MXPA99009294A - Novel metal complex pigments - Google Patents

Abstract

La presente invención se refiere a complejos metálicos de un compuesto azo el cual se conforma a la fórmula (I) o una de sus estructuras tautoméricas (Ver Fórmula) en donde:R y R'son independientemente OH, NH2, NH-CN, acilamino o arilamino, R1 y R1'son independientemente -OH o -NH2, y los cuales contienen al menos un compuesto huésped, caracterizado porque los complejos metálicos corresponden a los mono-, di-, tri-, y tetraaniones de los compuestos azo de la fórmula (I) con los metales seleccionados del grupo que consiste de Ca, Zn, Cu, Fe, Co, Sr, Ba, Cr, Sn, Al, Mg, Cd, Pb y La.

Description

NEW METALLIC COMPLEX PIGMENTS Field of the Invention This invention relates to new metallic complex pigments, to processes for producing them and to their use.

Background of the Invention EP-A-73-63 discloses colorant-valuable pigments. However, these still have disadvantages of the application. In particular, strong photoresist red pigments are not described there. Accordingly, it is an object of the present invention to provide new pigments which are free from the disadvantages described above. The invention accordingly provides metal complexes of an azo compound which conforms to formula (I) or one of its tautomeric structures Ref.031462 where R and R 'are independently OH, NH2, NH-CN, arylamino or acylamino, R1 and R1 'are independently -OH or -NH2, and which contain at least one host compound, characterized in that the metal complexes correspond to the mono-, di-, tri- and tetraanions of the azo compounds of the formula (I) with the metals selected from the group consisting of Ca, Zn, Cu, Fe, Co, Sr, Ba , Cr, Sn, Al, Mg, Cd, Pb and La. The aryl substituents in the formula (I) are preferably phenyl or naphthyl, which may each be substituted for example by halogen such as F, Cl, Br, -OH, alkyl with Ci-Cß, alkoxy with C? -C6 , -NH2, -N02 and -CN.

The acyl substituents in the formula (I) are preferably (Ci-Ce-alkyl) -carbonyl, phenylcarbonyl, Ci-Ce-alkylsulfonyl, phenylsulfonyl, carbamoyl optionally Ci-Cβ-alkyl-, phenyl- and naphthyl-substituted, sulfamoyl Ci -C.sub.-alkyl-, phenyl- and naphthyl-substituted optionally or Ci-Ce-alkyl-, phenyl- or naphthyl-substituted guanyl, wherein said alkyl radicals can be substituted for example by halogen, such as Cl, Br, F , -OH, -CN, -NH2 or alkoxy with Ci-Cß and the mentioned phenyl and naphthyl radicals can be substituted for example by halogen such as F, Cl, Br, -OH, alkyl with C? -C6, alkoxy with C? ? -C6, -NH2, -N02 and -CN. The term "metal complexes" will also be understood herein to mean metal salts. 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 their tautomeric structures of the formula (II) where R and R 'are independently selected from the group consisting of OH and NHCN, and include at least one other compound. Particular preference is given here to organic metal complexes of those azo compounds of the formula (II) which, in the form of their free acid, correspond to one of the tautomeric structures of the formulas (lia a líe); Particularly preferably, the compounds of the formula (I) are the azo metal complexes 1: 1 which conform to the formula (Ia) or one of its tautomeric forms where It corresponds to one of the metal centers mentioned above, R and R 'are each as defined above, and R1 and R1 'are independently = 0 or -NH.

