DE1262958B - Process for the production of water-insoluble azo dyes on textile material made of cellulose or protein fibers - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. α .:

Number:
File number:
Registration date:
Display day:

D 06 ρ

German class: 8 m - 1/01

1,262,958
F 42458IV c / 8 m
March 28, 1964
March 14, 1968

It has been found that water-insoluble azo dyes on textile material made of cellulose or Protein fibers can be produced if the textile material is treated in an alkaline bath, which an azo component and a diazoamino compound of the formula

COOMe

RN = NN - / \
Alc

(D

-SO ₃ Me

where R is the residue of an aromatic amine with a dissociation constant <1 · ICT ¹⁰ , Alk is a lower straight-chain or branched alkyl group and Me is an alkali or alkaline earth metal, as well as a wetting or dispersing agent and optionally an inorganic salt, and then by a treatment brings about the formation of the dye with acidic agents below 40 ^{° C.}

According to this process, water-insoluble azo dyes can be applied to the in a simple manner Create fiber.

The process is carried out in such a way that the textile material in the form of hank yarn, bobbins, tops or loose material is treated in an alkaline bath, which contains an azo component with high substantivity and a diazoamino compound of the specified composition and a wetting or dispersing agent and optionally a inorganic salt, for example sodium chloride, a sodium phosphate or sodium sulfate. The treatment is carried out for at least 10 minutes in order to give the azo component the possibility of sufficient and uniform fixation on the textile material. In general, the reaction is advantageously carried out at room temperature or at slightly elevated temperature below 35 ⁰ C. When the azo component is largely raised and has equalized itself, it is an organic acid, for example formic acid, acetic acid, tartaric acid, citric acid, lactic acid or glycolic acid, or Mixture of these acids or a mixture of an inorganic acid, for example hydrochloric acid or sulfuric acid, and an organic acid, or a mixture of an inorganic acid with the salt of an organic acid in the bath in such an amount that the total amount of alkali in the bath and on the Textile material is neutralized and a pH value between about 3 and 7 is reached.

Process for the production of water-insoluble
Azo dyes on textile material
Cellulose or protein fibers

Applicant:

Farbwerke Hoechst Aktiengesellschaft
formerly Master Lucius & Brüning,
6000 Frankfurt

Named as inventor:

Dipl.-Chem. Dr. Hasso Hertel,

Dipl.-Chem. Dr. Werner Kirst, 6050 Offenbach - -

The pH value required for optimal color yield depends primarily on the one used Diazoamino compound of the formula (1). He is z. B. for compounds with R = chlorophenyl, methoxychlorophenyl or methylchlorophenyl at about 5, for compounds with R = sulfamylphenyl at about 4.5, for compounds with R = nitromethoxyphenyl at about 4.5, for compounds with R = nitromethylphenyl at about 3.5 and for compounds with R = trifluoromethylphenyl at about 3.

The temperature should be below 4O ⁰ C. The formation of the dye occurs on the textile material. It is then washed in a neutral or acidic bath, if appropriate in the presence of dispersants, and the dyeing is completed in the usual way. This gives dyeings which are very fast to rubbing.

Piece goods can be dyed in such a way that the goods are placed on a two- or multi-roll foulard impregnated with a mixture of the azo component and excess diazoamino compound, rolls up the goods and after a dwell time, for example of half an hour, through a Passage through an organic acid, a mixture of organic acids or a mixture of organic acids and inorganic acids below 40 ° C brings about the coupling. This development can go through a passage in a compartment of a roller runner or through several passages on the jigger or on a reel skid, with additions of inorganic

809 518/637

sometimes see salts and dispersants in impregnation and development have a very beneficial effect. In this mode of operation, the additional drawing power of the Azo component accordingly, the concentration of the azo component in the preparation bath compared to the im Make-up bath be lowered, while the concentration of the diazoamino compound in the make-up bath compared to which is not lowered in the make-up bath. This way of working is very energy-saving; intermediate drying before developing the dye is not necessary.

