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Publication numberUS3502424 A
Publication typeGrant
Publication dateMar 24, 1970
Filing dateMar 23, 1965
Priority dateMar 28, 1964
Also published asDE1262958B, DE1279638B, DE1279638C2, DE1296122B, DE1296122C2, DE1297072B, DE1297072C2
Publication numberUS 3502424 A, US 3502424A, US-A-3502424, US3502424 A, US3502424A
InventorsHertel Hasso, Kirst Werner
Original AssigneeHoechst Ag
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Process for the production of water-insoluble azo dyestuffs on textile material of cellulose or protein fibers
US 3502424 A
Abstract  available in
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Description  (OCR text may contain errors)

United States Patent US. Cl. 845 3 Claims ABSTRACT OF THE DISCLOSURE Production of water-insoluble azo dyestuffs on textile materials of cellulose or protein by treating the textile in an alkaline bath containing 1) a coupling component highly substantive for the textile, (2) an alkali metal or alkaline earth metal salt of a diazoamino compound of the formula:

OOOH

wherein R represents the radical of an aromatic amine having a dissociation constant of l.l0 A represents lower molecular weight alkyl, hydroxyalkyl or carboxyalkyl, Y represents hydrogen, halogen, nitro, carboxylic acid, sulfonic acid, alkylsulfonyl, aralkylsnlfonyl, sulfonic acid aryl ester and sulfonic acid mono or dialkylamide wherein the alkyl groups may be substituted or closed to form a heterocyclic ring, and Z represents a hydrogen or halogen atom, (3) a wetting or dispersing agent and, if desired, a mineral salt, and then causing formation of the dyestuff by a treatment with an acid agent at temperatures below 40 C. without intermediate drying of said textile material.

The present invention provides a process for the pro- COOH in which R represents the radical of an aromatic amine having a dissociation constant of l.l0-" A represents a lower molecular weight straight-chain or branched alkyl, hydroxyalkyl or carboxyalkyl group, Y represents a hydrogen or halogen atom, a nitro, carboxylic acid, sulfonic acid, alkylsulfonyl, aralkylsulfonyl, sulfonic acid aryl ester, sulfonic acid monoor dialkylamide group, in which the alkyl groups may be substituted or closed to form a heterocyclic ring, and Z represents a hydrogen or halogen atom, and a wetting or dispersing agent and, if desired, a mineral salt, and then causing formation of the dyestuff by a treatment with an acid agent at temperatures below 40 C.

3,502,424 Patented Mar. 24, 1970 ICC The present process permits the production of water-insoluble azo dyestuffs on the fiber by a simple method of operation.

The process of the present invention may be carried out by treating the textile material in the form of yarn hanks, wound bodies, slubbings or piece goods in an alkaline bath which contains a coupling component having high substantivity and a diazoamino compound of the given formula as well as a wetting or dispersing agent and, if desired, an inorganic salt for example, sodium chloride, sodium phosphate or sodium sulfate. The treatment may be carried out for at least 10 minutes in order to ensure that the coupling component is sufliciently and uniformly fixed on the textile material. In general, the process may be carried out at room temperature or at a slightly elevated temperature, suitably below 35 C. When the coupling component has been substantially fixed and has levelled, an organic acid, for example, formic acid, acetic acid, tartaric acid, citric acid, lactic acid or glycollic acid or a mixture of these acids, or a mixture of a mineral acid, for example, hydrochloric acid or sulfuric acid, with an organic acid, or a mixture of a mineral acid with the salt of an organic acid, is added to the bath in a quantity such that the total quantity of alkali in the bath and on the textile material is neutralized and a pH-value of between about 3 and 7 is attained. The pH-value required for obtaining optimum dyestuif yield depends, above all, on which diazoamino compound of Formula 1 is used. For example, in the case of compounds in which R is chlorophenyl, methoxychlorophenyl or methylchlorophenyl, the pH-value is at about 5, for compounds in which R is sulfamylphenyl it is at about'4.5, for compounds in which R is nitromethoxyphenyl it is at about 4.5, for compounds in which R is nitromethylphenyl it is at about 3.5 and for compounds in which R is trifiuoromethylphenyl it is at about 3.

The temperature required for the dyestutf formation is below 40 C. After the formation of the dyestuif on the textile material has taken place, the material is subsequently washed in a neutral or acid bath, if desired or required in the presence of dispersing agents, and the dyeing is finished in the usual manner. In this manner, dyeings are obtained which exhibit very good fastness to rubbing.

Piece goods can be dyed by impregnating them on a two or multiple roller foulard with a mixture of the coupling component and an excess of diazoamino compound, the goods are wound up and after say half an hour, coupling is effected at temperatures below 40 C. by passing the goods through an organic acid, a mixture of organic acids or a mixture of organic and mineral acids. This dyestutf development may be effected by a single passage in a compartment of a roller "vat or by several passages in a jigger or winch beck; the addition of mineral salts and dispersing agents during impregnation and development may sometimes have a very advantageous effect. In this method of operation, the concentration of the coupling component in the initial bath must be lower in comparison with that of the second bath, corresponding to the higher afiinity of the coupling component, whereas the concentration of the diazoamino compound in the initial bath compared with that of the second bath must not be reduced. This method of operation saves energy; intermediate drying of the dyestuff prior to the development of the dyestuif is not required.