In general, the metal complex compound 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 complex compounds are metal compounds which form a crystal lattice which consists of essentially flat layers. The metal complexes that host other host compounds may be present in the form of inclusion compounds, intercalation compounds and also as solid solutions. Useful metal complexes also include metal complexes in which a compound containing a metal, for example, u_. metal complex or salt, is incorporated into the crystalline network of the metal complex. In this case, in the formula (I), a portion of the metal can be replaced by other metal ions, or the additional metal ions can be introduced in a more or less pronounced interaction with the metal complex. 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, S03H, halogen , N02, CN, -S02-alkyl, -S02-aryl, -O-alkyl, -O-aryl, > O-acyl The aryl substituents are preferably phenyl or naphthyl, which can each be substituted, for example, by halogen, such as F, Cl, Br, -OH, alkyl with C? -C6, alkoxy with C? -C6, -NH2, -N02 and -CN The alkyl substituents are preferably C 1 -C 6 alkyl, which may be substituted, for example, by halogen, such as chlorine, bromine, fluorine, -OH, -CN, -NH 2 or C 1 -C 6 alkoxy. The cycloalkyl substituents are preferably cycloalkyl with C3-C, especially cycloalkyl with C5-C6, which may be substituted for example by alkyl with C? -C6, alkoxy with C? -C6, halogen such as Cl, Br, F, alkoxy with C? -C6, -OH, -CN and NH2. The aralkyl substituents are preferably phenyl- or naphthyl-C? -C4-alkyl, which can be substituted in the aromatic radicals by halogen such as F, Cl, Br, -OH, alkyl with Ci-Ce, alkoxy with C? -C6, -NH2, -N02 and -CN, for example. The acyl substituents are preferably (Ci-Cd-alkyl) -carbonyl, phenylcarbonyl, C 1 -C 6 -alkylsulfonyl, phenylsulfonyl, optionally Ci-Cβ-alkyl-, phenyl- and naphthyl-substituted carbamoyl, sulfamoyl Ci-Cß-alkyl -, optionally substituted phenyl- and naphthyl-substituted or Ci-Cβ-alkyl-, phenyl- or naphthyl-substituted guanyl, wherein said alkyl radicals can be substituted for example by halogen such as Cl, Br, 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, Br, -OH, alkyl with C? -C6, alkoxy with Ci-C?, -NH2, -N02 and -CN. 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? 0-C2o or fatty acid amides, such as stearamide, stearic acid monoethanolamide, diethanolamide of stearic acid, stearonitrile, fatty amines, eg, 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, decahydrate -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, 4-nitrobenzamide, 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, acid 5-nitro-l- and 5-nitro-2-naphthalenesulfonic acid, mixtures of di-sec-butylnaphthalenesulfonic acids, bifunyl-4-sulfonic acid, 1,4-, 1,5-, 2,6-, 2,7-acid -naphthalenedisulfonic acid, 3-nitro-1, 5-naphthalenedisulfonic acid, 1-anthraquinonsulfonic acid, 2-anthraquinonsulfonic acid, biphenyl-4,4'-disulfonic acid, 1,3,6-naphthalene sulfonic acid and the salts of these sulphonic acids by Examples are sodium, potassium, calcium, zinc, nickel and copper salts; 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 metal complexes contain surface-active compounds included, especially surfactants, which are known, for example, from K. Lindner, Tenside-Textilhilfsmittel-Waschrohstoffe, 2 / a. Edition, Volume I, Wissenschaftliche Verlagsgesellschaft mbH, Stuttgart, 1964. They may be anionic, non-ionic or cationic or ampholytic compounds. Examples of suitable anionic compounds are authentic soaps, salts of aminocarboxylic acids, salts of lower or higher acylated aminocarboxylic acids, fatty acid sulfates, sulfates of fatty acid esters, amides, etc., primary alkyl sulfate, oxal sulfates alcohols, sulphates of secondary alkyls, sulfates of esterified or etherified polyoxy compounds, sulfates of substituted polyglycol esters (adducts of sulfated ethylene oxide), sulphates of acylated or alkylated alkanolamines, sulfonates of fatty acids, their esters, amides, etc., sulfonates of primary alkyls, secondary alkyl sulphates, alkyl sulfonates with acyl esters fixed in the ester mode, alkyl or alkylphenyl ether sulfonates, polycarboxylic ester sulfonates, alkylbenzenesulfonates, alkylnaphthalenesulfonates, aromatic fatty sulfonates, alkylbenzimidazole sulfonates, phosphates, polyphosphates, phosphonates, phosphinates , Thiosulfates , hydrosulfites, sulphinates, persulfates. Examples of suitable nonionic compounds are the esters and ethers of polyalcohols, 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, imidazoline simple and quaternary salts, alkyldianes and alkyl polyamines, acildiamines and acylpolydes, acylalkanolamines, alkanolamine esters, alkyl-OCH 2 salts -N-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. The 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. Polymers are also suitable for inclusion, preferably water-soluble polymers, for example propylene-ethylene oxide block polymers, preferably having an Mn of not less than 1000, especially from 1000 to 10,000 g / mol, polyvinyl alcohol, poly (meth) -acrylic acids, cellulose modified, 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 sulfomethylated aromatic substances. Preferred sulphonated aromatic substances are naphthalenesulfonic acids, phenolsulfonic acids, dihydroxybenzenesulfonic acids, sulfonated ditolyl ethers, 4,4'-dihydroxydiphenyl sulphone sulphonylated sulfonate, sulfonated diphenylmethane, sulfonated biphenyl, sulphonated 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 sulfone and dihydroxydiphenylmethane. 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 , sulfonated terphenyl and benzenesulfonic acids, H) 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 (III) 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 the 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 preferred inventive metal complexes of the azo compounds of the formula (I) which contain another compound as the host compound have a color site which is defined by the following ranges for the chromaticity coordinates x and y. The color sites are determined on alkyd-melamine varnishes according to DIN 53 238 in which the pigments are present in a completely dispersed state. X = 0.38 to 0.72, preferably 0.4 to 0.7 and = 0.14 to 0.36, preferably 0.17 to 0.35where x X and Y X + Y + z x + Y + z where X, Y and Z are tristimulus values, The standardized color system is described in Bayer Farben Revue, Sonderheft 3/2 D, 1986, p. 12-14. Inclusion compounds, intercalation compounds and solid solutions of metal complexes per se are already known from the literature. They and their preparation are described, for example, in EP 0 074 515 and EP 0 073 463. The preparation of these compounds can be carried out analogously to the one described for example in EP 0 073 464. The invention also provides a process for preparing the metal complexes of the invention, which is characterized in that the azo compound of the formula (I), preferably in the form of an alkali metal salt such as the Na, Li or K salt, is reacted with a metal salt of metals selected from the group consisting of Ca, Zn, Cu, Fe, Cp, Sr, Ba, Cr, Sn, Al, Mg, Cd, Pd and La, preferably at pH < 7, and the resulting metal complex is reacted with the compound to be included as the host compound, preferably at a pH of 1 to 7. A preferred embodiment of the process of the invention is characterized in that, following the reaction with the host compound, the pH is raised to 4.5 or greater, preferably 4.5 to 7, if the reaction with the host compound is carried out at a pH of less than 4.5. The metal salt is preferably selected from the water-soluble metal salts of the metals mentioned above, especially the chlorides, bromides, acetates, nitrates, etc. Preferred metal salts have a solubility in water of more than 20 g / 1, especially more than 50 g / 1, at 20 ° C. Suitable metal salts for preparing the salts and complexes of the azo compounds are, for example, magnesium chloride, magnesium sulfate, calcium chloride, calcium acetate, calcium formate, barium chloride, barium nitrate, barium acetate. , barium carbonate, strontium nitrate, manganese chloride, manganese sulfate, iron (III) chloride, iron (III) nitrate, iron (II) sulfate, cobalt chloride, cobalt nitrate, cobalt sulfate, aluminum sulfate, aluminum nitrate, chromium (III) sulfate, chromium (III) nitrate, zinc chloride, zinc sulfate, zinc acetate, cadmium chloride, cadmium sulfate, cadmium nitrate, copper sulfate (II), copper (II) chloride, copper (II) acetate and copper (II) formate, lanthanum nitrate and aluminum chloride hydrate.

