MXPA99011477A - 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, based on the perylene tetracarboxylic compound, a non-pigment cyclic anhydride or imide of formula (See Formula) 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 dotted line is an optional double bond representing R2-C = C-R3 or R3-C = C-R4, and ammonia or an alkyl-, aralkyl- or arylamine, optionally in the presence of (d) a solvent and / or (e) one or more dispersant

Description

PROCEDURE FOR THE PREPARATION OF HIGHLY CHROMATIC PERILENE PIGMNTS BACKGROUND OF THE INVENTION This invention relates to a process for the preparation of perylene pigment compositions in the presence of certain anhydrides or non-pigment cyclic midas. The perylenes, including the diimides of perylene-3, 4, 9, 10-tetracarboxylic acid, can be prepared by methods known in the art. For example, W. Herbst and K. Hunger, Industrial Organic Pigments, 2nd ed. (New York: VCH Pub- lishers, Inc., 1997), pages 9 and 476-479; H. Zollinger, Color Chemistry (VCH Verlagsgessellschaft, 1991), pages Ib 227-228 and 297-298, and M.A. Perkins, "Pyridines and Pyrido- nfes", in The Chemistry of Synthetic Dyes and Pigments, ed. II. A. Lubs (Malabar, Florida: Robert E. Krieger Piping Company, 1955), pages 481-482; see also US Pat. 4,431,806, 4,496,731, 4,797,162, 0 b.248.774, 5,264,034 and 5,466,807. The perylenes as initially isolated in the process of the present invention, which is often referred to as crude perylenes, are generally unsuitable for use as pigments and, therefore, must be subjected to one or more additional steps of finish that modify the particle size, the shape of the particle and / or the crystalline structure in such a way that a good pigment quality is obtained. See, for example, K. Merkle and H. Schafer, "Surface Treatment of Organic Pigments," in Pig-ment Handbook, Vol. III (New York: John Wiley &Sons, Inc., 1973), page 157; R.B. McKay, "The Development of Organic Pigments with Particular Reference to Physical Form and Consequent Behavior in Use," in Rev. Prog. Col-oration, 10, 25-32 (1979), R.B. McKay, "Control of the application performance of classical organic pigments", in JCCCA, 89-93 (1989). The addition of certain perylene derivatives to the ring closing step has also been described. For example, US Pat. No. 5,264,034 discloses the use of certain bisimides or perylene imide-anhydrides to improve the coloristic and relogical properties of the perylene pigments. U.S. Pat. No. 5,248,774 discloses certain zwitterionic petrylene bisimide derivatives for use as colorants or 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 organic pigments. These patents do not, however, describe the non-pigmentic anhydrides and cyclic amides of the present invention. It has now been found that the presence of certain non-pigment cyclic anhydrides and amides during the chemical synthesis of perylene bisimides provides perylene pigment compositions having better transparency and colopstic properties, even in the unfinished form which is micially isolated, and which are especially suitable for use in metal paints. The non-pigment cyclic anhydrides and anides of the type used in the present invention are known. Although some publications have described such statements as starting materials for dyes (eg, Japanese Patents 50 / 157,421, 49 / 125,671 and 50/39 735), many publications have described purposes that "bear no relation to the treatment". of pigments (e.g., U.S. Patents 4,992,204 and 5,076,831; European Patent Application 206,322; AM El-Naggar and 0 rol, Egypt, J. Chem., 24_, 127-130 (1981); Andersen et al., J. Pharm. Sci., 73, 106-108 (1984); JM Chapman, Ji and rol, J. Pharm. Sci., 7_8, 903-909 (1989); IH Hall col., Acta Pharm. Nord., 2, 387-399 (1990); YI Kuznetso and OA Luk 'yanchikov, Zasch, Met., 27, 64-71 (1991), and IH Hall et al., Anti-Cancer Drugs , 5, 75-82 (1994).) Substituted naphthalimides are 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., 10, 906-910 (1997). Naphthalimides, however, are described as phobic growth inhibitors as compared to perylene derivatives. Moreover, the article does not disclose the incorporation of naphthalimides during the synthesis of pigments. COMPENDIUM OF THE INVENTION This invention relates to a process for the preparation of perylene pigment compositions, which consists of reacting (a) a perylene tetracarboxylic compound; (b) about 0.01 to about 20% by weight (preferably 5 to 15% by weight), relative to the perylene tetracarboxylic compound, of a non-pigment cyclic anhydride or imide of formula (I) where is 0 or NR1; R1 is hydrogen, a metal, C? -C6 alkyl, C-C8 cycloalkyl, C7-C16 aralkyl, C6-C6 aryl or -Alk-X; R2, R and R4 are independently hydrogen, C?