MXPA99009295A - Metal complex pigments - Google Patents

Abstract

Metal complex(es) of an azo pyrimidine compound, optionally with condensed ring system(s), as pigment, and included compound(s) have a dispersion hardness less than 250. Metal complex(es) of an azo pyrimidine compound of formula (I), optionally with condensed ring system(s) as pigment, and included compound(s)have a dispersion hardness less than 250;X, Y=rings with 1 or 2 substituents selected from oxo (=O), thioxo (=S), imino (=NR7), amino (-NR6R7), -OR6, -SR6, -COOR6, cyano (-CN), -CONR6R7, -SO2R8, -N(CN)-R6, (cyclo)alkyl and ar(alk)yl, such that each ring has a total of 3 endo- and exocyclic double bonds;R6=hydrogen (H), (cyclo)alkyl or ar(alk)yl;R7=H, CN, (cyclo)alkyl, ar(alk)yl or acyl;R8=(cyclo)alkyl or ar(alk)yl;R1, R2, R3, R4=H, (cyclo)alkyl or ar(alk)yl or condensed 5- or 6-membered rings;R5=-OH, -NR6R7, (cyclo)alkyl or ar(alk)yl;m, n, o, p=1 or also 0 if there are double bonds from the ring N atoms;R1-8 may=groups with substituted CH groups. An Independent claim is also included for the preparation of the complexes.

Description

METALLIC COMPLEX PIGMENTS Field of the Invention The present invention relates to new metallic complex pigments, processes to produce them and their use.

Background of the Invention EP-A-73 4 L.3 discloses coloring pigments of value. However, these still have disadvantages in the application. For example, the pigments prepared in the manner described are very hard in texture and have to be shredded in dispersion processes that are relatively time consuming to obtain the desired color characteristics and hence the particle size conformation. Yet, such pigments still have some disadvantages in dispersibility and color intensity. Accordingly, an object of the present invention is to provide new pigment forms free of the disadvantages described above. Ref.031473 Metal complexes of an azo compound which, in the form of its tautomeric structures, conform to formula (I), are provided according to the invention. where the X and Y rings can each independently carry one or two substituents selected from the group consisting of = 0, = S, = NR, -NR6H7, -0R6, -SR6, -C00R6, -CN, -C0NR6R7, -S02R8 , alkyl, cycloalkyl, aryl and aralkyl, the total sum of the endo- and exocyclic double bonds is three for each of the X and Y rings, R6 is hydrogen, alkyl, cycloalkyl, aryl or aralkyl, R7 is hydrogen, cyano, alkyl, cycloalkyl, aryl, aralkyl or acyl, e is alkyl, cycloalkyl, aryl or aralkyl, R-R2 / 3 and R are each independently hydrogen, alkyl, cycloalkyl, aryl or aralkyl and furthermore, as indicated by the interrupted lines in formula (I), they may form 5 or 6 element rings to which they can merge additional rings, Rs is -OH, -NR6R7, alkyl, cycloalkyl, aryl or aralkyl, the substituents mentioned for Ri to R8 which contain the CH bonds can be substituted in turn, and m, n, o and p are each 1, if the atoms Nitrogen ring are the starting points for the double bonds, as indicated by the dotted lines in the formula (I), they can also be zero, and such metal complex metals host at least one compound as host compound, characterized in that they have a dispersion hardness of less than 250 (measured in accordance with DIN 53 775).

Preferred organic metal complexes are those of the azo compounds which, in the form of their free acid, conform to one of the tautomeric forms of the formula (I) wherein the ring X represents a ring of the formula where L and M are each independently = 0, = S or = NR6, i is hydrogen, -0R6, -SR6, -NR6R7, -C00R6, -C0NR6R7, -CN, alkyl, cycloalkyl, aryl or aralkyl, Mi is -0R6, -SR6, -NR6R7, -COOR6, -CONR6R7, -CN, -S02R8, alkyl, cycloalkyl, aryl or aralkyl, and the substituents Mi and Ri or Mi and R2 can form a 5 or 6 membered ring .

Particularly preferred organic metal complexes are those of the azo compounds which, in the form of their free acids, conform to one of their tautomeric structures of the formulas (II) or (III) where R's is -OH or -NH2, R'i, R "?, R'2 and R" 2 are each hydrogen, and M 'i and M "? Are each independently hydrogen, -OH, -NH2, -NHCN, arylamino or acylamino.

Particularly preferred metal complexes are those of the azo compounds of the formula (I) which, in the form of their free acid, conform to one of the tautomeric structures of the formula (IV) where M 'and M / r i are each independently OH or NHCN.

