DE1148678B - Process for the production of metal-containing, water-insoluble azo dyes - Google Patents

Description

Process for the preparation of metal-containing, water-insoluble azo dyes It has now been found that metal-containing, water-insoluble azo dyes are obtained if the diazonium compounds are obtained from amines of the general formula where Ri and R2 denote alkyl, aryl, aralkyl or cycloalkyl radicals, which can also be linked to form a heterocyclic ring, with arylamides of aromatic or heterocyclic o-oxycarboxylic acids in substance, on the fiber or on another substrate, wherein the components are chosen so that they are free of groups which make them soluble in water, such as sulfonic acid or carboxylic acid groups, and the dyes thus obtained are treated with metal donating agents.

The treatment of the water-insoluble substances obtainable according to the process Azo dyes with the meta-donating agents can be used during or after the coupling in substance or on the fiber in a known manner. In the preparation of the dyes on the fiber can be done in such a way that the metallization is carried out Adding the metal donating compounds to the development bath or these Already adding compounds to the primer bath. Treatment of the dyes with the metal-releasing agents after coupling can be done in a second bath, that is kept neutral, weakly alkaline or weakly acidic and that if necessary Dispersants and detergents, for example fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, Alkylnaphthol polyglycol ethers, fatty acid polyglycol esters or fatty acid amide polyglycol ethers copper, cobalt, nickel, iron and manganese-releasing compounds into consideration, in the form of their inorganic or organic salts, for example as chlorides, Bromides, sulfates, nitrates, formates or acetates, or as complex compounds, in particular with oxyalkylamines, for example diethanolamine, triethanolamine or N-methylethanolamine, or with aminocarboxylic acids, e.g. B. aminoacetic acid or nitrilotriacetic acid, or with aliphatic oxycarboxylic acids, e.g. B. citric acid, tartaric acid, gluconic acid or glycolic acid, or with alkali phosphates, e.g. B. alkali pyrophosphates or alkali polyphosphates, come into use. When using a cobalt-releasing agent works an addition of compounds of hexavalent chromium is beneficial to the metallization the end.

On vegetable fibers, including those made from regenerated Cellulose, is obtained using the dyeing and printing processes known from ice dye technology Dyes which have good general fastness properties, in particular very good Distinguish iron and light fastness.

Those using aryl amides of 2,3-oxynaphthic acid are particularly valuable available as azo components and nickel compounds as metal donors Shades of brown.

The production of the dyes on vegetable fibers can take place in long liquors. Piece goods, chains or ribbons can also be colored continuously or printed using the process of base or naphtholate printing.

The dyes can also be used on animal fibers, such as wool or silk, as well as on synthetic fibers such as polyamide, acetyl cellulose or polyvinyl alcohol fibers, are produced according to the dyeing processes customary for these fibers, and likewise valuable dyeings with good fastness properties can be obtained.

The dyes can also be produced in substance and through Treating with metal donating agents converting them into the metan complex compounds. The metallization can be in aqueous suspension or in an organic solvent, such as acetone or dimethylformamide. The metal complex compounds obtainable in this way are suitable for coloring of animal and synthetic fibers as well of high molecular weight organic plastic masses.

Arylamides can be used as azo components in the process according to the invention of aromatic or hetero-cyclic o-oxycarboxylic acids, for example 2,3-oxynaphthoic acid or their derivatives substituted in the 6-position, of 2-oxyanthracene-3-carboxylic acid, the 3-oxydiphenylenoxyd-2-carboxylic acid, the 2-oxycarbazole-3-carboxylic acid or the 5-Oxy-1,2,1 ', 2'-benzocarbazole-4-carboxylic acid find use.

The diazo components used in the process according to the invention are 1-aminobenzene-2-carboxylic acid dialkylamides, -alkylaralkylamides, -alkylarylamides, -alkylcycloalkylamides, -diarylamides, -dicycloalkylamides, -diaralkylamides, -arylcycloalkylamides, -aralkyleycloalkylamides, -arylaralkylamides and 1-aminobenzene-2-carboxamides, in which R, and R, to form a heteroeyclic ring are considered.

