MXPA99009293A - Pigment preparations - Google Patents

Abstract

In solid pigment formulations containing metal complex(es) of an azopyrimidine compound, optionally with condensed ring system(s), as pigment, and included compound(s), the novelty is that a suspension of the formulation in 20 times the amount of water has pH over 6.5. In solid pigment formulations containing metal complex(es) of an azopyrimidine compound of formula (I), optionally with condensed ring system(s) as pigment, and included compound(s), the novelty is that a suspension of the formulation in 20 times the amount of water has pH over 6.5. 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 production of the pigment formulation.

Description

PREPARATIONS OF PIGMENTS.

Field of the invention.

The invention relates to new preparations of pigments, to processes for their preparation and to their use.

Description of the prior art.

Patent pigments EP-A-73 463 are already coloristically valuable pigments. However, these still have disadvantages from the point of view of industrial application. In this way, the pigments produced in various manners are still, for example, very hard grains and relatively expensive dispersion processes have to be comminuted in time to achieve the desired color and, therefore, the corresponding particle size. At the same time, such pigments still have some drawbacks in terms of their dispersibility as well as the intensity of their color.

REF. : 31476 Detailed description of the invention.

The task of the present invention was therefore to make available new forms of pigments that no longer presented the drawbacks described above. The invention relates to solid preparations of pigments which contain as pigment at least one metal complex of an azo compound, which corresponds in the form of its tautomeric structures to the formula (I) wherein the rings designated with X and Y can carry, independently of each other, one or two substituents of the series consisting of = 0, = S, = NR7, NR6H7 -0R6, -SR6, -C00R6, -CN, - CONR6R7, -S02R8, -N-CN, Re alkyl, cycloalkyl, aryl and aralkyl being three the < sum of the endocyclic and exocyclic double bonds for each of the X and Y rings, R6 signifies hydrogen, alkyl, cycloalkyl, aryl or aralkyl and R7 signifies hydrogen, cyano, alkyl, cycloalkyl, aryl, aralkyl or acyl and Rs signifies alkyl, cycloalkyl, aryl or aralkyl, Ri, R2, R3 and R4 independently of one another, mean hydrogen, alkyl, cycloalkyl, aryl or aralkyl and further, as indicated in formula (I) by means of discontinuous trace lines, can form rings with 5 or 6 members, on which other rings may be condensed, R 5 means -OH, -NRgR, alkyl, cycloalkyl, aryl or aralkyl, the substituents listed for Ri up to R 8, which contain CH bonds, may be substituted for their part and m, n, o, p mean 1 or, in the case where double bonds of the ring nitrogen atom are split, as indicated by dashed lines in formula (I), they may also mean zero, and with has incorporated at least one other compound, characterized in that a suspension of the solid pigment preparations with a 20 times greater amount of water has a pH value of > 6.5.

The preferred organic metal complexes in this case are those of the azo compounds, which correspond in the form of their free acids to one of their tautomeric forms of the formula (I), in which the ring designated by X means a ring of the formulas in which L and M, independentipeiite each other, mean = 0, = S or = NR6, Li means hydrogen, -0R6, -SR6, -NR6R7, -C00R6, -CONR6R-, -CH, alkyl, cycloalkyl, aryl or aralkyl and Mx means -OR6, -SR6, -NR6R7, -COOR6, -CONR6R7, -CN, -S02Rs, -N-CN, alkyl, cycloalkyl, aryl or R6 aralkyl, the substituents Mi and Ri or Mi and R2 being able to form a ring with 5 or 6 members. Particularly preferred organic metal complexes are in this case those of the azo compounds, which correspond, in the form of their free acids, to one of their tautomeric structures of the formulas (II) or (III) in which R'5 means -OH or -NH2, R'i / "i / R'2y R" 2 respectively mean hydrogen and M'i and M "?, independently of each other, mean hydrogen, -OH, -NH2 , -NHCN, arila ino or acylamino.

Especially preferred metal complexes are in this case those of the azo compounds of the formula (I), which correspond in the form of their free acids to one of their tautomeric structures of the formula I-L V) in which M "? and M - ^ 'i, independently of one another, mean OH and NHCN.First of all, the organic metal complexes of the azo compounds of the formula (I), which correspond in the form of its free acids to one of the tautomeric structures of the formula (V) In the above formulas, the substituents preferably have the following meaning: Substituents in the meaning of alkyl designate preferably alkyl with 6 carbon atoms, which may be substituted for example by halogen, such as chlorine, bromine or fluorine, by -OH , -CN, -NH2 or by alkoxy with 1 to 6 carbon atoms. Substituents in the meaning of cycloalkyl are preferably cycloalkyl with 3 to 7 carbon atoms, especially cycloalkyl with 5 or 6 carbon atoms, which may be substituted, for example, by alkyl having 1 to 6 carbon atoms, or alkoxy with 1 to 6 carbon atoms. carbon atoms, by halogen such as Cl, Br or F, by alkoxy with 1 to 6 carbon atoms, by -OH, -CN as well as by NH2. Substituents in the meaning of aryl are preferably phenyl or naphthyl, which may be substituted, for example, by halogen, such as F, Cl or Br, by -OH, by alkyl with 1 to 6 carbon atoms, by akoxy with 1 to 6. carbon atoms, by -NH2, by -N02, by -CN. Substituents in the meaning of aralkyl preferably represent phenyl- or naphthyl-alkyl with 1 to 4 carbon atoms, which may be substituted in the aromatic radicals, for example by halogen, such as by F, Cl or Br, by -OH, by alkyl with 1 to 6 carbon atoms, by alkoxy with 1 to 6 carbon atoms , by -NH2, by -N02 as well as by -CN. Substituents in the meaning of aciio preferably mean (C 1 -C 6 -alkyl) -carbonyl, phenylcarbonyl, alkylsulfonyl with 1 to 6 carbon atoms, phenylsulfonyl, carbamoyl optionally substituted by alkyl with 1 to 6 carbon atoms, by phenyl and by naphthyl, sulphamoyl optionally substituted by alkyl having 1 to 6 carbon atoms, by phenyl and naphthyl or guanyl substituted in the case of 1 to 6 alkyl by 1 to 6 carbon atoms, by phenyl and by naphthyl, the alkyl radicals mentioned for example by halogen such as Cl, Br or F, by -OH, by -CN, by -NH2 or by alkoxy with 1 to 6 carbon atoms and the phenyl and naphthyl radicals mentioned can be substituted. for example by halogen such as by F, Cl or Br, by -OH, by alkyl with 1 to 6 carbon atoms, by alkoxy with 1 to 6 carbon atoms, by -NH2, by -N02 and by -CN. In the case where M? Rx or M? R2 or M? R2 or Ri, R2, R3, R / form rings with 5 or ß-members, as indicated in formula (I) by dashed lines, preferably it will be ring systems of triazole, imidazole or benzimidazole, pyrimidine or quinazoline .