Preference is given especially to the organic metal complexes of those azo compounds of the formula (I) which, in the form of their free acid, conform to one of the tautomeric structures of the formula (V) In the preceding formulas, the substituents preferably have the following meanings: The alkyl substituents are preferably alkyl with Ci-Cβ, which can be substituted, for example, by halogen, such as chlorine, bromine or fluorine, -OH, -CN, -NH2 or alkoxy with C? -C6. The cycloalkyl substituents are preferably cycloalkyl with C3-C7, especially cycloalkyl with Cs-C6, which may be substituted for example by alkyl with C? -C6, alkoxy with C? -C6, halogen such as Cl, Br or F, alkoxy with C? -C6, halogen such as Cl, Br or F, alkoxy with C? -C6, -OH, -CN or NH2. The aryl substituents are preferably phenyl or naphthyl, which may each be substituted for example by halogen such as F, Cl or Br, -OH, alkyl with C? -C6, alkoxy with C? -C6, -NH2, -N02 or -CN. The aralkyl substituents are preferably phenyl- or naphthyl-C? -C-alkyl, which may be substituted on the aromatic radicals by halogen such as F, Cl or Br, -OH, alkyl with C? -C6, alkoxy with Ci -Ce, -NH2, -N02 or -CN, for example. The acyl substituents are preferably (C_-C6-alkyl) -carbonyl, phenylcarbonyl, Ci-C-alkylsulfonyl, phenylsulfonyl, optionally substituted C, -C6-alkyl-, phenyl- and naphthyl-substituted carbamoyl, sulfamoyl, C, -C6-alkyl. - optionally substituted phenyl- and naphthyl-substituted or optionally C- -C6-alkyl-, phenyl- or naphthyl-substituted guanyl, wherein said alkyl radicals can be substituted, for example, by halogen such as Cl, Br or F, -OH , -CN, -NH2 or alkoxy with C! -C6 and the mentioned phenyl and naphthyl radicals can be substituted for example by halogen such as F, Cl or Br, -OH, alkyl with C? -C6, alkoxy with C? Ce, -NH2, -N02 or -CN. If M1R1 or M? R2 or MXR2 and R1 R2, R3, R4, as indicated by the interrupted lines in formula (I), form rings of 5 or 6 elements, these are preferably ring systems of triazole, imidazole or benzimidazole, pyrimidine or quinazoline. The metal complexes, which are also to be understood as meaning metal salts, of the formulas (I) to (V) preferably include the salts and the complexes of the mono-, di-, tri- and tetraanions with the Li metals, Cs, Mg, Cd, Co, Al, Cr, Sn, Sn, Pb, particularly preferably Na, K, Ca, Sr, Ba, Zn, Fe, Ni, Cu and Mn. Particular preference is given to the salts and complexes of the formulas (I) to (V) with the di- or trivalent metals, very particularly the nickel salts and the complexes. Metal complexes which contain at least one compound, especially the organic compound, such as the host, can be present as host-host compounds, intercalation compounds and also as solid solutions. They are very particularly inclusion compounds, intercalation compounds and solid solutions in which the nickel / azobarbituric acid 1: 1 complex conforms to one of the tautomeric forms of the formula and includes at least one other organic compound. In general, the metal complex forms a stratified crystal lattice in which the junction within a layer is essentially by means of hydrogen bonds and / or metal ions. Preferably, the metal complexes are metal complexes which form a crystal lattice which consists essentially of planar layers.

For the purposes of the present invention, the metal compounds of the azo compounds of the formula (I) which contain at least one compound as the host compound and have a dispersion hardness of less than 250, are referred to as pigments in accordance with the invention. In a preferred embodiment, the pigments according to the invention have a hardness by dispersion of less than 200, especially less than 150. The hardness by dispersion is measured in accordance with DIN 53 775 Part 7, the temperature of cold rolling is 25 ° C and the hot-rolled temperature of 150 ° C. All the dispersion hardnesses reported here were determined by this modified DIN method. In a preferred embodimentCR. , the pigment according to the invention has a BET specific surface area of less than 150 m2 / g, especially 50 to 130 m2 / g. Useful metal complexes also include metal complexes in which a compound containing a metal, for example a salt or metal complex, is incorporated into the crystal lattice of another metal complex, for example of the nickel complex. In this case, in the formula (VI), a portion of the metal, for example of nickel, can be replaced by other metal ions, or additional metal ions can be introduced in a more or less pronounced interaction with the metal, preferably the complex of nickel. The compounds included can be organic compounds and inorganic compounds. The compounds which can be included come from a very wide variety of classes of compounds. For purely practical reasons, preference is given to such compounds when they are liquid or solid under normal conditions (25 ° C, 1 bar). Of the liquid substances, preference is given in turn to those which have a boiling point (1 bar) of 100 ° C or higher, preferably 150 ° C and higher. Suitable compounds are preferably preferably acyclic and cyclic organic compounds, for example aliphatic and aromatic hydrocarbons, which can be substituted, for example by OH, COOH, NH2, substituted NH2, C0NH2, substituted CONH2, S02NH2, substituted S02NH2, SO3H, halogen , N02, CN, -S02-alkyl, -S02-aryl, -O-alkyl, -O-aryl, -O-acyl. The specific examples are paraffins and paraffin oils; triisobutylene, tetraisobutylene, mixtures of aliphatic and aromatic hydrocarbons as they are produced in the fractionation of petroleum for example; chlorinated paraffin hydrocarbons such as dodecyl chloride or stearyl chloride; alcohols with C10-C30 such as 1-decanol, 1-dodecanol, 1-hexadecanol, 1-octadecanol and mixtures thereof, olein alcohol, 1,12-octadecanediol, fatty acids and their salts and mixtures, for example formic acid, acetic acid, dodecanoic acid, hexadecanoic acid, octadecanoic acid, oleic acid, fatty acid esters, for example methyl esters of fatty acids with C? or C2o, fatty acid amides, such as stearam, monoethanolamide of stearic acid, stearic acid diethanolamide, stearonitrile, fatty amines, for example dodecylamine, cetylamine, hexadecylamine, octadecylamine and others; salts of fatty amines with sulfonic and carboxylic acids, isocyclic hydrocarbons such as cyclododecane, decahydronaphthalene,, o-, m-, p-xylene, mesitylene, mixtures of dodecylbenzenes, tetralin, naphthalene, 1-methylnaphthalene, 2-methylnaphthalene, biphenyl, diphenylmethane, acenaphthene, fluorene, anthracene, phenanthrene, m-, p-terphenyl, o-, p-dichlorobenzene, nitrobenzene, 1-chloronaphthalene, 2-chloronaphthalene, 1-nitronaphthalene, isocyclic alcohols and phenols and their derivatives such as benzyl alcohol, decahydro-2-naphthol, diphenyl ether, sulfones, for example diphenyl sulfone, methyl phenyl sulfone, 4,4'-bis-2- (hydroxyethoxy) diphenyl sulfone; isocyclic carboxylic acids and their derivatives such as benzoic acid, 3-nitrobenzoic acid, cinnamic acid, 1-naphthalenecarboxylic acid, phthalic acid, dibutyl phthalate, dioctyl phthalate, tetrachlorophthalic acid, 2-nitrobenzamide, 3-nitrobenzamide, -nitrobenzamide, 4-chlorobenza ida, sulfonic acids, such as 2, 5-dichlorobenzenesulfonic acid, 3-nitro-, 4-nitro-benzenesulfonic acid, 2,4-dimethylbenzenesulfonic acid, 1- and 2-naphthalenesulfonic acid, -nitro-l- and 5-nitro-2-naphthalenesulfonic acid, mixtures of di-sec-butylnaphthalenesulfonic acids, biphenyl-4-sulfonic acid, acid 1,4-, 1,5-, 2,6-, 2, 7- Naphthalenedisulfonic acid, 3-nitro-1, 5-naphthalenedisulfonic acid, 1-anthraquinonsulfonic acid, 2-anthraquinonsulfonic acid, biphenyl-4, -disulfonic acid, 1,3,6-naphthalene sulfonic acid and the salts of these sulphonic acids, for example salts of sodium, potassium, calcium, zinc, nickel and copper; sulfonamides such as benzenesulfonamide, 2-, 3- and 4-nitrobenzenesulfonamide, 2-, 3- and 4-chlorobenzenesulfonamide, 4-methoxybenzenesulfonamide, 3,3'-sulfonylbisbenzenesulfonamide, 4,4'-oxybisbenzenesulfonamide, 1- and 2-naphthalenesulfonamide.

