Title of Invention

A PROCESS FOR TRANSFORMING CRUDE HALOGENATED COPPER PHTHALOCYANINE PIGMENTS INTO A USEFUL PIGMENTARY STATE

Abstract

ABSTRACT 2264/MAS/98 A process for transforming crude halogenated copper phthalocyanine pigment into a useful pigmentary state. The present invention relates to a process for transforming crude halogenated copper phthalocyanine pigments having a chlorine of from 4 to 50.3% by weight into a brilliant, transparent pigments having better rheological properties than the starting phthalocyanine pigment comprising the steps of treating the crude pigment at 80 to 200 C with an acidic aromatic organic compound of the general formula I I where X is hydroxy! or carboxyl and the benzene ring D may additionally bear up to two identical or different substituents selected form the group consisting of nitro, C|-C4-alkyl, C2-C4-alk:enyl, chlorine and bromine and may be benzofused, in the presence of a copper phthalocyanine derivative selected from the group consisting of the copper phthalocyanine-sulfonic and -carboxylic acids and their alkali metal, ammonium and alkylammonium salts, the amino-substituted and aminomethylated copper phlhalocyanines, and their reaction products with alkylating agents, sulfonic acids, sulfonyl chlorides and carbonyl chlorides, the imidomethylene- and amidomethylene-substituted copper phthalocyanines, the alkyl-, aryl- and cyano-substituted copper phthalocyanines and the hydroxyl- and alkoxy substituted copper phthalocyanines, if desired in the presence of water and isolating the pigment through filtering off after converting the organic medium into its water soluble alkali metal salt by adding aqueous base.

Full Text

' The present invention relates to a novel process for transforming crude halogenated copper phthalocyanine pigments having a chlorine content of from 4 to 50.3% by weight into a useful pigmentary state. The halogenation of copper phthalocyanine customarily produces amorphous to microcrystalline products which, owing to their pronounced tendency to agglomerate, have no utility for pigment applications. Various methods are known to transform crude pigments into a useful pigmentary state, for example mechanical comminution or treatment with concentrated sulfuric acid or with organic solvents at elevated temperature. The solvents used for treating polyhalogenated copper phthalocyanines are mainly xylene (DE-A-20 13 818), trichlorobenzene, chloronaphthalene or nitrobenzene (DE-A-24 49 231), 2-nitrophenol (DB-A-12 42 180), naphthol (GB-A-1 088 736), benzoic acid and/or alkylbenzoic acids (EP-A-58 888) or aliphatic ketones (DE-A 36 36 428) in the presence or absence of water. jp-A 336 556/1994 describes a process wherein polyhalogenated copper phthalocyanines are heated in mixtures of water and aromatic solvents in the presence of copper phthalocyanine derivatives; acidic solvents are not used. These known processes frequently provide only unsatisfactory results and, what is more, are limited to copper phthalocyanines having a high degree of halogenation (chlorine content > 38.5% by weight, ie. at least 10 chlorine atoms on the CuPc structure). It is an object of the present invention to provide a process whereby not just polyhalogenated, but especially also crude incipiently halogenated (chlorine content We have found that this object is achieved by a process for transforming crude halogenated copper phthalocyanine pigments having a chlorine content of from 4 to 50.3% by weight into a useful pigmentary state, which comprises treating the crude pigment at elevated temperature with a liquid acidic aromatic organic medium in the presence of a copper phthalocyanine derivative selected from the group consisting of the copper phthalocyanine-sulfonic and -carboxylic acids and their alkali metal, ammonium and alkylammonium salts, the amino-substituted and aminomethylated copper phthalocyanines and their reaction products with alkylating agents, sulfonic acids, sulfonyl chlorides and carbonyl chlorides, the imidomethylene- and