Metal complexes, which will also include metal salts of the formula (I) to (V), preferably include the salts and complexes of the mono-, di-, tri- and tetraanions with the metals Li, Cs. , Mg, Cd, Co, Al, Cr, Sn, Pb, particularly preferably Na, K, Ca, Sr, Ba, Zn, Fe, Ni, Cu and Mn. Particularly preferred are the salts and complexes of the formulas (I) to (V) with divalent or trivalent metals, especially the salts and nickel complexes. The metal complexes, which contain at least one other compound, in particular an organic compound, can be present as addition compounds, intercalation compounds as well as solid solutions. Particularly preferred are inclusion compounds, intercalation compounds and solid solutions, in which the 1: 1 complex of azobarbituric acid-nickel, corresponding to one of the tautomeric forms of the formula and which contains at least one other compound included. The invention also relates to metal complexes of an azo-compound, which in the form of its tautomeric structures corresponds to the formula (V), and which at least contains another compound incorporated, characterized in that the metal complexes correspond to the mono-, di-, tri or tetraanions of the azo-compounds of the formula (V) with the metals chosen from the group consisting of Li, Cs, Mg, Cd, Co, Al, Cr, Sn, Pb, Na, K, Ca, Sr, Ra, Zn, Fe, Cu and Mn. Preferred included compounds are those designated below. In general, the metal complex forms a crystalline network in stratified form, the junction being verified within the layer mainly through hydrogen bridges and / or metal ions. Preferably, in this case, it is metal complexes that form a crystalline lattice which consists essentially of flat layers.

Metal complexes also include those in which a metallized compound, such as for example a salt or a metal complex, is incorporated into the crystal lattice of the nickel compound. In this case, in the formula (VI), for example, a part of the nickel may be replaced by other metal ions or other metal ions may be present in a more or less strong interaction with the nickel complex. Both organic compounds and inorganic compounds may be occluded. The compounds, which may be occluded, come from the most diverse classes of compounds. For purely practical reasons, those compounds that are liquid or solid under normal conditions (25 ° C, 1 bar) will be preferred. Among the liquid substances, those which have a boiling point of 100 ° C, above this value, preferably greater than or equal to 150 ° C to 1 bar are also preferred. Suitable compounds are preferably acyclic and cyclic organic compounds, for example aliphatic and aromatic hydrocarbons, which may be substituted, for example by OH, COOH, NH2, substituted NH2, substituted C0NH2 / C0NH2, S02NH2, substituted S02NH2, S03H, halogen , N02, CN, -S02-alkyl, -S02-aryl, -O-alkyl, O-aryl, -O-acyl.

