DE1262957C2 - 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

SCHES

PATENT OFFICE

PATENT LETTERING

Int. α .:

German class:

Number:

File number: Registration date:

Interpreted »»:

Issue date:

C09b

8 m -1/01

22a-l

1,262,957 F41036rVc / 8m October 19, 1963 March 14, 1968 3rd October 1968

The patent specification corresponds to the patent specification

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 or tetrazoamino compound of the formula

1 1

R 4 -N = NN-CN _n

where R is the radical of an aromatic or heterocyclic amine, Me is an alkali or alkaline earth metal and η is 1 or 2, as well as a wetting or dispersing agent and optionally an inorganic salt, and then by treatment with acidic agents below 40 "C the dye formation brings about.

The procedure is carried out in the manner that the textile material in the form of hank yarn, bobbins, sliver or loose material treated in an alkaline bath, which has an azo component with high substantivity and a Diazoamino or tetrazoamino compound of the specified composition and a network or Contains dispersant and optionally an inorganic salt, for example sodium chloride, a sodium phosphate or sodium sulfate. The treatment is carried out for at least 10 minutes to give the azo component the possibility of adequate and uniform fixation on the textile material. Generally one works at Room temperature or at a slightly elevated temperature, expediently below 35'C After the Azo component is largely absorbed and has equalized, if an organic acid is used, for example formic acid, acetic acid, tartaric acid, citric acid, lactic acid or glycolic acid or a mixture of these acids, or a mixture of an inorganic acid, for example hydrochloric acid or sulfuric acid, and an organic one Add acid to 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 4 and 7 is reached. The temperature should be below 40 C. The formation of the Dye on the textile material. It is then washed in a neutral or acidic bath, if appropriate in the presence of dispersants and the staining completed in the usual way. This gives dyeings which are very rubbing fast.

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

Patented for:

Farbwerke Hoechst Aktiengesellschaft formerly Master Lucius & Brüning, 6000 Frankfurt

Named as inventor: Dipl.-Chem. Dr. Hasso Hertel, Dipl.-Chem. Dr. Werner Kirst, 6050 Offenbach

Piece goods can be dyed in such a way that the goods are impregnated on a two- or multi-roll foulard with a mixture of the azo component and excess diazoamino or tetrazoamino compound, the goods are rolled up and, after a dwell time, for example of half an hour, through a passage an organic acid, a mixture of organic acids or a mixture of organic and inorganic acids below 4O ⁰ C brings about the coupling. This development can take place through a passage in a compartment of a roller runner or through several passages on the jigger or on a reel runner, with the addition of inorganic salts and of dispersants in the impregnation and in the development sometimes having a very beneficial effect. In this mode of operation, the concentration of the azo component in the make-up bath must be reduced compared to that in the make-up bath, in accordance with the additional drawability of the azo component, while the concentration of the diazoamino or tetrazoamino compound in the make-up bath is not decreased compared to that 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. H. Azo components, which at a liquor ratio of 1:20, 30 minutes dyeing time at 30 C, a concentration of 1 g in liter of water without Addition of salt and an excess of 4.5 g of sodium

a04 "24/24"

3 4

hydroxide per liter of liquor cine such a high noun ity. The method according to the invention is compared

have that at least 9 g per 1 kg of cotton using the usual dyeing process with ice colors

wind up. Suitable connections are essential simplifications. In the case of the known

for example 2,3 - Oxynaphthoylaminobcnzole, such as dyeing process is after impregnation with the

1- (2 ', 3'-Oxynaphthoylamino) -2,5-dimethoxy-4-chloro-5 azo component usually the dyebath from-

benzene or l- (2 ', 3'-oxynaphchoylamino) -2-methoxy- left, the goods thrown, vacuumed or

4-chloro-5-methylbenzene, 6-bromo- or 6-methoxy- and the dye in a second

2,3-oxynaphthoic acid arylamides, such as 1- (6-bromine bath developed with a diazonium compound.

2,3'-oxynaphthoylamino) -2-methoxybenzene, Kon- In contrast, the present seduction unites

Densation products from 2,3-oxynaphthocic acid and io the primer and development in one bath,

polynuclear isocyclic or heterocyclic and after the fixation of the azo component

Amines, such as 2- (2 ', 3 ^/ -oxynaphthoylamino) -naph- required Zeil, the coupling takes place without

thalin, 2 - (2,3 - oxynaphthoylamino) - carbazole. any intermediate operations, like that

2- (2 ', 3'-O.xynaphthoylamino) -3-methoxydiphcnylen- that achieved a significant reduction in working hours

oxide, 6 - (2 ', 3 - oxynaphthoylamino) - benzimidazole, 15 will.

