systems has to be substituted in the rings, for example, with C 1 -C 6 alkyl, C 7 -C 6 aralkyl, C 6 -C 0 aryl, alkoxy c 5 -r 5, sulfonyl, amino, ammonium and halogen, as described above. Preferred cyclic anhydrides and imides include the aromatic compounds of formula (la) wherein W is defined as above and wherein R 4, R 5, R 6 and R 7 are independently hydrogen, C 1 -C 7 alkyl, C 1 -C 6 alkoxy, a sulfonyl, amino, ammonium, hydroxy, nitro or halogen group, or any two adjacent groups R4, R5, R6 and F ie, R4 and R ?, R5 and R6 or R6 and R7), taken together, scam a fused ring (preferably, a benzene ring) and / or a group represented by the formula (where W is defined as above) and the remaining groups R4, R5, Rf and / or R 'are independently hydrogen, Ci-Cd alkyl, C6-C6 alkoxy, a sulfonyl, amino, ammonium, hydroxy, nitro or halogen For compounds of formula (la) in which W is NR1 (ie, imides), the group Rx is preferably hydrogen, a metal, C? -Cd alkyl or -Alq-X, where Alk is C? -C alkylene? 8 and X is -S03 or -C00"electrically balanced with hydrogen or a metal ion, Examples of suitable cyclic anhydrides and imides of this type include phthalic anhydride, phthalimide, 1,2, 5-benzenetetracarboxylic dianhydride, anhydride 1, 2-naphthalic and 2, 3-naphthalic anhydride Suitable cyclic anhydrides and imides, but generally less preferred, include non-aromatic compounds of formula (I) in which the dashed line represents a carbon-carbon double bond and R 2 and R 3 are independently hydrogen, C 1 -C 6 alkyl, C 7 -C 6 aralkyl or C 6 -C 6 aryl, or less preferably, R 2 and R 3 together form a fused cycloalkane ring Examples of suitable cyclic anhydrides and imides of this type include maleic anhydride, maleimide and anh drido Lclohexeno c acid-1, 2-dicarboxylate. The cyclic anhydrides of formula (I) (in which W is O) can be obtained commercially or by conversion of the corresponding dicarboxylic acids in the anhydrides using known methods, for example by heating or by treating with a strong acid or other dehydrating agents . For example, A. Streitweiser, Jr. and C.H. Heathcock, Introduction to Organic Chemistry, 3rd edition ("lew York: Macmillan Publishing Company, 1985), pages 495 and 866. The imides of formula (I) (where W is NR1) can, in turn, be prepared to starting from corresponding acids, esters or anhydrides by known methods, preferably by reacting a corresponding cyclic anhydride with at least a slight molar excess of a suitable amine in a suitable solvent In a preferred method for preparing imides in which R 1 is not contains ionic groups, t_- 1 anhydride and the amine react in water heated to approximately 80 ° C to 100 ° C at ambient pressure, or to temperatures up to about 140 ° C in an autoclave or other sealed reactor, typically for about two hours. at four hours In a preferred method for preparing rmides wherein R 1 contains anionic groups (e.g., carboxylate, sulfonate or phosphonate groups), the protonated amino group of the zwitterionic amine precursor is converted to a free amino group by the addition of an equivalent of a base (such as sodium or potassium hydroxide) to the reaction mP7cla, after which the reaction is carried out under essentially the same conditions as those used for the reaction. nonionic compounds. However, if the resulting anionic compound is water-soluble, it must be α-Siao, for example, by acidification of the reaction mixture and isolation of the free acid, increasing the ionic strength of the mixture and isolating the otherwise soluble metal salt ( that is, sodium or potassium), or precipitating the imide by the addition of a polyvalent metal salt (for example, CaCl 2, BaCl 2 or FeCl 2). Imide salts of formula (I) in which W is NR1 can be prepared and R1 is a metal from the corresponding "free" imides in which R1 is hydrogen. Suitable iodide salts of formula (I) are those in which each R! represents 1 / n molar equivalents of an n-valent cation Mn + (such as Li +, Na +, K +, Mg + \ Ca ++, Ba ++, Al +++, Fe or Fet ++). Said salts are formed whenever they are exposed to the imides of formula (I) in which R1 is hydrogen to strongly basic metals., either under the reaction conditions used to prepare the peryleneimide or by adding a strong base to the free imide. Component (c) includes ammonia and primary amines having the formula RA-NH 2, wherein RA is C 1 -C 6 alkyl, C 7 -C 6 aralkyl or C 6 -C 0 aryl. Examples of suitable primary amines include alkylamines such as methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine and their isomeric forms; aralkylamines, such as benzylamine and phenethylamine, and arylamines, such as aniline, anisidine, phenetidine, toluidine and various isomers of xylidine. It is necessary to use at least a slight excess of ammonia or amine (c) in relation to the anhydride and / or imide groups of the