In particular, mention may be made, for example, of paraffins and paraffin oils; triisobutylene, tetraisobutylene, mixtures of aliphatic and aromatic hydrocarbons, such as those obtained, for example, in the fractionation of petroleum; chlorinated paraffinic hydrocarbons, such as dodccyl chloride or stearyl chloride; alcohols with 10 to 30 carbon atoms such as 1-decanol, 3-dodecanol, 1-hexadecanol, 1-octadecanol and their mixtures, 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 the methyl esters of fatty acids with 10 to 20 carbon atoms, fatty acid amides, such as stearic acid amide , stearic acid monoethanolamide, stearic acid diethanolamide, stearic acid nitrile, fatty amines, for example dodecylamine, cetylamine, hexodecyamine, octadecylamine and others; salts of fatty amines with sulfonic and carboxylic acids, hydrocarbons, such as cyclododecane, decahydronaphthalene, o-, m-, p-x'ylene, estylene, mixtures of do-decylbenzene, tetralin, naphthalene, 1-methylnaphthalene, 2-methylnaphthalene, biphenyl, biphenylmethane, 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 alcohol benzyl, decahydro-2-naphthol, diphenylether, suifones, for example diphenylisuiphone, methylphenylsulfone, 4,4'-bis-2- (hydroxyethoxy) -diphenylsulphone; isocyclic carboxylic acids and their derivatives such as benzoic acid, 3-nitrobenzoic acid, cinnamic acid, 1-naphthalenecarboxylic acid, italic acid, dibutyl phthalate, dioctyl phthalate, tetrachlorophthalic acid, 2-nitrobenzamide, 3-nitrobenzamide, 4-nitrobenza ida , 4-chlorobenzamide, sulfonic acids, such as 2, 5-dichlorobenzenesulfonic acid, 3-nitro-, 4-nitro-benzenesulfonic acid, 2,4-dimethylbenzenesulfonic acid, 1- and 2-naphthalenesulfonic acid, 5-nitro-l acid - and 5-nitro-2-naphthalenesulfonic acid, mixtures of di-sec-butyl-naphthalenesulfonic acids, biphenyl-4-sulfonic acid, 1,4-, 1,5-, 2,6-, 2,7-naphthalenesulfonic acid , 3-nitro-l, 5-naphtalindisulfonic acid, anthraquinone sulfonic acid-1, anthraquinone sulfonic acid-2, diphenyl-4,4'-disulfonic acid, 1,3-naphthalenedisulfonic acid and the salts of these sulphonic acids, for example the sodium salts of potassium, calcium, zinc, nickel and cobalt; sulfonamides such as benzenesulfonamide, 2-, 3- and 4-nitrobenzenesulfonamide, 2-, 3- and 4-chlorobenzenesulfonamide, 4-methoxybenzenesulfonamide, 3,3'-sulfonylbisbenzenesulfonamide, 4,4'-oxybisbenzenesulfonic acid amide, 1- and 2-naphthalenesulfonic acid. Amides of carboxylic acids and sulfonic acids are a preferred group of compounds to be occluded, especially suitable are urea and substituted ureas, such as phenylurea, dodecylurea and others as well as their polycondensates with aldehydes, especially formaldehyde; heterocyclic such co or barbituric acid, benzimidazolone, benzimidazolon-5-sulfonic acid, 2, 3-dihidroxiquinoxaline., 2,3-dihidroxiquinoxaiin-6-suifónico, carbazole, carbozo acid-3, 6-disulfonic, 2-hydroxyquinoline, 2 , 4-dihydroquinoline, caprolactam, melamine, 6-phenyl-1, 3-5-triazin-2,4-diamine, 6-methyl-1,3,5-triazine-2,4-diamine, cyanuric acid. Preferred metal complexes contain occluded surfactants, particularly surfactants which are known for example from K. Lindner, Tenside-Textilhilfsmittel-Waschrohstoffe, 2nd Edition, Volume I, Wissenschaftliche Verlagsgesellschaft mbH, Stuttgart, 1964. In this case can be anion-active compounds , non-ionic or active cation or ampholytes. Compounds anion suitable active are eg real soaps, salts of aminocarboxylic acids, salts of aminocarboxylic acids lower or higher acylated, sulfates of fatty acids, sulfates esters, fatty acid amides or primary alkyl sulfates, oxo, alkyl side, esterified sulfates or etherified poiioxicompuestos, sulfates of substituted polyglycol ethers (sulfated adducts of ethylene oxide, acylated sulfates or alkylated alkanolamines, sulfonates of fatty acids, their esters, amides or primary alkyl, secondary alkyl sulfonates, alkylsulfonates with acileno linked as ester, alkyl- or alquilfenilétersulfonatos sulfonates esters policarboxílieos acids, alquilbencenosuifonatos, alquilnaftalinasulfonatos, fatty aromatic sulfonates, alquilbcncimidazolsulfonatos, phosphates, polyphosphates, phosphonates, phosphinates, thiosulphates, dithionites, sulf inatos, persulfates. Suitable nonionic compounds are, for example: esters and ethers of polyalcohols, alkyl polyglycol ethers, acyl polyglycol ethers, aikaryl polyacryl ethers, acylated or alkylated alkanolamino polyglycol ethers. Compounds cation suitable active are eg alkylamine salts, quaternary ammonium salts, salts alquilpiridinium salts simple imidazoline quaternary, alkyldiamines or alkyldiamines, acildiaminas or acilpoliaminas, acilalcanolaminas, esters of alkanolamine salts of alkyl-OCH2 -N-pyridinium, alkyl-CO-NH-CH2-N-pyridinium salts, alkylethylene-ureas, sulfonium-compounds, phosphonium-compounds, arsenium-compounds, alkyiguanidines, aciidiguanidines. Suitable ampholytes are, for example: alkylbetaines, sulfobetaines and aminocarboxylic acids. Preference is given to using ionic surfactants, in particular the addition products of ethylene oxide of fatty alcohols, fatty amines as well as octyl- or nonylphenol. Another important group of occluded compounds are natural resins and resin acids such as, for example, abietic acid and its reaction products and salts. Such reaction products are, for example, hydrogenated, dehydrogenated and disproportionate abietic acids. These can also be dimerized, polymerized or modified by the addition of maleic acid anhydride and fumaric acid. Also important are resin acids modified in the carboxyl group, such as, for example, the methyl, hydroxyethyl, glycol, glycerin and pentaerythritol esters, as well as the nitrites of the resin acids and the amines of the resin acids as well as the dehydroabietil -alcohol. Also suitable are polymers for incorporation, preferably water-soluble polymers, for example ethylene-propylene oxide block polymers, preferably with an M p greater than or equal to 1,000, especially from 1,000 to 10,000 g / mol, polyvinyl alcohol, polyhydric acids, (meth) -acrylics, modified cellulose such as carboxymethiiceiulose, hydroxyethiyl and -propylcellulose, methyl- and ethylhydroxyethylcellulose. Also suitable for the incorporation of condensation products based on A) sulfonated aromatic hydrocarbons, B) aldehydes and / or ketones and, if appropriate, C) one or more compounds selected from the group consisting of non-branched aromatic hydrocarbons, urea and urea derivatives. The expression "based on" means that the condensation product has, if appropriate, been prepared from other reagents in addition to A, B and, if appropriate, C. The condensation products will preferably be prepared within the scope of this application, but only from A, B and, if appropriate C. As sulfonated aromatic hydrocarbons of the components A), sulfonated aromatic hydrocarbons will also be understood within the scope of this application. The preferred sulphonated hydrocarbons are: naphthalenesulfonic acids, phenolsulfonic acids, dihydroxybenzenesulfonic acids, sulfonated ditolylethers, 4,4'-dihydroxydiphenylsulfone sulfomethylated, diphenylmethanesulfonated, sulfonated biphenyl, sulphonated hydroxybiphenyl, especially 2-hydroxybiphenyl, sulfonated terphenyl or benzenesulfonic acids. Suitable aldehydes and / or ketones of components B) are especially aliphatic, cycloaliphatic as well as aromatic. Aliphatic aldehydes are preferred, with formaldehyde as well as other aliphatic aldehydes with 3 to 5 carbon atoms being particularly preferred. Suitable unsulfonated aromatic hydrocarbons of components C) are, for example, phenol, cresol, 4,4'-dihydroxydiphenylsulphone or dihydroxydiphenylmethane. Examples of urea derivatives which may be mentioned are dimethylolurea, alkylurea, melamine or guanidine. Preferred condensation products are one based on A) at least one sulfonated aromatic hydrocarbon selected from the group of naphthalenesulfonic acids, phenolsulfonic acids, dihydroxybenzenesulfonic acids, ditolyl ether sulfonates, 4,4 '-dihydroxydiphenylsulfone sulfomethylated, sulfonated diphenylmethane, sulfonated biphenyl, sulphonated hydroxybiphenyl, especially 2-hydroxybiphenium, suifonated terphenyl and benzenesulfonic acids, B) formaldehyde and optionally C) one or more compounds, selected from the group consisting of phenol, cresol, 4,4'-dihydroxydiphenylsulphone, dihydroxydiphenyl ethane, urea, dimethylurea , melamine and guanidine. The preferred condensation products are those based on 4,4'-dihydroxydiphenylsulfone, ditolylethersulfonate and formaldehyde; 4,4'-dihydroxydiphenylsulfone, phenolsulfonic acid and formaldehyde; 4, '-dihydroxydiphenylsulfone, sodium bisulfite, formaldehyde and urea; Naphthalenesulfonic acid, 4,4'-dihydroxydifeniisuifona and formaldehyde; sulfonated terphenyl and formaldehyde; and / or 2-hydroxybiphenyl and formaldehyde as well as naphthalenesulfonic acid and formaldehyde. Particularly preferably, melamine or melamine derivatives, especially those of the formula (VII), are used as incorporated compounds wherein R6 means hydrogen or alkyl having 1 to 4 carbon atoms, which is optionally substituted by OH groups, very particularly preferably wherein R6 means hydrogen. The amount of substance which can be incorporated into the crystal lattice of the metal compounds is, as a rule, from 5% to 200% by weight, in particular from 5 to 120% by weight, based on the amount of the host compound. In particular, 10 to 100% by weight will be incorporated. In this case it is about quantities of substance that can not be eliminated by washing with suitable solvents and that are deduced by the elemental analysis. Of course, an amount greater or less than the indicated amount of substance can be added, and an excess can be removed if necessary by washing. Amounts of 10 to 150% by weight are preferred. The pH value of an aqueous suspension formed by the pigment preparation according to the invention and a 20 times higher amount of water is preferably greater than 6.5 to 11, especially 7 to 9. The preparations according to the invention may contain other additives . Preferred additives may be organic or inorganic bases. As bases can be mentioned: alkali hydroxides such as for example NaOH, KOH or organic amines, such as alkylamines, especially alkanolamines or alkylalcanolamines. Mention may be made, as particularly preferred, of methylamine, dimethylamine, trimethylamine, ethanolamine, n-propanolamine, n-butanolamine, diethanolamine, triethanolamine, methylethanolamine or dimethylethanolamine. Other additives are, for example, dispersing agents, carboxylic acid amides and sulphonic acids as well as customary pigment preparation additives. Dispersant agents in the scope of this application will be understood as a substance stabilizing the pigment particles in their finely particulate form in aqueous media. By finely particulate, a fineness distribution of 0.001 to 5 μm, in particular 0.005 to 1 μm, particularly preferably 0.005 to 0.5 μm, is preferably understood. Suitable dispersing agents are, for example, anionic, cationic, amphoteric or nonionic. Suitable anionic dispersing agents are, in particular, condensation products of aromatic sulfonic acids with formaldehyde, such as condensation products of formaldehyde and of alkylnaphthalenesulfonic or formaldehyde acids, naphthalenesulfonic acids and / or benzenesulfonic acids, phenol condensation products, given substituted, with formaldehyde and sodium bisulfite. In addition, dispersing agents from the group of sulfosuccinic acid esters as well as alkylbenzene sulfonates are suitable. In addition, alcohols of sulfated fatty acids, alkoxylates or their salts. Alcohols of alkoxylated fatty acids are understood especially as those alcohols of fatty acids having 6 to 22 carbon atoms endowed with 5 to 120, preferably 5 to 60, especially 5 to 30 ethylene oxide, which are saturated or unsaturated, especially; ohol. especially preferred is an alkoxylated stearylalcohol with 8 to 10 ethylene oxide units. The alkoxylated sulphated fatty acid alcohols are preferably present as salts, in particular as alkali or amine salts, preferably as the diethylamine salt. In addition, lignin sulfonates, for example those obtained by the sulphite or Kraft process, are especially suitable. Preferably they are products that are partly hydrolyzed, oxidized, propoxylated, sulphonated, sulfomethylated or desulphonated or that are fractionated according to known processes, for example according to molecular weight or according to the degree of sulfonation. Mixtures consisting of lignin sulphonates to sulfite and sulfur lignin suifonates and kraft are also perfectly effective. Especially suitable are lignin sulfonates with an average molecular weight of between 1,000 and 1,000,000, an active