amidomethylene-substituted copper phthalocyanines, the alkyl-, aryl- and cyano-substituted copper phthalocyanines and the hydroxyl- and alkoxy-substituted copper phthalocyanines, if desired in the presence of water. The organic medium used is preferably a compound of the general formula I where X is hydroxyl or carboxyl and the benzene ring D may additionally bear up to two identical or different substituents selected from the group consisting of nltro, Ci-C4-alkyl, preferably Ci-C2-alkyl, C2-C4-alkenyl, preferably C2-C3-alkenyl, chlorine and bromine and may be benzofused. when X is carboxyl ("solvent" based on benzoic acid), the benzene ring D is preferably substituted by an additional Ci-C^-alkyl, especially Ci-C2-alkyl, group or particularly preferably unsubstituted. When X is hydroxyl (phenolic "solvent"), the benzene ring D preferably bears one of the aforementioned substituents in addition; if the benzene ring D is benzofused, it preferably bears no further substituents. The organic medium should have little, if any, solubility in water at room temperature and should be liquid at the process temperature. The melting point of said compounds 1 should therefore generally be Examples of suitable acidic aromatic organic media are: benzoic acid, 2-, 3- and 4-methylbenzoic acid, 2-, 3- and 4-ethylbenzoic acid, phenol, 2-, 3- and 4-nitrophenol, 2-, 3- and 4-methylphenol (-cresol), 2-, 3- and 4-ethylphenol, 2-allylphenol, 2-, 3- and 4-bromophenol, 2,4-dibromophenol, 2,4-dichlorophenol, 2-chloro-6-nitrophenol, 2-chloro-4-nitrophenol, 2,4-dinitrophenol, 3-methyl-4-nitrophenol, 1- and 2-naphthol and l-bromo-2-naphthol and mixtures thereof, of which 3- and 4-nitrophenol and 1- and 2-naphthol are preferred and 2-nitrophenol is particularly preferred, The amount of organic medium used per g of crude copper phthalocyanine pigment is generally within the range from 1 to 20 g, preferably within the range from 1 to 6 g. The pigment treatment of the present invention can be carried out both in the absence and in the presence of water. That is, the crude halogenated copper phthalocyanine pigment can be used in dried form or else advantageously directly in the form of the as-halogenated, water-moist (water content customarily within the range of from 50 to 90% by weight) filter press cake. The amount of water in the pigment treatment of the present invention is not critical, but excessively large quantities of water should be avoided so as not to lower the space-time yields unnecessarily. The pigment treatment of the present invention is carried out in the presence of one of the aforementioned copper phthalocyanine derivatives, including, of course, mixtures of the derivatives. The copper phthalocyanine derivatives serve both to control crystal growth during recrystallization and to modify the surface of the resulting pigment. Their choice depends on the degree of chlorination of the crude pigment, the property profile desired for the recrystallized pigment and the later application medium. R5 is p-{Cio-C2o-alkyl)phenyl, m is an integer or fraction > 0 to 4, n is an integer or fraction from 0 to 4, subject to the proviso that the sum m + n is from 0.1 to 4, especially from 1.0 to 3.5. Specific examples of the radicals A and B in the formula II, and of their substituents, are: straight-chain or branched Ci-C2o-alkyl radicals such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, 2-methylpentyl, heptyl, 1-ethylpentyl, octyl, 2-ethylhexyl, isooctyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tridecyl, isotridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl (the designations isooctyl, isononyl, isodecyl and isotridecyl are trivial designations derived from the alcohols obtained by the oxo process ~ cf. Ullmann's Encyklopadie der technischen Chemie, 4th edition, volume 7, pages 215 to 217, and also volume 11, pages 435 and 436); straight-chain or branched Ca-C2o-alkenyl radicals such as ethenyl, propenyl, isopropenyl, butenyl, isobutenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl