DE3625575A1 - Metal complex pigments - Google Patents

Abstract

Compounds of the formula I <IMAGE> in which each R1 independently of the other is a monocyclic or bicyclic radical of aromatic or heteroaromatic character which is free from water-solubilising substituents, each R2 independently of the other is methyl or phenyl, and Me denotes nickel, copper, cobalt or zinc, are suitable as pigments for colouring plastics compositions.

Description

It has been found that the compounds of the formula I in which the two R ₁ independently of one another have a mono- or dinuclear radical of aromatic or heteroaromatic character free from water-solubilizing substituents, the two R ₂ independently of one another denote methyl or phenyl and Me nickel, copper, cobalt or zinc, excellent as pigments, in particular for dyeing of plastic masses.

Preference is given to the compounds of the formula I in which the two R _{1 are} phenyl, which can carry up to three substituents from the series consisting of chlorine, bromine, methyl, methoxy and ethoxy, or benzimidazolonyl-5.

The compounds of the formula I in which the two R _{2 are} methyl are also preferred.

Me in the compounds of formula I is preferably nickel.

The new compounds are prepared by amidation (formation of the imine) and metallization of 2 moles of a compound of the formula II. with 1 mol of a, preferably water-soluble, nickel, copper, cobalt or zinc salt in an ammonia-alkaline environment at temperatures between about 50 and 100 ° C.

The compounds of formula II are at least partially known, their Manufacturing takes place e.g. B. by reacting a compound of formula III

with a nitrite, preferably sodium nitrite, in weakly acidic, preferably acetic acid solution, at temperatures between -5 and 20 ° C.

The amidation and metallization of a compound of formula II can (generally) in water, but also in organic, miscible with water Solvents, e.g. B. low alcohols, glycol, glycol ethers etc. and be carried out in mixtures of these solvents with water.

As is known, the compounds of the formula I prepared in this way can by (heat) treatment with higher-boiling solvents, especially dimethylformamide, in which the new compounds, however are not soluble, be cleaned and formed so that the Noticeably improve pigment properties.

The pigments of the formula I according to the invention are outstandingly suitable for coloring plastic masses, including solvent-free and understood solvent-based masses made of plastics or synthetic resins (in paints on an oily or watery basis, in Varnishes of various types, for spin dyeing viscose or cellulose acetate, for pigmenting polyethylene, polystyrene, polyvinyl chloride, Rubber and synthetic leather). You can also print inks for that graphic industry, for pulp dyeing, for coating of textiles or for pigment printing.  

The dyeings obtained are distinguished by their excellent Fastness to heat, light and weather, chemical resistance, their Migration, efflorescence, overpainting and solvent fastness, their Color strength and the very good applicative properties, e.g. B. Fastness to flocculation, fastness to crystallization and fastness to dispersion out.

In the following examples, parts are by weight and Percentages by weight. The temperatures are in degrees Celsius specified.

example 1

70.8 parts of acetoacetic anilide are stirred in a mixture of 300 parts of water and 60 parts of glacial acetic acid, cooled to 5 °, mixed with 28 parts of sodium nitrite in the form of a four-normal aqueous solution and stirred at 5 to 10 ° for 12 hours. Then the resulting nitroso compound (of formula II) is filtered off, washed with cold water, taken up in 200 parts of approximately 25 percent ammonia solution, mixed with a solution of 51.2 parts of nickel acetate tetrahydrate in 300 parts of water, for 12 hours at 80 ° stirred, the precipitate (the pigment of formula I, wherein R ₁ = phenyl, R ₂ = methyl) is filtered off hot, washed with water and dried. The pigment thus obtained is refluxed in dimethylformamide for about 30 minutes, filtered cold, washed with methanol and dried and can then be used as a yellow pigment after conditioning.

The following table shows other pigments of the formula I and the shade of their colorations in coconut aldehyde melamine resin lacquer. R ₂ in all cases means methyl and Me nickel.

table

Examples 13, 14, 15

The pigment of Example 12 is not with nickel, but with copper (Ex. 13) or cobalt (Ex. 14) metallized, is obtained in coconut aldehyde Melamine resin colors of brown shades; metallized with zinc (Ex. 15) gives the pigment colorations a light yellow shade.

Example 16

Analogous to the information in Example 1 but with 109.2 parts of benzoacetic anilide Instead of 70.8 parts of acetoacetic anilide, a pigment was used manufactured, the coconut aldehyde melamine resin paints in yellowish brown Tones colors.  

Application example 1

4 parts of the pigment according to Example 1 are mixed with 96 parts of a mixture
50 parts of a 60 percent solution of coconut aldehyde melamine resin with 32% fat content in xylene,
30 parts of a 50 percent melamine resin solution in butanol,
10 parts of xylene and
10 parts of ethylene glycol monoethyl ether
Milled in a ball mill for 24 hours. The dispersion obtained is sprayed onto aluminum sheet, left to air dry for 30 minutes and then baked at 120 ° for 30 minutes. This gives a brilliant yellow film with very good light and weather resistance.

Example of use 2

Example for the production of a 0.1% colored PVC film (blend of colored pigment to white pigment 1: 5):
16.5 parts of a plasticizer mixture consisting of equal parts of dioctyl phthalate and dibutyl phthalate are mixed with
0.05 parts of pigment according to Example 1 and
0.25 parts of titanium dioxide mixed. Then be
33.5 parts of polyvinyl chloride were added. The mixture is rolled with friction on a two-roll mill for 10 minutes, the fur that is being formed being cut and rolled up continuously using a spatula. One roller is kept at a temperature of 40 °, the other at a temperature of 140 °.

The mixture is then drawn off as fur and added for 5 minutes 160 ° pressed between two polished metal plates.

So you get a yellow colored PVC film of high brilliance and very good migration and light fastness.

Claims (4)

1. The compounds of formula I. wherein the two R ₁ independently of one another are mono- or dinuclear radicals of aromatic or heteroaromatic character free from water-solubilizing substituents, the two R ₂ independently of one another denote methyl or phenyl and Me nickel, copper, cobalt or zinc. 2. The compounds of formula I, according to claim 1, wherein the two R ₁ phenyl, which can carry up to three substituents from the series chlorine, bromine, methyl, methoxy or ethoxy, or benzimidazolonyl-5, the two R _{2 are} methyl and Me mean nickel. 3. A process for the preparation of compounds of formula I, according to claim 1, characterized in that 2 moles of a compound of formula II metallized in the presence of ammonia with 1 mole of a nickel, copper, cobalt or zinc salt. 4. The use of compounds of the formula I according to claim 1 as pigments, for coloring plastic masses.