6- (2 ', 3'-Oxynaphthoylaminoj-indazole, 5- (2', 3'-O. \ Y- 'From the German Palentschrift 624 765 is

naphthoylamino) - 2 - metbylbenzthiazole or known that diazoamino compounds from diazo-

4- (2 ', 3'-Oxynaphthoylatnino) -diphenyl and its animal aromatic amines and cyanamide for

Substitution products, 4.4'-bis (2 ", 3" -oxynaphthoyl- production of azo dyes on the fiber

amino) -diphenyl and its substitution products, 20 can be used by using such di-

such as 4,4'-bis (2 ", 3" -oxynaphthoylamino) -3,3'-di-azoamino compounds mixed with azo components,

methoxydiphenyl, 1.4- bis - (2 ", 3" - oxynaphthoyl- imprints the resulting mixtures and through a

amino) -bcnzol and its substitution products, acid treatment developed the dye. This

4.4 '- bis - (2 ".3" - Oxynaphthoylamino) - syllables, but the patent does not reveal that

4,4'-bis (2 ", 3" -oxynaphthoylamino) -azobenzene and 25 such mixtures also for dyeing the fiber in

its substitution products, 4,4'-bis- (2 ", 3" -Ox \ ·· all processing states, also in wound packages,

naphthoylamino) -diphenylharnstorT, 2-Oxyanthraeen- can be used without intermediate drying of the goods

3-carboxylic acid arylamides, such as l- (2'-oxyanthracene-can.

3'-carboylamino) -2-methylbenzene, 2-oxycarbazole- From German patent 1057 061 is

3-carboxylic acid arylamides, such as 1 - (2'-oxycarbazole 30 also known that water-insoluble azo color

V carboylamirio) · 4 - chlorobenzene, 5 - oxy - 1,2, substances on vegetable fibers can produce by

l ', 2'-bcnzocarbazol - 4 - carboxylic acid carylamide, how these fibers are used in long liquor ratios in

1 - (5'-Oxy- r, 2 ', 1 ", 2" -ben2ocarbazole -4'-carboyl- treated with a bath which contains an azo component

amino) -4-methoxybenzene or 1- (5'-oxy- V, 2 '. and a diazo or tetrazoamino compound without

1 ", 2" - benzocarbazole -4-carboylamino) -2 -methyl- 35 contains solubilizing groups, and then

4-methoxybenzene, ferric tercphthaloyl-bis-cacetic acid- the azo dye by treating in an acidic

arylamides, such as terephthalovl-bis- (l-acetylamino- bath.

2.4-dimethoxy-5-chlorobenzene) or terephthaloyl

bis- (l-acetylamino-2-methoxy-4-chloro-5-methyl- method according to the invention using

benzene). 40 substantive azo components and diazoamino

As diazoamino or tetra / .oamino compounds or tetrazoamino compounds from diazotized

in particular those made from aromatic aromatic mono- or diamines and cyanamide

Mono- or diamines into consideration, for example, is carried out from the fact that the development

Mono- or dichloroanilines, toluidines, chlorine and dyes at low temperatures

Toluidinen, Chloranisidinen, Xylidinen, Phenetidinen, 45 can be taken and an increase in

Nitranilines, Nitrotoluidincn, Nitroariisidinen, Ni temperature not required after the addition of acid

Troxylidinen, Nitrophenctidinen, Cyantoluidincn, is. Another advantage of the present method

Cyananisidines, aminobenzenesulfonic acid amides, consists in the fact that the diazoamino or tetrazo

Aminophenylalkylsulfoncn, aminobenzene carbonamino compounds with cyanamide as stabilizer

acid amides, aminodiphenyl ethers. monoacylated 50 are present as dissolved alkali salts in an alkaline bath

Phenylenediamines, aminoazobenzenes. Benzidine, di- and thereby complete penetration of the

anisidine or tolidine, as well as from heterocyclic dyed goods, which lead to a complete coupling

