DE2025428A1 - Metal complex pigment dyes - from 1,2,4,5- tetramino - benzene deriv and 2-hydroxy 3-formyl 4-methyl pyridone-(6) derivs - Google Patents

Abstract

Metal complex pigment dyes - from 1,2,4,5-tetramino benzene derivs. and 2-hydroxy 3-formyl 4-methylpyridone-(6) derivs. The yes are of formula (in which R1 is H, Cl, or methyl, R2 is as R1, R3 is cyano- or carbonamido-, R4 is alkyl or cycloalkyl with 1 to 8C atoms which may contain 1-3C alkoxy gps. benzyl, phenyl, methyl phenyl, methoxy phenyl, chlorophenyl or phenyl sulphonamide gp. and Me is Ni, Cu Zn or Co). The dyes are almost insoluble in all usual solvents and hence suitable for use as pigments. They have intense and brilliant colours, and can be used for printing or paint colours and for plastics.

Description

Metal complex dyes The invention relates to new metal complex dyes of the formula I. in which R1 is a hydrogen or chlorine atom or a methyl group, R2 is a hydrogen or chlorine atom or a methyl group, R3 is a cyano or carbonamide group, R4 is a hydrogen atom or an alkyl or cycloalkyl group with 1 to 8 carbon atoms, the alkoxy radicals with 1 can contain up to 3 carbon atoms, a benzyl, phenyl, methylphenyl, methoxyphenyl, chlorophenyl or phenylsulfonamide group and Me a nickel, Eupfer, zinc or cobalt atom.

As alkyl groups for R4, for. B. alkyl, n- or i-propyl, n- or i-butyl, isooctyl, n-hexyl or cyclohexyl groups, but especially methyl groups into consideration. The alkyl groups can also be replaced by alkoxy radicals with 1 to 3 0 atoms, as substituted by methoxy, ethoxy or i-propoxy groups.

Such dyes are of particular technical interest the Formula I, in which the radicals R1 and R2 are hydrogen atoms, R3 is a cyano or carbonamide group, R4 is a phenyl group, a hydrogen atom or a methyl group and Me is a nickel or Mean copper atom.

The new metal complex dyes are in all common solvents difficult to very difficult to dissolve and are therefore suitable as pigments. They are strong in color and brilliant and can be used for coloring lacquers, printing inks or paints or plastics be used. The pigments can by known finishing operations such as Grinding, repelling, swelling or incorporation of additives into the for the respective Intended use can be brought into optimal shape.

The new dyes of the formula I can be prepared, for example, by using 1,2,4,5-tetraaminobenzene derivatives of the general formula according to methods known per se with aldehydes of the general formula converts and metallizes the condensation products.

The reaction of components II and III with one another is expedient in solvents such as glacial acetic acid, N-methylpyrrolidone, butyrolactone or ß-methoxyethanol before.

Instead of the tetraaminobenzene compounds of the formula II, one can also their salts, e.g. B. the hydrochloride, use.

It is useful for the conversion of these salts into the Amines required amount of an acid-binding agent, like ammonia, Add sodium carbonate and preferably sodium acetate.

It is sufficient to expediently the mixture for about 4 to 7 hours under a nitrogen atmosphere to temperatures of 80 to 135.degree. C., preferably 100 up to 120 ° C, to be heated.

The metallization can then be carried out without isolating the metal-free Condensation products by adding the metal salts, e.g. Bo in the form of Chlpride, Sulphates, formates or, preferably, acetates for the reaction mixture and further heating be made under the same conditions.

The metallization takes approximately another 3 to 7 hours.

The aldehydes of the general formula III are derivatives of 2,6-dihydroxypyridine or of 2-hydroxypyridone- (6).

Examples include: 2-Hydroxy-3-formyl-4-methyl-5-cyano-pyridone- (6), 2-HydroKy-3-formyl-4-methyl-pyridon- (6) -5-carbonamide, 1-methyl-2-hydroxy-3-formyl-4-methyl-5-cyano-pyridon- (6), 1-I {ethyl-2-hydroxy-3-formyl-4-methyl-pyridone- (6) -5-carbonamide, 1-ethyl-2-hydroxy-3-formyl-4-methyl-5-cyano-pyridone ( 6), 1-Ethyl-2-hydroxy-3-formyl-3-methyl-pyridone- (6) -5-carboxamide, 1-benzyl-2-hydroxy-3-formyl-4-methyl-5-cyano-pyridone- (6 ), 1-Benzyl-2-hydroxy-3-formyl-4-methyl-pyridone- (6) -5-carboxamide, 1-phenyl-2-hydroxy-3-formyl-4-methyl-5-cyano-pyridone- (6 ), 1- (p-chlorophenyl) -2-hydroxy-3-formyl-4-methyl-5-cyano-pyridon- (6), 1-lolyl-2-hydroxy-3-formyl-4-methyl-5- cyan-pyridon- (6), 1-Benzyl-2-hydroxy-3-formyl-4-methyl-5-cyano-pyridone- (6-).