-Cd alkyl, C7-C ?6 aralkyl or Cs-Cio ar aryl, or R² and R3 together are fused rings (preferably, fused rings of cycloalkane or aromatic LO) and R 4 is hydrogen Ci-Ce alkyl, C7-C16 aralkyl or Cß-Cι aryl, or R 2, R 3 and R 4 together are fused rings (preferably fused rings of cycloalkane or aromatics); 15 the dotted line is an eventual double bond representing R2-C = C-R3 or R3-C = C-R4 (including a formal double bond of any aromatic fused ring formed by R2 and R3 taken together or by R2, 20 R "and R4 taken together); Alk is C? -C18 alkylene or c5-c8 cycloalkylene, and X is (1) an ammonium group selected from -SO3", -COO", -P03 =, -PO'ORx) 0 ~ (where Rx is C-alkyl? -C6), -0-P03 = and -0- P0 (0R) 0 ~ (where Ry is C? -C6 alkyl), each such ammonium oxide being electrically balanced with a stoichiometric amount of a cation (preferably a hydrogen and a metal ion and / or ammonium); (II) a cationic group having the formula -NRaRbRc + (wherein Rd, Rb and Rc are independently hydrogen, C ^ -C6 alkyl, C7-C16 aralkyl or C6-C6 aplo), 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); (III) NRdRe, where Rd is hydrogen, C 1 -C 6 alkyl, C 7 -C 16 aralkyl, Ce-Cι aryl, C 2 -C 6 alkanoyl, C 7 -C n aroyl or sulfonyl and R is hydrogen, Ci-Ce alkyl, C 7 aralkyl C6 or C6-C10 aryl; (iv) 0Rf, where Rf is hydrogen, C? -C6 alkyl or C6-C? 0 aryl; (v) COORg, where Rg is C? -C6 alkyl, C7-C16 aralkyl or Cg-C? 0 aryl; (vi) sulfonyl; or (vii) C6-C6 aryl, and c) an excess of equivalents, relative to the total amount of components (a) and (b), of ammonia or of a primary amine of formula RA-NH2, where R? ' Is it alkyl? ~ Ce, aralkyl C7-C? E or aryl Cd-C? 0; 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 Perylene tetracarboxylic compounds which can be used for the preparation of the perylene pigment compositions of the present invention include various cyclic carboxylic acids, carboxylic esters, carboxamides, cyclic anhydrides and / or cyclic imides of formula (II) where E1 and? '' are independently OR or NR'R "and E2 and E4 are independently OR, or E1 and E2 together are 0 or NA1 and E3 and E4 together are 0 or NA2, each R is independently hydrogen (ie, for free acid groups) ), a metal or ammonium ion (i.e., for salts), Ci-Ce alkyl (ie, for alkyl esters), C7-C aralkyl (ie, for aralkyl esters) or aryl C & -C- 0 (that is, for aryl esters), each R 'and R "are independently hydrogen, alkyl C: -Ce or C7-C16 aralkyl; A1 and A 'are independently (but preferably identically) hydrogen, a metal, C 1 -C 6 alkyl or substituted C 1 -C 6 alkyl, C 5 -C 8 cycloalkyl or substituted C 5 -C 8 cycloalkyl, C 7 -C aralkyl ? 6 or substituted C7-C? 6 aralkyl or Cd-Cio aryl or substituted C6-C10 aryl; B is C 1 -C 6 alkyl, Ci-Ce 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 component (a) are tetracarboxylic perylene acids and / or esters, as well as their salts, where? groups E1, E2, E3 and E4 are independently OH or salt forms thereof or C ^ -C6 alkoxy (preferably, tetracarboxylic acids or salts thereof in which E1, E2, E3 and E4 are OH identical in form or corresponding salt); bisanhydrides in which E1 and E2 together and E3 and E4 together are oxygen atoms, and bisimi-das in which E1 and E2 together and E3 and E4 together are independently NH or substituted nitrogen atoms (preferably, symmetrical bisimides wherein both nitrogen atoms have the same substituent). The preferred perylene tetracarboxylic compounds do not have aromatic ring substituents B (ie, p is zero), but substituted tetracarboxylic periiene compounds in which at least one of the eight substitutable carbon atoms of the aromatic ring of this perylene has at least one group B (ie, that p is not zero) are also suitable. Some of the tetracarboxylic perylene compounds used as component (a) may be pigments themselves, 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 "CL-C6 alkyl" refers to straight or branched chain aliphatic hydrocarbon groups having 1 or 6 carbon atoms. Examples of C 1 -C 10 alkyl are ethyl, ethyl, propyl, butyl, pentyl, hexyl and their isomeric forms. The term "cycloalkyl C ^ -Cs" refers to cycloaliphatic hydrocarbon groups having from 8 carbon atoms. Examples of C5-CH cycloalkyl are cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl. The term "Cß-Cio aryl" refers to phenyl and 1- or 2-naphthyl. The term "C 7 -C 6 aralkyl" refers to C 6 -C 6 alkyl substituted with C 6 -C 0 aryl, such that the total number of carbon atoms is from 7 to 16. Examples of C 7 aralkyl are C? 6 benzyl, phenethyl and naphthylmethyl. Substituted alkyl groups are those in which one or more carbon atoms are substituted with alkoxy, halogen, hydroxy (including oxo tautomeric forms), alkoxycarbonyl, aryloxycarbonyl, cyano, and nitro, as defined herein. 