The coupling components which may be used in the process of the present invention are preferably those compounds which are distinguished by a high substantivity towards the textile material used, i.e. coupling components, which, at a goods to liquor ratio of 1:20, and impregnating period of 30 minutes at 30 C., a concentration of 1 g. per liter of water without addition of salt and with an excess of 4.5 g. of sodium hydroxide per liter of bath, have so high a substantivity that at least 9 g. are adsorbed on 1 kg. of cotton. Suitable compounds are, for example, 2,3-hydroxynaphthoylaminobenzenes such as 1 (2',3' hydroxynaphthoylamino)-2,5-dimethoxy-4- chlorobenzene or 1 (2',3' hydroxynaphthoylamino)-2- methoxy-4-chloro-S-methylbenzene; 6-bromoor 6-rnethoxy-2,3-hydroxynaphthic acid aryl amides such as 1- (6 bromo 2,3'-hydroxynaphthoylamino)-2-methoxybenzene; condensation products of 2,3-hydroxynaphthoic acid and polynuclear isocyclic or heterocyclic amines such as 2 (2,3-hydroxynaphthoylamino)-naphthalene, 2-(2,3'-hydroxynaphthoylamino)-carbazole, 2-(2,3'-hy droxynaphthoylamino) 3-methoxydiphenylene oxide, 6- (2,3 hydroxynaphthoylamino)-benzimidazole, 6-(2',3 hydroxynaphthoylamino) -indazole, 2'3 '-hydroxynaphthoylamino) 2-methylbenzthiazole or 4-(2',3'-hydroxynaphthoylamino)-diphenyl and substitution products thereof, 4,4-bis-(2",3-hydoxynaphthoylamino) -diphenyl and substitution products thereof such as 4,4'-bis-(2,3"- hydroxynaphthoylamino) 3,3 dimethoxydiphenyl, 1,4- bis (2,3" hydroxynaphthoylamino)-benzene and substitution products thereof, 4,4'-bis-(2,3"-hydroxynaphthoylamino -stilbene, 4,4-bis- 2",3 "-hydroxynaphthoylamino)-azobenzene and substitution products thereof, 4, 4'-bis-(2",3"-hydroxynaphthoylamino)-dipheny1 .urea, 2- hydroxyanthracene-3-carboxylic acid aryl amides such as 1 (2' hydroxyanthracene-3-carboylamino)-2-methylbenzene, 2-hydroxycarbazole-3-carboxylic acid aryl amides such as 1-(2'hydroxycarbazole-3-carboylamino)- 4 chlorobenzene, 5 hydroxy-1,2,1',2-benzocarbazole-4- carboxylic acid arylamides such as 1-(5'-hydroxy-1,2, 1",2" benzocarbazole4-carboylamino)-4-methoxybenzene or 1 (5 hydroxy-1,2,1",2"-benzocarbazole-4- carboylamino)-2-methyl-4- methoxybenzene, or terephthaloyl-bis-acetic acid aryl amides such as terephthaloylbis (1 acetylamino-2,4dimethoxy-5-chlorobenzene) or terphthaloyl bis-(l-acetylamino-Z-methoxy-4-chloro-5- methylbenzene) As diazoamino compounds there may be used the compounds obtained by coupling diazotized aromatic amines having a dissociation constant of 1.10- with 2-alkylamino-4-sulfobenzoic acids, Z-alkylamino-5-sulfobenzoic acids, 1-alkyl-amino-Z-carboxyphenyl-4-alkylsulfones, 1- alkylarnino 2 carboxyphenyl-4-aralkylsulfones, l-alkylamino-2-carboxybenzene-4-sulfonic acid aryl esters, 1- alkylamino-2-carboxybenzene-4-sulfonic acid monoor -dialkylamides, in which the alkyl group of the sulfonic acid amide group may carry further substituents for example, hydroxy, sulfonic acid or carboxylic acid groups, or in which the alkyl groups of the sulfonic acid amide group may be closed to form a heterocyclic ring as, for example in 1-alkylamino-2-carboxybenzene-4-sulfonic acid-piperidides or -morpholides, further with 2-hydroxyalkylamino or 2-carboxy -alkylamino-benzoic acids which may contain in the benzene radical halogen atoms, a nitro, alkylsulfonyl, aralkylsulfonyl, sulfonic acid aryl ester group or a sulfonic acid monoor -dialkylamide group, in which case the alkyl groups may also be substituted or closed to form a heterocyclic ring, or with l-alkylaminobenzene-2,4- or -2,5-dicarboxylic acids, l-hydroxy-alkylamino-benzene-2,4- or -2,5-dicarboxylic acids or 1- carboxy-alkylaminko-benzene-ZA- or -2,5-dicarboxylic acids.

