DE1109359B - The coloring of high molecular weight organic products with pigment dyes - Google Patents

Description

The coloring of high molecular weight organic products with pigment dyes To organic pigments used for coloring polymeric organic products, such as lacquers, plastic masses such as polyvinyl chloride, printing inks or rayon can be used, the most diverse claims are made.

The most important of these are: extensive insolubility in organic Solvents, high light fastness even in weak colors, good migration fastness as well as temperature resistance.

While in the field of blue and green dyes in the phthalocyanines or chlorinated phthalocyanine pigments have been found that meet all of these claims largely sufficient, there were in the yellow and red series, especially in the field the vat dyes, so far no pigments that met all of the conditions mentioned.

It has now been found that anthraquinone dyes of the general formula in which X is a sulfur atom or a - NH group, meet the conditions mentioned at the outset to a high degree and are outstandingly suitable for dyeing organic high molecular weight products.

Some of these compounds were previously known as vat dyes and can be prepared by known processes, in particular by heating the compounds of the formula in which X has the meaning given, can be obtained with alkalis.

With the dyes to be used now, colorations of high light and migration fastness.

If the proposed pigments are not finely divided from the outset Form and / or in the for their use is particularly suitable modification, it is advisable to subject it to conditioning before application, for example by converting the dye into concentrated sulfuric acid into the sulphate and converting the latter back to the dye or by grinding in dry or water-moist form, expediently in the presence of an organic one water-soluble or water-insoluble solvent or by kneading or Grinding the crude pigment in the presence of solid auxiliaries, e.g. B. leachable salts. Also by heating the raw pigment in water to temperatures above 100 "C and below Good conditioning is achieved under pressure. Also the combination of different Methods, e.g. B. Swelling of the crude pigment in sulfuric acid and subsequent treatment with organic solvents, can lead to good results. In many cases it is advantageous to convert the crude pigment into a finely divided form, to be ground with the substrate to be colored or a component thereof.

In the French patent 824 111 the use of N, N'-Diisopropyl-dipyrazolanthronyl for coloring lacquers and plastic materials recommended. In contrast, the dyes to be used according to the invention stand out by a significantly better migration fastness.

In the examples below, the parts unless they mean nothing otherwise stated, parts by weight, percentages percentages by weight.

Example 1 5 parts of diisothiazolanthrone, prepared according to German Patent 343 065 by heating isothiazole anthrone with potassium hydroxide in alcohol, are mixed with 95 parts of dioctyl phthalate and so long in a ball mill grind until the dye particles are smaller than 3 u.

0.8 parts of this dioctyl phthalate paste are mixed with 13 parts of polyvinyl chloride, 7 parts of dioctyl phthalate, 0.1 part of cadmium stearate and 1 part of titanium dioxide are mixed and then rolled out on the two-roll mill at 1400 C for 5 minutes.

A yellow coloration of very good fastness to light and migration is obtained.

(To test the migration, the colored film was covered with a white Foil covered and these two foils under a pressure of 1.009 g per square centimeter Heated to 80 ° C. for 24 hours. Example 2 40 parts are made in a rod mill of a nitrocellulose lacquer, 2.375 parts of titanium dioxide and 0.125 parts of dipyrazole anthrone, which was obtained according to German patent 255 641 by heating pyrazolanthrone ground with potassium hydroxide in alcohol for 16 hours. The varnish obtained is on an aluminum foil spread in a thin layer.

A yellow lacquer coating with very good fastness properties is obtained.

Example 3 To a mixture of 100 parts of pyridine, 10 parts of the Potassium salt of the product used in Example 2 is 10 parts with stirring Benzoyl chloride entered. Then reflux for 1 hour, allow to cool to 20 C, filtered and dried.

32 parts of the yellow powder obtained are treated in a kneader with 32 parts of acetyl cellulose (54.5 01o bound acetic acid), 32 parts of ammonium chloride and 80 parts of methyl glycol to achieve the desired degree of fineness of the Pigment of 1.4. Then add 100 parts of water and knead until a fine-grain pulp has arisen. This is brought to a suction filter and the ammonium chloride was completely washed out with water. It is dried in a vacuum oven at 85 ° C and grinds in a hammer mill.