Carboxamides and sulfonamides are a preferred group of compounds to be included, particularly urea and substituted ureas such as phenylurea, dodecylurea and others and also their polycondensates with aldehydes, especially formaldehyde; heterocycles such as barbituric acid, benzimidazolone, 5-benzimidazolonsulfonic acid, 2,3-dihydroxyquinolaline, 2,3-dihydroxyquinolalin-6-sulfonic acid, carbazole-3,6-disulfonic acid, 2-hydroxyquinoline, 2,4-dihydroxyquinoline, caprolactam , melamine, 6-phenyl-1,3,5,5-triazine-2,4-diamine, 6-methyl-1,3,5-triazine-2,4-diamine, cyanuric acid. Preferred solid solutions, intercalation compounds or inclusion compounds contain surface-active compounds included, especially surfactants, which are known, for example, from K. Lindner, Tenside-Textilhilfs ittel-aschrohstoffe, 2 / a. edition, Volume I, Wissensc aftliche Verlagsgesellschaft bH, Stuttgart, 1964. They may be anionic, non-ionic or cationic or ampholyte compounds. Examples of suitable anionic compounds are authentic soaps, salts of acids to incarboxylic acids, salts of lower or higher acylated aminocarboxylic acids, fatty acid sulfates, fatty acid ester sulfates, amides, etc., primary alkyl sulfates, sulphates of oxo alcohols, secondary alkyl sulfates, sulfates of esterified or etherified polyoxy compounds, sulfates of substituted polyglycol esters (sulphated ethylene oxide adducts), sulphates of acylated or alkylated alkanolamines, fatty acid sulfonates, their esters, amides, etc., primary alkyl sulphonates, secondary alkyl sulphates, alkyl sulfonates with acyl esters fixed in the ester form, alkyl or alkylphenyl ether sulfonates, polycarboxylate ester sulphonates, alkylbenzene sulfonates, alkylnaphthalenesulfonates, aromatic fatty sulfonates, alkylbenzimidazole sulfonates, phosphates, polyphosphates, phosphonates, phosphinates, thiosulfate s, hydrosulfites, sulphinates, persulfates. Examples of suitable nonionic compounds are the esters and ethers of polyalcoal esters, alkyl polyglycol ethers, acyl polyglycol esters, alkylaryl polyglycol esters, acylated and alkylated alkanolamine polyglycol ethers. Examples of suitable cationic compounds are alkylamine salts, quaternary ammonium salts, alkyl pyridinium salts, simple and quaternary imidazoline salts, alkyldiamines and alkylpolyamines, acyldiamines and acylpolyamines, acylalkanolamines, alkanolamine esters, alkyl-0CH2-N salts pyridinium, alkyl-CO-NH-CH2-N-pyridinium salts, alkylethylene-ureas, sulfonium compounds, phosphonium compounds, arsenic compounds, alkylguanidines, acyl-biguanidines. Examples of the suitable ampholytes are alkylbetaines, sulfobetaines and aminocarboxylic acids. Preference is given to the use of nonionic surfactants, especially the addition products of ethylene oxide of fatty alcohols, fatty amines and also of octyl or nonylphenol. A further important group of the host compounds are natural resins and resin acids such as, for example, abietic acid and its conversion products and salts thereof. Examples of such conversion products are hydrogenated, dehydrogenated and disproportionate abietic acids. These can be additionally dimerized, polymerized or modified by the addition of maleic anhydride and fumaric acid. Also of interest are resinous acids modified in the carboxyl group such as, for example, esters of methyl, hydroxyethyl, glycol, glyceryl and pentaerythritol and also nitriles of resinous acids and amines of resinous acids and also dehydroabietyl alcohol.