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 "Ci-Cβ alkoxy" refers to straight or branched chain alkyloxy groups having from 1 to 6 carbon atoms. Examples of C 1 -C 6 alkoxy methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy and its isomeric forms are examples. The term "sulfonyl group" refers to -S02-R1 groups, such as alkylsulfonyl (wherein R1 is alkyl, for example, methylsulfonyl or ethanesulfonyl), arylsulfonyl (wherein R1 is aryl, for example, phenylsulfonyl, 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 ^ R1"1, where R11 and R111 are independently hydrogen, alkyl, cycloalkyl, aralkyl or aryl.) The terms "amino" and "ammonium" refer, respectively, to -NR1VRV and -NR1VRVRV1 +, wherein R1V, Rv and RV1 are independently hydrogen, alkyl C C6 or C7-Ci6 aralkyl and each ammonium group is electrically balanced with a stoichiometric amount of an anion The term "halogen-free" includes fluorine, chlorine, bromine and iodine It is possible to use salt forms of perylene tetracarboxylic compounds if at least one of the E1 groups, E2, E3 and E4 of the formula (II) represents a carboxylate anion or an imide form. Suitable carboxylic salts are those in which each carboxylate anion is electrically balanced with 1 / n molar equivalents of an n-valent cation Mn + (such as Li ', Na1, Mg ++, Ca ++, Ba ++, Al +++, Fe ++ or Fe +++) or an ion ammonium having the formula R ^^ R ^ R ^ N * (where R1, R11, R111 and P '"' are independently hydrogen, Ci-Cß alkyl, C 1 -C 6 hydroxyalkyl or C 7 -C 6 aralkyl). 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 A "represents 1 / n molar equivalents of an n-valent cation Mn + (such as Li +, Na +, K +, Mg ++, Ca ++, Ba + , Al + +, Fe ++ or Fe +++). These salts are formed whenever they are exposed to the imides of formula (II) in which A1 and / or A "is hydrogen to strongly basic media, either under the reaction conditions used for prepare the perylene imide or by adding a strong base. The tetracarboxylic perylene compounds described above, some of which are crude or conditioned perylene pigments and some of which are perylene 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 Pub-lishers, Inc., 1997), pages 476-479; H. Zollinger, Color Cnemistry (VCH Verlagsgessellschaft, 1991), pages 227-228; 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, and F. Graser, "Perylenes," in the Pig-ment Handbook, 2nd edition, Vol. III (New York: John Iley Sons, Inc., 1988), pages 653-658. A critical feature of the invention is the use of non-pigment cyclic anhydrides or 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 tetracarboxylic perylene compounds and the perylene pigment compositions with which they are used. That is, that suitable cyclic anhydrides or imides of formula (I) would not themselves have practical utility as pigments. The term "substantially colorless" does not mean that the anhydrides or cyclic imides should be absolutely 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 an order of magnitude less) than those of the perylene precursors and the petrolylene pigment compositions with which they use. When used to describe non-pigment cyclic anhydrides or imides of component (b) (including the compounds described below), the terms "C?-C6 alkyl", "C5-C8 cycloalkyl", "C-7-C aralkyl" , "," C6-C10 aryl "," C6-C6 alkoxy "," sulfonyl group "," amino "," ammonium "and" halogen ", have the same meanings as those given above for the tetracarboxylic compounds of perylene. The term "alkylene C? ~ 0 |" "refers to straight or branched chain aliphatic hydrocarbon groups of 1 to 18 carbon atoms and - on c binding sites. Examples of C? -Ci8 alkylene are methylene, ethylene, propylene, butylene, pentylene, hexylene and longer hydrocarbon chains, including both straight and branched chain groups. The term "C5-C8 cycloalkylene" refers to hydrocarbon-two cycloaliphatic groups having from 5 to 8 carbon atoms and two binding sites. Examples of C ', 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-Cp