lignin sulfate content of at least 80% and preferably with a low content of polyvalent cations. The degree of sulfonation can vary within wide limits. Suitable ionic dispersing agents are, for example: reaction products of alkylene oxides with alkylating compounds, such as, for example, fatty alcohols, fatty amines, fatty acids, phenols, alkylphenols, arylalkylphenols, such as styrene-phenol condensates, amides of carboxylic acids and resin acids. This is, for example, ethylene oxide adducts of the class of reaction products of ethylene oxide with: al) saturated and / or unsaturated fatty alcohols with 6 to 22 carbon atoms or bl) alkylphenols with 4 to 12 carbon atoms in the alkyl moiety or cl) amines saturated and / or unsaturated fats with 14 to 20 carbon atoms or di) saturated or unsaturated fatty acids with 14 to 20 carbon atoms or the) hydrogenated and / or unhydrogenated resin acids . Particularly suitable alkylagen oxide adducts are the alkylatable compounds mentioned under (a) to), with 5 to 120, in particular 5 to 100, in particular 5 to 60, particularly preferably 5 to 30 moles of ethylene. Suitable dispersing agents are also esters, as defined by DE-A-19 712 486 prior to the priority or by DE-A 19 535 246, of the alkoxylation products of the formula (X), corresponding to the formula (I) as well as, if appropriate, in a mixture with the compounds, on which they are based, of the formula (X). The alkoxylation product of a styrene-phenol condensate of the formula (X) is defined as follows: wherein R15 means hydrogen or alkyl having 1 to 4 carbon atoms, R16 means hydrogen or CH3, R17 means hydrogen or alkyl having 4 carbon atoms, alkoxy with 4 carbon atoms, alkoxycarbonyl having 1 to 4 atoms carbon or phenyl, means a number from 1 to 4, n means a number from 6 to 120, R18 is the same or different for each of the units with the index n and means hydrogen, CH3 or phenyl, where in the case of concomitant presence of CH3 in the various groups - (-CH2CH (Rld) -0-), e ,. O up to 60% of the total value of n, R18 signifies CH3 and in 100 to 40% of the total value n, R18 signifies hydrogen and where, in the case of the concomitant presence of phenyl in the various groups - (- CH2-CH (R18) -0-), in an O up to 40% of the total value n, R18 means phenyl and in 100 to 60% of the total value of n, R18 means hydrogen. The esters of the alkoxylation products (X) correspond to the formula (XI), wherein R15 '', R ± 6 ', R17', R18 ', m' and n 'take the meanings of R15, R16, R17, R18, or m or n, however independently of them, x means the groups - S03, -S02, -P03 or -CO- (R19) -C00, Kat means a cation of the group consisting of H, Li, Na, K, NH4 or H0-CH2CH2-NH3, the cations being present in the case of X = -P03 and R ± 9 means a divalent aliphatic or aromatic radical, preferably it means alkyl with 1 to 4 carbon atoms, especially ethylene, straight monounsaturated with 2 to 4 carbon atoms, especially acetylene or optionally substituted phenylene, especially ortho-phenylene , with the possible substituents preferably being alkyl having 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms, alkoxycarbonyl having 1 to 4 carbon atoms or phenyl. Special individual compounds of the formula (XI) are known, for example, from DE-A-19 712 486 and mixtures of formulas (X) and (XI) are known, for example, from DE-A-19 535 256, which are respectively an integral part of this. request. As a preferred dispersing agent, the compound of the formula (XI) will be used. Preferably a compound of the formula (XI), wherein X means a radical of the formula -CO- (R19) -C00- and R19 has the meaning indicated above. Also preferred is the use as dispersing agent of a compound of the formula (XI) together with a compound of the formula (X). Preferably, the dispersing agent contains in this case from 5 to 99% by weight of the compound (XI) and from 1 to 95% by weight of the compound (X). Suitable polymer dispersing agents are, for example, water-soluble types as well as emulsifiable substances in water, for example homo-, and also copolymers, such as statistical or block copolymers. Particularly preferred especially preferred dispersing agents are polymeric dispersing agents, such as, for example, block copolymers AB, BAB and ABC. In block copolymers AB or BAB, segment A is a hydrophobic homopolymer or copolymer, which ensures a binding with the pigment and block B is a hydrophilic homopolymer or copolymer or a salt thereof and ensures the dispersion of the pigment in aqueous medium. Such polymeric dispersing agents and their synthesis are known, for example, from EP-A 518 225 as well as from EP-A 556 649. The dispersing agent is preferably used in an amount of 0.1 to 100% in this case, especially in a 0.5 to 60% by weight, based on the pigment used in the pigment preparation. Suitable amines of carboxylic acids and sulfonic acids are, for example, urea and substituted ureas, such as phenylurea, dodecylurea and others; heterocyclics such as barbituric acid, benzimidazolone, benzimidazole-5-sulphonic acid, 2,3-dihydroxyquinolaline, 2,3-dihydroxy-quinoline-6-sulphonic acid, carbazole, 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. The preparation according to the invention preferably contains from 80 to 100% by weight, especially from 90 to 99. 9% by weight of the above pigment and from 0 to 20% by weight, especially from 0 * 1 to 10% by weight of an inorganic or organic base, respectively referred to the sum of these two components. In a particularly preferred embodiment, the pigment preparation according to the invention contains from 30 to 99.9% by weight of at least one of the pigments mentioned above, from 0.1 to 20% by weight of an inorganic or organic base and 99% by weight. from O up to 50% by weight of a dispersing agent, referred respectively to the preparation. Obviously, the preparation may also contain other additives. Thus, for example, additives which reduce the viscosity of an aqueous suspension and which increase the solids content, such as the amines of the carboxylic acids and sulfonic acids mentioned above, in an amount of up to 10% by weight can be added for example. , referred to the preparation. Particularly preferably, the preparation according to the invention contains more than 90, in particular more than 95, preferably more than 97% by weight of pigment, base and optionally dispersing agent. The invention also relates to a process for obtaining the preparation of pigments according to the invention, characterized in that a) a metal complex of an azo compound, which corresponds in the form of its tautomeric structures of the formula (I), and which contains incorporated at least one compound, whose suspension with a 20 times greater amount of water has a pH value of < 6.5, preferably from 2 to 5, b) is adjusted to a pH value of > 6.5, - by addition of an inorganic and / or organic base, having a suspension of a), - based on the dry mass of a), with a quantity 20 times greater than water and, if necessary, after the addition of others additives c) dry. In a special embodiment of the process, the pigment is used as starting material, which is obtained after complex conversion of the azo compound of the formula (I) with the metal salt in the acid range, preferably at a pH of 2 to 6.0, isolation and subsequent washing with water or water-acid mixtures, such as dilute HCl. Preferably, the following bases are used for the adjustment of the pH value: NH3, alkali hydroxides, such as NaOH, KOH and LiOH and organic amines such as alkylamines, especially alkanolamines or alkylalcanolamines. Particularly preferred are methylamine, dimethylamine, triethylamine, ethanolamine, diethanolamine, triethanolamine, methylethanolamine, di-ethylethanolamine and also NH 3. Preferably, the base will be used in an amount such that a pH value of a suspension dc a), based on the dry mass a), is adjusted to 20 times more water, greater than 6.5 to 14. If used a non-volatile base during subsequent drying, such as alkali hydroxide or organic amine, the pH value will preferably be adjusted to a value greater than 6.5 to 11, particularly preferably 7 to 9, especially 7 to 8.5. If, on the other hand, a volatile base is used during the subsequent drying, preferably ammonia, which can be used with aqueous ammonia solution, it will then be preferable to adjust a pH value from 7 to 14. It is also possible to use volatile and non-volatile bases together . In this case, the amount of the non-volatile base will be chosen during drying in such a way that a pH value of preferably 7 to 9 can be adjusted with the same. The amount of the non-volatile base during drying, preferably NH 3, is it will preferably be chosen in such a way that it is possible to adjust therewith a pH value up to pH = 14. The aqueous suspension preferably obtained after the addition of the base, if appropriate, of other additives, preferably has a solids content from 10 to 40% by weight, especially from 15 to 30% by weight. As long as other additives, additives are to be used, they will be added preferably before drying. As such, for example, the aforementioned components of the preparation according to the invention come into consideration: -3? Suitable dryers for drying c) are basically all, for example, vacuum dryers, dryers with air circulation, especially spray drying, especially drying machines for one and two products as well as drying machines with rotating discs. Furthermore, fluidized-bed drying processes are suitable. As dryers with nozzles for a single product, for example, those with a percussion chamber nozzle are suitable. In a very particularly preferred embodiment of the process according to the invention, ammonia, if appropriate together with other non-volatile bases, will be used as a base during the drying process and the aqueous slurry obtained in this way is spray-dried, preferably with a solids content. from 5 to 40%. This embodiment of the process according to the invention leads to particularly advantageous granules, which are characterized by a very good dispersion capacity, color intensity and gloss in the substrate. They are also strewn and extremely poor in dust. The inclusion compounds, the intercalation compounds and the solid solutions of the metal compounds are known per se from the literature. These are described in the same way as their manufacture, for example, in EP 0 074 515 and in EP 0 073 463. The products, which are obtained according to the production processes described therein, are however made up of hard-grain shapes and difficult to disperse, which makes its use as pigments very difficult. The preparation of these compounds, as described for example in EP 0 073 464, is carried out in such a way that, after the synthesis of the azo-compound, the complex is formed with a metal salt and then, with or without intermediate isolation. of the metal complex, the reaction with the compound to be intercalated is verified. In the case of the technically interesting metal complexes, which have at least one other compound incorporated, of the di- and trivalent metals, especially the economically and industrially important intercalation compound of the azobarbituric acid-nickel complex, the complex formation and intercalation as well as subsequent isolation in the acidic pH range. During the drying of the products produced in this way, however, irrespective of the drying conditions, they are in most cases obtained with very hard and hardly dispersible pigments, which often do not have the desired color intensity either. The problem of the hardness of the grain of dispersibility occurs especially also in the case of the industrially interesting intercalation compounds of the azobarbituric acid-nickel complex and in this case in a very particular amount in the case of the melamine intercalation compound . which has considerable industrial as well as economic significance. It is known to improve the grain hardness, the dispersibility and the color intensity of the pigments by various methods. For example, such methods are known from DE-A-2 214 700, DE-A-2 064 093 and DE-AL 753 357. All of these methods, however, are very expensive and often lead to losses in space efficiency. weather. The use of some of these methods in the intercalation compounds of the metal complexes of the azo compounds of the formula (I) fail partly because these pigments are not stable under conditions of the final treatment, as in the case of pasting. from mineral acids. In a completely surprising way it was found that the pigment preparations according to the invention are of a considerable grain softness and that they can be dispersed much better. Furthermore, the substrates pigmented therewith have a comparatively greater color intensity as well as a higher brightness.