and eicosenyl; I straight-chain or branched Ci-C^-alkoxy radicals such as uiethoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, tert-butoxy, pentoxy, isopentoxy, neopentoxy, tert-pentoxy and hexoxy; Cs-Cfl-cycloalkyl radicals which can contain hetero atoms such as oxygen and/or nitrogen as replacement for one or more carbon atoms, but are not attached via these, such as cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, tetrahydrofuryl, pyrrolidyl, piperidyl, piperazyl and morpholinyl; aryl radicals such as naphthyl and especially phenyl; p-{Cio-C2o'all^yl)phenyl radicals such as p-decyl-, p-undecyl-, especially p-dodecyl-, also p-tridecyl-, p-tetradecyl-, p-pentadecyl-, p-hexadecyl-, p-heptadecyl-, p-octadecyl-, p-nonadecyl- and p-eicosyl-phenyl; carboxyl, preferably sulfo and mono(Cio-C20-alkyl)ammonium sulfonate radicals such as monodecyl-, monoundecyl -, monododecyl-, monotridecyl-, monotetradecyl-, monopentadecyl-, especially monohexadecyl-, also monoheptadecyl-, monooctadecyl-, / monononadecyl- and monoeicosyl-ammonium sulfonate radicals; mono- and di {Ci-Cg-alkyl) amino radicals such as mono- and dimethylamino, mono- and especially diethylaraino, mono- and dipropylamino, mono- and diisopropylamino, mono- and dibutylamino, mono- and diisobutylamino, mono- and dipentylamino and mono- and dihexylamino and also especially mono- and preferably di (Ci-Cg-alkyl)amlnomethyl radicals in which the amino radicals mentioned are attached to the phthalocyanine structure via a methylene group; reaction products of mono- and di {Ci-Cg-alkyl)amino radicals and preferably of the corresponding aminomethyl radicals with Cio-C2o-alkylphenylsulfonic acids such as p-decyl-, p-undecyl-, especially p-dodecyl-, also p-tridecyl-, p-tetradecyl-, p-pentadecyl-, p-hexadecyl-, p-heptadecyl-, p-octadecyl-, p-nonadecyl- and p-eicosyl-phenylsulfonic acids, the alkyi radicals being disposed ortho, meta or preferably para to the sulfonic acid group, eg. -CH2-N (C2H5) 2-H03S-Ph-4-C12H25 and -CH2-NH(C2H5)■HO3S-Ph- 4 - C12H25; heterocycloalkyl and hetaryl radicals containing the amine nitrogen atom and attached therethrough, such as 4-morphoiinyl, pyrrolidyl, piperidyl, piperazyl, pyrazolyl, pyrryl, pyrazyl, imidazyl, especially N-phthaiimidyl and N-saccharinyl and also preferably the corresponding radicals attached to the phthalocyanine structure via -CH2-; mono(Ci-C2o-alkylcarbonyl)amino radicals such as monomethyi-, monoethyl-, monopropyl-, monoisopropyl-, monobutyl -, monoisobutyl-, tert-monobutyl-, monopentyl-, monoisopentyi -, mononeopentyl-, tert-monopentyl-, monohexyl-, 2-monomethylpentyl-, monoheptyl-, 1-monoethylpentyl-, monooctyl -, 2-monoethylhexyl-, monoisooctyl-, monononyl-, monoisononyi -, monodecyl-, monoundecyl-, monododecyl-, monotridecyl -, monotetradecyl-, monopentadecyl-, especially monohexadecyl-, also monoheptadecyl-, monooctadecyl-, monononadecyl- and monoeicosyl-carbonylamino and also the corresponding amino radicals attached to the phthalocyanine structure via -CH^-; mono (Ci-C20'alk:ylsulfonyl) amino radicals such as monomethyi-, monoethyl-, monopropyl-, monoisopropyl-, monobutyl-, monoisobutyl-, tert-monobutyl-, monopentyl-, monoisopentyi -, mononeopentyl-, tert-monopentyl-, monohexyl-, 2-monomethylpentyl-, monoheptyl-, 1-monoethylpentyl-, monooctyl-, 2-monoethylhexyl-, monoisooctyl-, monononyl-, monoisononyi-, monodecyl-, monoundecyl-, monododecyl•, monotridecyl-, monotetradecyl-, monopentadecyl-, especially monohexadecyi-, also monoheptadecyl-, monooctadecyl-, monononadecyl- and monoeicosyl-sulfonylamino and also the corresponding amino radicals attached to the phthalocyanine structure via -CHj-,- mono(Ci-C2o-alkylamino)sulfonyl radicals such as monomethyi-, monoethyl-, monopropyl-, monoisopropyl-, monobutyl-, monoisobutyl-, tert-monobutyl-, monopentyl-, monoisopentyl ■, mononeopentyl-, tert-monopentyl-, monohexyl-, 2-monomethylpentyl-, monoheptyl-, 1-monoethylpentyl-, monooctyl-, 2-monoethylhexyl-, monoisooctyl-, monononyl-, monoisononyi-, monodecyl-, monoundecyl-, monododecyl -, monotridecyl -, monotetradecyl-, monopentadecyl-, especially monohexadecyi-, also monoheptadecyl-, monooctadecyl-, monononadecyl- and monoeicosyl-aminosulfonyl, it being possible for the alkyl radicals to bear a terminal amino, mono- or di (Ci-Ce-alkyl)amino group; mono(Ci-C2o-alkylamino)carbonyl radicals such as monomethyi-, monoethyl-, monopropyl-, monoisopropyl-, monobutyl-, monoisobutyl-, tert-monobutyl-, monopentyl-, monoisopentyl-, mononeopentyl-, tert-monopentyl-, monohexyl-, 2-monomethylpentyl-, monoheptyl-, 1-monoethylpentyl-, monooctyl-, 2-monoethylhexyl-, monoisooctyl-, monononyl-, monoisononyi-, monodecyl-, monoundecyl-, monododecyl-, monotridecyl -, monotetradecyl-, monopentadecyl-, especially monohexadecyi-, also monoheptadecyl-, monooctadecyl-, monononadecyl- and monoeicosyl-aminocarbonyl, it being possible for the alkyl radicals to bear a terminal amino, mono- or di {Ci-Cg-alkyl)amino group, The phthalocyanine derivatives II are known per se and are preparable according to known methods (eg. EP-A-535 774, DE-A-25 16 054, EP-A-538 784 and DE-A-29 05 114). The copper phthalocyanine derivative II is used in the process of the present invention in an amount which is generally within the range from 0.1 to 20% by weight, preferably within the range from 1 to 10% by weight, each percentage being based on the crude copper phthalocyanine pigment. Suitable process temperatures are generally within the range from 80 to 200°C, preferably within the range from 80 to 120°C, the temperature also having to be conformed in each case to the melting point of the acidic aromatic organic medium. In the presence of water, the pigment treatment of the present invention is carried out preferably at > lOO^C in a sealed reactor under autogenous pressure. The pigment treatment customarily takes from 2 to 10 h, especially from 2 to 5 h. The higher the selected temperature, the faster the recrystallization. The process of the present invention is advantageously carried out at follows: A mixture of crude halogenated copper phthalocyanine pigment, which is preferably present as a water-moist filter cake, copper phthalocyanine derivative and acidic aromatic organic medium is heated to the desired temperature and stirred at that temperature for from 2 to 10 h. To isolate the pigment, aqueous base (eg. from 2 to 60% strength by weight alkali metal hydr'oxide solution) is added at from 50 to 100°C in at least the amount which is stoichiometrically required to convert the organic medium into its water-soluble alkali metal salt. The pigment is subsequently filtered off, washed with water and dried. The organic medium can be reprecipitated by acidification of the alkali metal salt solution using mineral acid and cooling at room temperature and reused for a pigment treatment. The process of the present invention provides an advantageous way to obtain brilliant, transparent and strong halogenated (both incipiently halogenated and polyhalogenated) copper phthalocyanine pigments having excellent rheological properties, suitable for use in both conventional and waterborne coating systems. Accordingly the present invention provides a process for transforming crude halogenated copper phthalocyanine pigments having a chlorine of from 4 to 50.3% by weight into a brilliant, transparent pigments having better rheological properties than the starting phthalocyanine pigment comprising the steps of treating the crude pigment at 80 to 200X with an acidic aromatic organic compound of the general formula I where X is hydroxyl or carboxyl and the benzene ring D may additionally bear up to two identical or different substituents selected fonn the group consisting of nitro, Cj-C^-alkyl, Cj-C^-alkenyl, chlorine and bromine and may be benzofused, in the presence of a copper phthalocyanine derivative selected from the group consisting of tiie copper phthalocyanine-sulfonic and -carboxylic acids and their alkali metal, ammonium and alkylammonium salts, the amino-substituted and aminomethvlated copper