It is also possible to use mixtures of these salts, which may also contain several of some of the mentioned metals. The use of such mixtures of salts is especially contemplated to obtain shades or intermediate shades for the colored final products. The metal complexes obtained accordingly according to the invention can then be isolated in the form of aqueous compressed cakes by filtration of their aqueous suspensions. These compressed cakes can be dried according to the usual drying processes, for example after washing with hot water. Useful drying processes include for example drying with propellers or paddles or spray drying of the aqueous watered pastes appropriately. The pigment may subsequently be post-molded. If the metal complexes according to the invention are too rough in texture, they can be converted into soft texture pigments, for example by the method described in DE 19 847 586. The aqueous compressed cake is preferably spray dried as a aqueous suspension, the aqueous suspension preferably contains ammonia and / or an organic or inorganic base. Similarly it is preferable for the metal complexes of the invention, if they have a dispersion hardness of > 250, which 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 to pH of 9 to 13, preferably 10 to 11, and at a temperature of 80 to 180 ° C, preferably 90 to 140 ° C, especially 95 to 110 ° C. The heat treatment is preferably supplemented when the metal complex of the invention, which contains a host compound, has a hardness by dispersion of less than 250. The invention therefore also provides inventive metal complexes having a roughness in the dispersion of less than 250 (measured on the lines of DIN 53 775 Part 7), the temperature of cold rolling which is 25 ° C and the temperature of hot rolling which is 150 ° C. All roughness in the dispersion here was determined by this modified method. The metal complexes of an azo compound of the formula (I) which contains at least one host compound, are referred to herein as pigments. The invention therefore also provides preparations of pigments comprising at least one pigment according to the invention and a 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. The pigment preparations are preferably solid preparations, which are present in a powdery or granular form. 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 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 as meaning in particular those alcohols of C6 ~ C22 fatty acids 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 1 ^ units of ethylene oxide. The alcohols of the sulphated 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 desulfonated and fractionated according to known processes, for example according to the molecular weight or according to the degree of sulfonation. 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 - resinous acids. They are, for example, ethylene oxide adducts of the class of 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: wherein R is hydrogen or alkyl with C1-C4, R is hydrogen or CH3, R 17 is hydrogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 alkoxycarbonyl 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 'R16', R17 ', R18', m 'and n' assume or adopt the meaning range of R15, R16, R17, R18, m and n, respectively, but independently of them, '- 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 case X = -PO3- two cations are present, and R 19 is a divalent aliphatic or aromatic radical, preferably C 1 -C 4 alkylene, especially ethylene, mono-unsaturated C 2 -C 4 radicals, especially acetylene, or optionally substituted phenylene, especially ortho-phenylene, the preferred substituents being C 1 -C 4 alkyl, C 1 -C 4 alkoxy, alkoxycarbonyl with C 1 -C 4 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 known 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) -COO "and R19 ^ - is as defined above.The preference for use as a dispersing agent is likely to be 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 preparation of the pigment. The preparation may contain additional additives, of course. For example, additives which reduce the viscosity of an aqueous suspension and increase the solids content, such as the carboxamides and sulfonamides mentioned above, can be added in an amount of up to 10% by weight, based on the preparation. Examples of the additional additives are organic and inorganic bases and also customary additives for the preparation of the pigment. Suitable bases are alkali metal hydroxides, for example NaOH and KOH, organic amines such as alkylamines, especially alkanolamines or alkylalcanolamines.