Examples of the above-specified benzene-dicarboxylic acids are: 1-n1ethylaminobenzene-2,4-dicarboxylic acid, l-methylaminobenze'ne 2,5 dicarboxylic acid, 1 ethylaminobenzene-2,4 dicarboxylic acid, 1 ethylaminobenzene-2,5 dicarboxylic acid, 1 propylaminobenzene-2,4- dicarboxylic acid, 1 propylaminobenzene 2,5 dicarboxylic acid, l-isopropylaminobenzene 2,4 dicarboxylic acid, 1 isopropylaminobenzene 2,5 dicarboxylic acid, 1 isobutylaminobenzene 2,4 dicarboxylic acid, l-isobutylaminobenZene-2,5 dicarboxylic acid, 1 butylaminobenzene 2,4 dicarboxylic acid, 1 butylaminobenzene- 2,5 dicarboxylic acid, 1 carboxyrnethylaminobenzene- 2,4 dicarboxylic acid, 1 carboxymethylaminobenzene- 2,5 dicarboxylic acid, 1 fi carboxyethylaminobenzene- 2,4 dicarboxylic acid, 1 fi carboxyethylaminobenzene- 2,5 dicarboxylic acid, 1 B hydroxyethylaminobenzene- 2,4 dicarboxylic acid, 1 5 hydroxyethylaminobenzene- 2,5 dicarboxylic acid, 1 [3, dihydroxypropylaminobenzene 2,4 dicarboxylic acid or 1-,B,'y-dihydroxypropylamino-benzene-2,5-dicarboxylic acid.

Suitable Z-hydroxyalkylamino-benzoic acids or 2 carboxyalkylamino-benzoic acids are for example: 2-:car boxymethylaminobenzoic acid, 2 0L carboxyethylaminobenzoic acid, 2 f3 carboxyethylamino-benzoic acid, Z-acarboxypropylamino-benzoic acid, 2-a-carboxybutylamino-benzoic acid, 2 a carboxy [3 methylpropylaminobenzoic acid, 2-carboxymethylamino 5 bromobenzoic acid, 2 carboxymethylamino 5 chlorobenzoic acid, 2 carboxy methylamino 4 chlorobenzoic acid, 2 8- carboxyethylamino 5 chlorobenzoic acid, 2 carboxymethylamino 3,5 dichlorobenzoic acid, 2 carboxymethylamino 3,5 dibromobenzoic acid, 2 B hydroxyethylaminobenzoic acid, 2 B hydroxyethylamino 5- bromobenzoic acid, 2 fl hydroxyethylamino 4 chlorobenzoic acid, 2 [3 hydroxyethylamino 5 chlorobenzoic acid, 1-carboxymethylaminobenzene 2 carboxylic acid- 4 sulfonic acid diethyl amide, 1 carboxymethylaminobenzene 2 carboxylic acid 4 sulfonic acid diethyl amide, 1 'y hydroxypropyl aminobenzene- 2 carboxylic acid 4 sulfonic acid diethyl amide, l-ca-rboxymethylamino 2 carboxyphenyl 4 benzylsulfone, 1 ,8 hydroxyethylamino 2 carboxyphenyl-4 benzylsulfone, 1 B hydroxyethylamino 2 carboxyphenyl 4 n butylsulfone, 1 carboxymethylaminobenzene-2-carboxylic acid-4-sulfonic acid-morpholide or 1-5- hydroxyethylaminobenzene 2 carboxylic acid 4 sulfonic acid-morpholide.

Suitable aromatic amines are, for example: chloroanilines, dichiloroanilines, chlorotoluidines, chloroanisidines, nitroanilines, nitrotoluidines, nitroanisidines, aminobenzenesulfonic acid amides, aminophenylalkylor aralkylsulfones, trifluoromethylanilines or aminochlorodiphenyl ethers.

As Wetting or dispersing agents, the compounds generally employed in the ice colour technique may be used, for example, condensation products of high molucular fatty acids and protein degradation products, condensation products of high molecular 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 of natural or regenerated cellulose, cyanoethylated cellulose, wool, natural silk or regenerated protein fibers.

Compared with the usual methods for dyeing with ice colours, the process of the present invention is considerably simpler. In the known dyeing methods, the dyebath is usually drained after impregnating with the coupling component, the goods are centrifuged, suctioned or rinsed intermediately and the dyestufi is developed with a diazonium compound in a second bath. In contradistinction thereto, in the process of the present invention impregnating and development are carried out in one bath and after the time required for fixing the coupling component, coupling is effected without any other intercalated operation. This saves operational time to a considerable extent.

It is known that diazoamino compounds of the Formula 1 may be used for the production of azo dyestuffs on the fiber, by printing such diazoamino compounds in admixture with coupling components on the material and developing the dyestuff by an acid treatment. This process is at present widely used in industry. However, it has hitherto been known, and in view of the state of the art this is very surprising, that such mixtures can also be used for the dyeing of fibers at any processing stage, even for dyemg wound bodies, without intermediate drying of the goods.

It is known that water-insoluble azo dyestuffs can be produced on vegetable fibers by treating them at a long goods to liquor ratio in a bath containing a coupling component and a diazo or tetrazoamino compound not containing hydrosolubilizing groups and subsequently developing the azo dyestuff by treatment with an acid bath (German patent specification No. 1,057,061).