The parts given in the examples are unless otherwise noted, parts by weight.

Example 1 13.2 parts 1.2. 4.5-tetraaminobenzene hydrochloride is mixed with 40 parts of 1,4-dimethyl-2-hydroxy-3-formyl -5-cyano-pyridone- (6) in 150 parts of glacial acetic acid. The mixture is heated to 100 to 110 oC for 5 hours, then allowed to cool and filtered off with suction. The moist suction cake is treated for 4 hours at 10000 with 20 parts of nickel acetate. 100% in 150 parts of β-methoxyethanolO It is allowed to cool to 50 ° C., filtered off with suction and the residue is washed with β-methoxyethanol and then with hot water. After drying, 44 parts of a brown pigment of the formula are obtained 20 parts of the pigment obtained are rubbed with 80 parts of book or offset varnish in the usual way on a three-roll mill. The printing ink produced in this way gives prints of excellent color strength and very good lightfastness when processed in letterpress and offset printing.

5 parts of the pigment are made with 95 parts of acrylic resin varnish from 80 parts of acrylic resin solution and 20 parts of melamine resin solution, on the attritor rubbed. A deeply colored brown varnish is obtained which, after stoving (30 Minutes at 130 0 ") has excellent light and overspray fastness properties.

Example 2 37 parts of 2. 6-dihydroxy-3-formyl-4-methyl-5-cyano-pyridine and 13.2 parts of 1.2.4.5-tetraaminobenzene hydrochloride are mixed with 14 parts of anhydrous sodium acetate in 150 parts of ß-methoxyethanol under a nitrogen atmosphere Heated to 100 to 110 oC for hours. Then 20 parts of cobalt acetate are added and the mixture is heated to 110,000 for 4 hours under a nitrogen atmosphere. The residue is filtered off with suction at about 40 ° C. and washed with β-methoxyethanol and then with hot water. 40 parts of a brown pigment of the formula are obtained Example 3 13.2 parts of 1,2.4,5-tetraaminobenzene hydrochloride are suspended in 100 parts of glacial acetic acid. 45 parts of 1,4-dimethyl-2-hydroxy-3-formylpyridone- (6) -5-carboxamide (calculated 100%) are added to this mixture as 50 goat aqueous paste. The mixture is heated to 100 to 110,000 for 8 hours and then 18 parts of copper sulfate calculated as 100 ffi are added as a hot, saturated aqueous solution. The mixture is then refluxed for a further 5 hours and the precipitate formed is then filtered off at about 40 ° C. and washed with glacial acetic acid, β-methoxyethanol and hot water. 45.5 parts of a red-brown pigment of the formula are obtained The dyes characterized in the following table by specifying the substituents (see formula I) are obtained analogously to the procedures described in the preceding examples: Example R1 R2 R3 R4 Me color tone 4 HH -CN H Ni red-brown 5 Cl H -CN H Ni red-brown 6 HH -CONH2 H Ni red 7 CH) H -CN CH3 Ni brown 8 HH -CN -C2H5 Ni brown 9 HH -CONH2 C2H5 Ni red-brown 10 HH -CN i-O3H7 Ni brown 11 HH -CN 4 Ni brown 12 HH -CH -CH2 e Ni brown 13 HH -CN to-Cl Ni brown 14 HH -CONH2 H Cu red 15 HH -CN CH3 Ni brown 16 HH -CN H Zn brown 17 HH -CN H Ni brown 18 HH -CN H Cu brown 19 HH -CN i-Octyl Ni brown 20 HH -CN - w, CE3 Ni brown 21 HH -CN II Cu brown 22 HH -CN i-Octyl Cu brown 23 HH -CN wca A CH2 ffi gi brown 24 HH -CN Ni brown -CH2CE2CH20C (CH3) 2

Claims (3)

Claims 1. Metal complex dyes of the formula in which R1 is a hydrogen or chlorine atom or a methyl group, R2 is a hydrogen or chlorine atom or a methyl group, pure cyano or carbonamide group, R4 is a hydrogen atom or an alkyl or cycloalkyl group with 1 to 8 carbon atoms, the alkoxy radicals with 1 to May contain 3 carbon atoms, a benzyl, phenyl, methylphenyl, methoxyphenyl, chlorophenyl or phenylsulfonamide group and Me a nickel, copper, zinc or cobalt atom. 2. Preparation of dyestuffs according to Claim 1, characterized in that 1,2.4,5-tetraaminobenzene derivatives of the general formula are used according to methods known per se with aldehydes of the general formula converts and metallizes the condensation products. 3. Use the dyes according to claim 1 as pigment dyes.