Particular preference is given to methylamine, dimethylane, trimethylamine, ethanolamine, n-propanolamine, n-butanolamine, diethanolamine, triethanolamine, methylethanolamine or dimethylethanolamine. Examples of suitable carboxamides and sulfonamides are urea and substituted ureas such as phenylurea, dodecylurea and others; heterocycles such as barbituric acid, benzimidazole-5-sulfonic acid, 2,3-dihydroxyquinolaline, 2,3-dihydroxyquininoaline-6-sulfonic acid, carbazole, carbazole-3,6-disulfonic acid, 2-hydroxyquinoline, 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. The base is optionally present in up to an amount of 20% by weight, preferably up to 10% by weight, based on the pigment. But it is particularly preferred for the preparation of the invention, which contains more than 90%, especially more than 95%, preferably more than 97%, by weight of the pigment according to the invention, the dispersing agent and optionally the base. The invention further provides a process for preparing the pigment preparation of the invention, characterized in that the pigment and the dispersant and optionally additional additives are mixed. The metal complexes of the invention are very useful for all applications of the pigment. They are useful, for example, for pigmenting varnishes of all kinds for the production of printing colors, colors for tempera painting or binding colors, for the serial coloration of synthetic, semi-synthetic or natural macromolecular substances, especially polyvinyl chloride, polystyrene , polyamide, polyethylene or polypropylene, etc. They are also useful for dyeing by centrifugation of natural, regenerated or artificial fibers, for example cellulose fibers, polyester, polycarbonate, polyacrylonitrile, and also for printing textiles and paper. watery, stable, finely divided, of the emulsion and the colors of the paint which are useful for the coloring of the paper, for the printing with pigments of the textiles, for lamination and also for the dyeing by centrifugation of the viscose, by grinding or kneading in the presence of nonionic surfactants, anionic or cationic.

Examples Example 1 425 g of a water-moistenable paste of an azobarbituric sodium salt compound having a solids content of 40%, corresponding to 170 g in the dry state, are converted into a homogeneous suspension in 5000 ml of distilled water using an agitator of laboratory, heated to 95 ° C, mixed with 61.1 g of CaCl2 and stirred at 95 ° C for 2 hours. Then 63.1 g of melamine are added and added and stirred at 95 ° C for 1 hour. The pH is then adjusted to 5.0 with a solution of sodium hydroxide. The product is then isolated by suction filtration, dried at 80 ° C in a vacuum drying cabinet and milled for about 2 minutes in a common laboratory mill. The pigment powder thus obtained is dispersed according to DIN 53 238 in an alkyd-melamine lacquer system.

Color site: X = 31.6 Y = 20.9 Z 6.5 Example 2 Example 1 is repeated with CaCl 2 which is replaced by 57.3 g of BaCl 2. The suspension of the pigment thus obtained is isolated, dried and milled, each step is carried out as described in Example 1. The powder of the pigment thus obtained is then incorporated in an aqueous binder.

Site of Color: X = 26 Y = 17 Example 3 485 g of a water-moistenable paste of an azobarbituric sodium salt compound having a solids content of 35%, corresponding to 170 g in the dry state, are suspended homogeneously in 5000 ml of distilled water using a laboratory stirrer, they are heated to 95 ° C, mixed with 69.7 g of FeCl2 and then stirred at 95 ° C for 2 hours. Then 129 g of melamine are added and stirred at 95 ° C for 1 hour. The pH is then adjusted to 5.0 with a solution of sodium hydroxide. The product is then isolated by suction filtration, dried at 80 ° C in a vacuum drying cabinet and milled for about 2 minutes in a common laboratory mill.

Color site: X = 8.81 / Y = 9.4 / Z 9.81, The pigment powder thus obtained is dispersed according to DIN 53 238 in an alkyd-melamine lacquer system.

Color site: X = Y = 9.4 Z = 9.8 Example 4 425 g of the water-moistenable paste of an azobarbituric sodium salt compound 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 mixed with 100.8 g of CdCl2 and 129 g of melamine, heated to 95 ° C, and stirred at 95 ° C for 2 hours.

The pH is then adjusted to 5.0 with a solution of sodium hydroxide. The product is then isolated by suction filtration, dried at 80 ° C in a vacuum drying cabinet and milled for about 2 minutes in a common laboratory mill.