In comparison with this process, the process of the present invention, which is carried out with substantive coupling components and diazoamino compounds of the above Formula 1 is distinguished by the fact that the development of the dyestufl can be eifected at low temperatures and that it is not necessary to raise the temperature after the addition of the acid. Another advantage of the process of the present invention is that the diazoamino compound of the Formula 1 is present in the bath in the form of a dissolved alkali metal salt, which ensures complete penetration of the material to be dyed thus ensuring complete coupling, whereas, if water-insoluble diazoamino compounds are used they are only deposited on the surface of the material to be dyed which results in unsatisfactory dyeings and poor fastness to rubbing.

The following examples illustrate the invention, but they are not intended to limit it thereto:

EXAMPLE 1 Cross-wound cotton bobbins were treated at a goods to liquor ratio of 1:10, at 30 C., in an aqueous solution containing, per liter, 1.8 g. of 2-(2',3-hydroxynaphthoylamino)naphthalene, dissolved in 3 cc. of denatured ethyl alcohol, 0.75 cc. of a sodium hydroxide solution of 38 B., and 3.6 cc. of hot water, and l g. of a condensation product of an aminoalkylsulfonic acid and a higher moleuclar fatty acid, 7 cc. of a sodium hydroxide solution of 38 B., 20 g. of sodium chloride, and 3.46 g. of the diazoaminocompound from diazotized 1-amino-2-methyl-5-chlorobenzene and the disodium salt of 2-ethylamino-5-sulfobenzoic acid. After 30 minutes, 14.6 cc. of a 50% acetic acid were added per liter of bath and the bobbins were dyed for 30 minutes at a pH- value of about 5.5. The bobbins were then thoroughly rinsed, soaped for about 15 minutes, at 60 C., with 2.5 g. of a mixture of 63% perchloroethylene, 17% of the reaction product of about mols of ethylene oxide with 1 mol of nonylphenol, and 20% of isopropyl alcohol, and 2 g. of a solution of 25% strength of the sodium salt of nitrilotriacetic acid per liter of Water, rinsed and soaped for minutes at a temperature in proximity of the boiling temperature with 2 g. of a condensation product of an aminoalkylsulfonic acid and a higher mo lecular fatty acid and 2 g. of a 25% solution of the sodium salt of nitrotriacetic acid per liter of water, rinsed and dried. A vivid red dyeing was obtained.

When using, instead of 3.46 g. of the diazoamino compound of diazotized 1-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-2methoxybenzene-S-sulfonic acid -n-butylamide and the disodium salt of Z-ethylamino-S-sulfobenzoic acid, a yellowish red dyeing exhibiting good fastness to rubbing was obtained.

When using, instead of 3.46 g. of the diazoamino compound of diazotized 1-amino-2-methyl-S-chlorobenzene zene and the disodium salt of Z-ethyIamino-S-sulfobenzoic acid, 4.05 g. of the diazoamino compound from diazotized 1-amino-2-methoxy-5-chlorobenzene and the disodium salt of 2-ethylamino-5-sulfobenzoic acid, a Bordeaux dyeing exhibiting good fastness to rubbing was obtained.

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-sulfobenzoic acid or 3.78 g.

of the diazoamino compound from diazotized 1-amino-2- methyl-4-chlorobenzene and the dipotassium salt of 2-methylamino-5-sulfobenzoic acid, red dyeings having good fastness to rubbing were obtained.

EXAMPLE 2 Cross-wound cotton bobbins were treated, at a goods to liquor ratio of 1:10, at 30 C., for 30 minutes, in an aqueous solution containing, per liter, 2 g. of 2-(2',3'-hydroxynaphthoylamino) 3 methoxy diphenylene oxide, dissolved in 4 cc. of denatured ethyl alcohol, 1 cc. of sodium hydroxide solution of 38 B. and 4 cc. of Water having 60 C., and 1 g. of a condensation product of an aminoalkylsulfonic acid and a higher molecular fatty acid, 6 cc. of sodium hydroxide solution of 38 B., 10 g. of sodium chloride, and 3.78 g. of the diazoamino compound from diazotized 2-amino-4-chloro-diphenyl ether and the disodium salt of 2-ethylamino-5-sulfobenzoic acid. Then, a mixture of 6.6 cc. of hydrochloric acid of 20 B. and 6.35 cc. of a 50% acetic acid, per liter of bath, was slowly added to the bath, and treatment was continued for 30 minutes. The bobbins were then rinsed and aftertreated as described in Example 1. A red dyeing showing good fastness to rubbing was obtained.

When using, instead of 3.78 g. of the diazoamino compound from diazotized 2-amino-4-chloro-diphenyl ether and the disodium salt of 2-ethylamino-S-sulfobenzoic acid, 3.21 g. of the diazoamino compound from diazotized 1-amino-2,5-dichlorobenzene and the disodium salt of 2-ethylamino-5-sulfobenzoic acid, a yellowish red dyeing showing good fastness to rubbing was obtained.

The following table lists a number of other components which may be used according to the present invention and the tints of the azo dyestulfs produced on cellulose fibers.

Diazoamino compound from 2-ethylamino-5- sulfobenzoic acid and benzene. acetylamino-zmethoxy- 4 ehloro-5-methylbenzene) 1-(2hydroxycarbazole-3'- earboylamino)-4- ehlorobenzene.

1-amino-2,5-diehloro benzene.

