DE2061357A1 - Process for the production of insoluble azo dyes on cellulose fibers - Google Patents

Description

The present invention relates to a method for dyeing cellulose fibers which allows the water consumption to be countered to reduce conventional processes to a large extent and thereby also the associated problems of wastewater disposal to bypass.

According to the known methods of the ice color technique, insoluble Azo dyes on woven or knitted fabrics made from cellulose fibers

man

continuously produced in such a way that / the material to be colored first with the aqueous, alkaline solution of a coupling component impregnated, dried and then treated with the aqueous, weakly acidic solution of a diazo component. the According to this process, dye formation takes place when the material to be dyed passes through the solution of the diazo component or during the subsequent air passage. After coupling, the goods are first passed through aqueous rinsing baths and treated Coloring then to completion with alkaline, detergent-containing aqueous solutions at boiling temperature. Finally v. Ground the dyed articles dried.

Hei the production of insoluble azo dyes on cellulose fibers however, the procedure can also be such that this is done simultaneously in the aqueous, alkaline solution of a coupling component

2098 25/107 1

Diazoanino compound of a primary aromatic amine dissolves both Brings components together by impregnation on the goods and then by treating the primed in this way Textile material with acid diluted with water, by acid steaming or by dry heat treatment with or without additives of acid-releasing Wittein brings about the dye formation. The dyeing is then completed by rinsing and aftertreatment in aqueous liquors and then dried.

In these known dyeing methods are thus in particular for Rinsing and post-treatment processes consume considerable amounts of water. In addition, the goods must evaporate for drying Considerable energy is expended in the water. Due to its significant size, throws from the technical point of view the water consumption for the completion of the dyeings in the dyeing practice depending on the local conditions more or fewer major difficulties with regard to the clarification of wastewater, which is detrimental to the economic viability of such processes influence.

It has now been found that in the preferably continuous production of insoluble azo dyes on textile materials from cellulose fibers the water consumption and consequently the Reduce the amount of waste water for the overall dyeing process to a minimum if, after the coupling and diazo components have been applied from aqueous liquor, the dyeings are completed in organic solvents.

According to the measures for carrying out the invention The textile material, for example a fabric web, is mixed with the aqueous, alkaline solution of a coupling component impregnated, dried and passed through the aqueous solution of a couplable diazonium compound, which is alkali binding agent in the form of a volatile organic acid. The resulting color is then in the moist or dried Condition treated continuously with hot, organic solvents by passing through 3 to 8 baths. The one on the cellulose fiber The dye pigments present should have a limited solubility in the solvents used. In the According to the process, organic solvents can also be used if necessary

209825/10 71

small amounts of water must be emulated. Finally, the color produced dried with recovery of the solvent.

According to the present invention, one of the particulars is coloring simplifying procedure in the preparation of the insoluble Azo dye from coupling component and the diazoamino compound or the antidiazotate of a primary aromatic amine possible. In such a case, one can do the pre-dye coupling required release of the couplable diazonium compound carry out in the hot solvent, which for this purpose is mixed with the solvent in question, organic Acid adds. As part of the variant just mentioned are coupling component and the diazo component in the form of a cleavable diazoamino compound or an antidiazotate in aqueous, alkaline solution at the same time brought to a web of fabric. The impregnated goods are then placed in the moist or dry state by 3 to 8 baths with hot, organic Solvents out, with the first bath an additive of volatile, organic acid.

As has been found on the basis of the procedures described above, the water requirement is in the dyeing according to the invention and finishing the dyeings minimally compared to the amounts of water used in making the corresponding insoluble ones Azo dyes required on cellulose fibers by known processes are.

For carrying out the process according to the invention, coupling components with low to medium substantivity towards the textile material are considered as coupling components. Such compounds are the arylides of ß-hydroxynaphthoic acid, z. B. 2,3-hydroxynaphthoic anilide, l- (2 *, 3'-hydroxynaphthoyamino) -2-methoxybenzene, l- (2, 3'-hydroxynaphthoylamino) -2-methyl - ^ - chlorobenzene, l- (2, 3 ¹ -hydroxynaphthoylamino) -2, ^ - dimethoxy-S zol or 1- (2 ·, 3 ¹ -hydroxynaphthoylamino-3-nitrobenzene,

the arylides of 6-methoxy-2,3-hydroxynaphthoic acid, e.g. B. 6-methoxy-2,3-hydroxynaphthoic anilide or

: 20982 5/1071

1- (6-methoxy-2, 3 ¹ -hydroxynaphthoylamino) -2, S-di

Acetoacetylamino compounds, e.g. B.