alkanoyl are acetyl, propanoyl, butanoyl, pentanoyl, hexanoyl, its isomeric forms. The term "C7-Clx aroyl" refers to benzoyl and 1- or 2-naphthoyl, wherein the arylc portion may optionally be substituted as previously described for "aryl". Preferred cyclic anhydrides and imides are those in which R2 and R3 together form fused hydrocarbon rings (preferably, cycloalkane ring systems and, more preferably, fused aromatics, such as benzene or 1,2- or 2,3-naphthalene) and R 'is hydrogen, C 1 -C 6 alkyl, C 7 -C 6 aralkyl or C 1 -C 8 aryl (preferably hydrogen), or wherein R 2, R 3 and R 4 together form multiple fused hydrocarbon rings (more preferably , polyaromatic ring systems, such as 1,8-naphthalene). Each of the fused ring systems can, of course, be subsituted in the ring, for example with C.sub.1 alkyl groups, C.sub.7 -C.sub.6 alkyl, C.sub.6 -C.sub.10 aryl, C.sub.1 -C.sub.6 alkoxy, sulfonyl, ammo, ammonium and halogen such as those described above. For the compounds of formula (I) wherein W is NR1 ie imides), the group R1 is preferably hydroquinone, a metal, alkyl Cj-C6 or -Alq-X, where Alk is alkylene C? C? Ey X is -S0 ~ o -COO ~ electrically balanced with hydrogen or a metal ion. Particularly preferred cyclic anhydrides and imides include naphthalene compounds of formula (la) where W is defined as before; R5 and R ° are independently hydrogen, C?-C6 alkyl, C?-C6 alkoxy, a sulfonyl, amino, ammonium, hydroxy, nitro or halogen group, or Rb and R "Lominated together are a group represented by the formula O "W" O (doñee W is defined as before); each R7 is independently Ci-Cß alkyl, a sulfonyl, amino, ammonium, hydroxy, nitro or halogen group, and m is zero or an integer of _. to 4. For the compounds of formula (la) wherein W is NR1 (ie, imides), the group R1 is preferably hydrogen, a metal, C1-C6 alkyl or -Alq-X, where The Alk is alkylene C? ~ C? 8 and X is -S03 ~ or -C00 electrically balanced with hydrogen or a metal ion. Examples of suitable cyclic anhydrides include naphthalic anhydride (ie, 1,8-naphthalenedicarboxylic anhydride) and 1,4,5,8-L-naphthaletracarboxylic dianhydride. Examples of suitable cyclic imides include naphthalimide (ie, 1,8-naphthalenedicarboximide), N-methylnaphthalimide, N- (2-sulfacetyl) naphthalimide and their salts, N- (2-sulfoethyl) -4-sulfonaphthalimide and their salts and diimide N, N'-bis (2-sulfoethyl) -1,4,5,8-naphthaletracarboxylic acid and its salts. Cyclic anhydrides of form-mule (I) (where 0 is) can be obtained commercially or by conversion of the corresponding dicarboxylic acids into 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. Heath-cock, Introduction to Organic Chemistry, 3rd edition (New York: Macmillan Publishing Company, 1985), pages 495 and H66. The imides of formula (I) (in which it is NR) can, in turn, be prepared from corresponding acids, esters or anhydrides by known methods, preferably by reaction of 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 R1 does not contain ionic groups, the anhydride and the amine react in water heated at about 80 ° C to 100 ° C at ambient pressure, or at temperatures up to about 140 ° C in an autoclave or another sealed reactor, typically for about two to four hours. In a preferred method for preparing imides wherein Rx contains anionic groups (eg, 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 one equivalent of a base ( such as sodium or potassium hydroxide) to the reaction mixture, after which the reaction is carried out under essentially the same conditions as those used for nonionic compounds. However, if the resulting anionic compound is water-soluble, it must be isolated, for example, by acidification of the reaction mixture and isolation of the free acid, increasing the ionic strength of the mixture and isolating the metal salt otherwise luble (i.e., sodium or potassium), or precipitating imitation by addition of a polyvalent metal salt (eg, CaCl 2, BaCl 2 or FeCl 2) - Imide salts of formula (I) in which it is NR 1 and R1 is a metal from the "free" counterparts in which R1 is hydrogen. Suitable imide salts of formula (I) are those in which each R1 represents 1 / n molar equivalents of an n-valent cation Ml (such as Li, Na +, K +, Mg ++, Ca ++, Ba ++, Al +++, Fe ++ or Fe +++). Said salts are formed whenever exposed to the imides of formula (I) wherein R1 is hydrogen to strongly basic media, either under the reaction conditions used to prepare the erylene imide or by adding a strong base to the imida li-ore.