Preferred pigment preparations are also those which have in an alkyl resin / melanin resin system according to DIN 53 238, part 31, and after a dispersion time of 2 hours, a color intensity greater than at least 3, preferably greater by 10, more preferably 20% higher than the pigment whose suspension with a 20 times greater amount of water gives a pH of < 6.5, after a corresponding dispersion for 2.5 or 2 hours. The solid pigment preparations are suitable in an excellent manner for all the application purposes of the pigments. They are suitable for the pigmenting of all kinds of paints for the manufacture of printing inks, tempera paints or plastic paints, for the mass coloring of synthetic, - isynthetic, - or macromolecular natural products, - such as for example polyvinyl chloride, polystyrene, polyamide, polyethylene or polypropylene. Natural, regenerated or synthetic fibers, such as, for example, cellulose, polyester, polycarbonate, polyacrylonitrile or polyamide fibers, as well as for the printing of textiles and paper, can also be used for spinning dyeing. pigments can be manufactured a finely divided, stable, aqueous pigment, suitable for dispersion paints for brush application, for coloring paper, for stamping with textile pigment, for printing laminates or for spinning viscose , by grinding or kneading in the presence of nonionic, anionic or cationic surfactants.

Examples Example 1 (comparative example analogous to EP-A-73 463). obtaining the melamine intercalation compound of the azobarbituric acid-nickel complex. 0.1 moles of paste moistened with water of the Na salt of azobarbituric acid in 500 ml of distilled water was agitated homogeneously with a laboratory stirrer and heated to 95 ° C. 0.105 mol of a 24% aqueous solution of nickel chloride • 6H20 were added dropwise. It was stirred for 30 minutes to obtain the coating. 0.2 moles of melamine are introduced and stirred until the intercalation reaction is complete. It is adjusted to pH = 5 with sodium hydroxide solution and the product is filtered off and washed until electrolyte is absent. It results in a paste moistened with water with a dry matter content of 43%.