pigment precursor of peri-1 ene (a) and the non-pigment cyclic anhydride or imide (pl. , about 1.1 to about 10 moles (preferably 1.5 to 5 moles) of ammonia or primary amine (c) are used per mole of the anhydride and imide groups of components (a) and (b). , in general, preferred, it is possible to use higher amounts of ammonia or primary amine (c), which, if liquid under the reaction conditions, can even serve as a solvent or as a cosolvent with component (d). suitable (d) are liquids which are capable of dissolving or suspending the components of the reaction mixture without significantly decomposing or otherwise reacting during the reaction Examples of suitable solvents include water: monofunctional alcohols, particularly alkanol it is inferior, such as methanol, ethanol, butanol, pentanol, hexanol and its isomeric forms; amides, such as dimethylformamide and dimethylacetamide; ketones and ketonic alcohols, such as acetone and diacetone alcohol; ethers, such as tetrahydrofuran and dioxane; alkylene glycols and thioglycols, such as ethylene glycol, propylene glycol, butylene glycol, triethylene glycol, hexylene glycol, diethylene glycol and thiodiglycol; po-i-alkylene glycols, such as polyethylene glycol and polypropylene glycol; other polyols, such as glycerol and 1,2,6-hexanetriol; lower alkyl ethers of polyhydric alcohols, such as 2-methoxyethanol, 2- (2-ethoxyethoxy) ethanol, 2- [2- (2-methoxyethoxy) ethoxy] ethanol and 2- [2- (2-ethoxyethoxy) ethoxy] ] ethanol; aromatic and heteroaromatic liquids, such as benzene, pyridine and quinoline, and other organic liquids such as are known in the art. Water, methanol and quinoline are particularly preferred solvents in the art. Of course, other solvents can also be used often, but it is generally advisable to avoid solvents that can react with the reactive components. The amount of solvent is not critical in general, but it must be a sufficient amount to dissolve or suspend the components of the reaction mixture, but not so large as to necessitate eliminating excessive amounts after completion of the reaction. Typical amounts of solvent vary between about 5 and about 20 parts by weight (preferably, 7 to 15 parts by weight) relative to the total amount of components (a) and (b). Solvents (d) may not be necessary if one or more of components (a), (b) or (c) are themselves liquid or if the mixture of components (a), (b) and (o) can be melted without significant decomposition to unwanted suoproducts. The optional additives (e) can be any of the usual additives for the preparation of pigments known in the art which serve, for example, to improve the color properties, to reduce or avoid flocculation, to increase the stability of the dispersion of pigment and to reduce the viscosity of the coating. Suitable additives include, for example, dispersants or surfactants and various pigment derivatives. Examples of suitable dispersants include anionic compounds, such as fatty acids (such as stearic or oleic acid), salts of fatty acids (es-ole, jaoons such as alkali metal salts of fatty acids), taupdas or N-methyl taurides of fatty acids, alkylbenzene sulfonates, alkylnaphthalenesulfonates, alkyllenol polyglycol ether sulfates, naphthenic acids or reamic acids (such as abietic acid); cationic compounds, such as quaternary ammonium salts, fatty amines, or fatty amines ethylates and fatty amine polyglycol ethers, and nonionic compounds, such as fatty alcohol polyglycol ethers, esters of fatty alcohols and polyglycol and alkylphenol polyglycol ethers. Examples of suitable pigment additives include organic pigments which The present invention has one or more sulfonic acid groups, sulfonamide groups, carboxylic acid, carboxamide and / or (cyclo) aliphatic groups containing (hetero) aryl. Said additives may be incorporated in amounts ranging from about 0.05 to 20% by weight (preferably, between 1 and 10% by weight), based on the amount of pigment). The perylene pigment compositions of the present invention can be prepared by mixing components (a), (b) and (c) and the eventual components (d) and (e) in essentially any sequence. Preferably, in erriDargo, the tetracarboxylic compound of perylene (a) 5 the cyclic anhydride or non-pigment imide (b), as well as any dispersant (e), are added to the solvent (d) and stirred at a temperature of about 0 ° C. at about 30 C (preferably at room temperature or below this, more preferably from 0 ° C to 5 ° C) before the addition of ammonia or amine (c). The mixture is heated to a temperature of about 50 ° C to about 150 ° C (preferably 80 ° C to 100 ° C) until the reaction is complete, typically for a period of about two to six hours. Particularly preferred embodiments in lds that component (c) is methylamine, a mixture of the perylene tetracarboxylic compound and the non-pigment cyclic