Yellow brown.

l-amino-Z-rnethoxy- 2-(2,3-hydrox ynaph- Red.

benzene-5-sulfonic acidthoylamino)-naphthadiethylamide. lene. 1-amino-2,5-diehloro- 1-(5'-hydroxy-1,2,1,2- Bluish violet.

benzene. benzocarbazole-4-oa.r-

boylamino)-4-methoxybenzene. 1-amino-2-nitro-4- do Black.

methoxybenzene.

EXAMPLE 3 Cotton yarn was treated, at a goods to liquor ratio of 1:20, in a 30 C. hot, aqueous solution containing, per liter, 1 g. of 2-(2,3'-hydroxynaphthoylamino)-3- methoxy-diphenylene oxide, 1 g. of a condensation product of oleic acid and methyl-taurine, 8 cc. of sodium hydroxide solution having a strength of 32.5%, 20 g. of sodium chloride, and 2.87 g. of diazoamino compound of the formula After about 45 minutes, 4.45 cc. of hydrochloric acid of 20 B. and 7.7 cc. of a 50% acetic acid were added per liter of bath and treatment was continued for 30 minutes at a pH-value of about 5; the bobbins were then thoroughly rinsed and soaped for 15 minutes at 60 C. and for 15 minutes at the boiling temperature with 2 g. of a condensation product of oleic acid and rnethyl-taurine and 0.5 g. of the sodium salt of nitrilotriacetic acid and 1 g. of sodium carbonate per liter of water, rinsed and dried. An intense yellowish red dyeing showing excellent fastness to rubbing was obtained.

The following table lists further diazoamino compounds which may be used instead of the diazoamino compound (a) mentioned in the above example, their quantity as well as the tints obtained with these compounds:

Quantity, Diazoamino compound grams Tint 0 H3 CH3 l CH N=NN S Oz--N 2. 1 Red.

l C Ha N 0 2 C 0 0Na 0 CH; C 2H5 I CH3 S Oz-CzHs CH3 CH3 I COONa 0 o ONa 01 0 CH3 C2H5 I CH3 -N=NN s OzN 2. 67 Red.

sozNnclm COONa ('31 ?H;; CH3

N=NN s 0.-N H x 2. 25 Red brown.

C 0 O Na on, 0H3

F1 01- N=N-N s 0.-N H 0 2. 25 Red.

c o ONa 00H. omom);

I CH3 N=N-N S O 2N\ 2. 26 Bordeaux.

CH3 o1 COONa CH3 CH3 1 C r c1- N=N-N s OzN-OH2CH2- s OaNa 2.6 Red.

I o 0 0Na 0 CH3 OH;

I a ON=NNQ s OWN-0112c 0 0Na 2. 04 Red.

N 0 2 o 0 ON;

01 o 0 ON?! l /C Ha ON=NNOS 02N\ 1. as Red brown.

C H3 CH3 Quantity, Diazoamlno compound grams Tint on, 30 ONE. N=N-T- -sozo 2.26 Red. or CH;

( 31 o o ONa N=NNS Oz-N H 2. a Red brown.

EXAMPLE 4 and the disodium salt of 2-carboxymethylamino-3,S-dibro- Cotton yarn was treated at a goods to liquor ratio of 1:20 in an aqueous solution having 30 C. and containing, per liter, 1.5 g. of 1-(5-hydr0xy-1',2',l",2-benzocarbazole-4'-carboylamino)-4-methoxy-benzene, 0.75 cc. of formaldehyde having a strength of 33%, 1 g. of a condensation product of oleic acid and methyl-taurine, 8.5 cc. of sodium hydroxide solution of 38 B, 20 g. of sodium chloride, and 3.4 g. of the diazoamino compound of the formula (EOONB After about 45 minutes, 6.8 cc. of hydrochloric acid of 20 B. and 7 cc. of 50% acetic acid were added per liter of bath and treatment was continued for about 30 minutes at a pH-value of about 4.4 to 4.8. The yarn was then rinsed, soaped first for minutes at 60 C. and then in a fresh bath at the boiling temperature with 2 g. of a condensation product of oleic acid and methyl-taurine, 0.5 g. of the sodium salt of nitrilotriacetic acid and 2 g. of sodium carbonate per liter of water, rinsed and dried. A black dyeing exhibiting a good fastness to rubbing was obtained.

EXAMPLE 5 JJOONa After about 45 minutes, 4.45 cc. of hydrochloric acid of B. and 7.2 cc. of a 50% acetic acid were added per liter of bath and treatment was continued for 30 minutes at a pH-value of about 5 and at a temperature of 32-35 C.

The yarn was then rinsed and soaped for 15 minutes at 60 C. and subsequently for 15 minutes at the boiling temperature with 2 g. of a condensation product of oleic acid and methyl-taurine, 0.5 g. of the sodium salt of nitrilotriacetic acid, and 1 g. of sodium carbonate, per liter of water, rinsed and dried. A reddish brown dyeing exhibiting good fastness to rubbing was obtained.