These compounds can be prepared by known processes take place, for example by condensation of o-nitrobenzoic acid with secondary Amines and subsequent reduction of the nitro group, for example with iron, in weakly acidic solution or catalytic with nickel as a catalyst.

In most cases the compounds are obtained after the reduction in sufficiently pure form so that a purification before use as a diazo component is not required.

Compared to the nickel complex compound of the azo dye known from Example 3 of US Pat. No. 2,416,248 of diazotized 1-aminobenzene-2-carboxylic acid and 1- (2,3'-oxynaphthoylamino) -4-chlorobenzene, the dyes obtainable according to the process have an analogous composition by the better washfastness of the cotton dyeings. Example 1 Cotton yarn is in the liquor ratio 1 -. 20 45 minutes at 35 ° C in the primer bath described below, spun off and first developed for 10 minutes at 20 ° C and then after slow heating to 90 to 95 ° C for 20 to 30 minutes at 90 to 95 ° C in the developing bath described below . Then it is rinsed with 3 cc hydrochloric acid of 201 B6 per liter of water, first 15 minutes at 60 ° C, then 15 minutes at 95 ° C with 1 g of an action product of about 10 moles of ethylene oxide to 1 mole of isododecylphenol and 3 g of calcined soda per liter Soaped in water, rinsed and dried. Primer bath 1.75g2- (2 ', 3'-oxynaphthoylamino) -naphthalene are added to 3.5 ccm of denatured ethyl alcohol, 0.9 ccm of 38' B6 sodium hydroxide solution , 1.8 ccm of warm water and 0.9 ccm of formaldehyde (330 / ( The solution obtained in this way is adjusted from 38 ° B6 to 11 with water at 35 ° C., 3 g of a condensation product of higher molecular weight fatty acids and protein degradation products and 10 cc of sodium hydroxide solution.

Development bath 1.35 g of 1-aminobenzene-2-carboxylic acid-N-methyl-N- (2'-methyl) -phenylamide are diazotized with 4 cc hydrochloric acid of 20 'B6 and 4 cc sodium nitrite solution 1 : 5 and the diazo solution prepared in this way is diazotized in a bath given the (/ oig 501) in water 11 2 g of the action product of about 20 moles of ethylene oxide to 1 mole Oetadecylalkohol, 3 cc of acetic acid 10 g sodium acetate and 2.9 g NiS04 - contains 7 H, 0th

A red-brown dyeing with good fastness properties is obtained.

Example 2 Cotton fabric is made on the padder with the following solution padded and dried.

12.8 g 2,3-Oxynaphthoylaminobenzol be made into a paste with 20 g of a wetting agent of the type of ölsulfonate 17ccm and sodium hydroxide solution from 38'B6 and adjusted with boiling water. 11 The dried material is developed on the padder with a solution containing 12 g of 1-aminobenzene-2-carboxylic acid-N-methyl-N- (2'-methyl) -phenylamide, diazotized with 20 cc of hydrochloric acid of 20 'B6 and 20 ccm of sodium nitrite solution 1 - 5 contains 2 g of an action product of about 20 moles of ethylene oxide to 1 mole of octadecyl alcohol and 20 g of sodium acetate.

After 30 seconds of air passage and a passage of hot water, the dyeing is aftertreated for 5 minutes at 60 ° C. with 5 g of soap per liter of water and dried. The dried fabric is printed with a printing paste containing 1 kg of 200 g of sodium formaldehyde sulfoxylate, 25 g of sodium benzylsulfanil, 50 g of potassium carbonate, 30 g of anthraquinone dough (301 / oig) and starch tragacanth as a thickener.