4,4'-bis-acetoacetylamino-3,3'-dimethyl-diphenyl, or the arylides of hydroxycarbazole carboxylic acid, ζ. Β. 1- (2'-Hydroxycarbazole-3-carboylamino) -4-chlorobenzene.

With small impregnation containers and fast goods flow, coupling components with high Use substantivity for cellulosic fibers, e.g. B. "

2- (2 ', 3-hydroxynaphthoylamino) naphthalene, or

1- (5-Hydroxy-1 »2, 1", 2 "-benzocarbazole-4 · - carboyl amino) -4-methoxy-

benzene.

As diazo components in the present process in the form of their diazonium compounds, their cleavable diazoamino compounds, or - if they can be produced - the following primary amines are used in the form of their antidiazotates: Chloranilines, chlorotoluidines, anisidines, chloranisidines, trifluorine methylaniline, nitroaniline, nitrotoluidines, nitroanisidines, aminophenylsu3 £> acid amides, Aminophenylcarbonsaureamxde, Aminodiphenylether, Aminoazobenzenes, N-substituted phenylenediamines,

di ^
Diaminophenyls or aminoanthraquinones.

Sodium hydroxide is used as the alkali to dissolve the coupling component, Potash lye or strong organic bases, e.g. B. Ethyl diethanolamine, in question. As protective colloids in the alkaline impregnation bath can protein condensation products, sulfonated castor oils, condensation products from naphthalenesulfonic acids with formaldehyde, or condensation products from oleic acid with N-methyltaurine will.

As acidic agents in aqueous solutions of diazonium compounds or as an acid additive to organic solvents to release the coupling-capable diazonium compounds from the compounds according to the invention applicable diazoamine compounds or antidiazotics volatile organic acids reach, ζ. B. acetic acid, formic acid or propionic acid, are used.

209825/107 1 _BAD ORIGINAL

Suitable organic solvents for use in accordance with the present invention are in pure form, mixed with one another or in emulsion with the addition of up to 6 % water, halogenated hydrocarbons, e.g. B.

Trichlorethylene, perchlorethylene, tetrachloroethane, methylene chloride or trifluorotrichloroethane,.
aromatic hydrocarbons, e.g. B. benzene or xylene, and ■. .

aliphatic or cycloaliphatic hydrocarbons, e.g. B. Tetralin.

example 1

Cotton fabric is continuously heated through the 60 - 90 C temperature Solution A of the composition given below carried out,

on

and between rollers a liquor pick-up of 80 % of the weight of the dry goods is squeezed off. The padded fabric is then dried with hot air at 100-120 ° C., then passes through the cold solution B of the preparation described below and is again squeezed between rollers to a liquor pickup of 80 Ji. This is followed by an air pass of 30-60 seconds at room temperature and then the padding is passed through two to five perchlorethylene baths at temperatures between 60 and 120 C. Finally, the dyed goods are dried with recovery of the solvent. A full red dyeing with good fastness properties is obtained.

When carrying out the above dyeing, the perchlorethylene treatment baths 1 - 5> ° water can be emulsified. At Instead of perchlorethylene, trichlorethylene, tetrachloroethane, xylene, or tetralin can also be used as the treatment liquid fluorinated hydrocarbons can be used. The treatment temperature is then adjusted to the respective boiling point of the solvent.

Solution A:

15 g of l- (2 ', 3 ¹ -hydroxynaphthoylamino), -2-methoxybenzöl are dissolved by boiling in 15 ecm sodium hydroxide solution (32.5%) and 1 liter of soft water, and 3 g of a condensation product of naphthalenesulfonic acid and formaldehyde are added .