Also suitable for inclusion are polymers, preferably water-soluble polymers, for example polypropylene oxide-ethylene block polymers, preferably those having an Mn greater than 2000, especially greater than 2000 and less than 10,000 g / mol, alcohol polyvinyl, poly (meth) -acrylic acids, modified cellulose, such as carboxymethylcelluloses, hydroxyethyl- and -propylcelluloses, methyl- and ethyl-hydroxyethylcelluloses. Other suitable host compounds are the condensation products based on A) sulfonated aromatic compounds, B) aldehydes and / or ketones and optionally C) one or more compounds selected from the group of urea and urea derivatives, aromatic, non-sulphonated.

Based on, it means that the condensation product was optionally prepared from other reagents in addition to A, B and optionally C.

Preferably, however, the products of the condensation for the purposes of this invention are prepared only from A, B and optionally C. The sulfonated aromatics of component A) will be understood in the context of this invention which also include aromatic substances sulfomethylated. Preferred sulphonated aromatic substances are naphthalenesulfonic acids, phenolsulfonic acids, dihydroxybenzenesulfonic acids, sulfonated ditolyl ethers, 4,4'-dihydroxydiphenyl sulfone sulphomethylated, sulfonated diphenylmethane, biphenyl sulfonates, sulfonated hydroxybiphenyl, -hydroxybiphenyl, sulfonated terphenyl or benzenesulfonic acids. The aldehydes and / or ketones useful as component B) include in particular some aliphatics, cycloaliphatics and also aromatics. Preference is given to aliphatic aldehydes, particularly preferably formaldehyde and other aliphatic aldehydes of 3 to 5 carbon atoms. Examples of non-sulfonated aromatic substances useful as component C) are phenol, cresol, 4, '-dihydroxydiphenyl sulphone and dihydroxyphenemethane. Examples of urea derivatives are dimethylolurea, alkylureas, melamine and guanidine.

Preference is given to a condensation product based on: A) at least one sulfonated aromatic substance selected from the group consisting of naphthalenesulfonic acids, phenolsulfonic acids, dihydroxybenzenesulfonic acids, sulfonated ditolyl ethers, 4,4'-dihydroxydiphenyl sulfone sulphomethylated, sulfonated diphenylmethane, sulfonated biphenyl, sulphonated hydroxybiphenyl, especially 2-hydroxybiphenyl , terphenyl, and benzene sulphonic acids, B) formaldehyde and optionally C) one or more compounds selected from the group consisting of phenol, cresol, 4,4'-dihydroxydiphenyl sulfone, dihydroxydiphenylmethane, urea, dimethylolurea, melamine and guanidine.

The preferred condensation products are the condensation products based on 4,4 '-dihydroxydiphenyl sulfone, sulfonated ditolyl ether and formaldehyde; 4, 4'-dihydroxy-diphenyl sulfone, phenolsulfonic acid and formaldehyde; 4, 4 '-dihydroxydiphenyl sulfone, sodium bisulfite, formaldehyde and urea; Naphthalenesulfonic acid, 4,4'-dihydroxydiphenyl sulfone and formaldehyde; sulfonated terphenyl and formaldehyde; and / or sulfonated 2-hydroxybiphenyl and formaldehyde and also naphthalenesulfonic acid and formaldehyde. Particular preference is given for its use as host compounds to melamine or melamine derivatives, especially those of the formula (VII) where R6 is hydrogen or alkyl with C? ~ C4, which is optionally substituted by OH groups, it is very particularly preferred where R6 is hydrogen.

The amount of the substance that can be incorporated as host compounds in the crystal lattice of the metal complex is generally from 5% to 200% by weight, based on the amount of the host compound. Preference is given to an amount of the host compound of 10 to 100% by weight. The quantity referred to here is the amount of the substance which is not removed by washing by suitable solvents and which is obtained from the elemental analysis. Of course, it is also possible to add more or less of the abovementioned amount of the substance, and it can optionally be distributed to wash an excess. Preference is given to amounts of 10 to 150% by weight. The invention further relates to a process for preparing the pigments of Claim 1, characterized in that the metal complexes of an azo compound of the formula (I) which contains a compound as the host compound and have a dispersion hardness greater than 250. (in accordance with DIN 53 755), they are treated with heat in the presence of water and optionally organic solvents either at a pH of 1 to 4, preferably 1 to 3, especially 1.5 to 2.5, or at a pH of 9 to 13, preferably 10 to 11, and to a temperature of 80 to 180 ° C, preferably 90 to 140 ° C, especially 95 to 110 ° C. The process is preferably complemented when a dispersion hardness of less than 250 has been reached.