It is then steamed for 7 minutes at 102 to 103 ° C , washed with hot, dilute soda solution, rinsed and aftertreated for 15 minutes at 90 to 95 ° C with a solution containing 1 g of an action product of about 10 moles of ethylene oxide to 1 mole in liter of water Contains isododecylphenol, 1 g soda, 3 g aminoacetic acid and 2.8 g NiS04 - 7 H "0.

Then it is rinsed and dried.

A white etch on a red-brown background is obtained. The use of vat dyes in the printing paste also enables colorful effects to be produced on a red-brown background. Example 3 Woolen yarn is treated in a liquor ratio of 1:30 45 minutes at 55 ° C. in the subsequent primer bath and then rinsed for 5 minutes at 18 to 20 ° C. with 40 g of common salt and 3 g of soda per liter of water. It is then allowed to drain and treated first for 20 to 30 minutes at 18 ° C. and, after slowly heating the bath to 90 to 95 ° C., for 15 to 30 minutes at 90 to 95 ° C. in the developing bath. Then first 20 minutes at 40 ' C with 1 g of an action product of about 20 moles of ethylene oxide on 1 mole of octadecyl alcohol and 1 ccm of ammonia (25%) in the liter of water and then 20 minutes at 85' C with 1 g of a condensation product from a Aminoalkylsulfonic acid and a higher molecular weight fatty acid and 0.5 cem acetic acid (501 / uig) soaped in one liter of water, rinsed and dried.

Primer bath 1 g of 1- (2 ', 3'-oxynaphthoylamino) -2-methyl-4-chlorobenzene and 0.6 g of sodium hydroxide are denatured in 5 cc of ethyl alcohol, 4 cc of water at 60 ° C, 0.5 g of a condensation product higher molecular weight fatty acids and protein degradation products and 1.2 cem formaldehyde solution (33%) dissolved and adjusted to 11 with water at 60 ° C., 2.5 g of a condensation product of higher molecular weight fatty acids and protein degradation products and 3 g soda.

Development bath 0.85 g of 1-aminobenzene-2-carboxylic acid-N-ethyl-N- (4'-methyl) -phenylamide are diazotized with 2 cc of hydrochloric acid of 20 'B6 and 2 cc of sodium nitrite solution 1 : 5 . The diazo solution obtained is placed in a bath containing 2 g of the action product of about 20 moles of ethylene oxide to 1 mol octadecyl alcohol, 2 cc of acetic acid (501 / oig), 10 g of sodium acetate and 1.8 g CuS04 - contains 5 H20.

A yellowish brown coloration with good fastness properties is obtained.

If, in the above example , 1.6 g of COC12 - 6 H.0 are used instead of 1.8 g of copper sulphate - 5 H., 0, you get a brownish scarlet coloration; when using 2.1 g N'S04 - 7 H20 gives a red-brown of likewise good fastness properties. Example 4 Polyamide yarn is treated in a liquor ratio of 1:20 for 1 hour at 80 'C with a solution containing 1 g of 1- (2', 3'-oxynaphthoylamino) -2-methoxybenzene, 0.5 ccm of 38 ' sodium hydroxide in one liter of water. B6, 10 cc of denatured ethyl alcohol, 2 g of a wetting agent of the oil sulfone type and 0.5 g of 1-aminobenzene-2-carboxylic acid N-phenyl-N-benzylamide.

It is then rinsed and treated for 50 minutes at 20 ° C. with a solution which contains 2 g of sodium nitrite and 3 cc of 20 ° B6 hydrochloric acid in one liter of water. It is then treated for 10 minutes at 60 ° C. with a solution which contains 0.5 cem of concentrated ammonia and 4 g of sodium acetate per liter of water. Then, it is rinsed and treated for 30 minutes at 90 to 95 'C with a solution containing per liter of water, 2.5 g CuS04 - contains 5 H, 0th It is then rinsed, soaped for 15 minutes at 90 ° C. with 1 g of an action product of about 10 moles of ethylene oxide to 1 mole of isododecylphenol and 3 g of soda per liter of water, rinsed and dried.