anhydride or imide in water is cooled to about 5 C and then heated with methylamine. complete- (ii) In the reaction, the reaction mixture is cooled if necessary and the pigment is collected, for example by filtration, centrifugation or other known methods. During the process of the present invention, the ammonia or amine of component (c) can react with acid anhydrides and / or imides that are present in the compounds of formulas (I) and / or (II) to form the corresponding imides wherein at least some of the groups R1, A1 and / or A are substituted with hydrogen (from the ammonia) or with the group R "(from the amine RA-NH2). However (? the perylene tetracarboxylic compounds and the starting non-pigmentary cyclic anhydrides are transformed by the component (c), the resulting perylene pigment compositions exhibit better transparency and color properties when compared to perylene pigments prepared in the absence of anhydride The pigment composition can optionally be conditioned using methods known in the art, such as solvent treatment or milling in combination with the treatment with solvents. The final particle size of the pigment can be controlled by varying the post-treatment method. For example, the pigments can be made to be more transparent by reducing the particle size or more opaque by increasing the particle size. Suitable milling methods include dry milling methods, such as jet milling, ball milling and the like, with or without additives, or wet milling methods, such as mixing with salts, grinding with sand, grinding with pearls and the like, in water or organic solvents, with or without additives. 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, stearate aluminum or magnesium behenate; quaternary ammonium compounds, such as tri [(C 1 -C 4 alkyl) benzyl] ammonium salts; plasti-ficants, such as epoxidized soybean oil; waxes, such as polyethylene wax; resin acids, such as abietic acid, rosin soap, hydrogenated or dimerized rosin; C 2 -C 8 parafinadisulfonic acids; alkylphenols; alcohols, such as stearyl alcohol; amines, tails with laurylamine or stearylamine, and aliphatic 1,2-diols, such as dodecane-1,2-diol. Said additives can be incorporated in amounts ranging from about 5 to 0.05 to 20% by weight (preferably from 1 to 10% by weight), based on the amount of pigment. The pigment compositions can also be mixed (preferably by dry mixing) with one or more pigment derivatives known in the art, particularly sul-0 lomeo, sulfonamide and phthalimide acid derivatives. Due to their stability against light and their migratory properties, the perylene 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 highly photo-resistant pigmented systems. Examples include pigmented mixtures with other materials, pigment plasmids, paints, printing ink, or 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 (rutile) or cement, or other inorganic pigments. Examples of pigment formulations 5 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 oxidation-drying lacquers, oven-drying enamels, reactive paints, two-component paints, solvent-based paints or in water, emulsion paints for watertight and tempered coatings. Printing inks include those known for use in printing on paper, fabrics and tin. 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 poly-condensates. Examples of the macromolecular substances produced are 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 perylene pigment compositions of the present invention may have any desired shape or conformation. The pigment compositions according to this invention are highly water resistant, oil resistant, acid resistant, lime resistant, alkali resistant, solvent resistant, overcoat stable, scorch stable, sublimation stable, heat shrinkable. They are resistant and resistant to vulcanization, and still give a very good dyeing performance and are easily dispersible (for example, in plastic materials). The following examples illustrate even more details for the process of this invention. The invention, which has been set forth in the foregoing description, should not be limited in spirit or scope by these examples. Those skilled in the art will readily understand that known variations of the conditions of the following procedures can be used. Unless otherwise indicated, all temperatures are in Cel-sius degrees and all percentages are percentages by weight. EXAMPLES Test methods Paints based tests were carried out Water in diimide N, N'-dimethylperylenetetracarboxylic acid prepared according to the invention using a waterborne base coat paint system / solvent supported clear coat. Untreated N, N'-dimethylperylenetetracarboxylic diimide made by the same method as a control was used. Aqueous dispersions were prepared using a mixture of 12.4% acrylic resin ARO-LONUJ 559-G4-70 (Reichhold Chemicals, Inc.), 