Example 2 * The paste, moistened with water, prepared according to example 1, is dried at 8 ° C in the vacuum drying cabinet and milled for approximately 2 minutes in a conventional laboratory mill. A pH value of < 6 in a suspension with a 20 times greater amount of water.

EXAMPLE 3 186 g of the paste moistened with water of a melamine intercalation compound, prepared according to example i, of the barbituric acid-nickel complex, are stirred homogeneously with 814 ml of distilled water, with a stirrer dc. The laboratory is heated to 80 ° C and adjusted to pH 7.0 to 7.5 with approximately 1.3 g of N'N-dimethylethanolamine and stirred for 2 hours at this pH value and at 80 ° C. It is then isolated on a nuke by suction, dried at 80 ° C in the vacuum drying cabinet and milled in a conventional laboratory mill for about 2 minutes. A pH value of > 7 in a suspension with a 20 times greater amount of water. The pigment, obLended in this way, is evaluated in a white coat of paint. For this, the pigment is used according to the indications given in DIN 53 238, part 31, in a resin system with a resin / melamine content. After a dispersion time of 1 hour, - the paint coat of this pigment shows a color intensity 3.7% greater than that of the paint coat of the pigment obtained after 2.5 hours of dispersion under the conditions indicated above according to the example 2 Example 4. They are shaken, homogeneously, 186 g of water-moistened paste, of a melamine intercalation compound, - prepared according to example 1, - of the complex of azobarbituric acid-nickel, in 814 ml of distilled water with a laboratory stirrer, heat at 80 ° C and adjust to pH 8.5 with approximately 4.9 g of ethanoiamine is stirred for 2 hours at this pH value and at 80 ° C. The pigment is then isolated on a nutcha by suction, dried at 80 ° C in the vacuum drying cabinet and milled in a conventional laboratory mill for about 2 minutes. A pH value of <is adjusted7 in a suspension with a 20 times greater amount of water. The pigment, obtained in this way, was dispersed in an aqueous binder system. In comparison with the pigment of example 2, the paint coat of the pigment of this example has a color intensity that is 12.5% higher.

EXAMPLE 5 - 186 g of paste, hydrated with water, of a, according to example 1, in 814 ml of distilled water with a laboratory stirrer, are heated to 80 ° C. and are stirred homogeneously. adjust to pH 8.5 with approximately 1.8 g of sodium hydroxide solution at 40% by weight and stir for 2 hours at this pH value and at 80 ° C. The pigment is then isolated in a nutcha by suction, dried at 80 ° C in the vacuum drying cabinet and milled in a conventional laboratory mill for about 5 minutes. A pH value of > 7 in a suspension with an amount 20 \ eces greater than water. The pigment, obtained in this way, was dispersed in an aqueous binder system. Compared to the pigment of Example 2, the pigment paint hand of this example has a color intensity that is 12.5% higher.

EXAMPLE 6 18.6 kg of paste, moistened with water, of a melamine intercalation compound prepared according to Example 1, of the complex of azobarbituric acid-nickel with a dry matter content of 39% are stirred homogeneously. which corresponds to 8.0 kg of dry product, in 20.2 kg of distilled water and 6.4 kg of aqueous ammonia solution with 25% by weight of NH3 at room temperature under a rapid stirrer for 6 hours. It is then spray-dried in a nozzle dryer for two products with an inlet temperature of 180 ° C and an outlet temperature of 80 ° C with a residual humidity of 2%. A yellow-brown powder is obtained. A 5% suspension in water of this pigment shows a pH value of 7.5. If the dispersion is carried out as described in Example 3, however - the painting hands are prepared after 10, 20, 30, 60 and 150 minutes of dispersion and if the pigment used is dispersed according to the same scheme. for the spray drying, according to example 2, the following color intensities are obtained: Table: Relative color intensity of the pigment.

From example 2 From example 3. (min) 10 87 o. "o 20 97% 30 104 o o 60 .00% 112 150 128% A l In this comparison, the dispersion of 60 minutes of the pigment according to example 2 was taken as a standard. With higher color intensities, the dispersion times required in the case of the spray-dried product from the ammonia suspension are significantly lower than in the case of the starting product isolated and dried in a conventional manner (according to example 2).

Example 7. If you proceed as described in the example 6, spray drying is however carried out in a dryer with nozzles for a single product with an inlet temperature of 180 ° C and an outlet temperature of 80 ° C with a residual humidity of approximately 2%, it obtains a granulate practically free of dust, spread, brown. A suspension of 5% of this granulate in distilled water shows a pH value of approximately 7.5. If it is dispersed as described in example 6, the following relative color intensities are obtained compared to the pigment of example 2. 4? Table: relative color intensities of the pigment. t From example 2 from example 7 (min) 10 87% 20 94% 30 100% 60 100% 108% 150 132% Example 8. 18.6 kg of paste, moistened with water, according to example 1, are agitated homogeneously with 15 kg of distilled water, 6.4 kg of ammonia solution with 25% by weight and 0.12 kg of e-caprolactam at room temperature, under a rapid stirrer for 6 hours. ? then it is dried as in example 7. A 5% suspension of this granulate in distilled water shows a pH value of approximately 7.0. If the dispersion is made as described in example 4, however the paint coat is prepared after 10, 20, 30, 60 and 150 minutes of dispersion time and the pigment used is dispersed in the same way for the spray drying according to example 2, the following color intensities are obtained.