A yellowish brown coloration with good fastness properties is obtained.

If, in the above example in place of 2.5 g CuS04 - 5 R, 0 2.4 g CoC1, - 6 H20, one obtains a rotsticfiige Braunfär # ung-, when using 2.8 g NiS04 - 7 H .0 a rust-red coloration with good fastness properties is obtained. Example 5 Polyvinyl alcohol yarn is treated in a liquor ratio of 1:30 for 1 hour at 90 to 95 ° C. in the following solution: 1 g of 2,3-oxynaphthoylaminobenzene and 0.5 g of 1-aminobenzene-2-carboxylic acid-N-methyl-N- ( 2'-methyl) -phenylamide are dissolved in 5 ccm of denatured ethyl alcohol, 5 ccm of dimethylformamide, 0.5 ccm of 38 ' B # sodium hydroxide solution and 2.5 ccm of water and introduced into a bath containing 2 liters of water & a wetting agent from Type of oil sulfonates and 5 cc. Contains caustic soda of 38 ' B6.

It is then rinsed and treated for 30 minutes at 65 ° C. with a solution which contains 2 g of sodium nitrite and 3 ccm. Contains hydrochloric acid of 20 'B6. Then allowed to drip and treated for 15 minutes at 95 'C in a bath g per liter water 4 sodium acetate, 2 g of the action product of about 10 moles of ethylene oxide to 1 mole isododecylphenol and 2 g CuS04 - 5 H20 contains. Then it is rinsed and dried.

A yellowish brown coloration with good fastness properties is obtained.

Is used in the above example in place of 2 g CuS04 - 5 H20 2 g CoC4 - 6 H20, we obtain a brownish scarlet coloring; when using 2 g of NiS04 * 7 H20, a red-brown coloration with likewise good fastness properties is obtained. Example 6 Natural silk is a liquor ratio of 1: 30 for 45 minutes at 25 'C in the following Grundierungsbad treated, centrifuged, and then 15 minutes at 201 C and after slowly warming to 95 in the following developing bath' develops C for 20 minutes at this temperature. Then it is rinsed, acidified with 3 g of hydrochloric acid of 20 'B6 per liter of water, rinsed and soaped for 15 minutes at 95 ° C. with 5 g of soap per liter of water, rinsed and dried. Priming bath 3 g of 2,3-oxynaphthoylaminobenzene are dissolved in 6 cc of denatured ethyl alcohol, 1.5 cc of 38B # sodium hydroxide solution, 3 cc of warm water and 1.5 cc of formaldehyde solution (33 # ”/ oig) water at 25 'C, 5 g of a condensation product of higher molecular weight fatty acids and protein degradation products, 4 cc of sodium hydroxide solution of 38' B # and 10 g Natriumehlorid adjusted to 11. developing bath 1.82 g of 1-aminobenzene-2-earbonsäure-N-phenyl-N- benzylamide are diazotized with 2.35 cc of hydrochloric acid of 20 'B6 and 2.4 cc of sodium nitrite solution 1: 5. The diazo solution is introduced into a bath containing 2 g of an action product of about 20 moles of ethylene oxide on 1 mole of octadecyl alcohol, 3 cc of acetic acid ( 501 / oig), 10 g sodium acetate and 2 g NiS04 * 7 H, 0 and adjusted to 11 with water.

A red-brown dyeing with good fastness properties is obtained.

Is used in the above example in place of 2 g NiS04 - 7 H20 1.75 g CuS04 - 5 H # O, then one obtains a rust-red coloration; at Verwendäng of 1.65 g CoQ, - 6 H, 0 is obtained a brownish scarlet coloring also good fastness properties.