3.2% hydrodispersant SOLSPERSE © 27000 (Zeneca, Inc.) , 1.6% of 2-amino-2-methyl-1-propanol (Angus Chemical) and 18% pigment, which gave a pigment-to-binder ratio of 18:12 and a total solids content of 30% The pigment-to-binder ratio was then reduced to 10:40 with additional acrylic resin AROLONT 559-G4-70 (total amount, 26%) and 25% melamine / formaldehyde resin CYMEL® 325 (Cytec Industries), which gave a total solids content of 50%. Measurements of mass tone and transparency were made using films applied at 76 μm and 38 μm wet film thickness, respectively, and allowed to stand at room temperature for fifteen minutes and at 100 ° C for five minutes. Transparent layers containing a mixture of 80% resin AROPLAZ® 1453-X-50 (Reichhold Chemicals, Inc.) and 20% melamine / formaldehyde resin CYMEL® 325 were then applied at a total solids level of 57% on the base layer at a wet film thickness of 76 μm and allowed to stand at room temperature for fifteen minutes and at 121 ° C for fifteen minutes. Transparencies were calculated using the 38 μm films by subtracting the value? C from the mass tone measured on a black background from the? C value of the mass tone measured on a white background. Low-tone dye paints were prepared from the reduced aqueous dispersions described above, which had a pigment-to-binder ratio of 10:40 by the addition of additional acrylic resin AROLON® 559-G4-70, melamine resin / CYMEL® 325 formaldehyde and 35% white TINT-AYD® dispersion CW-5003 (Daniel Products Company), which gave a pigment-to-binder ratio of 1: 1.1, a total solids content of 55% and a ratio Ti02-ap gment of 90:10. Color measurements were made using films applied at a wet film thickness of 38 μm and allowed to stand at room temperature for fifteen minutes and at 100 C for five minutes. Transparent layers were then applied and baked as described above. Metal paints were prepared from the above-described dispersion having a pigment-aligner ratio of 18:12 using a water dispersible aluminum pigment (available as HYDRO PASTE® 8726, from Silberline Mar.ufacturing Co., Inc.), acrylic resin AROLON® 559-G4-70 and melamine / formaldehyde resin CYMEL® 325, in amounts that gave a pigment-to-binder ratio of 1: 2, a dluminium-to-pigment ratio of 20:80 and a total content in solids 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. Starting materials The following commercially available cyclic anhydrides were used in the examples: ib) (1) maleic anhydride (from Aldrich Chemical Company), which has the formula f: 2) phthalic anhydride (from Aldrich Chemical Company), which has the formula ib) () dianhydro 1,2,4,5-tetrabenzenetetracarboxylic acid (from Aldrich Chemical Company), which has the formula A cyclic imide used in the examples according to the invention was prepared as described below. Preparation N-Methylphthalimide (imide (b) (4)) To a suspension of 25.0 g (0.17 mol) of phthalic anhydride in 200 ml of water was added 30 g (0.38 mol) of an aqueous solution of 40% methylamine. The mixture was heated at reflux for four hours, after which about 50 ml of the aqueous amine i) was removed or distillation and the mixture was allowed to cool. The resulting precipitate was collected by filtration to obtain, 3 g of N-methylphthalimide (cyclic imide (b) (4)). EXAMPLE 1 A mixture of 50 g (0.13 mol) of perylene-3, 4, 9, 10-tetracarboxylic dianhydride and 2.7 g (0.028 nol) of phthalic anhydride in a mixture of 1,000 g of water and 500 g was stirred. ice. To the cold slurry was added 127 g (1.64 mol) of 40% aqueous methylamine over a period of 15 minutes. After stirring for one hour, during which the temperature was raised to about 15 C, the mixture was heated to 80 C and maintained at that temperature for four hours. The reaction mixture was cooled, after which the crude pigment was filtered and washed with water. About 10% by weight (based on the pigment) of a high molecular weight copolymer pigment dispersant, a base for adjusting to pH 8 to 9 and sufficient water to obtain a suspension containing approximately 10 to about 20% by weight of pigment. The suspension was milled in a horizontal wet mill for eight hours. The ground pigment was removed from the mill and acidified to less than pH 4 using hydrochloric acid. After stirring for 15 minutes, the pigment was collected by filtration, washed with water until free of acid and dried in an oven at 80 C to obtain a bright red pigment. The test data for the crude pigment are given in Table 1 and the test data for the ground pigment are given in Table 2. Examples 2-4 The method of Example 1 was repeated using similar mixtures of perylene-3 dianhydride, 4, 9, 10-tetracarboxylic and other cyclic anhydrides and imides according to the invention. Each cyclic and imide anhydride is identified in the following table and the test data is given therein.