Amines, e.g. B. aminocarbazoles. Their production leads to development, while when using water-insoluble

can, for example, by the method of German Licher diazoamino compounds, these superficially

Patent 614 198 take place. 55 are deposited on the material to be dyed, causing it to

As a wetting or dispersing agent, which can result in insufficient coloration,

the ice color technique usual compounds in a feedback of the diazonium compound with

Consideration, for example, condensation products from the cyanamide can not take place, since in the

higher molecular weight fatty acids and protein breakdown - cleavage in addition to the diazonium compound neutral

Products, condensation products, are formed from higher molar salts and urea. To this

Cular fatty acids and aminoalkyl sulfonic acids. Way will take full advantage of the deployed

Formaldehyde condensation products obtained with naph dye components,

lhalinsulfonic acids, or purified sulfite cellulose- _. . . ,

waste liquor. ~ For example

The process can be applied to textile material from ⁶ 5 A cheese with 500 g of cotton yarn is applied

natural or regenerated cellulose, cyanithy- a dyeing machine with about 6 liters of content 30 minutes

lated cellulose, wool, natural silk or regenerated ^{treated with a 20 0} C solution (circu-

Perform protein fibers. lation from the inside out), which is 8.1 g of the

Diazoamino compound from diazotized! 1-amino-2,5-dichlorobenzene and sodium cyanamide and 3 g of the sodium salt of ethylene, diamine tetraacetic acid contains approximately 5.8 l of water, with venting of the coil interior occurs. Then you add one after the other 24 g of a dispersant, which 16% of a condensation product from partially degraded Casein and palm kernel fatty acid as well as 8 "/ o of a condensation product from u-ethyl-oxylchlorocarboxylic acid ester and contains n-ethylhexyltaurine sodium, and 42 ecm sodium hydroxide solution of 38 ° Be added, whereby the last air pockets in the coil disappear. With a liquor circulation from the outside to the inside, a solution of 7.5 g l- (5'-Oxy-l ', 2',

1 ", 2" - benzocarbazole - 4 '- carboylamino) - 4 - melhoxybcnzol in a mixture of 30 ecm denatured ethyl alcohol, 4.25 ecm sodium hydroxide solution of 38 "Be. 15 ecm water at 70 ⁰ C and 7.5 ecm 30% igcr Formaldchydlosung and after changing the direction of the liquor for about 30 minutes while changing the direction of the liquor in a rhythm of

Treated further for 2 minutes / 4 minutes at 20 "C. Then 120 g of sodium chloride are added and the treatment is continued for a further 20 minutes. Then 6 ecm of an action product of about 20 mol of ethylene oxide is passed on to Krcsylcamphan, 51.3 ecm of hydrochloric acid of 20 ⁰ Be and 48 ecm of 50% acetic acid, a pH of 4.4 to 4.6 being established and the coupling commencing.

After about 30 minutes, the bath is drained off, rinsed carefully and soaped at 60 ° C. for 15 minutes 16.5 g of a mixture of 63% perchlorethylene, 17% of an action product of about 10 mol Ethylene oxide on 1 mole of nonylphenol and 20% isopropyl alcohol and 13 g of a 25% solution of sodium nitrilotriacetate in water, drains, rinses, soaps 15 minutes at boiling temperature with 13 g of an action product of about 10 moles of ethylene oxide to 1 mole of nonylphenol and 13 g of a 25% solution of sodium nitrilotriacetate in 6 l of water, rinses and dries. A very good fastness, dark violet coloration is obtained.

Compared to normal coloring with priming with the azo component, intermediate rinsing and Developing with a diazotized amine results in a substantial time saving.

Example 2

In the same way as in Example 1, a cheese with 500 g of cotton yarn in a dyeing apparatus of 61 capacity is mixed with the solution of 9.6 g of the diazoamino compound from diazotized! l-Amino-2-methoxy-5-chlorobenzene and sodium cyanamide and 6 g of sodium ethylenediaminetetraacetate in 61 water at 20 ° C. Then 24 g of a dispersant, which contains 16% of a condensation product of partially degraded casein and palm kernel ^{fatty acid and 8 1} Vo of a condensate product of α-ethylhexylchlorocarbonic acid ester and -ethylhexyltaurine sodium, and 42 ecm sodium hydroxide solution of 38 ^c Be, and then a solution of 9 g of 2- (2 ', 3'-oxynaphthoylamino) -3-methoxydiphenylene oxide in a mixture of 20 ecm of denatured ethyl alcohol. 45 ecm sodium hydroxide solution at 38 ° Βέ and 9 ecm hot water were added. Then dyeing is carried out for 30 minutes while changing the direction of the liquor, 120 g of sodium chloride are added and treatment is continued ^{at 20 ° C. for 20 minutes.} Then 6 ecm of an action product of about 20 mol of ethylene oxide on cresylcamphane, 51.3 ecm of hydrochloric acid of 20 ° Be and 36 ecm