Example 7 23 parts by weight of 1-aminobenzene-2-carboxylic acid-N-methyl-N-phenylamide hydrochloric acid are diazotized n-20,5Volumteilen with 5N sodium nitrite solution at 30'C in 400Volumteilen water and 50 parts by volume. 5 The cleared yellow diazo solution is allowed to run at 40 ° C. into a suspension of 26.1 parts by weight of 2,3-oxynaphthoylaminobenzene in 100 parts by volume of water, 10 parts by volume of vinegar, 68 parts by weight of sodium acetate and 1 g of a dispersant.

After the coupling has ended, the mixture is neutralized with sodium hydroxide solution and, after the addition of 25 parts by weight of crystallized copper sulfate and 60 parts by weight of triethanolamine, the mixture is heated to 80 to 90 ° C. with stirring.

After the metallization has ended, the copper complex compound formed is filtered off while hot, first washed neutral with water and then washed with 100 parts by volume of methyl alcohol. After drying at 70 to 80 ° C. , the copper complex compound is obtained in the form of a reddish-tinged brown powder which is sparingly soluble in alcohol and easily soluble in benzene. If, in the above example for the metallization in place of 25 parts by weight copper sulfate and 60 parts by weight Triäthanolanlin 28 parts by weight NiS04 - 7 H, 0 to 30 parts by weight of aminoacetic acid, one obtains the nickel complex compound of the dyestuff in the form of a red powder that is difficult in alcohol, in Benzene is easily soluble. In the same way, using 28 parts by weight of crystallized cobalt sulfate and 30 parts by weight of aminoacetic acid, the cobalt complex compound of the dye is obtained in the form of a red-brown powder which is sparingly soluble in alcohol and easily soluble in benzene.