The pigment powder thus obtained is dispersed according to DIN 53 238 in an alkyd-melamine varnish system.

Room of color; X 49.5 Y = 38 Z = 5.4 Example 5 Example 4 is repeated with CdCl2 which is replaced by 104.3 g of SnCl2. The suspension of the pigment thus obtained is isolated, dried and ground, each step is carried out as described in Example 1. The pigment powder thus obtained is dispersed according to DIN 53 238 in an alkyd varnish system. melamine.

Color site: X = 21.3 Y = 16.4 Z = 6.3 Example 6 485 g of the water-moistenable paste of an azobarbituric sodium salt compound having a solids content of 35%, corresponding to 170 g in the dry state, are suspended homogeneously in 5000 ml of distilled water using a laboratory stirrer, heated at 95 ° C, mixed with 61.1 g of CaCl2 and stirred at 95 ° C for 2 hours. Then 63.1 g of melamine and 60 g of Pluronic®738 (a polycondensate of propylene oxide-ethylene oxide from BASF) are added and stirred at 95 ° C for 1 hour. The pH is then adjusted to 5.0 with a solution of sodium hydroxide. The product is then isolated by suction filtration, dried at 80 ° C in a vacuum drying cabinet and milled for about 2 minutes in a common laboratory mill. The pigmeryl powder thus obtained is incorporated into PVC by cold rolling on a roller mill.

X = 68.97 Y = 67.98 30.08 Example 7 485 g of water-wettable paste of an azobarbituric sodium salt compound having a solids content of 35%, corresponding to 170 g in the dry state, are homogeneously suspended in 5000 ml of distilled water using a laboratory stirrer, heated at 95 ° C, mixed with 6.1 grams of CaCl 2 and stirred at 95 ° C for 2 hours. Then 120 g of Pluronic® 738 (a polycondensate of propylene oxide-ethylene oxide, molar mass of about 2000 g / mol, of BASF) are added and stirred at 95 ° C for 1 hour. The pH is then adjusted to 5.0 with a solution of sodium hydroxide. The product is then isolated by suction filtration, dried at 80 ° C in a vacuum drying cabinet and milled for about 2 minutes in a common laboratory mill. The pigment powder thus obtained is incorporated into PVC by cold rolling on a roller mill. - ' X = 58.6 Y = 56.6 22.9 Example 8 485 g of the water-moistenable paste of an azobarbituric sodium salt compound having a solids content of 35%, corresponding to 170 g in the dry state, are suspended homogeneously in 5000 ml of distilled water using a laboratory stirrer, heated at 95 ° C, mixed with 61.1 g of CaCl2 and stirred for 2 hours. Then 120 g of Tetronic® 707 (a condensate block of propylene oxide-ethylene oxide initiated with ethylene diamine from BASF) are added and stirred at 95 ° C for 1 hour. The pH is then adjusted to 5.0 with a solution of sodium hydroxide. The product is then isolated by suction filtration, dried at 80 ° C in a vacuum drying cabinet and milled for about 2 minutes in a common laboratory mill. The pigment powder thus obtained is incorporated into the PVC by cold rolling on a roller mill.

Site of Color: X '61 .8 Y = -54.9 Z = 31.43 Example 9 . Example 1 was repeated with CaCl 2 which is replaced by 138.1 g of Mn (N02) 2 * 4H20. The suspension of the pigment thus obtained is isolated, dried and milled, each step is carried out as described in Example 1. The powder of the pigment thus obtained is then incorporated in an aqueous binder.

Color site: X = 46 Y = 41 Z = 27 Example 10 Example 1 is repeated with CaCl 2 which is replaced by 100.9 g of Zn (CH 3 C00) 2. The suspension of the pigment thus obtained is isolated, dried and ground, each step is carried out as described in Example 1. The pigment powder thus obtained is then dispersed according to DIN 53 238 in an alkyd lacquer system. melamine.

Color site: X 31.1 X * "£ - X • -Ü5? Example 11 Example 3 is repeated with FeCl2 which is replaced by 133 g of AlCl3 * »6H20. The suspension of the pigment thus obtained is isolated, dried and milled, each step is carried out as described in Example 3. The powder of the pigment thus obtained is then incorporated in an aqueous binder. The binder is extracted, dried and measured with a commercially available colorimeter to determine the color site.

Color site: X = 62 Y = 52 Z = 9 Example 12 Example 3 is repeated with FeCl2 which is replaced by 146.5 g of CrCl3 * «6H20. The suspension of the pigment thus obtained is isolated, dried and ground, each step is carried out as described in Example 3. The pigment powder thus obtained is then processed by means of an extruder in a PP fiber.

Site of color: X = 64.5 Y = 62.1 Z = 40.15 Example 13 Example 1 was repeated with CaCl2 which is replaced by 101.7 g of MgCl2 * »6H20. The suspension of the pigment thus obtained is isolated, dried and ground, each step is carried out as described in Example 1. The pigment powder thus obtained is then incorporated in PVC.