Tab l a i: Results of p e ra cial testing;; ompos? ^ l u nc. of the crude pigment of Examples 1 - 4 All values for? H,? C and transparency are relative to the untreated control. Positive values for? H,? C and transparency correspond to more yellow, more chromatic and more transparent samples, respectively. Table 2: Test results for the ground pigment compositions of Examples 1-3 All values for? H,? C and transparency are relative to the control 0 not treated. Positive values for? H,? C and transparency correspond to more yellow, more chromatic and more transparent samples, respectively.

The data in the tables show that the pigment compositions prepared according to the invention were more yellow and more transparent than the untreated pigment.

Claims (9)

1. CLAIMS 1. A process for the preparation of a perylene pigment composition, consisting of the reaction of (a) a perylene tetracarboxylic compound; (b) about 0.01 to about 20% by weight, relative to the perylene tetracarboxylic compound, of a cyclic anhydride or non-pigment imide having the formula where W is 0 or NR1; R 1 is hydrogen, a metal, C 1 -C 6 alkyl, C 5 -C 8 cycloalkyl or -Alk-X; R 2 and R 3 are independently hydrogen, C 1 -C 6 alkyl, C 7 -C 6 aralkyl or C 6 -C 0 aryl, or R 2 and R 3 together are fused rings; the dashed line is an eventual double bond representing R2-C = C-R3; Alk is C? -Ci8 alkylene or C5-Cs cycloalkylene, and X is (i) an anionic group selected from -S03", -C00", -P03 =, -PO (ORx) 0"(where Rx is C5 alkyl) ? -C6), -0-P03 = and -0-PO (ORy) 0"(where R? Is C? -C6 alkyl), each such anionic group being electrically balanced with a stoichiometric amount of a cation; (Ii) a cationic group having the formula -NRaRbRc + (wherein Ra, Rb and Rc are independently hydrogen, C? -C6 alkyl, C7-C6 aralkyl or C6-C? 0 aryl), each of said cationic groups 15 electrically balanced with a stoichiometric amount of an anion; (iii) NRdRe, where Rd is hydrogen, C 1 -C 6 alkyl, C 7 -C 16 aralkyl, C 8 -C 0 aryl, C 2 -C 6 alkanoyl, C -C n aroyl or sulfonyl and Re is hydrogen, C 1 -C 6 alkyl, C 7 -C 6 aralkyl or C 1 -C 6 aryl; (iv) ORf, where Rf is hydrogen, C? -C6 alkyl or Ce-Cio aryl; (v) COORg, where Rg is C? -C6 alkyl, C? 6 aralkyl or C6-C10 aryl; (vi) sulfonyl; or (vii) C6-C6 aryl, and (c) ammonia or a primary amine of formula RA-NH2, where RA is C6-C6 alkyl, C-C6 aralkyl or C6-C6 aryl; optionally in the presence of (d) a solvent and / or (e) one or more additives.
2. 2. A process according to Claim 1, wherein the perylene tetracarboxylic compound is a compound of formula where EJ and E3 are independently OR or NR 'R "and E2 and E4 are independently OR, or E1 and Ez together are 0 or NA1 and E3 and E4 together are 0 or NA2; each R is independently hydrogen, a metal or ammonium cation, C? -C6 alkyl, C7-Ci6 aralkyl or Cg-Cio aryl; each R 'and R "is independently hydrogen, alkyl C? C6 or aralkyl C - / - C? 6; A "and A'J are independently hydrogen, C? -C6 alkyl or substituted C? -C6 alkyl, C5-C8 cycloalkyl or substituted C-C8 cycloalkyl, C7-Ci6 aralkyl or substituted C7-C? 6 aralkyl or C6-aryl C? 0 or C6-C? Or substituted aryl, B is Ci-Cd alkyl, C? -C6 alkoxy, a sulfonyl, amino, ammonium, hydroxy, nitro or halogen group, and? Is zero or an integer of 1 to 8.
3. A process according to Claim 2, wherein, in the perylene tetracarboxylic compound, E1, E2, E5 and E4 are independently OH or a salt form thereof and B is absent.
4. 4. A process according to Claim 2, wherein the perylene tetracarboxylic compound is a bisanhydride where E1 and E2 together and E3 and E4 together are oxygen atoms and B is absent.