EXAMPLE 6 1 kg. of cotton was treated, at C., in an aqueous solution containing, in 20 liters, 19.8 g. of 2-(2'-3'-hydroxynaphthoylamino) 3 methoXy diphenylene oxide, dissolved in 44 cc. of denatured alcohol, 11 cc. of sodium solution of 38 B. and 44 cc. of water having 60 C., and 69.5 g. of the diazoamino compound from diazotized 1-amino-2-methoXy-benzene-5-sulfonic acid diethylamide mobenzoic acid, 149 cc. of sodium hydroxide solution having 38 B., 20 g. of a condensation product of oleic acid and methyl-taurine and 400 g. of sodium chloride.

After 30 minutes, a mixture of 87 cc. of hydrochloric acid of 20 B. and 201 cc. of a 5 0% acetic acid was added and treatment was continued for 30 minutes at a temperature which adjusted to about 30 C. The cotton was then rinsed, soaped at first at 60 C. and then in a fresh bath at 95 C., rinsed and dried. A bluish red dyeing exhibiting good fastness to rubbing was obtained.

EXAMPLE 7 1 kg. of cotton was treated, at 25 C., in an aqueous solution containing, in 20 liters, 21 g. of 2-(2',3'-hydroxynaphthoylamino)-naphthalene, dissolved in 44 cc. of denatured alcohol, 88 cc. of a sodium hydroxide solution of 38 B., 44 cc. of water having 60 C., and 22 cc. of a formaldehyde solution having a strength of 30%, and 74 g. of the diazoamino compound from diazotized l-amino- 2-methyl-4-chlorobenzene and the disodium salt of 2-carboxymethylamino-3,S-dibromobenzoic acid, 151.2 cc. of sodium hydroxide solution of 38 B., 20 g. of a condensation product of oleic acid and methyl-taurine, and 400 g. of sodium chloride. After 30 minutes, a mixture of 87 cc. of hydrochloric acid of 20 B. and 200 cc. of a 50% acetic acid was added and treatment was continued for 30 minutes at 30 C. The cotton was then rinsed, soaped at 60 C. and at 70 C., rinsed and dried. A red dyeing exhibited good fastness to rubbing was obtained.

EXAMPLE 8 1 kg. of cotton was treated, at 25 C., with an aqueous solution containing, in 20 liters, 19.8 g. of 2-(2,3'-hydroxynaphthoylamino)-3-methoxy-diphenylene oxide, dissolved in 44 cc. of denatured alcohol, 11 cc. of sodium hydroxide solution of 38 B. and 44 cc. of water having 60 C., and 56.2 g. of the diazoamino compound from diazotized l-amino-2methyl-3-chlorobenzene and the disodium salt of 2-carboxymethylamino 3,5 dibromobenzoic acid, 149 cc. of sodium hydroxide solution of 38 B., 20 g. of a condensation product of oleic acid and methyltaurine and 400 g. of sodium chloride.

After 30 minutes, a mixture of 87 cc. of hydrochloric acid of 20 B. and 240 cc. of a 50% acetic acid was added, and treatment was continued for 30 minutes; the cotton was then rinsed, soaped at 60 C. and at 95 C., rinsed and dried.

A brownish red dyeing exhibiting good fastness to rubbing was obtained. When using, in the above example, instead of 19.8 g. of 2-(2',3'-hydroxynaphthoylamino)-3- methoxy-diphenylene oxide, 17.2 g. of 1-(2'-hydroxycarbaZole-3'-carboylamino)-4-chlorobenzene, a brown dyeing was obtained.

EXAMPLE 9 1 kg. of cotton was treated, at 25 (3., in an aqueous solution containing, in 20 liters, 37 g. of 1-(2,3'-hydroxynaphthoylamino) 2 methoxy 4 chloro 5 methylbenzene, dissolved in cc. of denatured alcohol, 20 cc.

of sodium hydroxide solution of 38 B6, 80 cc. of water having 60 C. and 40 cc. of a 30% formaldehyde solution, and 120 g. of the diazoamino compound from diazotized l-amino-2-methyl-5-chloro'benzene and the disodium salt of 2-carboxymethylamino-3,5-dibromobenzoic acid, 140 cc. of sodium hydroxide solution of 38 B., 20 g. of a condensation product of oleic acid and methyltaurine and 600 g. of sodium chloride. After 30 minutes, a mixture of 87 cc. of hydrochloric acid of 20 Be. and 200 cc. of 50% acetic acid was added, and treatment was continued for 30 minutes, the cotton was then rinsed, soaped at 60 C. and at 95 C., rinsed and dried. A red dyeing having a good fastness to rubbing was obtained.

When using in the above example, instead of 37 g. of 1 (2,3' hydroxynaphthoylamino) 2 methoxy 4- chloro-S-methylbenzene, 41.3 g. of 1-(5'-hydroxy-1,2', 1",2" benzocarbazole 4' carboylamino) 4 methoxy-benzene, a black-violet dyeing was obtained.

The following table lists a number of other components which may be used according to the present invention and the tints of the dyestuffs produced on cellulose fibers.

Diazoamino compound from disodium salt of 2-carboxy-methylamino- 3,5-dibromobenzoic acid and diazotized Coupling component Tint 1-amino-2-methoxy-4- 2-(2',3'-hydroxynaph- Red.

ethylsulfonylbenzene. tl11oyl-amino)-napha one. 2-amlno-4,4-dichlorodi- 1-(2,3-hydroxyneph- Red.

phenyl-ether. thoyl-amino)-2,5-dimethoxyi chlorobenzene. Do l-(2-hydroxycarbazole- Brown.