To one consisting of 100 parts of acetyl cellulose and 376 parts of acetone Acetate silk spinning mass is added to 1.33 parts of the pigment preparation obtained.

The mixture is stirred for 3 hours, which is sufficient for complete distribution of the dye suffice. The usual way after the dry spinning process from this mass The thread obtained is yellow in color and has very good fastness properties.

Example 4 0.25 parts of the dye used in Example 1 are used with 40 parts of an alkyd melamine stoving enamel, which contains 500in solids, and 4.75 parts of titanium dioxide were ground in a rod mill for 24 hours. The received Varnish is spread on an aluminum foil in a thin layer and 1 hour at Baked at 120 "C. A yellow lacquer coating with excellent lightfastness is obtained.

Example 5 4.8 parts of the dye used in Example 2 are used with 4.8 parts of dinaphthylmethanedisulfonic acid and 22.1 parts of water as long in ground in a ball mill until all the dye particles are smaller than 1. The so pigment suspension obtained has a pigment content of about 15%.

If this aqueous suspension is added to viscose spinning mass, it is obtained a yellow-colored cellulose thread of very good quality is obtained by the usual spinning process Fastnesses.

Example 6 A dyebath is ordered containing 1000 parts of water 15 parts of a copolymer latex composed of 85.8 parts of isobutyl acrylate and 9.6 parts Acrylonitrile and 4.6 parts of acrylic acid, 15 parts of a 700/0 emulsion with one Turkish red oil emulsified methylol melamine allyl ether modified with soy fatty acid, 50 parts of a water-soluble methyl ether of a urea-formaldehyde condensation product, which contains more than 2 moles of formaldehyde condensed per mole of urea, 5 parts the pigment suspension obtained according to Example 5, paragraph 1 and 20 parts 100 / ge Formic acid.

Cotton fabric is dry in the above dye liquor at room temperature inserted, squeezed off at the padder with a liquid absorption of 65 to 800in, normal, possibly dried under tension (clips or needle frames) and finally cured at 145 to 1500 C for 5 minutes.

A yellow coloration is obtained, which is characterized by excellent fastness properties, especially lightfastness.

Example 7 162 parts of an aqueous filter cake containing 15% of the dye used in Example 1, with 9 parts of a dry content of about 750 / o having butyl alcoholic solution of one etherified with n-butanol Melamine-formaldehyde condensation product and 9 parts of one with 500 / o dioctyl phthalate plasticized polyvinyl chloride polyvinyl acetate copolymer and 9 parts Xylene added. The mixture is mixed in a kneading machine until the »flushing process« has ended, d. H. processed up to the union of the pigment with the resin phase. The secluded, Butanol-containing water is removed and the residue is further washed four times with water extracted. Finally, 49 parts of a soft pigment-resin composition are obtained.

14 parts of a condensation product are added to this kneadable pigment-resin dough from 1 mole of nonylphenol and 10 moles of ethylene oxide, knead carefully and dilute with 37 parts of water.

The resulting paste has a good distribution and is suitable in combination with aqueous binders excellent for textile printing.

Example 8 10,000 parts of a paper pulp, containing per 100 parts Water, 4 parts of cellulose, are treated in the Hollander for about 2 hours. During this time, 4 parts of resin glue are added every quarter of an hour, then 30 parts of the according to Example 5, Paragraph 1, pigment dispersion obtained and then add 5 parts of aluminum sulfate.

After completion on the paper machine, a strong yellow color is obtained Paper with excellent lightfastness.

Claims (2)

PATENT'S CLAIMS: 1. Use of the anthraquinone dyes of the general formula wherein X represents a sulfur atom or an -NH- group, for coloring high molecular organic products. 2. Use of the dyestuffs according to Claim 1, characterized in that the pigments used are diisothiazolanthronyl of the formula used. Documents considered: French patent specification No. 824 111.