Suitable azo components in the process according to the invention are compounds which are characterized by a high substantivity to the textile material used, d. i.e., azo components, which at a liquor ratio of 1:20, 30 minutes dyeing time at 30 ° C, one concentration of 1 g per liter of water without added salt and an excess of 4.5 g sodium hydroxide per liter of liquor have such a high substantivity that at least 9 g are absorbed per 1 kg of cotton. Suitable compounds are, for example, 2,3-oxynaphthoylaminobenzenes, such as l- (2 ', 3'-oxynaphthoylamino) -2,5-dimethoxy-4-chlorobenzene or l- (2 ', 3'-oxynaphthoylamino) -2-methoxy-4-chloro-5-methylbenzene, 6-bromo or 6-methoxy-2,3-oxynaphthoic acid arylamides, like l- (6'-bromo-2 ', 3'-oxynaphthoylamino) -

2 - methoxybenzene, condensation products of 2,3-oxynaphthoic acid and polynuclear isocyclic acids or heterocyclic amines, such as 2- (2 ', 3'-oxynaphthoylamino) naphthalene, 2- (2 ', 3'-oxynaphthoylamino) - carbazole, 2 - (2', 3 '- oxynaphthoylamino) -

3 - methoxy diphenylene oxide, 6 - (2 ', 3' - Oxynaphthoy 1-amino) -benzimidazole, 6- (2 ', 3'-oxynaphthoylamino) indazole, 5- (2', 3'-oxynaphthoylamino) -2-methylbenzthiazole or 4- (2 ', 3'-oxynaphthoylamino) diphenyl and its substitution products, 4,4'-bis (2 ", 3" -oxynaphthoylamino) diphenyl and its substitution products, such as 4,4'-bis (2 ", 3" -oxynaphthoylamino) - 3,3 '- dimethoxydiphenyl, 1,4 - bis (2 ", 3" - oxynaphthoylamino) benzene and its substitution products, 4,4'-bis- (2 ", 3" -oxynaphthoylamino) -stilbene, 4,4'-bis- (2 ", 3" -oxynaphthoylamino) -azobenzene and its substitution products, 4,4 '- bis - (2 ", 3" - oxynaphthoylamino) - diphenylurea, 2 - oxyanthracene-3-carboxylic acid arylamides, such as l- (2'-oxyanthracene-3'-carbonylamino) -2-methylbenzene, 2- oxycarbazole-3-carboxylic acid arylamides, such as l- (2'-oxycarbazole-3'-carboylamino) - 4 - chlorobenzene, 5 - oxy -1,2,1 ', 2' - benzocarbazoM-carboxylic acid arylamides, such as l- (5'-oxy-r, 2 ', 1 ", 2" - benzocarbazole - 4' - carboylamino) - 4 - methoxybenzene or l- (5'-oxy-l ', 2', l ", 2" -benzocarbazole-4'-carboylamino) -2-methyl-4-methoxybenzene, also terephthaloyl-bis-acetic acid arylamides, such as terephthaloyl-bis- (l-acetylamino-2,4-dimethoxy-5-chlorobenzene) or terephthaloyl-bis- (1-acetylamino-2-methoxy-4-chloro-5-methylbenzene).

As the aromatic diazoamino compounds by coupling diazotized amines with a Dissoziationskonstar · 'e <1 ■ 10 ~ ¹⁰ come with 2-alkylamino-4- or 5-sulfobenzoic acids available compounds. Suitable aromatic amines are e.g. B. chloranilines, dichloranilines, chlorotoluidines, chloranisidines, nitroanilines, nitrotoluidines, nitroanisidines, aminobenzenesulfonic acid amides, aminophenylalkyl- or aralkylsulfones, trifluoromethylanilines or aminochlorodiphenyl ethers.

Suitable wetting or dispersing agents are the compounds customary in ice color technology, for example condensation products from higher molecular weight fatty acids and protein degradation products, Condensation products from · higher molecular weight fatty acids and aminoalkylsulfonic acids, condensation products of formaldehyde with naphthalene sulfonic acids, or purified sulfite cellulose waste liquor. The process can be applied to textile material made from natural or regenerated cellulose, cyanethylated Carry out cellulose, wool, natural silk or regenerated protein fibers.