Site of color: X = 72.4 and 66 Z = 56.15 Example 14 Example 1 was repeated with CaCl 2 which is replaced by 152.9 g of PbCl 2. The suspension of the pigment thus obtained is isolated, dried and milled, each step being carried out as described in Example 1. The pigment powder thus obtained is dispersed according to DIN 53 238 in an alkyd lacquer system. melamine.

Site of color: X = 40.6 Y = 28.5 Z = 5, Example 15 Example 1 is repeated with CaCl 2 which is replaced by 93.8 g of CuCl 2 * 2 H 20. The suspension of the pigment thus obtained is isolated, dried and milled, each step is carried out as described in Example 1. The pigment powder thus obtained is dispersed according to DIN 53 238 in an alkyd-melamine varnish system. .

Color site: X = 17. 7 Y = 15.21 Z = 6. 33 Example 16 Preparation of cyaniminoazobarbituric acid 4. 9 moles of diazobarbituric acid (755 g) and 5.0 moles of cyaniminobarbituric acid are suspended in 10 liters of H20 and heated to 80 ° C. While a temperature of 80 ° C is reached, the pH is adjusted to 5 with 30% NaOH and the suspension is stirred for 3 hours. The red product is filtered and washed with hot water (10 liters). * • 'The diazobarbituric acid of the formula It is prepared as follows.

Preparation of guanyl azide An initial charge of technical grade hydrochloric acid and distilled and demineralized water is indirectly cooled gradually up to about 0 ° C. Subsequently, aminoguanidine bicarbonate is added at about 10 ° C in the course of about 30 minutes. After this, the batch is indirectly cooled gradually to about 0 ° C, and sodium nitrite solution is added to max. 15 ° C in the course of approximately 3 hours. This is followed by stirring with an excess of nitrite for 15 minutes. Directly prior to the transfer of the azo groups, the excess nitrite is removed with amidosulfonic acid.

Transfer of the group 'azo? - * The barbituric acid is then only introduced into the guanyl azide solution. This is followed by indirect heating to about 70 ° C and subsequently stirring at this temperature for about 4 hours. The batch is then externally cooled gradually to 0 ° C and fully compressed.

Example 17 Preparation of cyaniminoazobarbituric acid 0.14 Moles of the sodium salt of cyaniminoazobarbituric acid (47.8 g) are refluxed with 0.15 mol of MnCl2.4H20 (30.6 g) in 300 ml of H20 for 2.5 hours. The pH of the dispersion is between 2 and 6, preferably between 3.5 and 5. After 2 hours, 0.28 moles (35.3 g) of melamine are added. The batch is buffered with sodium acetate until pH = 4.5 and filtered, and the filter cake is washed with 1 liter of hot water. The product is dried at 95 ° C for 12 hours and milled in a laboratory mill. The pigment powder thus obtained is dispersed according to DIN 53 238 in an alkyd-melamine lacquer system.

Site of color: X 12.7 8.7 Z = 5 Example 18 Example 16 was repeated using 0.15 moles of SnCl2"2H20 (33.8 g) in place of manganese chloride. The pigment powder obtained is incorporated into a formulation of the aqueous binder.

Site of color: X = 33.9 24.1 Z = 7.96 Example 19 Example 17 was repeated using 0.15 mole of CuCl2.2H20 (25.6 g) in place of manganese chloride. The pigment powder obtained after the working process is cold rolled in PVC. 0.1 parts of Bayer Ag Bayertitan® R-FK-2 pigment are incorporated in 100 parts of PVC.

Site of color: X 47.46 Y = 46.23 Z = 28.8 Example 20 Example 17 was repeated using 0.15 moles of CoCl2.2H20 (35.65 g) in place of manganese chloride.

The pigment powder obtained after the working process is incorporated in a melamine-alkyd varnish (DIN 53 238).

Site of color: X 26.2 5.9 Z = 5 Example 21 Example 17 was repeated using 0.15 moles of AICI3 (20 g) in place of manganese chloride. The pigment powder obtained after the working process is incorporated in accordance with DIN 53 238 in a melamine-alkyd varnish.

Color site: X = 26.67 Y = 17.3 Z = 5.1 Example 22 Example 17 was repeated using 0.15 moles of CrCl3.6H20 (40 g) in place of manganese chloride. The pigment powder obtained after; of the working procedure is incorporated in an aqueous binder.

Site of color: X 32.1 Y = 24.05 7.9 Example 23 Example 17 was repeated using 0.15 moles of ZnCl2 (20.44 g) in place of manganese chloride. The pigment powder obtained after the working process is laminated in PVC analogously to Example 19 Color site: X = 60 Y = 55. 3 Z = 32. 46 Example 24 Example 17 is repeated using 0.15 moles of FeS04 »H20 (41.7 g) in place of manganese chloride. The pigment powder obtained after the working process is laminated to the PVC in a manner analogous to Example 19.