The process is carried out at temperatures above 100 ° C, preferably in an autoclave. The possible organic solvents are water-soluble or water-miscible solvents. It is also possible to use mixtures of different solvents and also optionally high-boiling, polymeric solvents, which have a boiling point higher than 250 ° C. According to the invention, there is no restriction with respect to the solvents that are to be used. More particularly, the compounds of the group of the aliphatic, cycloaliphatic or aromatic hydrocarbons and the terpene hydrocarbons, also alcohols, glycol and polyglycol ethers, esters and ketones, are suitable. It is also possible to use aminic solvents, especially those based on primary, secondary and tertiary amines, aliphatic and also aromatic or cycloaliphatic and their mixtures and derivatives. Suitable organic solvents are alcohols with C? -C4, such as methanol, ethanol, isopropanol, n-propanol, n-butanol, isobutanol or tert-butanol, aliphatic ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or diacetone alcohol, polyols, such as ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, triethylene glycol, trimethylolpropane, polyethylene glycol having an average molecular weight of 100 to 4000, preferably 400 to 1500, g / mol or glycerol, monohydroxyethers, preferably monohydroxyalkyl ethers, particularly preferably mono-C? -C4-alkyl glycol ethers such as ethylene glycol monoalkyl, monomethyl, diethylene glycol monomethyl ether or diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, dipropylene glycol monoethyl ether, thiodiglycol, triethylene glycol monomethyl ether or monoethyl ether , also 2-pyrrolidone, N-methyl-2-pyrrolidone, N-ethylpyrrolidone, N-vinylpyrrolidone, 1,3-dimethylimidazolidone, dimethylacetamide Measure and also dimethylformamide. They preferably have a boiling point greater than 100 ° C / atmospheric pressure. The pH is preferably fixed using organic or inorganic acids or bases. Preferred acids are HCl, H3P0, H2S? , Hl, HBr, Acetic acid and / or formic acid. Preferred bases are LiOH, KOH, NaOH, Ca (OH) 2, NH 3, ethanolamine, diethanolamine, triethanolamine, and / or dimethylethanolamine. In a preferred embodiment, the heat treatment is carried out at pH values of 1 a. The pigments used in the process of the invention because they have a dispersion hardness greater than 250 are preferable pigments, particularly those which are obtained directly by the reaction of the azo compounds of the formula (I) with metal salts, preferably those having a solubility in water of more than 20, especially more than 50, g / 1 at 20 ° C and subsequently by the reaction with the compound to be intercalated. Pigments having a dispersion hardness of greater than 250, hereinafter referred to as educts, are preferably obtained as follows in a manner such that the reaction with the metal compound is carried out at a pH < 2. The subsequent intercalation is preferably carried out at a pH of 1 to 7. If the intercalation is carried out at pH < 4, it is subsequently preferable to raise the pH to more than 4.5, preferably 4.5 to 7. This suspension of the educt can then be filtered and the remaining educt washed, preferably with water, especially hot water, to remove the non-intercalated fractions, the salts and other impurities. The thus dried product, optionally isolated in an intermediate manner, can then be heat treated in the range of 80 to 180 ° C at a pH of 1-4 or 9 to 13.

Alternatively, this suspension of the educt can be readjusted to a pH of 1 to 4 or a pH of 9 to 13 and treated with heat at a temperature of 80 to 180 ° C. The heat-treated suspension containing the pigment according to the invention is preferably readjusted again at a pH of 4.5 to 7 after the heat treatment. After that, it is filtered preferentially. The compressed cake thus obtained can be dried optionally after washing with water. Useful drying processes include on the one hand conventional drying processes such as drying with blades or propellers, etc. Such processes of drying and subsequent grinding of the pigment in a conventional manner make it possible to obtain powdery pigments. Preferably, the compressed cake is dehydrated by spray as an aqueous suspension. Particularly preferably, this is effected by the spray drying of a suspension which contains ammonia to increase the solids content. The suspension to be dehydrated by spray preferably has a solids content of 10 to 40% by weight, especially 15 to 30% by weight.

The slurry or slurry may additionally contain viscosity reducing additives such as the carboxylic acid and sulfonic acid amides in an amount of up to 10% by weight, based on the slurry or slurry. Examples of useful carboxamides and sulfonamides are urea and substituted ureas such as phenylurea, dodecylurea and others; heterocycles such as barbituric acid, benzimidazolone, benzimidazole-5-sulfonic acid, 2,3-dihydroxyquinolaline, 2,3-dihydroxyquinolines-6-sulphonic acid, carbazole, carbazole-3,6-disulfonic acid, 2,4-dihydroxyquinoline, caprolactam, melamine, 6-phenyl-1,3,5-triazine-2,4-diamine, 6-methyl-1,3,5-triazine-2,4-diamine, cyanuric acid. If additional additives are to be used, they are preferably added prior to drying.

Examples of the useful additives are, for example, the ingredients mentioned hereinafter of the preparations according to the invention. Suitable dryers for drying include in principle all dryers, for example vacuum dryers, air-forced dryers, especially one and two materials and also rotary disk dryers. The drying processes in a fluidized bed are also suitable. Examples of suitable single-material nozzle dryers are those having a nozzle with a spiral chamber. In a very particularly preferred embodiment of the process according to the invention, the base used is ammonia optionally together with additional bases which are not volatile during the drying and the resulting aqueous suspension, which preferably has a content of salts of 5 to 40% in weight, it is spray dried. This use of the ammonia-containing pastes leads to particularly advantageous granules, distinguished by very good dispersibility, color intensity and brightness on the substrate. In addition, they can flow freely and have an extremely low amount of dust. The invention further provides pigment preparations comprising at least one pigment according to the invention and at least one dispersant. Dispersants for the purposes of the present invention are substances which stabilize the pigment particles in their fine particulate form in the aqueous medium. The finely particulate materials are preferably understood to mean a fine division from 0.001 to 5 μm, especially from 0.005 to 1 μm, particularly preferably from 0.005 to 0.5 μm. Suitable dispersing agents are, for example, anionic, cationic, amphoteric or nonionic. Suitable anionic dispersants are in particular condensation products of aromatic sulfonic acids with formaldehyde, such as the condensation products of formaldehyde or alkylnaphthalenesulfonic acids or of formaldehyde, naphthalenesulfonic acids and / or benzenesulfonic acids, condensation products of phenol optionally substituted with formaldehyde and sodium bisulfite. Also suitable are dispersing agents from the group of sulfosuccinic esters and alkylbenzene sulfonates. Also the alcohols of alkoxylated, sulfated fatty acids, or the salts thereof. The alcohols of alkoxylated fatty acids are to be understood to mean in particular those alcohols of fatty acids with Ce-C22 which are provided with 5 to 120, preferably 5 to 60, especially 5 to 30, units of ethylene oxide and are saturated or unsaturated, especially stearyl alcohol. Particular preference is given to an alkoxylated stearyl alcohol with 8 to 10 ethylene oxide units. The alcohols of the sulfated alkoxylated fatty acids are preferably present as salts, especially as amine or alkali metal salts, preferably as the diethylamine salt. Also particularly suitable are ligninsulfonates, for example those which are obtained by the sulphite process or the kraft process. Preferably they are products which are partially hydrolyzed, oxidized, propoxylated, sulphonated, sulfomethylated or desulphonated and fractionated according to known processes, for example according to molecular weight or according to the degree of sulpholation. Mixtures of sulfite ligninsulfonates and the kraft process are also very effective. Particularly suitable are ligninsulphonates having an average molecular weight of between 1000 and 100,000, an active lignin sulfonate content of not less than 80% and preferably a low level of polyvalent cations. The degree of sulfonation can vary widely. Examples of the useful nonionic dispersants are the products of the reaction of the alkylene oxides with alkylating compounds, for example fatty alcohols, fatty amines, fatty acids, phenols, alkylphenols, arylalkylphenols, such styrene-phenol condensates, carboxamides and acids resinous They are, for example, ethylene oxide adducts of the class of the reaction products of ethylene oxide with: al) saturated and / or unsaturated fatty alcohols of 6 to 22 carbon atoms or bl) alkylphenols having 4 to 12 carbon atoms in the alkyl radical or cl) saturated and / or unsaturated fatty amines of 14 to 20 carbon atoms or di) saturated and / or unsaturated fatty acids of 14 to 20 carbon atoms or el) hydrogenated and / or non-hydrogenated resinous acids.