Component (c) includes ammonia and primary amines having the formula RA-NH2, wherein RA is C? -C6 alkyl, C7-Ci6 aralkyl or C6-C6 aryl? - Examples of suitable primary amines include alkylamines such as methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine and its 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 io) in relation to the anhydride and / or imide groups of the perylene pigment precursor (a) and the non-pigment cyclic anhydride or imide (b). In general, 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) . Although it is not generally preferred, it is possible to use larger amounts of ammonia or primary amine (c), which, if liquid in the reaction conditions, can even serve as a solvent or as a cosolvent with the component ( d). Suitable solvents (d) are liquids that 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 lower alkanols, such as methanol, ethanol, butanol, pentanol, hexa-nol and their isomeric forms; amides, such as dimethyl formamide and dimethylacetamide; ketones and ketone alcohols, such as acetone and diacetone alcohol; ethers, such as tetrahydrofuran and dioxane; alkylene glycols and thio glycols, such as ethylene glycol, propylene glycol, butylenglycol, triethylene glycol, hexylene glycol, diethylene glycol and thiodiglycol; polyalkylene 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-methoxyethoxy) ethanol, 2- [2- (2-methoxyethoxy) ethoxy] ethanol and 2- [2- (2-ethoxyethoxy) ethoxy] ] ethanol; aromatic and heteroaromatic liquids, such as benzene, oiridine and quinoline, and other organic liquids known in the art. Water, methanol and quino-Lina 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 need to remove excessive amounts after the 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) in relation 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 (c) can be melted without significant decomposition to unwanted byproducts. 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 pigment dispersion 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 (i.e., soaps such as alkali metal salts of fatty acids), taurides or acid N-methyl taurides. fatty acids, alkylbenzene sulfonates, alkylnaphthalenesulfonates, alkylphenol polyglycol ether sulphates, naphthenic acids or resin acids (such as abietic acid); cationic compounds, such as quaternary ammonium salts, fatty amines, fatty amine 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 contain one or more sulfonic acid groups, sulphonamide groups, carboxylic acid, carboxamide and / or aliphatic (cyclo) groups containing (hetero) aryl. Said additives can 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, however, the perylene (a) tetracarboxylic compound and the non-pigment cyclic anhydride (b), as well as any dispersant (e), are added as solvent (d) and stirred at a temperature of about 0. ° C at about 30 ° C (preferably at room temperature or below this, more preferably 0 ° C to 5 ° C) before adding ammonia or amine (c). After adding component (c), the ezc is heated to a temperature of about 50 ° C to about 150 ° C (preferably, 80 ° C to 100 ° C) until the reaction is completed, typically a period of about two hours. to six hours. For example, in particularly preferred embodiments where component (c) is methylamine, a mixture of the perylene tetracarboxylic compound and the non-pigment cyclic or imide anhydride in water is cooled to about 5 ° C and then heated with methylamine . Upon completion of 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 in the at least some of the groups R1, A1 and / or A2 are substituted with cidrogen (of ammonia) or with the group RA (of the amine HA-NH <;). However, regardless of whether the perylene tetracarboxylic compounds and the starting non-pigment bicyclic anhydrides or imides are transformed by the component (c), the resulting perylene pigment compositions exhibit better transparency and color properties when compared to pigments. of perylene prepared in the absence of anhydride or imide The non-pigment cyclicals. The pigment composition can optionally be conditioned using methods known in the art, such as solvent treatment or milling in combination with solvent treatment.

L5 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. , milling 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 ^ 0 minutes of aluminum or magnesium behenate; quaternary ammonium compounds, such as tri [(C 1-1) alkyl benzyl] ammonium salts; plasticizers, such as epoxidized soybean oil; waxes, such as polyethylene wax; resin acids, such as abietic acid, co-ibono soap, hydrogenated or dimerized rosin; para-finadisulfonic acids C 2 -C 8; alkylphenols; alcohols, such as stearyl alcohol; amines, such as laurylamine or stearylamine, and aliphatic 1,2-diols, such as dodecane-1,2-diol. These 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. The pigment compositions can also be mixed (preferably by dry mixing) with one or more pigment derivatives known in the art, particularly sulfonic acid, sulfonamide and phthalimide derivatives. Due to its stability against light and its 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 p > They can be used as a colorant (or as one of two or more colorants) for highly photoresistive pigmented systems. 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 (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, oven drying enamels, reactive paints, two component paints, solvent or water based paints, 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 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. Examples of synthetically produced macromolecular substances include plastic materials, such as polyvinyl chloride, polyvinyl acetate and polyvinyl propionate.; polyolefins, ta-Les 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, over spray stable, sublimation stable, heat resistant and resistant. to vulcanization, and still give a very good tmtopal 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 variations known from the conditions of the following procedures can be used. Unless otherwise indicated, all temperatures are in degrees Celsius and all percentages are percentages by weight. EXAMPLES Test Methods Water-based paint tests were carried