DE911531C - Process for the production of pigment dyes - Google Patents

Description

It has been found that valuable, solvent-fast pigment dyes are obtained if i, 4-Diaminoanthraquinones, which have at least one free Η atom on each nitrogen atom and also organic radicals with at least two together on one or both NH groups Containing amino groups, reacts with polyfunctional compounds.

Those that come into question as starting materials

ίο Substances are expediently manufactured through condensation of quinizarine, leucoquinizarine or leukoi, 4-diaminoanthraquinone with an excess Polyamines. By reacting ι mole of leuco diamine with at least 2 moles of aliphatic cycloaliphatic, aromatic, araliphatic or mixed cycloaliphatic-aromatic diamines obtained the symmetrical 1,4-diamino derivatives with two external amino groups. Through sales with Leukodiamine with 1 mole of a tri- or polyamine

ao and optionally a further mole of an aliphatic or aromatic monamine, unsymmetrical starting materials can be obtained. Suitable Diamines that react with 1,4-leuco diamines are ethylenediamine, 1,2-diamino-3-oxypropane, Hexahydro - ρ-phenylenediamine, hexahydrobenzidine, perhydro-2, 6-naphthylenediamine, N-methyl-i, 3-propylenediamine, 3-Amino-i-a-aminoethylbenzene, spermine i.a. m.

Especially the reaction products of diamines, their amino groups on a secondary carbon atom adhere, result in particularly valuable dyes.

Polyfunctional compounds that are primarily suitable as crosslinking components are: which polyadd and largely weaken the basicity of the external amino groups. Called be: aliphatic and aromatic diisocyanates, pyromellitic dianhydride, bis-ethylene oxide compounds etc. But also the phenyl esters of dicarboxylic acids, oxal esters, diphenyl carbonate, methane tricarboxylic acid esters, Melamine hexamethylol methyl ether, benzene disulphonethylene imide, benzene disulphochloride, cyanuric chloride, Terephthaloyl chloride, triacryloyl perhydrotriazine give good effects. Depending on the solubility

Ratios and the reactivity of the individual compounds, the molecular enlargement of the basic 1,4-diaminoanthraquinone derivatives can be carried out in aqueous suspension or in an organic solvent. This can also be carried out in such a way that the starting materials are condensed together with typical resin formers, _{if necessary after appropriate reforming of the NH 2 groups, e.g.} B.

O NH-CH ₉ -CH ₀₁ -NH-CO-Nh ₉

NH-CH ₉ -CH ₉ -Nh-CO-NH ₅ ,

with dimethylolurea.

The effect obtained in this way is obvious, because the starting compounds dissolve in most of them Cases easily occur in organic solvents, while the condensation products in all solvents are practically insoluble. This simple procedure on the basis of the technical makes it easy accessible 1,4-diaminoanthraquinones in hand, high quality violet, blue and green pigment dyes for a wide variety of applications.

example 1

32 parts by weight of 1,4-bis-aminoethylaminoanthraquinone, obtained by stirring leuco-1,4-diaminoanthraquinone with ten times the amount

Ethylenediamine and subsequent oxidation of the leuco compound formed by introducing Air, are dissolved in 300 parts by weight of nitrobenzene and mixed in the heat with 20 parts by weight Diphenyl carbonate. After a short time, the polyurea separates out as a blue precipitate. This is filtered off with suction, washed with methanol and dried.

The pigment obtained is very sparingly soluble in hot nitrobenzene, in concentrated sulfuric acid it dissolves with purple color.

If dimethyl oxalate is used instead of diphenyl carbonate, a pigment is obtained of similar properties. When using terephthalic acid chloride and pyridine also forms a pigment with good solvent fastness.

Example 2
43 parts by weight of the constitution dye

O NH

NH,

O NH

NH ₉

obtained by heating leuco-1,4-diaminoanthraquinone with ten times the amount of hexahydrop-phenylenediamine to 10 ° and subsequent treatment with air at 100 °, are in 100 parts by weight Dissolved nitrobenzene and put on a water bath with 175 parts by weight of a mixture of 2, 4- or 2, 6-T0-luylene diisocyanate implemented. A blue, fine-grained precipitate of the corresponding is formed immediately Polyurea, which is suctioned off, washed with methanol and dried. The received Pigment is insoluble in the usual solvents and is characterized by particularly good lightfastness and brilliant nuance.

Other di- or polyisocyanates and other dyestuff diamines, such as i, 4-bis-aminoethylaminoanthraquinone or 1,4-bisp-aminophenylaminoanthraquinone, to be used.

In another embodiment of this reaction, an aqueous solution of 1,4-bis-aminoethylaminoanthraquinone is treated with the potassium bisulfite addition compound of hexamethylene diisocyanate on the water bath and also receives a bright blue pigment.

Example 3

A solution of 43 parts by weight of the dye go of the constitution given in Example 2 and of 25 parts by weight of triacryloyl perhydrotriazine in 1000 parts by weight of water and 15 parts by weight of glacial acetic acid is neutralized with soda and stirred at 50 to 80 ° until the resulting precipitate has become insoluble in acid is. Then it is suctioned off, washed with water and dried. The obtained blue colored pigment is insoluble in organic solvents and also in concentrated sulfuric acid.

Claims (1)

PATENT CLAIM: Process for the production of pigment dyes, characterized in that one anthraquinone derivatives of the general formula NH-R NH-R ₁ wherein R and R _{1 represent} organic radicals, one 1 * 0 of the radicals can also be hydrogen, and wherein the radicals R and R ₁ together must contain at least two amino groups, reacts with those polyfunctional compounds that work with the external amino groups or their func - I »5 nell derivatives react. 9502 5.54