Suitable ethylene oxide adducts are in particular the alkylatable compounds mentioned under) to) when combined with 5 to 120, especially 5 to 100, especially 5 to 60, particularly preferably 5 to 30, moles of ethylene. Suitable dispersing agents also include the esters of the alkoxylation product of the formula (X) known from DE-A 19 712 486, which has a more recent priority date, or from DE-A 19 535 246, which conform or they adapt to the formula (XI) and also these optionally mixed with the original compounds of the formula (X). The alkoxylation product of the styrene-phenol condensate of the formula (X) is as defined hereinafter: where R, 15 is hydrogen or alkyl with C? ~ C4, R, 116 is hydrogen or CH3, R17 is hydrogen, alkyl with C? -C, alkoxy with C1-C4, alkoxycarbonyl with C? -C4 or phenyl, m is from 1 to 4, n is from 6 to 120, R18 is identical or different from each unit with the index n and represents hydrogen, CH3 or phenyl subjected to the condition that, in the case that CH3 is present in the various groups - (- CH2- CH (R18) -0-), R18 is CH3 at 0 to 60% of the total value of n and is hydrogen at 100 to 40% of the total value of n and in the case of the phenyl which is present in the various groups - (-CH2- CH (R18) -0-), R18 is phenyl at 0 to 40% of the total value of n and is hydrogen at 100 to 60% of the total value of n. The esters of the alkoxylation products (X) conform to the formula (XI) where R 15 'R 16' R, 17 ', R, 18, m' and n 'assume or adopt the meaning range of Rs, R, 160, R, 1x7', R ~, m and n, respectively, but independently thereof , X is -S03, -S02, -O3 or -CO- (R19s,) - COO, Kat is a cation selected from the group consisting of H +, Li +, Na +, K +, NH4 + and HO-CH2CH2-NH3 +, subject to the condition that in the case of. that X = -P03- two cations are present, and R19 is a divalent aliphatic or aromatic radical, preferably alkylene. with C? ~ C, especially ethylene, mono-unsaturated C2-C4 radicals, especially acetylene, or optionally substituted phenylene, especially ortho-phenylene, the preferred substituents are alkyl with C? -C4, alkoxy with C? ~ C, alkoxycarbonyl with C ? -C4 or phenyl. The specific individual compounds of the formula (XI) are known, for example, from DE-A 19 712 486 and mixtures of the formulas (X) and (XI) for example DE-A-19 535 256, which each form part of this request. A preferred dispersing agent is the compound of the formula (XI). Preferably a compound of the formula (XI) wherein X is a radical of the formula -CO- (R19) -C00"and R19 is as defined above.

The preference for use as a dispersing agent is likely to be given to a compound of the formula (XI) used in conjunction with a compound of the formula (X) In this case, the dispersing agent preferably contains 5 to 99% by weight of the compound (XI) and 1 to 95% by weight of the compound (X). Polymeric dispersing agents are, for example, soluble in water and also water-emulsifiable compounds, for example homo- and copolymers such as block or random copolymers. Particularly preferred polymeric dispersing agents are for example block copolymers AB, BAB and ABC. In AB or BAB block copolymers, segment A is a hydrophobic homopolymer or copolymer which provides a bond or bond for the pigment and block B is a hydrophilic homopolymer or copolymer or a salt thereof and ensures dispersion of the pigment in an aqueous medium Such polymeric dispersing agents and their synthesis are known, for example, from EP-A-518 225 and EP-A-556 649. The dispersing agent is preferably used in an amount of 0.1 to 100% by weight, especially 0.5 to 60% by weight , based on the level of use of the pigment in the pigment preparation.