out on N, N'-dimethylpeplenotetracarbo-xylica prepared according to the invention using a waterborne base coat / solvent-supported clear coat system. Untreated N, N'-dimet lpeplenotetracarboxilica dnmida made by the same method as control was used Aqueous dispersions were prepared using a mixture of 12.4% acrylic ream AROLON® 559-G4-70 (Reichhold Chemicals, Inc.), 3.2% of Imperspersante SOLSPERSE® 27000 (Zeneca, Inc.), 1.6% of 2-am? no-2-met? ll-propanol (Angus Chemical) and 18% of 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 repellent AROLON® 559-G4-70 (total amount, 26o) and 25% ream of melamma / formaldehyde CYMEL® 325 Cytec Industries), which gave a total content in solids of 50%. Measurements of mass tone and transparency were made using films applied at 76 μm and 38 μm thick wet film, respec tively, and allowed to stand at room temperature for fifteen minutes and at 100 C for five minutes. Clearcoats containing a mixture of 80% alkyd resin AROPLAZ® 1453-X- ^ 0 and Reichhold Chemicals, Inc.) and 20% ream of lamella / formaldehyde CYMEL © 325 were then applied at a level of total solids 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 AROLON® 559-G4-70 acrylic resin, melamine / formaldehyde resin CYMEL® 325 and a 35% white dispersion TINT-AYD® 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-a-pigment 90:10. The 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 dispersion described above having a pigment-to-binder ratio of 18:12 using a water dispersible aluminum pigment (available as HYDRO PASTE® 8726)., of Silberline Manufacturing 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, 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. Starting materials The following commercially available cyclic anhydrides were used in the examples, as component (b) according to the invention and as starting materials for other compounds within the definition of component (b): ib) (>; Naphthalene anhydride (from Aldpch Chemical Com- pany), which has the formula ibi \) dianhydrido 1, 4, 5, 8-naftalentetracarboxilico (from Aldpch Chemical Company), which has the formula Other cyclic anhydrides were prepared as used in the examples according to the invention as follows: Preparation 1 N-Methylnaphthalimide (cyclic amide (b) (3)) To a suspension of 125.0 g (0.634 mol) of naphthalic anhydride in 1.5 L of water was added 111.5 g i L, 44 mol) of a 40% aqueous solution of methylaram. The mixture was then stirred in a sealed autoclave at 145 C for 5.5 hours and was either cooled. The resulting precipitate was collected by filtration, washed with water and dried in an oven at 60 C, to obtain 125 g of N-methylnaphthalimide (cyclic amide (b) (3)). Preparation 2 N- (2-Sulfoethyl) naphthalimide, cyclic imide calcium salt (b) (4)) To a suspension of 39.8 g (0.2 mol) of naphthalic anhydride in 1.2 L of water were added 50 g (0.4 mol) of taurine and 26.4 g of 85% potassium flakes. %. The mixture was then stirred in a sealed autoclave at 150 C for five hours and allowed to cool. A solution of 40 g of calcium chloride dihydrate in 60 g of water was added to the resulting yellow suspension and the mixture was stirred for 30 minutes. The resulting precipitate was collected by filtration, washed with water until free of residual calcium and dried in an oven at 80 ° C, to obtain 70 g of N- (2-sulfoethyl) naphthalimide in the form of the calcium salt (imide). cyclical (b) (4)). Preparation 3 N- (2-Sulfoethyl) -4-sulfonaphthalimide, barium salt (cyclic imide (b) (5)) The method of Preparation 2 was repeated, except for the use of 15.8 g (0.05 mol) of the potassium salt of 4-sulfonaphthalic anhydride in place of naphthalic anhydride and 16 g (0.076 mol) of barium chloride in place of calcium chloride dihydrate, 22.1 g of N- (2-sulfoethyl) -4-sulfonaphthalimide being obtained as barium salt (cyclic imide (b) (5)). Preparation 4 Diimide N, N'-bis (2-sulfoethyl) -1,4,5,8-naphthalenetetracarboxylic, barium salt (cyclic imide (b) (6) The method of Preparation 2 was repeated, except for the use of 6.7 g (0.025 mol) of 1, 4, 5, 8-naphthaletracarboxylic anhydride in place of naphthalic anhydride and 15.6 g (0.075 mol) of barium chloride instead of calcium chloride dihydrate, 10.2 g of N, N'-bis (2-sulfoethyl) -1,4,5,8-naphthalenetetra-carboxylic diimide in the form of barium salt (cyclic imide i) (6) i. Preparation 5 Diimide N , N'-bis (2-sulfoethyl) -1,4,5,8-naphthaletracarboxylic acid, iron (II) salt (cyclic imide (b) (7)) The method of Preparation 4 was repeated, except for the use of 20 g (0.075 mol) of iron (II) chloride instead of calcium chloride dihydrate, yielding 5.45 g of N, N'-bis (2) diimide. -sulfoethyl) -1, 4, 5, 8-naphthaletracarboxylic acid as iron (II) salt (cyclic imide (b) (7)). Example 1 A mixture of 100 g (0.26 mol) of perylene-3, 4, 9, 10-tetracarboxylic dianhydride and 5.4 g (0.027 mol) of naphthalic anhydride in a mixture of 1,000 g of water was stirred and stirred. 500 g of ice To the cold suspension (less than 5"c) 244 g (3.15 mol) of 40% aqueous methylamine was added dropwise over a period of 15 minutes, after stirring for one hour, during which When the temperature rose to approximately 15 ° C, the mixture was heated to 80 ° C and maintained at that temperature for four hours.The reaction mixture was cooled and the crude pigment was filtered and washed with water. of the wet filter approximately 10% by weight: based on the pigment) of a high molecular weight limero pigment dispersant, a base for adjusting to pH 8 to 9 and sufficient water to obtain a suspension containing approximately 10 to approximately 20% by weight of pigment The slurry was milled in a horizontal wet mill for eight hours The milled 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 a oven at 80 ° C to obtain a bright red pigment. The test data for the crude pigment are shown in Table 1 and the test data for the ground pigment are shown in Table 2. Examples 2-7 The method of Example 1 was repeated using similar mixtures of perylene-3,4-dianhydride, 9, 10-tetracarboxylic and other cyclic anhydrides and imides according to the invention. Each cyclic anhydride and imide are identified and the test data are given in the following tables.