The method according to the invention is one compared to the usual dyeing process with ice colors substantial simplification.

In the known dyeing process, impregnation with the azo component is usually carried out the dye bath drained, the goods spun, vacuumed or rinsed and the dye developed in a second bath with a diazonium compound. In contrast, the present unites The process of priming and developing in a bath, and after that to fix the azo component required time, the coupling takes place without any intermediate operations, so that a substantial reduction in working hours is achieved.

It is known that diazoamino compounds are obtained from diazotized aromatic amines and alkylaminosulfobenzoic acids can be used to produce azo dyes on the fiber by using such diazoamino compounds in the Mixture with azo components is printed on and the dye is developed through an acid treatment. This Procedure is practiced extensively in the art. Unknown and according to the current status The technology was surprising, however, that such mixtures for dyeing the fiber in can be used in all processing states, even in wound packages, without intermediate drying of the goods can.

German Patent 1,057,061 discloses that water-insoluble azo dyes can be used Vegetable fibers can be produced by placing these fibers in long liquor ratios in a bath treated, which an azo component and a diazoamino or tetrazoamino compound without Contains solubilizing groups and then the azo dye by treating in an acidic Bathroom developed.

Compared to this method, the method according to the invention, which uses substantive azo components and diazoamino compounds from diazotized aromatic monoamines and alkylaminosulfobenzoic acids is carried out, in that the development of the Dyes can be made at low temperatures and an increase in temperature after the addition of acid is not required. Another advantage of the present method is in that the diazoamino compounds with alkylaminosulfobenzoic acids as a stabilizer in alkaline Bath in the form of dissolved alkali salts and thereby a complete penetration of the material to be dyed takes place, which leads to a complete coupling, while when using water-insoluble Diazoamino compounds these are deposited on the surface of the dyed goods, resulting in a deficient

staining and insufficient rubbing fastness can occur.

example 1

Cotton cheeses are treated in a liquor ratio 1:10 at 30 ° C with an aqueous solution containing 1.8 g per liter of 2- (2 ', 3'-oxynaphthoylamino) naphthalene, dissolved with 3.6 ecm of denatured ethyl alcohol, 0.75 ecm sodium hydroxide solution of 38 ° Be and 3.6 ecm hot water, as well as 1 g of a condensation product of an aminoalkylsulfonic acid and a higher molecular weight fatty acid, 7 ecm sodium hydroxide solution of 38 ^: Be, 20 g sodium chloride and 3.46 g of the diazoamino compound from diazotized l-amino -2-methyl-5-chlorobenzene and the disodium salt of 2-ethylamino-5-sulfobenzoic acid. After ¹ _1/2 hours, 14.6 ecm of 50% acetic acid are added per liter of liquor and dyeing is continued for ¹ _1/2 hours at a pH of about 5.5. Then you rinse thoroughly, soapy about ¹ I ₄ . Hour at 60 ^r C with 2.5 g of a mixture of 63% perchlorethylene, 17% of an action product of about 10 moles of ethylene oxide on 1 mole of nonylphenol and 20% isopropyl alcohol and 2 g of a 25% solution of sodium nitrilotriacetate in liter of water, rinses and soap ¹ I ₄ . Hour near boiling temperature with 2 g of a condensation product of an aminoalkylsulfonic acid and a higher molecular weight fatty acid and 2 g of a 25% solution of sodium nitrilotriacetate in liter of water, rinses and dries. A vivid red color is obtained.

Is used instead of 3.46 g of the diazoamino compound from diazotized l-amino-2-methyl-5-chlorobenzene and the disodium salt of 2-ethylamino-5-sulfobenzoic acid 4.94 g of the diazoamino compound from diazotized 1-amino-2-methoxybenzene-5-sulfonic acid-n-butylamide and the disodium salt of 2-ethylamino-5-sulfo-benzoic acid, the result is a yellowish red color which is fast to rubbing.

