DE929498C - Process for the production of water-insoluble azo dyes - Google Patents

Description

Process for the preparation of water-insoluble azo dyes It has been found that one arrives at water-insoluble azo dyes if one uses the diazo-. Tetrazo compounds from amines of the general composition: wherein Y is an optionally substituted AminoplienvIrest and Y is an optionally substituted Arvl- or Aminopheny lrest, with the azo components customary in ice dye technology, eg. ß. aromatic o-ozycarboxylic acid or acylacetic acid arvlamiden, in bulk or on a basis, while the components are selected so that they do not contain any water-solubilizing groups, e.g. ß. Sulphonic acid or carboxylic acid groups contain. Valuable dyes can be produced on acetyl cellulose, polyamide and polyurethane fibers from the components mentioned by the customary one-bath or two-bath processes, which, with good overall fastness properties, are particularly characterized by very good decatur and color fastness.

On the vegetable or animal fiber «earths according to known ones Dyeing and printing processes are also valuable dyeings with good general fastness properties obtain.

The dyes can and can also be produced in bulk are used in paint and printing ink technology; also let yourself be with process plastic pale to shaped structures.

The preparation of the diazo components required for the present `` "experience takes place by known processes, for example by condensation of a nitrobenzene carboxylic acid chloride with inonoacvlated Hydrazine, ring closure of the nitrobenzoyl hydrazine derivative thus obtained to the corresponding oxdiazole (i, 3, 4.) and subsequent reduction to the amino compound.

The new dyes are those known from patent specification 43o 58o, by coupling the diazo compounds from amino-substituted pseudoazimines with aryl amides of the 2,3-oxynaphthoic acid available water-insoluble azo dyes in the light fastness clearly superior.

Example i Polyamide silk is treated in a liquor ratio of 1:30 60 minutes in a bath containing 0.5 g of 2- (4'-aminophenyl) -5-phenyl-oxdiazole- (1, 3, .4) of the formula O C-`.... @ - N H. N (Melting point 182 °) -available by condensation of 4.-nitrobenzenecarboxylic acid chloride with benzoylhydrazine to form N-benzoyl-N '- (d-nitrobenzoyl) hydrazine, ring closure to 2 - (4'-nitrophenyl) - 5 - phenyloxdiazole - (1, 3, q .) and reduction to the corresponding amine] and 0.5 g of i - (- 2 ', 3'-oxycarbazole-carboylamino) -4-chlorobenzene, dissolved in 2.5 ccm of a mixture of equal parts diglycol and llonoethanolamine and 0.3 ccm caustic soda of 38 Be, and is charged with 8 g of a condensation product of higher molecular weight fatty acids and protein degradation products and 1 ccm 50% ammonia solution.

It is rinsed briefly and diazotized at 10 ° to 15 ° with 2 g of sodium nitrite and 10 cc hydrochloric acid at 20 ° B6 per liter of liquor.

It is then treated at 60 ° with 2 g of sodium acetate per liter of water, soaped and rinsed. A brown coloration of very good decatur and 1u is obtained Fastness to over-dyeing and very good fastness to washing, chlorine and superoxide.

If the same dye is produced by the usual dyeing methods on cotton thread, a yellow streaked brown of very good superoxy is obtained authenticity.

Example 2 Acetate rayon is treated in a liquor ratio of i: 3o 60 minutes in a bath containing 0.5 g of 2- (3'-aminophenyl) -5-phenyl-oxdiazole- (1,3,4) of the formula NH # o. I. -C C- NN (Melting point 185`) and 0.5 g of 1- (2 ', 3'-oxynaphthoylamino) -2-methyl-4.-methoxybenzene, dissolved in 2.5 cc of a mixture of equal parts of diglycol and monomhanolamine and 0.3 cc of 38 "Be sodium hydroxide solution, contains and is charged with 8 g of a condensation product of higher molecular weight fatty acids and protein degradation products and 1 ccm 50% ammonia solution.

