DE1110403B - The coloring of high molecular weight organic products with pigments - Google Patents

Description

To organic pigments used for coloring organic products such as lacquers, plastic Masses such as polyvinyl chloride, printing inks or rayon can be used as the different demands made. The most important of these are: Extensive insolubility in organic Solvents, high light fastness even in weak colors, good migration fastness as well Temperature resistance.

While in the field of blue and green dyes in the phthalocyanines and chlorinated, respectively Phthalocyanine pigments were found which largely meet these requirements alone, existed in the Yellow and red series, especially in the field of vat dyes, so far no pigments, all of which met the conditions mentioned.

It has now been found that anthraquinone dyes of the general formula
, N,

NH-Z (1)

wherein X is a hydrogen atom or a benzoyl group and Z is a hydrogen atom or a 1-Anthraquinonyl radical means those mentioned at the outset To a high degree, meet conditions and are used for coloring high molecular organic products excellent.

organic products

with pigment dyes

Applicant:
CIBA Aktiengesellschaft, Basel (Switzerland)

Representative: Dipl.-Ing. E. Splanemann, patent attorney,
Hamburg 36, Neuer Wall 10

Claimed priority:
Switzerland from May 8, 1957

Dr. Armin Caliezi, Basel, Dr. Kurt Weber,

Bottmingen, and Max Jost, Basel (Switzerland),

have been named as inventors

These compounds are known as vat dyes and can be prepared by known methods, e.g. B. according to that of German Patent 590 163 by condensation of 1 mole of cyanuric chloride with 2 or 3 moles of an amine of the anthraquinone series are obtained, a product being obtained in the first case whose third chlorine atom is clogged with ammonia or lrAminoanthraquinone replace is.

Among these dyes, the dye of the formula has particularly good properties

A-NH-C

C-NH-A

NH-A
from, wherein each A denotes the 1-anthraquinonyl radical, and the dye of the formula

C-NH

109 620/45 +

The last-mentioned dye is used in as pure a form as possible. This requires that one with its production either pure starting materials and solvents, especially in the implementation of the cyanuric chloride with the l-amino-4-benzoylamino-anthraquinone pure tertiary bases are used or the 6-chloro-2,4-bis obtainable in the first stage - [(4) -benzoylaminoanthraquinonyl- (1) -amino] -1,3,5-triazine e.g. B. purifies by recrystallization. at Use of a not completely pure product will be colorations of reduced light and in particular Maintain migration authenticity.

If the pigments to be used according to the present process are not in finely divided form and / or in the modification particularly suitable for their use, they are subjected to conditioning before use, e.g. B. by dissolving the dye in conc. Sulfuric acid and precipitation to the dye or by grinding in dry or aqueous moist form, expediently in the presence of an organic 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 crude pigment in water aj at temperatures above 100 ⁰ C under pressure is achieved a good conditioning. 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 proves to be advantageous, for the purpose of converting it into a finely divided form, to grind the crude pigment with the substrate to be colored or a component thereof.

Compared to the pigment described in British Patent 691507, they show according to the invention Pigments to be used have the advantage of at least as good light and migration fastness to be significantly easier to manufacture.

In the following examples, unless otherwise stated, parts are parts by weight and percentages are percentages by weight.

example 1

A mixture of 13 parts of polyvinyl chloride, 7 parts of dioctyl phthalate, 0.1 part of cadmium stearate, 1 part of titanium dioxide and 0.04 part of the dye of the formula

are melted on a two roll mill at 140 ⁰ C and rolled for 5 minutes. The yellow-colored polyvinyl chloride film is then removed and allowed to cool.

Even if this film is exposed for 400 hours in the fadeometer, there is no change in the Hue.

If the colored film with a white film covered g and these two sheets under a pressure of 1,009 per square meter heated 8O ⁰ C, the white film remains completely unstained.

The dye used in this example can e.g. B. obtained in accordance with Example 1 of German Patent 590 163 by condensation of 15 parts of 1-aminoanthraquinone with 3.7 parts of cyanuric chloride at 110 to 150 ⁰ C in phenol in good yield

will. . .

Example 2

If, instead of the dye given in Example 1, one of the formula is used

In this way, ruby-red colorations of excellent light and migration fastness are obtained on polyvinyl chloride.

The dye used in this example can be obtained as follows.

34.2 parts of 1-amino-4-benzoylamino-anthraquinone are in 300 parts of nitrobenzene Jtnit 9.2 parts Cyanuric chloride with the addition of 16.4 parts of pure diethylaniline heated to 125 ° C. for 24 hours. After cooling and after the addition of 6 parts of sodium carbonate, it is filtered off. The product will washed first with hot nitrobenzene, then with benzene, then with acetone and finally with water. After drying, 34.6 parts of 6-chloro-2,4 - bis - [- (4) -benzoylamino-anthraquinonyl- (1) -amino] -l, 3,5-triazine are obtained as fine red crystals.

NH ₂ 30 parts of the product thus obtained are placed in a stirred autoclave with 600 parts of nitrobenzene, and ammonia is introduced under a pressure of 4 to 5 atmospheres. The mixture is then slowly heated up and ^{stirred at 140 to 150 °} C. for 15 hours.

After cooling, the nitrobenzene is vaporized driven off, the precipitated product filtered off and washed with water. You get so 29 parts of a bluish-tinged red crystal powder, from which concentrated sulfuric acid by falling over at low temperatures pure 6-amino-2,4-bis - [- (4) -benzoylamino-anthraquinonyl- (l) -amino] -1,3,5-triazine can be obtained in fine crystals.