The preparation may of course contain additional additives. For example, additives which reduce the viscosity of an aqueous suspension and increase the solids content, such as the aforementioned carboxamides and sulfonamides for spray drying, can be added in an amount of up to 10% by weight, based on In the preparation. The additives which are customary for pigmentation preparations are also possible. However, it is particularly preferable for the preparation of the invention to contain more than 90%, especially more than 95%, preferably more than 97%, by weight of the pigment and optionally the dispersing agent. In the same way preference is given to pigment preparations having a viscosity of less than 80 mPa.s in an alkyd-melamine varnish system or less than 50 mPa-s1 in an aqueous coating system or less than 300 mPa. .s in an aqueous binder system, each measured in accordance with DIN 53 019. Inclusion compounds, intercalation compounds and solid solutions of the metal compounds are already known per se in the literature. They and their preparation are described, for example, in EP 0 074 515 and EP 0 073 463. The products obtained by the production processes described therein, however, are difficult to disperse, hard or rough, making their use very difficult. as pigments. The preparation for these compounds as described for example in EP 073 464, takes the form of the synthesis of the azo compound which is followed by the formation of a complex with a metal salt and thereafter, with or without intermediate isolation of the complex metallic, by the reaction with the compound that is going to be intercalated. In the case of the industrially useful intercalation compounds of the metal complexes, the di- and trivalent metals, especially the technically and economically important intercalation compound of the barbituric-nickel acid complex, the formation of the complex and the intercalation and also the Subsequent isolation is carried out in the acid pH range. However, the drying of the products thus produced usually, and with respect to the drying conditions, will produce pigments difficult to disperse and of hard or rough texture, which frequently do not possess any intensity of desired color. The problem of hard or rough texture and dispersibility arises in particular also in the case of the industrially useful intercalation compounds of the nickel-azibarbituric acid complex and here to a very particular degree in the case of the melamine intercalation compound, which has appreciable significance both technically and economically. It is already known to improve the hard or rough texture, the dispersibility and the color intensity of the pigments by various methods. Such processes are known, for example, from DE-A-2 214 700, DE-A-2 064 093 and DE-A-2 753 357. But all these methods are very complicated and, what is more, frequently lead to losses in the time-space performance. It has now been found, quite surprisingly, that the pigment preparations of the invention are appreciably softer in texture and much better dispersible. In addition, the substrates pigmented therewith have a comparatively higher color intensity and also a higher brightness. Also the preferred pigment preparations are those which, in an alkyd / melamine system according to DIN 53 238 Part 31, after a dispersion time of only 2 hours, have a color intensity which is not less than 3%, preferably no greater than 10%, particularly greater than 20%, higher than that of the pigment whose hardness or roughness is > 250, after a time of dispersion in the conformation of 2 hours. Solid pigment preparations are very useful for all applications of pigments. They are useful, for example, for pigment varnishes of all kinds for the production of printing colors, colors for tempera painting or binding colors, for the coloration in series of synthetic, semi-synthetic or natural macromolecular substances, especially polyvinyl chloride, polystyrene, polyamide, polyethylene or polypropylene, and for the dyeing by centrifugation of natural, regenerated or artificial, for example cellulose, polyester, polycarbonate, polyacrylonitrile or polyamide fibers, and also for the printing of printing and paper textiles. These pigments provide stable, finely divided aqueous pigmentations of the emulsion and colors for painting which are useful for coloring the paper, for printing with pigments of texiles, for lamination and also for the dyeing by centrifugation of the viscose, by grinding or kneading in the presence of nonionic, anionic or cationic surfactants.

Examples Example 1 425 g of paste moistened with water of a sodium salt of azobarbituric acid having a solids content of 40%, corresponding to 170 g in the dry state, are suspended homogeneously in 5000 ml of distilled water using a laboratory stirrer. After this, 122.4 g of NiCl2.6H20 and 126.1 g of melamine are added, and the suspension is subsequently heated to 95 ° C and stirred at 95 ° C for 2 hours. The suspension is then adjusted to pH 5.0 with sodium acetate. This is followed by isolation with a suction filter, electrolyte-free washing, drying in a cabinet for vacuum drying at 80 ° C and grinding in a common laboratory mill for about 2 minutes. The pigment powder thus obtained has a surface area of 160 m2 / g. Dispersion hardness: greater than 250 Example 2 657 g of paste moistened with water, of a melamine intercalation compound of the nickel-azobarbituric acid complex prepared according to Example 1, with a solids content of 45%, corresponding to 295.6 g in the dry state, are added to an initial charge of 5000 ml of distilled water and agitated in a homogeneous manner using a laboratory stirrer, and the suspension thus prepared is adjusted to an acidic pH with hydrochloric acid, then heated in an autoclave at a certain temperature and treated with heat at this temperature and this pH for 2 hours (see table). This is followed by gradual cooling to 95 ° C and adjustment of the pH to 5.0 with an aqueous sodium hydroxide solution to isolate the product. The product is then isolated on a suction filter, washed in an electrolyte-free condition, dried at 80 ° C in a vacuum drying cabinet and ground for 2 minutes in a common laboratory mill. When Example 2 is repeated with other heat treatment conditions, similar properties are obtained (see Table 1).