Site of color: X = 26.3 26.38 Z = 21.13 Example 25 Example 17 is repeated using 0.15 moles of La (N03) 3 (48.74 g) in place of manganese chloride. The product obtained after the working procedure is incorporated in accordance with DIN 53 238 in a melamine-alkyd varnish.

Site of color: X 19.6 Y = 12.6 Z = 5.9 Example 26 Example 17 was repeated using 0.15 moles of NoCl2.6H20) (35.64 g) in place of manganese chloride. The product obtained after the working procedure is incorporated in accordance with DIN 53 238 in a melamine-alkyd varnish.

Site of color: X 21.3 Y = 16.8 Z = 5.54 Example 27 Example 17 is repeated using 0.15 moles of CaCl2. 2H20 (22.05 g) in place of manganese chloride. The pigment powder obtained after the working process is incorporated into an aqueous binder.

Site of color: X = 44.6 33.4 Z = Example 28 Example 17 is repeated using 0.15 moles of MgCl2. 6H20 (30.5 g) in place of manganese chloride. The pigment powder obtained after the working process is incorporated into an aqueous binder.

Color site: X = 43.3 Y = 33. Z = 9.74 Example 29 Preparation of the sodium salt of dicyaniminoazobarbituric acid 1. 62 moles of HCl are preloaded as HCl at 37% with ice. 0.75 * iaols of aminobiguanidine carbonate are added in the course of 15 minutes. Gradually (60 ') 0.75 moles of NaN02 are added in a 37% solution with continuous cooling (below 5 ° C). The excess nitrite is destroyed by adding a solution of 30% amidosulfonic acid. The volume of the reaction is 6 liters. 0.75 moles of cyaniminobarbituric acid are added and the reaction mixture is stirred at 50-80 ° C for 3 to 5 hours, preferably at T < 65 ° C for 3 to 4 hours. Cyaniminoazobarbituric acid is formed. Another 0.75 moles of cyaniminobarbituric acid are then added to the reaction mixture.

A pH of from 5 to 9, preferably from 7 to 8.5, is fixed with 30% NaOH, before the batch is stirred at 95 ° C for 2 hours. The product is removed by filtration and washed with an equal volume of hot water at 80 °.

Example 30 0. 15 moles of sodium dicyaniminoazobarbiturate and 0.15 moles of CaCl2. 2H20 (20.05 g) are refluxed in 500 ml of water at pH 1- to 7, preferably at pH 3 to 5, for 2 hours. This is followed by the addition of 0.15 to 0.6 moles of melamine, preferably 0.15 to 0. 4 moles, and an additional hour of reflux. The reaction mixture is adjusted to pH 5 with sodium acetate, and the product is removed by filtration. The filter residue is washed with 1.5 1 of hot water at 80 ° C. The filter cake is dried at 95 ° C and 100 mbar for 12 h and milled in a laboratory mill. The pigment powder thus obtained is incorporated in accordance with DIN 53 238 in a melamine-alkyd varnish.

Color site: X 13.8 Y = 8.76 Z = 5.1 Example 31 Example 30 is repeated using 0.15 moles of BaCl2. 2H20 (36.6 g) in place of calcium chloride. The pigment powder obtained after the working process is incorporated in accordance with DIN 53 238 in a melamine-alkyd varnish.

Site of color: X = 9.27 Y = 7.6 Z = 5.4 Example 32 Example 30 is repeated using 0.15 moles of ZnCl 2 (20.4 g) in place of calcium chloride. The pigment powder obtained after the working process is incorporated into an aqueous binder.

Site of color: X 36.8 25.01 .21 Example 33 Example 30 is repeated using 0.15 moles of MnCl2.4H20 (30.6 g) in place of calcium chloride. The pigment powder obtained after the working process is incorporated into an aqueous binder.

Site of color: X = 23.9 Y = 17.75 10 Example 34 Example 30 is repeated using 0.15 moles of MgCl2. 6H20 (30.5 g) in place of calcium chloride. The pigment powder obtained after the working process is incorporated in accordance with DIN 53 238 in a melamine-alkyd varnish.

Site of color: X = 7.71 and 6.56 Z = 5.2 Example 35 Example 30 is repeated using 0.15 moles of AICI3 (20 g) in place of the calcium chloride and neutralizing the resulting HCl until the desired pH of the reaction has been reached. The pigment powder obtained after the working process is incorporated in accordance with DIN 53 238 in a melamine-alkyd varnish.

Color site: X = 9.7 Y = 7.5 Z = 5.1 Example 36 Example 30 is repeated using 0.15 moles FeCl2. 4H20 (29.8 g) in place of calcium chloride. The pigment powder obtained after the working process is incorporated in accordance with DIN 53 238 in a melamine-alkyd varnish.