50% acetic acid is added, the pH dropping to about 4.5 and coupling occurs. To a further 20 minutes, as described in example 1, post-treated, rinsed and dried. A rubbing, dark red coloration is obtained.

ίο Is used in the above example instead of 9.6 g of the diazoamino compound from diazotized 1-amino-2-methoxy-5-chlorobenzene and sodium cyanamide 9.6 g of the diazoamino compound from diazotized I-amino-2-methyl-4-chlorobenzene and sodium cyanamide, this gives a rub-proof, yellowish red coloration.

Example 3

Cotton yarn is used in a liquor ratio of 1; 20 treated at 20 'C in an aqueous solution, soft 1.1 g of 2- (2', 3'-oxynaphthoylamino) -3-methoxydiphenylene oxide, 3 g of a dispersant, which is 16% of a condensation product of partially degraded casein and palm kernel fatty acid per liter and 8% of a condensation product of u-ethylhexylchlorocarbonic acid ester and a-ethylhexyltaurine sodium, 5 ecm sodium hydroxide solution of 38 ^C Bc, 20 g of sodium chloride and 1.62 g of the diazoamino compound from diazotized l-amino-2-methoxybenzene-5-sulfonic acid-n-butylamide and contains cyanamide sodium. After 30 minutes, 5.5 cc of hydrochloric acid of 20 "Be and 3 cc of acetic acid 50% added per liter ig added and treated at a pH of about 5.5 for a further 30 minutes. It is then rinsed as usual at 6O ⁰ C and soaped, rinsed and dried at boiling temperature with 2 g of an action product of about 10 moles of ethylene oxide per 1 mole of nonylphenol and 0.4 g of sodium nitrilotriacetate per liter of water.

Is used in the above example instead of 1.62 g of the diazoamino compound from diazotized 1-Amino-2-methoxyben7ol-5-sulfonic acid c-n-butylamide and sodium cyanamide 1.4 g of the diazoamino compound from diazotized l-amino-2-methoxy-5-ethylsulfonylbenzene and sodium cyanamide and developed at a pH of about 5, a strong red color is also obtained.

_like example 4

Cotton yarn is treated in a liquor ratio 1:20 at 20 C in an aqueous solution, which 1.1 g of 2- (2 ', 3'-oxynaphthoylamino) -3-methoxydiphenylene oxide per liter, 3 g of a dispersant, which 16% of a condensation product from partially degraded casein and palm kernel fatty acid as well as 8% of a condensation product from α-ethylhexylchlorocarbonic acid ester and contains α-ethylhexyltaurine sodium, 5 ecm sodium hydroxide solution at 38 ° Be, 20 g sodium chloride and 1.16 g of the diazoamino compound from diazotized 1-amino-2-methyl-5-chlorobenzene and contains cyanamide sodium. After about 30 minutes, 5.5 ecm hydrochloric acid of 20 ° Be is added per liter and 5 ecm acetic acid 50% and treated at

«5 a pH value of 4 to 4.5 further for 30 minutes. Then it is rinsed, at 6O ⁰ C and boiling temperature for 15 minutes with 2 g of an action product of about 10 mol of ethylene oxide to 1 mol of nonyl

phenol and 0.4 g nitrilotriacetic acid!]! Sodium im Liters of water soaped, rinsed and dried. A strong red color is obtained.

If you use in the above example instead of the Diazoamino compound from diazotized 1-amino-2-methyl-5-chlorobenzene and sodium cyanamide 1.04 g of the diazoamino compound obtained from diazotized 1-amino-2-methyl-3-chlorobenzene and sodium cyanamide, a brown-red color is obtained.