Table 1: Heat treatment 1) heat treatment without intermediate isolation: the pigment suspension at pH 5 is not isolated, but is readjusted (with hydrochloric acid) to pH 2 and dried at 95 ° C for 2 hours. It is adjusted to pH 5 and isolated and worked up as described in Example 2. 2) measured in accordance with DIN 53 775 Part 7 3) measured using a rotary viscometer RV20 Haake 4) after incorporation into an aqueous binder ) after incorporation into an aqueous coating system 6) After incorporation into a solvent coating system (alkyd-melamine in accordance with DIN 53 019) Example 14 a) 425 g of the water-wettable paste of a sodium salt of azobarbituric acid having a solids content of 40%, corresponding to 170 g in the dry state, are suspended homogeneously in 5000 ml of distilled water using a stirrer from laboratory. After this, 122.4 g of NiCl2 are added. 6H20 and 126.1 g of melamine, and the suspension is subsequently heated to 95 ° C and stirred at 95 ° C for 2 hours. Then the suspension is adjusted to pH 5.0 with sodium acetate. This is followed by the isolation on a suction filter and washed in an electrolyte-free manner. b) Half of the paste is then suspended in 2500 ml of distilled water. This is followed by adjusting with hydrochloric acid to pH 2.0 and heating to 97 ° C and subsequent stirring at this temperature for 5 hours. The product is then isolated on a suction filter and washed in an electrolyte-free manner. 3287. 4 g of paste moistened with water of Example 14a having a solids content of 45%, corresponding to 147.8 g in the dry state, are then added to an initial charge of 29.6 g of the ammonia solution of 25% concentration by weight, 363 g of demineralized water, 2.4 g of diethanolamine and 2.3 g of e-caprolactam. The mixture is then stirred homogeneously using a laboratory stirrer, the resulting suspension has a solids content of 20.9%. The melamine intercalation compound of the azobarbituric acid-nickel acid complex according to Example 14b is added to 29.6 g of an ammonia solution of a concentration or intensity of 25% by weight, 130 g of demineralized water, 2.4 g of diethanolamine and 2.3 g of e-caprolactam. This is followed by homogeneous agitation with a laboratory stirrer. In contrast to the suspension of Example 14a, the solids content was 30.9%. These suspensions are used for spray dehydration. Hardness by dispersion: <; 250 A granular product with low dust content is obtained, which flows freely.

It is noted that in relation to this date the best method known by the applicant to carry out the aforementioned invention, is that which is clear from the present description of the invention.

. Having described the invention as above, property is claimed as contained in the following

Claims (11)

1. The metal complexes of an azo compound which in the form of its tautomeric structures conforms to the formula (I) where: the X and Y rings can each independently carry one or two substituents selected from the group consisting of = 0, = S, = NR7, -NR6H7, -0R6, -SR6, -COOR6, -CN, -C0NR6R7, -S02R8, alkyl, cycloalkyl, aryl and aralkyl, the total sum of the endo- and exocyclic double bonds is three for each of the X and Y rings, Rβ is hydrogen, alkyl, cycloalkyl, aryl or aralkyl, R7 is hydrogen, cyano, alkyl, cycloalkyl, aryl, aralkyl or acyl, Rs is alkyl, cycloalkyl, aryl or aralkyl, Ri / R2 and are each independently hydrogen, alkyl, cycloalkyl, aryl or aralkyl and further, as indicated by the interrupted lines in formula (I), can form rings of 5 or 6 elements to which rings can be fused additional, R5 is OH, -NR6R7, alkyl, cycloalkyl, aryl or aralkyl, the substituents mentioned for Rx to Rs which contain CH bonds can be substituted in turn, and m, n, o and p are each 1, or if the nitrogen atoms of the ring are the starting points for the double bonds, as indicated by the dotted lines in the formula (I), they can also be zero, and such metal complexes host at least one compound as the host compound, characterized in that they have a dispersion hardness of less than 250.

2. The metal complexes according to claim 1, characterized in that, in the compound of the formula (I), the ring X represents a ring of the formula where: L and M are each independently = 0, = S or = NR6, Li is hydrogen, -OR6, -SR6, -NR6R7, -COOR6, -CONR6R7, -CN, alkyl, cycloalkyl, aryl or aralkyl, Mi is -0R6, -SR6, -NR6R, -C00R6, -CONR6R7, -CN, -S02R8, alkyl, cycloalkyl, aryl or aralkyl, and the substituents Mi and Rx or Mi and R2 can form a 5 or 6 membered ring , Y Ri, R2 and R5 are each as defined in claim 1.

3. The metal complexes according to claim 1, characterized in that the azo compound of the formula (I) in the form of its free acid conforms to the formula (II) or (III) or one of its tautomeric formulas wherein: R '5 is -OH or -NH2, R'i / R "i /' 2 and R" 2 are each hydrogen, and M'i and M "? Are each independently hydrogen, -OH, -NH2, -NHCN, arylamino or acylamino.

4. The metal complexes according to claim 1, characterized in that the azo compound of the formula (I) conforms to the formula (V) or a tautomeric form thereof

5. The metal complexes according to claim 1, characterized in that the metal compounds of the azo compound of the formula (I) which are used are the salts and the complexes of the mono-, di-, and tri- and tetraanions with the metals Li, Cs, Mg, Cd, Co, Al, Cr, Sn, Pb, preferably Na, K, Ca, Sr, Ba, Zn, Fe, Ni, Cu and Mn.

6. The metal complexes according to claim 1, characterized in that the metal compound used is the Ni salt or the complex of the azo compound of the formula (I).

7. The metal complexes according to claim 1, characterized in that they host an organic compound cyclically or acyclicly, especially melamine, as the host compound.

8. The metal complexes according to claim 1, characterized in that they have a BET specific surface area of less than 150 m2 / g.

9. A process for preparing the metal complexes of claim 1, characterized in that the metal complexes of an azo compound of the formula (I) which contain a compound as the host compound and have a dispersion hardness greater than 250, are heat treated in the presence of water and optionally with organic solvents either at a pH of 1 to 4, preferably 1 to 3 , especially 1.5 to 2.5, or at a pH of 9 to 13, preferably 10 to 11, and at a temperature of 80 to 180 ° C, preferably 90 to 140. ° C, especially from 95 to 100 ° C.

10. The pigment preparations, characterized in that they comprise at least one metal complex according to claim 1 and a dispersing agent.

11. The use of the metal complexes of claim 1 to produce printing colors, tempera colors or binding colors, for the serial coloration of synthetic, semi-synthetic or natural macromolecular substances, especially poly-inyl chloride, polystyrene, polyamide, polyethylene or polypropylene, and for the dyeing by centrifugation of natural, regenerated or artificial fibers, for example cellulose, polyester, polycarbonate, polyacrylonitrile or polyamide fibers, and also for the printing of textile and paper materials.