The table below also contains a number of further components which can be used according to the invention and the color shades of the metal-containing azo dyes obtainable on the fiber, which likewise have good fastness properties. Hue of Diazo component azo component copper complex- 1 cobalt complex- nickel complex- connection : connection connection 1-Anünobenzol-2-earbon- 2,3-Oxynaphthoylaminobenzol Rust Rust Rust brown acid-N-ethyl-N- (2'-me- ethyl) phenylamide also 1- (2 ', 3'-Oxynaphthoylanüno) - rust yellowish- bluish- 3-nitrobenzene brown red-brown the same. 1- (2 ', 3'-Oxynaphthoylamino) - yellowish - rust costly red naphthalene brown Likewise 2- (2,3'-Oxynaphthoylamino) - yellowish rust red-brown naphthalene brown dese. 1- (2 ', 3'-Oxynaphthoylaraino) - Rust Rust Reddish brown 2-methoxy-4-chloro-S-methyl- benzene Likewise 1- (2 ', 3'-Oxynaphthoylan-iino) - brownish yellow yellowish reddish brown 2-methylbenzene brown likewise 1- (2 ', 3'-oxynaphthoylamino) - B yellowish yellow yellowish reddish brown 2-methyl-4-chlorobenzene brown likewise 1- (2 ', 3'-oxynaphthoylamino) - brownish yellow, yellowish-reddish brown 2-methyl-4-methoxybenzene brown d e sg, 1. 1- (2 ', 3'-Oxynaphthoylamino) - rust rust reddish brown 2,4-dimethoxy-5-chlorobenzene the same. 1- (2'.3'-Oxynaphthoylainino) - rust rust reddish brown 2,5-dimethoxy-4-chlorobenzene likewise 4,4'-bis (2 ", 3" -oxynaphthoyl-red-brown red-bralan red-brown amino) -3,3'-dimethoxy- diphenyl likewise 1- (2'-oxycarbazole-3'-carboyl- bluish-yellowish brown yellowish brown amino) -4-chlorobenzene red-brown dese. 1- (3'-oxydiphenylene oxide- red brown yellowish brown bluish tinge- 2'-carboylamino) -2,5-dimeth- red-brown oxybenzene likewise 1- (2'-oxyanthracene-3'-carboyl violet violet Bordo amino) -2-methylbenzene likewise 1- (2 ', 3'-oxynaphthoylamino) - reddish brown yellowish brown reddish brown 2-ethoxybenzene also 2- (2 ', 3'-Oxynaphthoylaraino) - yellowish brown 1 rust reddish brown 3-methoxydiphenylene oxide likewise 1- (6'-bromo-2 ', 3, -oxynaphthoyl- yellowish brown rust red brown amino) -2-methoxybenzene Hue of Diazo component azo component copper complex- cobalt complex- nickel complex- connection connection connection, - 1-aminobenzene-2-carbon- 1- (5'-oxy-l ', 2', 1 ", 2" -benzo- blackish- blackish- blackish- acid-N-ethyl-N- (2'-me-earbazole-4'-carboylamino) korinth korinth korinth ethyl) phenylamide 4-methoxybenzene the same. 1- (5'-Oxy-l ', 2', 1 ", 2" -benzo- blackish- blackish- blackish- carbazole-4'-carboylamino) - korinth korinth korinth 2-methyl-4-methoxybenzene likewise 1- (2 ', 3'-oxynaphthoylamino) - reddish brown rust reddish brown 2-methyl-5-chlorobenzene Likewise 1- (2 ', 3'-Oxynaphthoylamino) - reddish brown rust reddish brown 2,4-dimethylbenzene likewise 1- (2 ', 3'-oxynaphthoylamino) - reddish brown rust reddish brown 2,3-dimethylbenzene 1-aminobenzene-2-carbon- 1- (2 ', 3'-oxynaphthoylanüno) - yellowish brown yellowish brown reddish brown acid dicyclohexylamide 4-methoxybenzene also 1- (2 ', 3 # -oxynaphthoylanüno) - rust reddish-reddish brown 2-methoxybenzene brown desgL 1- (2 ', 3'-oxynaphthoylamino) - yellowish brown yellowish brown reddish brown 4-chlorobenzene likewise 1- (2 ', 3'-oxynaphthoylamino) - yellowish brown, reddish brown 2,5-dimethoxybenzene brown likewise 1- (2,3'-oxynaphthoylamino) - yellowish brown reddish brown 2-methoxy-5-chlorobenzene brown likewise 1- (2 ', j'-oxynaphthoylamino) - yellowish brown yellowish brown reddish brown 4-methylbenzene likewise 1- (2 ', 3'-oxynaphthoylamino) - yellowish brown yellowish brown reddish brown 4-ethoxybenzene the same. 