Is used instead of 3.46 g of the diazoamino compound from diazotized l-amino-2-methyl-5-chlorobenzene and the disodium salt of 2-ethyl

amino-5-sulfobenzoic acid 4.05 g of the diazoamino compound from diazotized l-amino-2-methoxy-5-chlorobenzene and the disodium salt of 2-ethylamino-5-sulfobenzoic acid, this gives a rubbing-fast Bordo dye. When using 4.12 g of the diazoamino compound from diazotized 1-amino-2-methoxy-5-nitrobenzene and the disodium salt of 2-ethylamino-5-sulfo-benzoic acid is obtained which is resistant to rubbing Red color.

Example 2

Cotton yarn packages are C ¹ I ₂ hour with an aqueous solution treated at a liquor ratio of 1:10 at 30 ⁰ which per liter of 2 g of 2- (2 ', 3'-oxynaphthoylamino) -3-methoxy-diphenylenoxyd dissolved in 4 cc of denatured ethyl alcohol , 1 cc of sodium hydroxide solution of 38 ° Be, and 4 cc of water at 6O ⁰ C, and 1 g of a condensation product of an aminoalkylsulfonic acid and a higher molecular weight fatty acid, 6 cc of sodium hydroxide solution of 38 ° Be, 10 g sodium chloride and 3.78 g of diazoamino compound obtained from diazotised Contains 2-amino-4-chlorodiphenyl ether and the disodium salt of 2-ethylamino-5-sulfobenzoic acid. Are then added per liter of liquor, a mixture of 6.6 cc of hydrochloric acid 20 ⁰ Be and 6.35 cc of 50% acetic acid and slowly treated ¹ J ₂ hours further. This is followed by rinsing and, as indicated in the example, aftertreatment. A rubbing red coloration is obtained.

If instead of 3.78 g of the diazoamino compound from diazotized 2-amino-4-chlorodiphenyl ether and the disodium salt of 2-ethylamino-5-sulfobenzoic acid, 3.21 g of the diazoamino compound from diazotized l-amino ^ S-dichlorobenzene and the disodium salt of 2-Ethylamino-5-sulfobenzoic acid, the result is a yellowish red color which is fast to rubbing.
The table below contains a number of further components which can be used according to the invention and the color shades of the azo dyes produced on cellulose fibers.

Azo component hue Diazoamino compound from 2-ethylamino
5-sulfobenzoic acid and diazotized 1-amino-3-nitrobenzene 2- (2 ', 3'-oxynaphthoylamino) -3-methoxy-
diphenylene oxide Brick red l-amino ^ -methylbenzene-S-sulfonic acid-
dimethylamide l- (2 ', 3'-oxynaphthoylamino) -2,5-dimeth-
oxy-4-chlorobenzene Red 1-amino-3-chlorobenzene l- (2 ', 3'-oxynaphthoylamino) -2-methoxy-
4-chloro-5-methylbenzene orange l-amino-2,5-dichlorobenzene Terephthaloyl-bis- (1-acetylamino-2-meth-
oxy-4-chloro-5-methylbenzene) yellow 1-amino-2,5-dichlorobenzene l- (2'-Oxycarbazole-3'-carboylamino) -
4-chlorobenzene Yellow-brown l-amino-2-methoxybenzene-5-sulfonic acid
diethylamide 2- (2 ', 3'-oxynaphthoylamino) naphthalene Red 1-amino-2,5-dichlorobenzene 1 - (5'-Oxy-l ', 2', I ", 2" -benzocarbazole-
4'-carboylamino) -4-methoxybenzene Corinth 1-amino-2-nitro-4-methoxybenzene the same black

Claims (1)

Claim: Process for the production of water-insoluble azo dyes on textile material made of cellulose or protein fibers, characterized that the textile material is treated in an alkaline bath containing an azo component and a diazoamino compound of the formula COOMe RN = NN
Alc wherein R contains an aromatic amine with a dissociation constant <1 x 10 ~ ^10, Alk is a lower straight or branched alkyl group, and Me is an alkali metal or alkaline earth metal, and a wetting or dispersing agents and, optionally, an inorganic salt to the residue, and then through a Treatment with acidic agents below 40 ^° C. brings about the formation of the dye. Considered publications:
German patent specification No. 1,057,061. When the application was announced, two coloring tables with explanations were laid out.