3-carboylamino)-4- chlorobenzene. 1-amino-2-chlorobenzcnc- 2-(2,3-hydroxynaph- Brown red.

tl1oy1-amino)-3-me- 3 5 thoxydiphenyleneoxide. l-amino-Ebchlorobenzene do Do. 2-amino-4 chlorodi- 2-(2,3-hydroxynaph- Red.

phenylether. thoyl-amino)-naphthalene. Diazoamino compound from disodium Salt o1 2-carboxymethylam1no- 5-bromobenzoic acid and diazotizcd. l-amino-Z-methoxy- 2-(2,3-hydroxynaph- Cherry red.

benzene-5-sulfonic acld thoyl-amino)-napl1- diethylamide. halene. 1-am1no-2-methyl-4- 1-(5'-hydroxy-1',2,1, Black.

nitro-b enzene. 2"-b enzocarb azole-4- carboyl-amino)+ methoxylbenzene. 1-amino-3-ch1orobenzene.. 2-(2,3'-hydroxynaph- Red brown.

thoyl-amino)-3-methoxydiphenyleneoxlde. Diazoamino compound from sodium salt 0t 2-fl-hydroxy-ethylaminobenzene-l-can boxylic acid-5-sulfomc acid dimethylamlde l-and diazotized.

amino-2-methoxy- 1-(2-hydroxycarbazole- Brown. benzene-5-sulfonic acid 3'-carboylamino) -4- l-diethylamide. chlorobcnzene. 5o

amino-2-methoxy-5- 1-(2' ,3-hydroxynaph- Red. benzene. thoyl-amino)-2 methoxy-4-chloro-5- methylbenzene. 1-amin0-2-methyl-5- Terepthaloyl-bis-(l- Yellow.

benzene. acetylammo-Z-methoxy- 4-chloro-5-methylbenzene.

EXAMPLE 10 Cotton yarn was treated at a goods to liquor ratio of 1:20 at about 20 C., in an aqueous solution containing, per liter, 1 g. of 2-(2,3'-hydroxynaphthoylamino)-3-methoxydiphenylene oxide, 1 g. of sodium salt of oleylmethyltaurine, 5.4 g. of sodium hydroxide and 4.8 g. of the diazoamino compound of the formula After about 45 minutes, 48 cc. of a 50% acetic acid were added per liter of bath and treatment was continued for about 30 minutes at a pH-value of about 4 which had adjusted itself; the yarn was thoroughly rinsed and soaped at first for 15 minutes at 60 C. and then for further 15 minutes at the boiling temperature with 2 g. of the sodium salt of oleylmethyl-taurine, 0.5 g. of sodium salt of nitrilotriacetic acid and 1 g. of sodium carbonate per liter of water, rinsed and dried. A red dyeing showing very good fastness to rubbing was obtained.

EXAMPLE 11 10 parts by weight of cotton yarn were treated in 200 parts by volume of an aqueous solution having 20 C. and containing 0.1% of 1-(5-hydroxy-1',2',1",2"-benz0- carbazole-4-carboylamino)-4-methoxy-benzene, 0.1% of the sodium salt of oleoylmethyl-taurine, 0.75% of sodium hydroxide and 0.48% of the diazoamino compound of the' formula 00H 200m EO N0. 5 K JOONa OONa After about 45 minutes, 6.8 parts by weight of a 50% acetic acid were added and treatment was continued for about 30 minutes. After thorough rinsing, the yarn was soaped at first for 15 minutes at 60 and then for 15 minutes at C. with an aqueous solution containing 0.2% of the sodium salt of oleylmethyl-taurine, 0.05% of the trisodium salt of nitrilotriacctic acid and 0.2% of sodium carbonate, rinsed again and dried. A dark brownish-Bordeaux dyeing exhibiting good fastness to rubbing was obtained.

EXAMPLE 12 10 parts by weight of cotton yarn were treated, at about 20 C. in a solution of 0.2 part by weight of 1-(5'-hydroxy-1',2',l",2-benzocarbazole 4' carboylamino)-2 methyl-4-methoxybenzene, 0.6 part by weight of a dispersing agent containing 1 6% of a condensation product of partially degraded caseine and palm nut oil fatty acid and 8% of a condensation product of a-ethyl-hexyl-chlorocarbonic acid ester and the sodium salt of m-ethylhexyltaurine, 1.5 parts by weight of sodium hydroxide and 0.96 part by weight of the diazoamino compound of the formula 0 on. 10 ONa fg O N02 5 boom OONa in 200 parts by volume of water. After about 45 minutes, 6.8 parts by weight of a 50% acetic acid were added and treatment was continued in the manner described in Example 11. A dark bluish violet shade exhibiting good fastness to rubbing was obtained.