Example 5

A cheese with 500 g of cotton yarn is vented in the liquor ratio 1: 2 at 20 ⁰ C with the aqueous solution of 5 g of the Diazoaminoverb.verbindungen from diazotized l-amino-2-methoxybenzene-5-carboxamide and sodium cyanamide, 3 g of sodium ethylenediamine , 24 g of a dispersant which contains 16% of a condensation product of partially degraded casein and palm kernel fatty acid and 8% of a condensation product of α-ethylhexylchlorocarbonic acid ester and u-ethylhexyltaurine sodium, and .120 g sodium chloride is treated with circulation from the inside out. Then 42 ecm of sodium hydroxide solution at 38 ° Be and after switching the liquor circulation 13.5 g of l- (2 ', 3'-oxynaphthoylamino) -2,5-dimethoxy-4-chlorobenzene, dissolved in 27 ecm of denatured ethyl alcohol, 5, 4 ecm sodium hydroxide solution of 38 ° Be, 13.5 ecm warm water and 13.5 ecm 30 ° / () formaldehyde solution. After about 20 minutes, 120 g of sodium chloride and then 6 ecm of an action product of about 20 mol of ethylene oxide on cresylcamphane are gradually added. After a further 15 minutes, the bath is acidified by adding 52.8 ecm of hydrochloric acid of 20 Be and 24 ecm of 50% acetic acid and treated for 30 minutes at 20 ° C. and a pH of about 5.4. It is then rinsed, soaped at 60 C for 15 minutes with 16.5 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 3 g of sodium nitrilotriacetate in 6 l of water , soaped at the boil for 15 minutes with 12 g of an action product of about 10 moles of ethylene oxide on 1 mole of nonylphenol, 1.5 g of sodium nitrilotriacetate and 6 g of soda in 61 water for 15 minutes, rinsed and dried. A bright red dyeing of good fastness to rubbing is obtained.

Example 6

A cheese with 500 g of cotton yarn in a liquor ratio of 1:12 at 20 C with the aqueous solution of 13.6 g of the diazoamino compound from diazotized 1-amino-2-methyl-3-chlorobenzene and sodium cyanamide, 3 g of the sodium salt of ethylenediaminetetraacetic acid, 60 g sodium chloride and 24 g of a dispersant which contains 16% of a condensation product of partially degraded casein and palm kernel fatty acid and 8% of a condensation product of u-ethylhexylchlorocarbonate and u-ethylhexyltaurine sodium. After about 30 minutes of circulation from the inside to the outside, 42 ecm of 38% caustic soda are added. After a few minutes, a solution of 12 g of 2- (2 ', 3'-oxynaphthoylamino) naphthalene in 24 ecm of denatured ethyl alcohol is passed through. 4.8 ecm sodium hydroxide solution of 38 Be. 12 cm of hot water and 12 cm of 30% formaldehyde solution. Then allowed under change of direction of circulation to proceed for 20 minutes at 20 ⁰ C, adds to 60 g of sodium chloride and treated for 15 minutes further. Then 6 ecm of an action product of about 20 mol of ethylene oxide on cresylcamphane, 51 ecm of hydrochloric acid of 20 "Be and 36 ecm of 50% acetic acid run in. The treatment is carried out at a pH value of about 5

ίο at about 2O ⁰ C for 30 minutes, rinsing, soapy for 15 minutes at 60 ⁰ C with 16.5 g of a mixture of 63% perchlorethylene, 17% of an action product of about 10 moles of ethylene oxide to 1 mole of nonylphenol and 20% isopropyl alcohol and 3 g of sodium nitrilotriacetic acid in 61 water and then 20 minutes at boiling temperature with 12 g of an action product of about 10 mol of ethylene oxide on 1 mol of nonylphenol and 1.5 g of sodium nitrilotriacetic acid in 61 water, rinses and dries. A scarlet dye of very good rub fastness is obtained.