■ 209 82 5/107 1

Solution B:

13 «5 g of the sulfate of l-atnino-2,5-dichlorobenzene are diazotized by pouring 27 ecm of hydrochloric acid (32 % ± g) , 27 ecm of water and ice, and an aqueous solution of 10 g of sodium nitrite, which gives the clear diazo solution is then placed in a bath of 1 l of cold water containing 2 g of a condensation product of 1 mole of octadecyl alcohol with 10 moles of ethylene oxide, 1K g of crystallized sodium acetate and 15 ecm of acetic acid (50 % xg) .

The following table shows further combinations of coupling and Diazo components are indicated with which full colorations with good fastness properties can also be produced by the process according to the invention.

20982 5/1071

Coupling component

Diazo component

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2,3-Hydroxynaphthoic anilide 1- (2x, 3 '-hydroxynaphthoylani3no) -2-methyl-4-chlorobenzene

1- (2 ', 3 · -liydroxynaphthoylamino) -2,4-dimethoxy-5-chlorobenzene

6-methoxy-2,3-hydroxynaphthoic anilide 1- (2 ^f -hydroxycarbazole-3 '~ carboylamino) -4-

NJ chlorobenzene

cd 4,4 · -Bis-acetoacetylamino-3 t 3'-dimethyldiphenyl

2- (2 ', 3' -liydroxynaphthoylamino) - naphthalene -> 1- (5'-Hydroxy-1 ·, 2 ·, 1 ", 2" -benzocarbazole-4 ·

carboyl-arnino) -4-methoxybenzene 2,3-hydroxynaphthoic acid anilide 2,3-hydroxynaphthoic anilide 2,3-hydroxynaphthoic anilide

2,3-hydroxynaphthoic anilide 1-amino-2-raethyl-4-chlorobenzene

l-Amino-2-methoxybenzene-5-diethylsulphonic acid anaide 1-amino-3-chlorobenzene 1-amino-2-methoxy-4-nitrobenzene

i-amino-2-methyl-3'-chlorobenzene '

1-amino-2-methyl-5-chlorobenzene 1-amino-2-methoxy-4-nitrobenzene

4-Amino-2 ', 3-dimethyl-1,1 * -azobenzene 4-amino-4-methoxydiphenylamine

1-amino-2,4-dimethoxy-4-benzoylaminobenzene

4,4'-diamino-3 »3 * -dimethoxy-diphenyl

S charlÄch red

Red

Bordo j 206 ' Brown CO
cn yellow Red S black garnet blue blue blue

Example 2

Cotton fabric is fed continuously through a kO - 50 C warm liquor which contains the following additives per liter of soft .'assers of kO C:

2g of a condensation product of oleic acid and N-methyltaurine, 7.5 ecm sodium hydroxide solution (32 / iig),

15 g l- (2 ¹ , 3 '-Hydroxynaphthoylaraiiio) -2-methylbenzene, dissolved in 15 ecm denatured alcohol, 7.5 can sodium hydroxide solution (32 % ± g) and 30 ecm water,

and the diazoamino compound

7.3 g of l-amino - ^ - methyl-S-chlorobenzene and sodium cyanamide, dissolved by pouring over 70 C hot water »

After impregnation, the fabric treated in this way is squeezed between rollers to a liquid absorption of 80% of the weight of the dry goods, dried and passed through a bath of 80 ° C. trichlorethylene, which contains 3 cc / l acetic acid (100 % ± g) . The time of action of the padding in the acetic acid solvent bath should be at least 15 seconds. The resulting dye is rinsed and finished in two to five subsequent baths of trichlorethylene between 60 and 80 ° C. A full red color is obtained. Finally, the dyed fabric is dried with recovery of the solvent.

When carrying out the above dyeing, water can be emulsified in the treatment baths 1-5 / 0. Instead of trichlorethylene Perchlorethylcm can also be used as the treatment liquid, Methylene chloride or fluorinated hydrocarbons are used. The treatment temperatures are then set to the boiling points matched to the respective solvent.

The following table shows further combinations of coupling components and diazo components indicated in the form of their diazoamino compounds or antidiazotates, with those according to the invention Procedure also full development of good quality properties can be produced.

209825/1071 ORIGINAL BATHROOM

Coupling component

Diazoamino compound. (DA) or antidiazotate (AN)

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1- (2 ', 3' -Iydroxynaphthoylamino) -2-methoxybenzene

1- (2 ', 3'-hydroxynaphthoylamino) -2-methylbenzene

ro.