EXAMPLE 13 1 part by weight of cotton yarn was treated with 10 parts by volume of an aqueous solution containing, per liter, 1.6 g. of 2-(2',3-hydroxynaphthoyl-amino)-naphthalene, 1 g. of the sodium salt of oleoylmethyltaurine, 5.6 g. of sodium hydroxide, 30 g. of sodium chloride and 9.6 g. of the diazoamino compound of the formula (|)CH C O ONa N 2 CH2 I COONa COONa After about 45 minutes, a mixture of 0.2 part of 5 N hydrochloric acid and 0.2 part of 50% acetic acid was added and treatment was continued for about 30 minutes. The yarn was then rinsed, then soaped for 15 minutes at 60 C. and 15 minutes at the boiling ternperaturewith 10 parts by volume of an aqueous solution containing, per liter, 2 g. of the sodium salt of oleoylmethyl-taurine, 0.5 g. of the sodium salt of nitrilotriacetic acid and 1 g. of sodium carbonate, rinsed thoroughly and dried. A red dyeing exhibiting good fastness to rubbing was obtained. 1

The following table lists a number of further components which may be used according to the invention and the tints of the dyestuffs produced on cellulose fibers.

Diazoamino compound from trisodium salt of l-carboxy-methylaminobenzene-2,5-dicarboxylic acid and diazotized Coupling component Tint;

l-amino-Z-methoxy-S- l'(2,3-hydroxynaph- Red.

nitrobenzene. Y

thoxy--chlorobenzene.

Do 4,4 -bis-(2 ,3 -hyrlr0xy- Red brown.

naphthoyl-arnino)-3,3- dimethoxy-rliphenyl.

Do 1-(2-hyd1'oxyanthraeene- Bordeaux.

3carboylamino)-2- methylbenzene.

Do l-(2-hydroxycarbazole-3- Brown.

earboyl-amino)-4- ehlorobenzene.

Do 'Ierephthaloyl-bis-(l- Yellow.

aeetylaminoQA-dimethoxy-5-chlorob enz ene) Do Terephthaloyl-bis-(l- Yellow.

acetylamino-Z-methoxy- 4-chloro-5-methylbenzene).

We claim:

1. A one bath exhaust dyeing process for the production of water-insoluble azo dyestuffs on cellulose or pr0 tein textile material comprising immersing the textile material in an aqueous alkaline dye bath which contains (1) a coupling component highly substantive for the textile material selected from the group consisting of arylamides of heterocyclic orthohydroxy carboxylic acids, mides of heterocyclic orthohydroxy carboxylic acids, arylamides of acyl acetic acids and arylamides of terephthaloyl-bis-acetic acid (2) alkali metal salts or alkaline 14 earth metal salts of a diazoarnino compound of the formula:

COOH

5 RN=N1YI wherein R stands for the radical of an aromatic amine having a dissociation constant of l.10 A stands for 0 lower-alkyl, hydroxyalkyl or carboxyalkyl, Y stands for hydrogen, halogen, nitro, carboxylic acid, sulfonic acid, alkylsulfonyl, aralkylsulfonyl, sulfonic acid arylester, sulfonic acid monoalkylamide, sulfonic acid dialkylamide, sulfonic acid piperidide or sulfonic acid morpholide and Z stands for hydrogen or halogen, and (3) a dispersing agent, and then subsequently adding to the dye bath containing the textile material, without intermediate drying, an acid agent selected from the group consisting of inor- 2 ganic mineral, organic carboxylic acids, and mixtures thereof at a temperature below 40 C.

2. The process as claimed in claim 1, wherein the treating of the textile material in the alkaline bath is carried out in the presence of an inorganic salt.

25 3. The process as claimed in claim 2, wherein a salt selected from the group consisting of sodium chloride, sodium phosphate and sodium sulfate is employed.

References Cited 30 UNITED STATES PATENTS 1,882,560 10/1932 Glietenberg et a]. 8-45 X 1,882,561 10,1932 Haller et al 845 2,088,506 7/1937 Chambers 845 r 2,897,186 7/1959 Miller et a1 8-45 X 30 2,926,986 3/1960 Petitcolas et a1. 8-45 FOREIGN PATENTS 1,057,061 5/ 1959 Germany.

GEORGE F. LESMES, Primary Examiner B. BETTIS, Assistant Examiner US. Cl. X.R. 8-46.41

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US1882560 *Apr 25, 1929Oct 11, 1932Gen Aniline Works IncManufacture of water-insoluble azo dyestuffs
US1882561 *Feb 12, 1930Oct 11, 1932Gen Aniline Works IncDyeing preparation
US2088506 *Apr 6, 1934Jul 27, 1937Du PontProcess and composition for applying and fixing diazoimino dyestuffs
US2897186 *Feb 21, 1956Jul 28, 1959Pharma Chemical CorpDiazoamino dye intermediates
US2926986 *Mar 12, 1958Mar 1, 1960 Solutions of diazoamino derivatives
DE1057061B *Dec 21, 1957May 14, 1959Hoechst AgVerfahren zur Erzeugung von wasserunloeslichen Azofarbstoffen auf pflanzlichen Fasern
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US7041143 *Feb 28, 2002May 9, 2006Ciba Specialty Chemicals CorporationMethod of coloring porous material
US20040083560 *Feb 28, 2002May 6, 2004Jean-Marie AdamMethod of clouring porous material
Classifications
U.S. Classification8/598, 8/665
International ClassificationD06P3/68, C09B41/00, D06P1/02, D06P3/58, D06P1/12
Cooperative ClassificationD06P1/127
European ClassificationD06P1/12F