Table 1: Test results for the crude pigment compositions of Examples 1-7 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 1-7 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.

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

Claims (12)

CLAIMS 1. A process for preparing a perylene pigment composition, which comprises reacting (a) a perylene tetracarboxylic compound; (b) about 0.01 to about 20% by weight, based on the perylene tetracarboxylic compound, of a non-pigment cyclic anhydride or imide of the formula where W is O or NR1; R1 is hydrogen, a metal, C? -C6 alkyl, C5-C8 cycloalkyl, C7-C16 aralkyl, C6-C? Aryl or -Alk-X; I? R 2, R 3 and R 4 are independently hydrogen, C 1 -C 6 alkyl, C 7 -C 6 aralkyl or C 6 -C 10 aryl, or R 2 and R 3 together are fused rings and R 4 is hydrogen, C 1 -C 6 alkyl, C 7 -C aralkyl ? 6 or aryl Cd-Cio, or R2, R3 and R4 together are fused rings; the dotted line is an eventual double bond representing R2-C = C-R3 or R3-C = C-5 R4; Alk is Ci-Ciß alkyl or C5-C8 cycloalkylene, and X is (i) an anionic group selected from -S03", -COO", -P03 =, -PO (ORx) 0 ~ (where Rx is C alkyl? -C6), -0-P03 = and -O-PO (0Ry) 0 ~ (where Ry 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, Ci-Ce alkyl, C7-C16 aralkyl or C6-C aryl),
1. Each of said cationic groups being electrically balanced with a stoichiometric amount of an anion; (iii) NRdRe, where Rd is hydrogen, C x C 6 alkyl, C 7 -C 6 aralkyl, C 6 -C 6 aryl, C 2 -C 6 alkanoyl, C 7 -C n aroyl or sulfonyl and Re is hydrogen, C 1 -C 6 alkyl , C 7 -C 16 aralkyl or C 6 -C 0 aryl; (iv) 0Rf, where Rf is hydrogen, Ci-Ce alkyl or C6-C? ar aryl; (v) COORg, where Rg is C? -C6 alkyl, C7-C16 aralkyl or C6-C? 0 aryl; (vi) sulfonyl; or (vii) aryl Ce-Cio, and (c) an excess of equivalents, in relation to the total amount of components (a) and (b), of ammonia or of a primary amine of formula RA-NH2, where RA is C C-C6 alkyl, C7-C ?6 aralkyl or Ce-Cio ar 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 E "and E3 are independently OR or NR 'R" and E2 and E4 are independently OR, or E1 and E2 together are O or
3. NA1 and E3 and E4 together are O or NA2; each R is independently hydrogen, a metal ion or ammonium, C 1 -C 6 alkyl, C 7 -C 6 aralkyl or C 6 -C 6 aryl; each R 'and R "are independently hydrogen, alkyl
4. Ci-Cd or aralkyl C7-C? E; A1 and A2 are independently hydrogen, a metal, Ci-Cß alkyl or substituted C?-C6 alkyl, C5-C8 cycloalkyl or substituted C5-Cs cycloalkyl, C7-C16 aralkyl or substituted C7-C16 aralkyl or C6-C10 aryl or aryl Cd-Cio substituted;
5. 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. A process according to Claim 2, wherein in the tetracarboxylic perylene compound, E1, E2,
6. E 'and E4 are independently OH or a salt form thereof and B is absent. 4. A process according to Claim 2, wherein the perylene tetracarboxylic compound is a bisanhydride in which E1 and E2 together and E3 and E4 together are oxygen atoms and B is absent. 5. A process according to Claim 2, wherein the perylene tetracarboxylic compound is a bisimide in which E1 and E2 together and E3 and E4 together are each independently NH or a nitrogen atom substituted with C? -C6 alkyl, C7 aralkyl -C? 6 or aryl C6-C? 0 and B is absent. 6. A process according to Claim 1, wherein, in the non-pigment cyclic anhydride or imide, R2 and R3 together form a fused hydrocarbon ring and R4 is hydrogen.