phthalocyanines, and their reaction products with alkylating agents, sulfonic acids, sulfonyl chlorides and carbonyl chlorides, the imidomethylene- and amidomethylene-substituted copper phthalocyanines, the alkyl-, aryl-and cyano-substiTuted copper phthalocyanines and the hydroxyl- and alkoxy substituted copper phthalocyanines, if desired in the presence of water and isolatmg the pigment through filtering off after converting the organic medium into its water soluble alkali metal salt by adding aqueous base. Examples A mixture of 50 g (reckoned 100%) of a crude halogenated copper phthalocyanine pigment having a chlorine content of xi% by weight (used in the form of an aqueous press cake having a water content of X2% by weight), 2,5 g of copper phthalocyanine derivative II' and 100 g of organic medium ill was heated to 100°C and stirred at that temperature for 5 h. After cooling to 80°C, 290 g of 31% strength by weight sodium hydroxide solution were added. The pigment was filtered off, washed with water and dried at 100°C. Further details concerning these experiments and their results are summarized in the following table: WE CLAIM 1. A process for transformmg crude halogenated copper phthalocyanine pigments having a chlorine of from 4 to 50.3% by weight into a brilhant, transparent pigments having better rheological properties than the starting phthalocyanine pigment comprising the steps of treating the crude pigment at 80 to 200'C with an acidic aromatic organic comoound of the general formula I where X is hydroxyl or caiboxyl and the benzene ring D may additionally bear up to two identical or different substituents selected form the group consisting of nitro, Cp ■alkenyl, chlorine-and bromine and may be benzofused, in the presence of a copper phthalocyanine derivative selected from the group consisting of the copper phlhalocyanine-sulfonic and -carboxyhc acids and their alkah metal, ammonium and alkylammoniuni salts, the amino-substituted and aminomethylated copper phthalocyanines, and their reaction products with alkylating agents, sulfonic acids, sulfonyl chlorides and carbonyl chlorides, the imidomethylene- and amidomethylene-substituied copper phthalocyanines, die alkyl-, ar>'l- and cyano-substituted copper phthalocyanines and the hydroxyl- and alkoxy substituted copper phthalocyanines. if desired in the presence of water and isolating the pigment through filtering off after converting the organic medium into its water soluble alkali metal salt by adding aqueous base. 2. The process as claimed in claim I, wherein the acidic aromatic organic compound of the formula 1 is 2-nitrophenol, 3-nitrQphenol, 4-nitrophenol, 1-naphthol or 2-naphthol 3. The process as claimed in claim I or 2, wherein the copper phthalocyanine derivative used has the general formula II where: A and B are independently of each other the following substituents: are each independently of the other which may contain one or more hetero atoms, or hydrogen, R^ and R4 are each independently of the other hydrogen, alkeny] or aryl or combine with tile nitrogen atom to form a 5- or 6-membered ring which optionally contains further hetero atoms or carbonly or sulfonyl groups and may be benzofiised, rt) is an integer or fraction > 0 to 4,0, n is an integer or fraction from 0 to 4.0. 4. The process as claimed in any of claims 1 to 3, wherein the copper phthalocyanine derivative used has the formula II where the variables have the following meanings: A and B are independently of each other the following substituents: r n is an integer or fraction from 0 to 4, subject to the proviso that the sum m + nis from 0.1 to 4. 5. The process as claimed in any of claims 1 to 4, wherein from 0.1 to 20% by weight of the copper phthalocyanine derivative of the formula II is used, based on the crude pigment. 6. A process for transforming crude halogenated copper phthalocyanine pigments substantially as herein described and examplified.

Documents:

2264-mas-1998 abstract-duplicate.pdf

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