1- (3'-Oxydiphenylenoxyd- red-tinged red-brown red-brown 2'-carboylanüno) naphthalene brown the same. 1- (3'-Oxydiphenylenoxyd- red-tinged red-brown red-brown 2'-carboylanüno) -2-ethoxy brown benzene 1-aminobenzene-2-carbon-4,4'-bis (2 ", 3" -oxynaphthoyl- red brown red brown red brown acid dimethylainide anüno) -3,3'-dimethoxy- diphenyl 1- aminobenzene-2-carbon- 1- (2 ', 3'-oxynaphthoylamino) - yellowish brown yellowish reddish brown acid diethylamide 2,5-dimethoxybenzene brown 1- aminobenzene-2-carbon- 1- (2 ', 3'-oxynaphthoylamino) - reddish brown yellowish brown reddish brown acid-di-n-butylanud 4-methoxybenzene 1- aminobenzene-2-carbon- 1- (2 ', 3'-oxynaphthoylamino) - brownish yellow yellowish reddish brown acid-N-ethyl-N-phenyl-2-methylbenzene brown amide 1- aminobenzene-2-carbon- 1- (2 ', j'-oxynaphthoylanüno) - reddish-yellowish brown reddish brown acid-N-methyl-N- (2'-me-2,5-dimethoxybenzene brown ethyl) phenylamide 1- aminobenzene-2-carbon- 1- (2 ', 3'-oxynaphthoylamino) - yellowish brown yellowish red brown acid-N-ethyl-N- (4'-me-2,4-dimethoxy-5-chlorobenzene brown ethyl) phenylamide 1-aminobenzene-2-carbon- 2- (2,3'-oxynaphthoylamino) - yellowish-yellowish-red-brown acid-N-methyl-N- (4'-menaphthalene brown brown ethyl) phenylamide 1-aminobenzene-2-carbon- 1- (2 ', - i'-Oxynaphthoylanüno) - yellowish brown reddish brown acid piperidide 2,5-dimethoxy-4-chlorobenzene brown Hue of Diazo component azo component cobalt iron kor # iplex- k ## TpglTx'- complex- connection connection connection connection 1-aminobr, nzol-2-carbon- 1- (2 *, 3 # -oxynaphthoylamino) - yellow- reddish- acid-N-methyl-N- (2'- 2-methoxy-4-chloro-5-meticulous brown chlorine) phenylamide ethylbenzene brown 1-aminobenzene-2-carbon- 1- (3 '# - oxydiphenyloxide- yellow- red-brown acid dibenzylamide 2'-carboylan-iino) -naphtha- ]in Brown 1-aminobenzene-2-carbon- 1- (2 ', 3'-oxynaphthoylamino) - red brown red brown acid morpholide 2,4-dimethoxy-S-chloro- benzene 1-aminobenzene-2-carbon- 2,3-oxynaphthoylamine in scarlet fever acid-N-phenyl-N-benzylbenzene amide Hue of the metal complex Diazo component Azo component Metal complex compound 1 connection 1-anünobenzene-2-carboxylic acid 1- (2,3 # -oxynaphthoylanlino) - rust red nickel complex- N-methyl-N- (2'-methyl) -phenyl-naphthalene compound amide also 1- (2 ', 3'-Oxynaphthoylanüno) - rust red copper complex- naphthalene compound the same 2,3-oxynaphthoylaminobenzene red-brown copper complex link desgL 2- (2 ', 3'-oxynaphthoylamino) - red-brown copper complex- naphthalene compound 1-aminobenzene-2,5-dicarboxylic acid- 2,3-oxynaphthoylaminobenzene red-brown nickel complex- di-N-methyl-N-phenylane: üd compound also 1- (2 ', 3'-Oxynaphthoylamino) - red-brown nickel complex- 2-methyl-4-chlorobenzene compound also 2- (2,3'-oxynaphthoylamino) - rust red nickel complex- 3-methoxydiphenylene oxide compound 1-A-rainobenzene-2,5-di-carboxylic acid 1- (2 ', 3'm-Oxynaphthoylamino) - red-brown nickel complex- di-N-methyl-N- (2'-chloro) -phenyl-3-nitrobenzene compound amide also 1- (2 ', 3'-Oxynaphthoylamino) - rust red nickel complex- 2-methoxy-4-chloro-5-methyl compound benzoi also 1- (2,3 "-oxynaphthoylan: dno) - rust red nickel complex- 2,4-dimethoxy-5-chlorobenzene compound 1-Amino-4-chlorobenzene-2-carbon- 1- (2,3'-Oxynaphthoylamino) - red-brown nickel complex- acid # -N-methyl-N-phenylamide 4-methoxybenzene compound de, sgl. 1- (2 ', 3'-Oxynaphthoylamino) - bluish nickel complex- 4-chlorobenzene red-brown compound also 1- (2 ', 3'-Oxynaphthoylamino) - red-brown nickel complex- 2-methyl-4-methoxybenzene compound also 2- (2 ', 3'-Oxynaphthoylairdno) - bluish tinted nickel