Used in the condensation of the l-amino-4-benzoylamino-anthraquinone If technical diethylaniline is used with the cyanuric chloride, it is advisable to the 6-chloro-2,4-bis - [- (4) -benzoylamino-anthraquinonyl- (l) -amino] -l, 3,5- obtained in the first stage to recrystallize triazine from nitrobenzene.

This product gives a very pure pigment after reaction with ammonia.

Example 3

If, instead of the dye given in Example 1, one of the formula is used

NH-C C-NH-;

O _N ν O =

NH

the 6-chloro-2,4-bis - [- (4) -benzoylamino film obtained by reacting according to the above information Spread in a thin layer and baked for 1 hour at 120 ° C. You get a yellow one

anthraquinonyl- (l) -amino] -l, 3,5-triazines with aniline 25 varnish with excellent lightfastness, can be obtained at 150 ° C., ruby red colorations of excellent color are also obtained on polyvinyl chloride Light and migration fastness. Example 7

45

Example 4 like this

In a rod mill, 40 parts of a nitrocellulose lacquer, which contains 25% solids, 2.375 parts of titanium dioxide and 0.125 parts of the dye of the formula (4) were ground for 16 hours. Of the The lacquer obtained is spread in a thin layer onto an aluminum foil. You get a yellow one Lacquer coating with excellent lightfastness.

Example 5

32 parts of the dye of the formula (4) are treated in a kneader with 32 parts of acetyl cellulose (54.5% bound acetic acid), 32 parts ammonium chloride and 80 parts methyl glycol until achieved the desired degree of fineness of the pigment of 1 μ. Then 100 parts of water are added and knead until a fine-grain pulp is formed. This is brought to a suction filter and completely washed out the ammonium chloride with water. It is dried in a vacuum oven 85 ° C and grinds in a hammer mill.

To an acetate silk spinning mass consisting of 100 parts of acetyl cellulose and 376 parts of acetone 1.33 parts of the pigment preparation obtained are added. The mixture is stirred for 3 hours, which is complete Distribution of the dye is sufficient. That in the usual way by the dry spinning process The thread obtained from this mass is yellow in color and has very good fastness properties.

Example 6

0.25 parts of the dye of the formula (4) are mixed with 40 parts of an alkyd melamine stoving varnish, which contains 50% solids, and 4.75 parts of titanium dioxide ground in a rod mill for 24 hours. The paint obtained is applied to an aluminum

55

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

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

Example 8

A dyebath is ordered containing 15 parts of a copolymer latex per 1000 parts of water 85.8 parts of isobutyl acrylate, 9.6 parts of acrylonitrile and 4.6 parts of acrylic acid, 15 parts of a 70% emulsion a methylol melamine allyl ether emulsified with Turkish red oil and modified with soy fatty acid, .50 parts of a water-soluble methyl ether of a -urea-formaldehyde condensation product, the contains more than 2 moles of formaldehyde condensed per mole of urea, 5 parts of the according to Example 7, Paragraph 1 obtained pigment suspension and 20 parts of 10% formic acid.

Cotton fabric is introduced dry into the above dye liquor at room temperature, with the padder a fluid absorption of 65 to 80% squeezed, normally possibly under tension (clips or pin frames) and finally cured at 145 to 150 ° C for 5 minutes.

A yellow dyeing is obtained which is distinguished by excellent fastness properties, in particular light fastness, excels.

Example 9

Containing 162 parts of an aqueous filter cake 15% of the dye of the formula (4) (see example

game 1) with 9 parts of a butyl alcoholic with a dry content of about 75% Solution of a melamine-formaldehyde condensation product etherified with n-butanol and 9 parts of a polyvinyl chloride-polyvinyl acetate copolymer plasticized with 50% dioctyl phthalate and 9 parts of xylene are added. The mixture is poured in a kneading machine the "flush process", i. H. processed up to the union of the pigment with the resin phase. The secluded, Butanol-containing water is removed and the residue is extracted a further four times with water. Finally, 49 parts of a soft pigment resin composition are obtained.

14 parts of a condensation product of 1 mol are added to this kneadable pigment resin dough Nonylphenol and 10 moles of ethylene oxide are added, carefully kneaded and diluted 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 10

10,000 parts of a paper pulp containing 4 parts of cellulose per 100 parts of water are used in the Hollander treated for about 2 hours. During this time you give every quarter of an hour

4 parts of resin glue, then 30 parts of the pigment dispersion obtained according to Example 7, paragraph 1, and then on

5 parts of aluminum sulfate.

After completion on the paper machine, a strong yellow colored paper of excellent quality is obtained Lightfastness.

Claims (1)

PATENT CLAIMS:
1. Use of the anthraquinone dyes of the general formula NH-Z wherein X is a hydrogen atom or a benzoylamino group and Z is a hydrogen atom or means a 1-anthraquinonyl radical, as pigment colors for high molecular organic products. 2. Use of the pigments according to claim 1, characterized in that the dyes according to the formula .N, A-NH-C C-NH-A NH-A are constructed in which each A denotes the 1-anthraquinonyl radical. 3. Use of the pigments according to claim 2, characterized in that the dyes according to the formula are constructed. HN —C
M. / < C-NH O 11
N \ f
C. N O NH 1 Considered publications: German Patent No. 933 144; British Patent No. 691507. 109 620/45 * 6.61