It is rinsed briefly and diazotized at 10 ° to 15 ° with 2 g of sodium nitrite and 10 cc hydrochloric acid at 20 ° Be per liter of liquor.

It is then treated at 60 ° with 2 g of sodium acetate per liter of water, soaped and rinsed. A light scarlet fever of very good decatur and color is obtained Fastness to overdyeing and very good fastness to washing.

Example 3 Polyamide silk is treated in a bath in a liquor ratio of 1:30 60 minutes, which contains 0.25 g of 2, 5-bis- (4'-aminophenyl) -oxdiazole- (1, 3, 4) of the formula O _ H, N @i \ -C / 0 \ .C @ ... N H. No (Melting point 25o to 251 °) and 0.5 g of acetoacetylamino-2, 5-dimethoxy-.l-chlorobenzene, dissolved in 2.5 cc of a mixture of equal parts diglycol and; @ lonoethanolamine and 0.3 cc of sodium hydroxide solution of 38 ° B6, and with 1 cc 50% ammonia solution and 8 g of a condensation product of higher molecular weight fatty acids and protein degradation products is charged.

It is rinsed briefly and diazotized at 10 ° to 15 ° with 2 g of sodium nitrite and 10 cc hydrochloric acid at 20 ° B6 per liter of liquor.

It is then treated at 60 ° with -2 g of sodium acetate per liter of water, soaped and rinsed. A golden yellow of very good fastness to decatur, over-dyeing and washing is obtained. Example .l cotton yarn is in a bath prepared as usual, which contains 1.8 g of 1- (2 ', 3'-oxynaphthoylamino) -2, 5-dimethoxy-q.-chlorobenzene, treated, spun off and in a diazole (-) solution, in which 2.37 g of 2- (3'-amino-4 .'-methoxyphenyl) -5-phenyl-oxdiazole- (i, 3, q.) of the formula NH, 0 CH30-- -C "C- N -N (Melting point 166 to rt37-) in the form of diazonium chloride, developed, soaped and rinsed.

A yellow-tinged red coloration of very good light, 'V Ash, chlorine and superoxide fastness. Is used in the above example instead of of 1.8 g of i- (2 ', 3'-oxynaphthoylamino) -2, 5-dimethoxy-: 1.-chlorobenzene 5 g of 1- (2', 3'-Oxynaphthoylamino) -2, 5-dimethoxybenzene, a medium red of very good fastness to washing, chlorine, light and superoxide. Using of 4.5 g of Z- (2 ', 3'-oxy-naphthoylamino) -4-methoxybenzene instead of 1.8 g of 1- (2', 3'-Oxynaplitlioy-lamino) -2, 5-dimethoxy-4-clilorbenzene, a red of very is obtained good light, washing, chlorine and superoxy fastness.

Example 5 13.4 parts by weight of 2- (3'-amino-4'-metlioxyphenyl) -5-phenyl-oxdiazole- (i, 3, 4) are diazotized in the usual `` '' way. The diazo solution is then left at 10 ° in a solution of 17.9 parts by weight of 2- (2 ', 3'-oxy-naphthoylamino) -naphthalene run in 25 cc of 2 N atron lye, 125 cc of denatured alcohol and 500 cc of water.

After the coupling has ended, the resulting dye is filtered off, well washed and dried. After recrystallizing from chlorobenzene, it provides shiny metallic red needles with a melting point of 258 to 26o °.

The `` 'eni-ending for coloring polymerisation products made of polyvinyl chloride happens as follows zoo parts by weight of a polymerization product from z'inyl chloride, 5o Ge -, @ - ichtsteile phthalic acid di-n-butyl ester, which acts as a plasticizer, 0.3 parts by weight of titanium dioxide and 0.45 parts by weight of the azo dye "ground mixed and then homogenized on the kneading drum for 10 minutes at 14o °.

A soft rubber-like mass of red color is obtained.