complex- naphthalene red-brown compound 1-Anünobenwl-2,5-di-carboxylic acid 2- (2,3'-Oxynaphthoylaniino) - red-brown nickel complex- bisdiethylamide naphthalene compound 1-anünobenzene-2,5-dicarboxylic acid 1- (2 ', 3'-oxynaphthoylamino) - red-brown nickel complex- dipiperidide 4-chlorobenzene compound also 1- (2 ', 3'-Oxynaphthoylanüao) - reddish rust nickel complex- 2-mathyl-5-chlorobenzene compound Hue of the metal complex Diazo component Azo component MetaH complex compound link 1-an # dnobenzene-2,5-di-carboxylic acid 1- - (2 ', 3'-oxynaphthoylamino) - red-brown nickel complex- dipiperidide 2-methyl-4-chlorobenzene compound 1-amino-4-chlorobenzene-2-carbon 2,3-oxynaphthoylaminobenzot red-brown nickel complex acid-di-n-butylamide compound also 2- (2,3'-oxynaphthoylamino) - red-brown nickel complex- naphthalene compound also 1- (2 ', 3'-Oxynaphthoylamino) - red-brown nickel complex- 2-methoxy-4-chloro-5-methyl compound benzene the same. 1- (2 #, 3'-Oxynaphthoylamino) - red-brown nickel complex- 2,5-dimethoxybenzene compound 1-Amino-3-chlorobenzene-2-carbon- 2- (2 ', 3'-OxynaphthoylamÜio) - rust red nickel complex- acid-N-methyl-N-phenylamide naphthalene compound also 1- (2 ', - i'-Oxynaphthoylamino) - rust red nickel coraplex- 4-ethoxybenzene compound 1-Anüno-4-chlorobenzene-2-carbon- 2,3-oxynaphthoylaminobenzene brownish nickel complex- acid diethylamide garnet compound also 1- (2 ', 3'-oxynaphthoylamino) - brownish nickel complex- 3-nitrobenzene garnet compound also 2- (2 ', 3'-Oxynaphthoylamino) - rust nickel complex- 3-methoxydiphenylene oxide compound the same. 1- (2 ', 3'-Oxynapht-hoylaraino) - red-brown nickel complex- 2,3-dimethylbenzene compound 1-aminobenzene-2,5-dicarboxylic acid 2- (2 ', 3'-oxynaphthoylaniino) - red-brown nickel complex- di-N-ethyl-N- (4'-methyl) -phenyl-naphthalene compound amide also 1- (2 ', 3'-Oxynaphthoylamino) - rust red nickel complex- naphthalene compound also 1- (2 ', 3'-Oxynaphthoylamino) - rust red nickel complex- 2,4-dimethoxy-5-chlorobenzene compound 1-aniinobenzene-2-carboxylic acid 1- (2 ', 3'-oxynaphthoylamino) - red-brown nickel complex- N-methyl-N-phenylanüd 4-methoxybenzene compound also 1- (2 ', 3'-oxynaphthoylamino) - brown-red nickel complex- 2-methoxybenzene compound

Claims (2)

PATENT CLAIMS: 1. Process for the preparation of metal-containing, water-insoluble azo dyes, characterized in that the diazonium compounds are obtained from amines of the general formula wherein R, and R2 are alkyl, aryl, aralkyl or Cycloalkyl radicals, which can also be linked to form a heterocyclic ring, are coupled with arylamides of aromatic or heterocyclic o-oxycarboxylic acids in bulk, on the fiber or on another substrate, the components being chosen so that they are free of water-solubilizing agents Groups are, and the dyes thus obtained treated with metal donors. 2. The method according to claim 1, characterized in that the treatment with the metal-releasing agents is carried out during the coupling. 3. The method according to claim 1, characterized in that the treatment with the meta-donating agents is carried out after coupling in a neutral, weakly acidic or weakly alkaline medium. 4. The method according to claim 1 and 3, characterized in that the treatment with the metal donating agents is carried out in the presence of dispersants and detergents. 5. The method according spoke 1 to 4, characterized in that there is used as the metal donating agent cobalt, nickel, iron, manganese or copper compounds. References Considered: U.S. Patent No. 2,416,248. An explanatory staining table was displayed in the publication of the application.