Example 7

A cheese with 500 g of cotton yarn is in a dyeing apparatus with about 6 1 Table 15 minutes with circulation from the inside to the outside with a 2O ⁰ C. solution treated which 9.8 g of diazoamino compound obtained from diazotised l-amino-2,5-dichlorbenzoI and sodium cyanamide and 6 g of sodium ethylenediaminetetraacetic acid. Then, one after the other, 24 g of a dispersant containing 16% of a condensation product of partially degraded casein and palm kernel fatty acid and 8% of a condensation product of -ethylhexylchlorocarbonate and -ethylhexyltaurine sodium and 42 ecm of 38% caustic soda are added. After the coil has been completely vented, circulation is allowed to run in alternating direction of the liquor, 9.6 g of terephthaloylbis (1 - acetylamino - 2,4 - dimethoxy - 5 - chlorobenzene), dissolved in 48 cm of denatured ethyl alcohol, 10.8 cm of sodium hydroxide solution are added 38 ° Be and 96 ecm of water are added in portions, and 60 g of sodium chloride are added to the mixture after a while.

Then 6 ecm of an action product of about 20 moles of ethylene oxide is added to cresylcamphane and a mixture of 56 ecm hydrochloric acid of 20 Be and 48 ecm acetic acid 50%. After about 20 minutes Coupling at pH 4.2, the bath is drained,

so rinse carefully, soapy for 15 minutes at 60 ⁰ C with a solution of 16.5 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 12 g of a 25% strength Solution of sodium nitrilotriacetate in water, rinsed and soaped with 12 g of an action product of about 10 moles of ethylene oxide to 1 mole of nonylphenol, 12 g. Calcined soda and 4 g of hydrosulfite in 6 l of water, by entering at 50 to 60 C, heating to the boiling temperature and maintaining this for about 10 minutes. Then it is rinsed hot and cold and dried. A yellow coloration which is fast to rubbing is obtained.

₆ j examples

A cheese with 500 g of cotton yarn is circulated on a dyeing machine with a capacity of 6 l inside out with a 20 C warm

9 10

Treated solution, which 8.4 g of diazoamino from 63% perchlorethylene, 17% of an action compound from diazotized! l-Amino-2-methoxy product of about 10 moles of ethylene oxide to 1 mole of 5-nitrobenzene and sodium cyanamide and 6-ethylene nonylphenol and 20% isopropyl alcohol and 12 g of sodium diamine tetraacetate. After about a 25% solution of nitrilotriacetic acid for 15 minutes, add 24 g of a dispersing agent, 5% sodium in 61% water, rinse warm and treat the 16% of a condensation product from about 15 minutes at boiling temperature with 12 g of a partially degraded casein and palm kernel fatty acid action product of about 10 moles of ethylene and 8 ⁽⁾ / o of a condensation product of u-ethyl oxide on 1 mole of nonylphenol, 6 g of calcined soda hexylchlorocarbonic acid ester and a-ethylhexyltaurine and 12 g of a 25% solution of nitrilotriene sodium, and after complete deaeration 10 acid sodium in 61 water, rinses thoroughly hot to the bobbin 42 ecm sodium hydroxide solution of 38 * Be. Then and cold and dry. The result is a red dyeing, one dyeing with changing direction of the liquor of good rub fastness,
circulation, adds a solution of 7.5 g 4,4'-bis- r ■ · 1 m

(2 "-oxycarbazole-3" -carboylamino) -3,3'-dimethoxy- υ e 1 s ρ 1 e 1 iu

Diphenyl in a mixture of 45 ecm of ethylene- 15 cotton terry fabric (about 100 kg) is added to glycol, 4 ecm of sodium hydroxide solution of 38 ° Be and 14 ecm of a reel vat with about 16001 content with water, after about 5 minutes 60 g of wetting agent is added with addition of soda thoroughly pre-wetted sodium chloride and left for another 15 minutes and rinsed. The reel skid will then circulate with one. Then 6 g of an action solution are charged which, in 100 liters of water, diazotized 3.6 kg of the product from about 20 mol of ethylene oxide to cresyl 20 diazoamino compound! 1-aminocamphane and then a mixture of 50 ecm 2-methoxy-4-nitrobenzene and sodium cyanamide, hydrochloric acid of 20 ° Be and 48 ecm acetic acid 50% 0.85 kg of a condensation product of oleic acid and coupled, about 20 minutes at pH 4 , 2. Then and contains methyl taurine and 2.8 kg of sodium sulfate, rinsing, treated with 16.5 g of a mixture of , 25 kg of l- (5'-Oxy-l ', 2 \ l ", 2" -benzoduktes of about 10 moles of ethylene oxide to 1 mole of carbazole ^' - carboylaminoH-methoxybenzene, dissolved in nonylphenol and 20% isopropyl alcohol and 12 g of 131 Denatured ethyl alcohol, 1.631 50% strength of a 25% strength solution of nitrilotriacetic acid sodium hydroxide solution, 6.51 water at 60 ° C. and 3.251 sodium in 61 water 15 minutes at 60 ° ^C. , rinsed 30% strength formaldehyde solution are added. The mixture is warmed and treated for 15 minutes Boiling with 12 g of 30 is about 1 hour at 30 "C, adds 17.81 60% acetic acid and ethylene oxide to 1 mole of nonylphenol and 12 g of a treated at a pH value in the course of an action product of about 10 moles of 5 minutes 25% solution of sodium nitrilotriacetate for 40 minutes, then drained and rinsed thoroughly h and soaps in water, rinses and dries. A dyeing of very good fastness to rubbing, which is yellow-brown for 20 minutes at 60 ° C. and at the boiling point, is obtained with 4.8 kg of Marseilles soap, 0.8 kg of sodium nitrilotriacetic acid and 0.8 kg of a condensation agent.