7. 7. A process according to Claim 1, wherein, in the non-pigment cyclic anhydride or imide, R ', R' and R4 together form a fused polyaromatic ring.
8. 8. A process according to Claim 1, wherein the non-pigment cyclic anhydride or imide is a compound of formula where W is O or NR1; R 1 is hydrogen, a metal, Ci-Ce alkyl or -Alk-X; R and K: are independently hydrogen, Ci-Cß alkyl, Ci-Cd alkoxy, a sulfonyl, amino, ammonium, hydroxy, nitro or halogen group, or R 5 and R 6 taken together form a group represented by the formula each R 'is independently Ci-Ce alkyl, Ci- C6 alkoxy, a sulfonyl, amino, ammonium, hydroxy, nitro or halogen group; Alk is C 1 -C 8 alkylene; X is -S03 ~ or -C00 ~ electrically balanced with hydrogen or a stoichiometric amount of a metal ion, and m is zero or an integer of 1 a.
9. 9. A process according to claim 1, wherein component (b) is naphthalic anhydride or 1,4,5,8-naphthaletracarboxylic dianhydride.
10. 10. A process according to Claim 1, wherein component (b) is naphthalimide, N-methylnaphthalimide, N- (2-sulfoethyl) naphthalimide or a salt thereof, N- (2-sulfoethyl) -4-sulfonaphthalimide or a salt thereof, or diimide N, N '-bis (2-sulfoethyl) -1, 4,5, 8-naphtha-tetracarboxylic lens or a salt thereof.
11. 11. A process according to Claim 1, wherein the component (c) is ammonia, an alkylamine Ci-Ce, benzylamine, phenethylamine, aniline, anisidine, phenetidine, toluidine or a xylidine.
12. 12. A perylene pigment composition prepared by a process consisting of reacting (a) a perylene tetracarboxylic compound; (b: about 0.01 to about 20% by weight, based on the perylene tetracarboxylic compound, a non-pigment cyclic anhydride or imide of the formula where W is 0 or NR1; R1 is hydrogen, a metal, C1-C3 alkyl, C5-C8 cycloalkyl, C7-C6 aralkyl, Cs-Cio aryl or -Alk-X; R 2, Ri and R 4 are independently hydrogen, C 1 -C 6 alkyl, C 7 -C 6 aralkyl or C 6 -C 6 aryl, or R 2 and R 3 together are fused rings and R 4 is hydrogen, Ci-Ce alkyl, C 7 aralkyl Ci6 or aryl Ce-Cio, or R2, R3 and R4 together are fused rings; the dotted line is an eventual double bond representing R2-C = C-R3 or R3-C = C-5 R4; Alk is Ci-Cis alkylene or C5-C8 cycloalkylene, and X is (i) an anionic group selected from -S03", -COO", -P03 =, -PO (ORx) 0"(where Rx is C-alkyl? -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; (ii) a cationic group having the formula -NRaRbRc + (where Ra, Rb and R ° are independently hydrogen, C? -C6 alkyl, C7-C6 aralkyl or Ce-Cio aryl), Each of said cationic groups being electrically balanced with a stoichiometric amount of an anion; (iii) NRdRe, where Rd is hydrogen, C 1 -C 6 alkyl, C 7 -C 6 aralkyl, C 1 -C 6 aryl, C 2 -C 6 alkanoyl, C 7 -C n aroyl or sulfonyl and Re is hydrogen, C 1 alkyl Cs, C7-C6 aralkyl or Ce-Cio aryl; (iv) ORf, where Rf is hydrogen, C? -C6 alkyl or C6-C? aryl; (v) COORg, where Rg is C? -C6 alkyl, C7-C16 aralkyl or Ce-Cio aryl; (vi) sulfonyl; or (vii) aryl C6-C? o, and (c) an excess of equivalents, relative to the total amount of components (a) and (b), of ammonia or of a primary amine of formula RA- NH2, where RA is C 1 -C 6 alkyl, C -C 16 aralkyl or C 6 -C 0 aryl; optionally in the presence of (d) a solvent and / or (or) one or more additives. SUMMARY OF THE INVENTION This invention relates to a process for preparing perylene pigment compositions by reacting (a) a perylene tetracarboxylic compound; (D) about 0.01 to about 20% by weight, based on the perylene tetracarboxylic compound, of a non-pigment cyclic anhydride or amide of the formula where W is O or NR1 (where R1 is hydrogen, an optionally substituted metal or alkyl, cycloalkyl, aralkyl or aryl), R2, R3 and R4 are various combinations of substituents and / or fused rings and the dotted line is an eventual double bond representing R2-C = C-R3 or R3-C = C-R4, and C, ammonia or an alkyl-, aralkyl- or arylamine; eventually in the presence of (d) a solvent and / or (e) one or more dispersants