Room of color; X = 4.5 Y = 4.7 Z = 4.9 Example 37 0. 14 moles of the sodium salt of cyaniminobarbituric acid (47.8 g) are refluxed with 0.15 moles of MnCl2. 4 H20 in 300 ml of H20 for 3.0 hours. The pH is maintained at 5. After 2 hours the pH is adjusted to 2.0 with concentrated HCl. Then they are stirred with 40 g of urea and 56 g of 37% formaldehyde. During the expiration of the third hour, the batch is buffered to pH 4.5 with sodium acetate and filtered, and the filter residue is washed with 1 liter of hot water. The product is dried at 95 ° C for 12 h and milled in a laboratory mill. The pigment powder thus obtained is dispersed according to DIN 53 238 in an alkyd-melamine lacquer system.

Color site: X = 14.54 Y = 10 Z = 5.3Í Example 38 Example 30 is repeated using 0.15 moles of CrCl3. 6H20 (40 g) in place of calcium chloride. The pigment powder obtained after the working process is incorporated in accordance with DIN 53 238 in a melamine-alkyd varnish.

Color site: X 7.1 Y - 6.1 Example 39 Example 30 is repeated using 0.15 moles of CoCl2. 6H20 (35.7 g) in place of calcium chloride. The pigment powder obtained after the working process is incorporated in accordance with DIN 53 238 in a melamine-alkyd varnish.

Site of color: X 6.65 6.16 Z = 5.1 Example 40 Example 30 is repeated using 0.15 moles of SnCl2.2H20 (33.8 g) in place of calcium chloride. The pigment powder obtained after the working process is incorporated into an aqueous binder.

Color site: X = 46.4 Y = 35.6 9.8 Example 41 Example 30 was repeated using 0.15 mole of CuCl2. 2H20 (25.6 g) in place of calcium chloride. The pigment powder obtained after the working process is incorporated in accordance with DIN 53 238 in a melamine-alkyd varnish.

Color site: X 5.7 Y = 5.44 Example 42 Example 30 is repeated using 0.15 moles of LaN03. 2H20 (25.6 g) in place of calcium chloride. The pigment powder obtained after the working process is incorporated according to DIN 53 238 is a melamine-alkyd varnish.

Site of color: X = 16.3 and 11 Z = 5.2 Example 43 (Ba salt of cyaniminoazobarbituric acid) Example 17 was repeated using 0.15 moles of BaCl2. 2H20 (36.6 g) in place of the calcium chloride. The pigment powder obtained after the working process is incorporated according to DIN 53 238 in an alkyd-melamine varnish.

Site of color: X = 15.13 and 10.39 5.83 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 (10)

1. The metal complexes of an azo compound which conforms to formula (I) or one of its tautomeric structures where: R and R 'are independently OH, NH2, NH-CN, acylamino or arylamino R1 and R1 'are independently -OH or -NH2, and which contain at least one host compound, characterized in that the metal complexes correspond to the mono-, di-, tri- and tetraanions of the azo compounds of the formula (I) with the metals selected from the group consisting of Ca, Zn, Cu, Fe, Co, Sr, Ba , Cr, Sn, Al, Mg, Cd, Pb and La.

2. The metal complexes according to claim 1, characterized in that the azo compound conforms to formula (I), to formula (II) or to a tautomeric form thereof where: R and R 'are independently selected from the group consisting of OH and NHCN.

3. The metal complexes according to claim 1, characterized in that the host compound is a cyclic or acyclic organic compound, especially melamine or melamine derivatives or polycondensates, preferably those based on urea and formaldehyde and also on copolymers of oxide blocks. ethylene-propylene oxide.

4. The metal complexes according to claim 1, characterized in that they are the azo metal complexes 1: 1 which conform to the formula (la) or one of its tautomeric forms where: Me denotes the metals mentioned in Claim 1, and R and R 'and R1 and R1' are each as defined in claim 1.

5. The metal complexes according to claim 1, characterized in that their color site is defined by the following chromaticity coordinates x and y: x = 0.38 to 0.72 y = • 0.14 to 0.36.

6. The metal complexes according to claim 1, characterized in that they have a dispersion hardness of less than 250.

7. A process for the preparation of the metal complexes according to claim 1, characterized in that the azo compounds of the formula (I) where : R and R 'are independently OH, NH2, NH-CN, acylamino or arylamino, R1 and R1 'are independently -OH or -NH2, they are bound by a complex with a metal salt of the metals selected from the group consisting of Ba, Ca, Zn, Cu, Fe, Co, Sr, Cr, Sn, Al, Mg, Cd, Pb and La, and the resulting metallic complex, are reacted with the compound to be included as the host compound.

8. A pigment preparation, characterized in that it comprises as a pigment at least one metal complex according to claim 1 and at least one dispersing agent.

9. The process for preparing the pigment preparation of Claim 8, characterized in that at least one metal complex according to claim 1 is mixed as the pigment and at least one dispersing agent.

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