ο k, k ¹ -Bis-acetoacetylamino-3 ■> 3 '-

cd '

Q ₀ dimethyl diphenyl

CTl · '·

**> 1- (2 ', 3' -hydroxynaphthoylamino) -2- O methyl - ^ - chlorobenzene

2- (2 ', 3'-Hydroxynaphthoylamino) -naphthalene DA from diazotized ^ l-amino-2-methoxy-5-chlorobenzene and N-methylaminoacetic acid sodium DA from diazotized! l-Amxno-2-methyl-3-chlorobenzene and cyanamide sodium
DA from diazotized l-amino-2-methyl-5-chlorobenzene and N-methylamxnoessxgsaurem sodium DA from diazotized! 4fc, V-diamino-3,3-dimethoxy-diphenyl. And N-methyltaurine

DA from diazotized l-amino-2,5-diethoxy-4-benzoylaminobenzene and sodium N-methylaminoacetate

bluish red

yellowish red

yellow

blue

blue

l- (2 *, 3 '-IIydroxynaphthoylamino) -2.4 dimethoxy-5-chlorobenzene

1- (2 ·, 3 * -hydroxynaphthoylamino) -Z- methoxy-'i-chloro-5-methylbenzene DA from diazotized 1-amino-2-methyl-3-chlorobenzene and sodium cyanamide

AN from diazotized i-amino-2-methoxy-5-chlorobenzene

dull, bluish

Red

bluish red

Coupling component

Diazoamino compound (DA) or antidiazotate (AN)

hue

l- (2 ¹ , 3 ¹ -hydroxynaphthoylamino) -2-methoxybenzene, _ ..

AN from diazotized! l-amino-2-chloro-5-tr i fluorine thylbenzene

yellowish red

l- (2'-Hydroxycarbazol-3 ¹ -carboylamino) - DA from diazotized l-amino-2-4-chlorobenzene and methyl-5-chlorobenzene

Cyanamide sodium
1- (5'-Hydroxy-1 ', 2', 1 ", ^" - benzocarbazole- DA from diazotized l-amino-2-

k '-carboylamino) -k- methoxybenzene

k, k * -bisacetoacetylamino-3>3'-dimethyl-diphenyl

2,3-hydroxynaphthoylamino-benzene

2,3-Hydroxynaphthoylamino-benzene, methoxy-4-nitrobenzene and Cyanamide sodium

DA from l-amino-ß-methyl-S-chlorobenzene and cyanamide sodium

Brown

black

yellow

DA from diazotized l-amino-2-red methyl-5-chlorobenzene and cyanami disodium

DA from diazotized l-amino-2-blue diethoxy-4-benzoylaminobenzene and Sodium N-methylaminoacetate

Claims (6)

Claims 1. Process for the preferably continuous production of insoluble Azo dyes on textile materials made from cellulose fibers, characterized in that after the application of Coupling and diazo component from aqueous liquor carries out the completion of the dyeing in organic solvents. 2. The method according to claim ¹ !, Characterized in that the resulting dyeing during the coupling is carried out in the water-moist or dried state for rinsing and aftertreatment by baths of hot, organic solvents. 3 · The method according to claim 1, characterized in that the with an aqueous-alkaline liquor composed of a coupling component and the cleavable diazoamino compound or the antidiazotate one primary aromatic amine impregnated textile material in the moist or dried state to release the couplable Diazonium compound and subsequent coupling through Baths of hot, organic solvents that lead to a volatile organic solvent that is miscible with the solvent in question Acid are added. k. Process according to Claim 1 or 2, characterized in that the treatment temperature is matched to the respective boiling point of the solvent used. 5. Process according to Claims 1 to k, characterized in that solvents are used in which the dye pigments produced have limited solubility. 6. Process according to Claims 1 to 5i, characterized in that one uses solvents which contain small amounts of emulsified water. 7. Process according to Claims 1 to 6, characterized in that the solvent used is aliphatic, cycloalophatic or aromatic Hydrocarbons, preferably halogenated hydrocarbons, are used. 2 0 9 8 2 5/1071 BAD