Table: Relative color intensities of the pigment. t From example 2 From example (min) 10 116 ¡20 117 - '30 60 i n n 9- 117 150 118 Example 9. 18.6 kg of paste moistened with water of example 1 is stirred homogeneously with 12.9 kg of distilled water, 6.4 kg of ammonia solution with 25% by weight, 0.12 kg of e-caprolactam and 0.13 kg of ethanolamine at room temperature under a rapid stirrer for 6 hours. It is then dried in a dryer with nozzles for a single component with an interval temperature of 130 ° C and an outlet temperature of 60 ° C with a residual humidity of approximately 2%. In this way, a dust-free, brown, dust-free granulate is obtained. A suspension of 5% of this granulate in distilled water shows a pH value of about 8.8. If dispersed as described in example A A 8 and the dispersion curve obtained in this way is compared with that of the pigment of Example 2, the following values are obtained for the color intensity.

Table: Relative color intensities of the pigment. t From example 2 from example 9 (min) 10 118% 20 118% 30 118% 60 100 119% 150 119%, Example 10. 18.6 kg of paste, wetted with water, of Example 1, are stirred homogeneously, with 18.8 kg of distilled water, 1.6 kg of ammonia solution with 25% by weight, 0.12 kg of e-caprolactam and 0.13 kg of diethanolamine at room temperature under a rapid stirrer for 6 hours. It is then dried in a dryer with nozzles for a single component with an inlet temperature of 180 ° C and an outlet temperature of 80 ° C with a residual humidity of approximately 2%. In this way, a dust-free, brown, dust-free granulate is obtained.

A 5% suspension of this granulate in distilled water shows a pH value of about 8.4. If it is dispersed as described in Example 6 and the color intensities thus obtained are compared with those of the pigment of Example 2, the values are obtained for the following color intensities.

Table: Relative color intensities of the pigment. t From Example 2 From Example 10 (mm) 10? o; 20"6 30 129% 60 100% 133 150 140 Example 11. 18.6 Kg of paste, moistened with water, in Example 1, are stirred homogeneously with 18.8 kg of distilled water, 1.6 Kg of ammonia solution with 25% by weight, 0.12 Kg of e-caprolactam and 0.13 Kg of ethanolamine at room temperature under a rapid stirrer for 6 hours. It is then dried in a dryer with nozzles for a single component with an inlet temperature of 130 ° C and an outlet temperature of 60 ° C with a residual humidity of approximately 2%. In this way, a granulate which is practically free of dust, brown, is obtained. A 5% suspension of this granulate in distilled water shows a pH value of about 8.8. If it is dispersed as described in Example 6 and the color intensities obtained in this way are compared with those of the pigment of Example 2, the values are obtained for the following color intensities.

Table: Relative color intensities of the pigment. t From Example 2 From Example 11 (min; 10 110% 20 120% 30 127% 60 100% 137% 150 138%.

Example 12. 18.6 kg of paste, moistened with water, of example 1, with 12.9 kg of distilled water, 6.4 kg of ammonia solution with 25% by weight, 0.12 kg of e-caprolactam, are stirred homogeneously. 0.10 Kg of dimctilctanolamine at room temperature under a rapid stirrer for 6 hours. It is then dried with a nozzle dryer for a single component with an inlet temperature of 180 ° C and an outlet temperature of 80 ° C with a residual humidity of approximately 2%. In this way, a dust-free, brown, dust-free granulate is obtained. A 5% suspension of this granulate in distilled water shows a pH value of about 8.3. Dispersing as described in Example 8 and comparing the color intensities obtained in this way with those of the pigment of Example 2, the values are obtained for the following color intensities.

Table: Relative color intensities of the pigment. t From Example 2 From example 12 (min) 10 111% 20 112% 30 112% 60 100 113% 150 113%.

Example 13. 18.6 kg of paste, moistened with water, of example 1, are stirred homogeneously with 16.0 kg of distilled water, 6.4 kg of ammonia solution with 25% by weight and 0.10 kg of dimethylethanolamine at room temperature. environment under a rapid stirrer for 6 hours. It is then dried with a nozzle dryer for a single component with an inlet temperature of 180 ° C and an outlet temperature of 80 ° C with a residual humidity of approximately 2%. In this way, a dust-free, brown, dust-free granulate is obtained. A 5% suspension of this granulate in distilled water shows a pH value of about 8.3. Dispersing as described in Example 6 and comparing the color intensities obtained in this way with those of the pigment of Example 2, the values are obtained for the following color intensities.

Table: Relative color intensities t From Example 2 From example 13 (min) 10 101% 20 116% 30 128% 60 100% 136% 150 138% Application example. The good suitability of the pigment preparations according to the invention of Examples 3 to 13 for the paper dyeing was tested by means of the following procedure: to} obtaining the raw material for the panel: A product mixture consisting of 70% by weight of bleached eucalyptus pulp 30% by weight of bleached sulphate pulp with a product density was milled in a Dutch laboratory stack. from 3% to 25 ° SR in water from the pipe. b) Leaf formation and coloring. Diluted in a dyeing flask (100 ml) was diluted 2.5 g of the fibrous product previously ground (solid) under continuous stirring in 600 ml of water from the pipe and 30% by weight of titanium dioxide pigment was added (Bayertitan ® R-PL-1, Bayer AG) referred to the solid product in the form of a 10% by weight aqueous dispersion. After 10 minutes of stirring, the amount necessary for the adjustment of a normalized standard density 1/25 (DIN 54000) of the corresponding pigment preparation (below) was added and, after a stirring time of 5 minutes, the mixture was added. minutes, 5% by weight of Nadavip DHF, Bayer AG, was added, based on the fibrous product. If necessary, the pH value was adjusted to 6.5-7.0 after another 10 minutes. The formation of the sheet was carried out in an installation for the formation of leaves (system RapidKbthen®) and then the sheet was dried at 95 ° C approximately in an approximate time of 8 minutes in the drying cabinet. The determination of the necessary amount of the corresponding pigment preparation for a standardized intensity of 1/25 was carried out by means of the procedure described above by measuring the difference in color intensity in a Macbeth type measuring device. Color Eye 7000 versus a corresponding coloristic textile sample (standard intensity 1/25) whose color intensity was taken as 100%. After determination of the amount required for the standardized intensity of 1/25 of the corresponding pigment preparation, an analogous stepwise solution was prepared in a laboratory paper machine, upwards, of the aforementioned recipes. These colored raw papers were tested in relation to light fastness (DIN 54004), solidity to styrene and plasticizers. (dibutylphthalate). The evaluation was verified after 24 hours of immersion of colored paper strips in relation to the bleeding and the eventual coloring of the solution. In the same way an acid fastness test (10% sulfuric acid) and the alkali fastness (10% sodium carbonate solution) were carried out by the action of one drop of the corresponding solution for 1 minute on the colored paper, elimination of the excess by means of filter paper and evaluation of the papers in the wet state. The use of the pigment preparations according to the invention provided strong dyeings, bright with excellent fastnes The pigment preparations according to the invention of Examples 3 to 13 were also particularly suitable for coloring so-called decorative laminated papers, such as those used for the manufacture of decorative laminate materials. By way of example, raw papers, which were manufactured as described above, were respectively coated with a 50% aqueous solution of elamina formaldehyde on a resin ratio of 56 & amp;; approximately, the precondensation was carried out according to the continuous passage process through a 5? dried for 2.5 minutes at 120 ° C to a residual moisture of about 4-6% by weight and pressed for 5 minutes at various temperatures from 150 to 180 ° C and at a pressure of 10 N / mm2 in a high pressure press to give a laminate. The constitution of the laminate was formed by: 1 press plate, chromed, 2 lightly pigmented backing papers (embedded with melamine resin) 2 soda kraft papers (embedded in phenolic resin) 1 pigmented decorative paper according to the invention (according to examples 3-13) 1 press plate, chrome-plated. The pigmented papers according to the invention (decorative papers) could be pressed perfectly in the indicated temperature range and provided highly glossy and intense-colored laminates. A migration of the color shades during the pressing at 150 ° C and 180 ° C could not be detected. It is noted that in relation to this date, the best method known to 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, the content of the following is claimed as property.