The table below also contains a number of further components which can be used according to the invention and the color shades of the azo dyes obtainable therefrom, which likewise have good fastness properties Diazo component Azo component fiber material (color shade 1. 2- (3 'Amino-4'-methoxypheny # 1) - 1- (2', 3'-Oxynaphthoylamino) - Cotton Red 5-phenyl-oxdiazole- (1, 3, 4) naphthalene 2. Likewise 1- (2 ', 3'-Oxynaphthoylamino) - - yellowish 2-methoxybenzene red 3. Likewise 1- (2 ', 3'-Oxynaphthoylamino) - - Red 2,4-dimethoxy-5-chlorobenzene 4. 2- (3 '-_ @ niino-4'-methoxypheny-1) - 1 - (- 2', 3'-oxy-carbazolecarboylamino) - cotton brown 5-phenvl-oxdiazole- (1, 3, 4) 4-chlorobenzene 5th des-l. 1- (3'-oxydiphenylene oxide = 2'-car- - brown boylamino) -2, 5-dimethoxybenzene 6. 2- (1'-aminoplienyl) -5-phenyl-4,4'-bis (acetoacetylamino) - - coffee brown oxdiazol- (1, 3,: 1) 3, 3'-dimethoxydiphenyl 7. Same black carbazole-4'-carboylamino) - 4 "methoxybenzene B. the same. Z "- (5'-Oxv-i ', 2', 1, 2-benzo- - black carbazole-4'-carboy iamino) - 2 "-methy 1-4" -methoxy benzene <@. likewise. 4,4'-bis (acetoacetylamino) acetate silk yellow 3, 3'-dimethoxydipheny-1 ok same. Same. Yellow polyamide fiber il. 2,5-bis (4'-aniinoplienyl) - 1- (2 ', 3'-oxynaphthoylamino) - - bluish red oxdiazole- (i, 3, 4) 2-methS-1-4-methoxybenzene 12, des-1. 1- (2 ', 3'-Oxyziaphthoylamino) - - Red 2-methylbenzene 1,;. desgl_ Z- (2 ', 3'-Oxvcarbazolcarboylamino) - - reddish brown 4-chlorobenzene 14. Lik. Lik. Cotton - i5. 2,5-bis- (3'-aminopheny-1) -1 acetoacetylamino-2,5-dimeth- acetate art- yellow - oxdiazole- (i, 3, 4) oxy-4-clilorbenzene ropes (Melting point -218-) iti. Likewise polyamide fiber yellow 17th de sgl. 2- (2 ', 3'-oxy-naplithoylamino) - acetate art- orange naphthalene silk Diazo component Azo component Fiber material Color shade 18. 2, 5-bis- (3'-methyl-4'-amino-1- (a ', 3'-oxynaphthoylamino) - cotton light Bordeaux red phenyl) oxdiazole (1, 3, q.) benzene (Melting point 238 to 24o °) 19. 2, 5-bis (3'-methyl-q .'-amino-1- (2 ', 3'-oxynaphthoylamino) - polyamide fiber blue red phenyl) -oxdiazole- (1, 3, q.) 2-methyl-q.-methoxybenzene (Melting point 238 to 2q.0 °) 20. Likewise 1- (2 ', 3'-Oxynaphthoylamino) acetate silk, bluish-tinted red 2-methoxybenzene 21. Likewise 1- (2 ', 3'-Oxynaphthoylamino) - - Bordo 3-nitrobenzene 22. 2- (4'-Amino-2'-chlorophenyl) - 1- (2 ', 3'-Oxycarbazolcarboyl- cotton yellowish- 5-phenyloxdiazole- (1, 3, q.) Amino) -4-chlorobenzene brown (Melting point 184 to 185 °)

Claims (1)

PATENT CLAIM: Process for the production of water-insoluble azo dyes, characterized in that the diazo or tetrazo compounds have the general composition where X denotes an optionally substituted aminophenyl radical and Y denotes an optionally substituted aryl or aminophenyl radical, couples with the azo components customary in ice dye technology in substance or on a base and thereby selects the components so that they do not contain any water-solubilizing groups, e.g. B. sulfonic acid or carboxylic acid groups contain. Referenced publications: German patent specification no. Q.3o 58o.