5. 5. A process according to Claim 2, wherein the perylene tetracarboxylic compound is a bisimide where E1 and E2 together and E3 and E4 together are each independently NH or a nitrogen atom substituted with Ci-Cβ alkyl, C7-C aralkyl? 6 or aryl Ce-Cio and B is absent.
6. 6. A process according to Claim 2, wherein the cyclic anhydride or imide is an aromatic compound of formula where W is O or NRJ R is hydrogen, a metal, C? -C6 alkyl or -Alk-X; R, RJ, R "and R 'are independently hydrogen, C? -C6 alkyl, C? -C6 alkoxy, a sulfonyl, amino, ammonium, hydroxy, nitro or halogen group, or any two groups R4, R5, R6 and Adjacent R7 taken together form a fused ring and / or a group represented by the formula and the rest of the groups R 4, R 5, R 6 and / or R 7 are independently hydrogen, C 1 -C 6 alkyl, Ci-C 1 alkoxy, a sulfonyl, amino, ammonium, hydroxy, nitro or halogen group; Alk is C? -C? 8 alkylene, and X is -S03 ~ or -C00? Electrically balanced with hydrogen or a stoichiometric amount of a metal ion.
7. 7. A process according to Claim 1, wherein component (b) is phthalic anhydride, dianhydride 1, 2, 4, 5-benzenetetracarboxyl? Co, 1,2-naphthalic anhydride or 2, 3-naphthalic? Co anhydride.
8. 8. A process according to Claim 1, wherein the component (b) is phthalimide.
9. 9. A perylene pigment composition prepared by a process consisting of the reaction of (a) a perylene tetracarboxylic compound; (o) about 0.01 to about 20% by weight, based on the perylene tetracarboxylic compound, cyclic anhydride or non-pigment imide of the formula where W is O or NR1; R 1 is hydrogen, a metal, C 1 -C 6 alkyl, C 5 -C 8 cycloalkyl or -Alk-X; R 2 and R 3 are independently hydrogen, C 1 -C 6 alkyl, C 7 -C 16 aralkyl or C 6 -C 6 aryl, or R 2 and R 3 together are fused rings; the dashed line is an eventual double bond representing R2-C = C-R3; Alk is C? -C? 8 alkylene or C5-C8 cycloalkylene, and X is (i) an anionic group selected from -S03", -C00", -P03 =, -PO (ORx) 0 ~ (where Rx is C? -C6 alkyl), -0-P03 = and -0-P0 (0Ry) 0 ~ (where R? Is C ^ Cd alkyl), each of such anionic groups being electrically balanced with a stoichiometric amount of a cation; (ii) a cationic group having the formula -NRñRbRc + (where Ra, Rb and Rc are independently hydrogen, C?-C6 alkyl, C7-C ?6 aralkyl or C6-C? ar ar aryl), each of said cationic groups electrically balanced with a stoichiometric amount of an anion; 15 (iii) NRdRe, where Rd is hydrogen, C? -C6 alkyl, C7-C6 aralkyl, C6-C? Aryl, C2-C6 alkanoyl, C7-Cu aroyl or sulfonyl, and Re is hydrogen, Ci-alkyl? Cβ, C 7 -C 6 aralkyl or C 6 -C 0 aryl; 20 (iv) 0Rf, where Rf is hydrogen, C x C 6 alkyl or C 6 -C 0 aryl; (v) COORg, where Rg is C 1 -C 6 alkyl, C 7 -C 6 aralkyl or Ce-Cι aryl; (vi) sulfonyl; or (vii) Ce-Cι aryl, and (c) ammonia or a primary amine of formula RA-NH 2, where RA is C 1 -Cto alkyl, C a C 6 alkyl or C 6 -C 0 aryl; optionally in the presence of (or) a solvent and / or (f-1) one or more additives. SUMMARY OF THE INVENTION This invention relates to a procedure for preparing pepler pigment compositions by reacting fa) a perylene tetracarboxylic compound; ib) about 0.01 to about 20% by weight, relative to the perylene tetracarboxylic compound, a cyclic anhydride or non-pigment imide of formula (I) where W is O or NR1 (where R1 is hydrogen, a metal or optionally substituted alkyl, cycloalkyl, aralkyl or aplo); R2, R3 and R4 are various combinations of substituents and / or fused rings, and the dashed line it is an eventual double bond that represents R2-C = C-R3; (c) ammonia or an alkyl-, aralkyl- or arylamine premium; eventually in the presence of 3í a solvent and / or (e) one or more dispersants