Claims (10)

1. Preparations of solid pigments containing as pigment at least one metal complex of an azo compound, which corresponds in the form of its tautomeric structures to the formula (I) wherein the rings designated with X and Y can carry, independently of each other, one or two substituents of the series consisting of = 0, = S, = NR7, -NR6H7, -0R6, -SR6, -C00R6, -CN , -CONR6R7, -S02R8, -N-CN, Re alkyl, cycloaikyl, aryl and aralkyl being three the sum of the endocyclic and exocyclic double bonds for each of the X and Y rings, R6 means hydrogen, alkyl, cycloalkyl, aryl or aralkyl and 5 A R7 means hydrogen, -cyano, -alkyl, -cycloalkyl, -aryl, aralkyl or acyl and R8 means alkyl, cycloalkyl, aryl or aralkyl, Ri / R2 / R3 and independently from each other, meaning hydrogen, alkyl, cycloalkyl, aryl or aralkyl and further, as indicated in formula (I) by discontinuous trace lines, may form rings with 5 or 6 members, on which other rings may be condensed, Rs means -OH, -NR6R, alkyl, cycloalkyl, aryl or aralkyl, the substituents listed for Ri to R8, which contain CH bonds and m, n, o, p may be substituted, or, in the case where double bonds of the nitrogen atom of the ring are split, as indicated by dotted lines in formula (I), they can also mean zero, and which contains at least one other compound, characterized by a suspension of solid pigment preparations with a 20-fold increase in water content. a has a pH value of > 6.5.

2. Pigment preparations according to claim 1, characterized in that in the compound of the formula (I), the rings designated by X mean a ring of the formulas in which L and M, independently of each other, mean = 0, = S or = NR6, Li means hydrogen, -0R6, -SR6, -NR6R7, -C00R6, -C0N6R7, -CN, alkyl, cycloalkyl, aryl or aralkyl and Mi means -0R6, -SR6, -NR6R7, -C00R6, -CONR6R7, -CN, -S02R8, -N-CN, alkyl, cycloalkyl, aryl or aralkyl, The substituents Mi and R2 or Mi and R2 can form a ring with 5 or 6 members, and Ri, R2 and R5 have the meanings indicated above.

3. Preparation of pigments according to claim 1, characterized in that the azo compound of the formula (1) corresponds in the form of its free acid to the formula (II) or (II) or to one of its tautomeric forms, in which R'5 means -OH or -NH2, R 'i / R "i / R'2 and R" 2 respectively mean hydrogen and M' i and M "?, independently of each other, mean hydrogen, -OH, - NK2, -NHCN, arylamino or acylamino.

4. Pigment preparations according to claim 1, characterized in that the azo compound of the formula (I) corresponds to the formula (V) or to a tautomeric form thereof

5. Preparation of pigments according to claim 1, characterized in that the metal compound of the azo-compound of the formula (I), which contains at least one other compound, corresponds to the mono-, di-, tri- and tct.raanions. of the azo-compounds of the formula (I) with the liquid metals of the group formed by Li, Cs, Mg, Cd, Co, Al, Cr, Sn, Pb, Na, K, Ca, Sr, Ba, Zn, Fe , Ni, Cu and Mn.

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

7. Pigment preparations according to claim 1, characterized in that the metal complex contains an organic cyclic or acyclic compound, especially melamine.

8. Pigment preparations according to claim 1, characterized in that the aqueous suspension has a pH value of 7 to 9.

9. Method for obtaining the pigment preparation according to claim 1, characterized in that a) a metal complex of an azo-compound, corresponding in the form of its tautomeric structures to the formula (I) and containing at least one other compound, whose suspension with a 20 times greater amount of water has a pH value of <; 6.5, preferably from 2 to 5, b) is adjusted to a pH value of > 6.5 by addition of an inorganic and / or organic base, having a suspension of a), based on the dry mass of a), with a quantity 20 times greater than water and, if necessary, after addition of other additives, c) it dries

10. Use of the pigment preparations according to claim 1, for obtaining RQ inks printing, - tempera paints or plastic paints, - for the mass coloring of synthetic, semi-synthetic or natural, macromolecular products, especially polyvinyl chloride, polystyrene, polyamide, polyethylene or polypropylene, as well as for the spinning dyeing of natural, regenerated synthetic fibers , such as for example cellulose, polyester, polycarbonate, polyacrylonitrile or polyamide fibers as well as for textile and paper printing. SUMMARY OF THE INVENTION Solid Pig Preparations < U6 contain as a pigment at least one metal complex of an azo compound, which corresponds in the form of its tautomeric structures to the formula (I) wherein the rings designated with X and Y can carry, independently of each other, one or two substituents of the series consisting of = 0, = S, = NR7, -NR6H7, respectively the alkyl, cycloalkyl, aryl and aralkyl being three the sum of the endocyclic and exocyclic double bonds for each of the X and Y rings, R6 means hydrogen, alkyl, cycloalicycium, aryl or arachidyl. or y -R-, «i rrp-i -F-i -a híHr? onr .. ríann, alOUÜO.- CÍCl? 5lGUÍl? - aryl, aralkyl or acyl and R8 means alkyl, cycloalkyl, aryl or aralkyl, Ri / R2 R3 and independently from each other, meaning hydrogen, alkyl, cycloalkyl, aplo or aralkyl and of discontinuous trace lines, can form rings with 5 or 6 members, on which other rings can be condensed, R5 means -OH, -NRgR, alkyl, cycloalkyl, aryl or aralkyl, the substituents mentioned can be substituted for their part for Ri up to R8, which contain in ± aces CH and m, n, o, p mean 1 or, in the case of ifn i 5 ring, as indicated by dotted lines in formula (I), may mean also zero, and containing at least one other compound, characterized in that a suspension of the sc-iass pigment preparations with a 20-fold greater amount of water has a rH value of ^ 6.5. ? R