^{B e i s} P ^{1 e} ' ⁹ product of oleic acid and methyl taurine in 16001

A package with 500 g cotton is placed on water, rinsed and dried. This gives a level, a dyeing apparatus with 61 contents, with circulation, rubbing-fast black dyeing,
inside out at 20 ° C in a bath 40

is, which 10.8g of the diazoamino compound Example 11

from diazotized! 1-amino ^ -methoxy-S-nitrobenzene

and sodium cyanamide, 60 g of sodium chloride and 1 kg of natural silk in a liquor ratio of 1:20

Contains 6 g of sodium ethylenediaminetetraacetate. treated at 25 ° C in an aqueous solution, which after 15 minutes is added to another Ent-45 per liter of 1.5 g of 2- (2 ', 3'-oxynaphthoylamino) naphthalene venting the coil 24 g of a dispersant, which Hn, 2.1 g of the diazoamino compound from diazo-16% of a condensation product of partially ab- tated l-amino-2-methyl-3-chlorobenzene and cyanized casein and palm kernel fatty acid and 8% sodium amide, 0.5 g of a condensation product of a condensation product from «- Ethylhexyl from oleic acid and N-methyltaurine, 2 g of a Disperchlorkohlensäureesterundu-Äthylhexyltaurinnodium 50 giermittel, which contains 16% of a condensation product, and lets circulate for another 15 minutes in the duct of partially degraded casein and palm cold. After adding 42 ecm of caustic soda and 8% of a condensation solution of 38 Be, a solution of 9.6 g of 2- (2 ', 3'-oxy-' -ethylhexyltaurine sodium, 1.6 g sodium hydroxide naphthoylamino) naphthalene in 19.2 ecm denatu- 55 and 23 g sodium chloride contains. After about 1 hour tured ethyl alcohol, 4 cc of sodium hydroxide solution of 38 Be, is added portionwise 8.1 cc of 50% acetic acid 9.6 cc 50 ⁰ C hot water, and 9.6 cc of shape to, and treated at a pH of about 5 to 30% aldehyde and continue to treat under rhythmic 5.5 ½ hour. Then rinsed thoroughly change the direction of flow of the liquor 15 micro 15 minutes at 6O ⁰ C and 1 g of a Kondensationsnuten further added 60 g of sodium chloride and, after 60 product of oleic acid and methyl taurine per liter, about 15 minutes, a solution of 6 g of a condensate Water, soapy at the boil for about 15 minutes with 5 g of oleic acid and methyl taurine to soap and 0.5 g of sodium nitrilotriacetate and coupled by adding a mixture of liters of water, rinsing and drying. A 50 ecm hydrochloric acid of 20 ^c Be and 48 ecm acetic acid vivid scarlet coloration is obtained. In the same way 50% at a pH of 4.2 to 4.4. In the course of 65 wool can be dyed. In this case, after about 30 minutes, the temperature rises to treatment with 1 g of a condensation product about 30 ° C. It is drained, rinsed and treated from oleic acid and methyl taurine and 0.5 g of nitrilotriet for about 15 minutes at 60 ° C. with 16.5 g of a mixture of sodium acetic acid in one liter of water at 60 ° C.

taken to avoid damaging the wool fiber to a red-violet coloration of very good fastness. properties.

Example 12

A cheese with 500 g of cotton is good wet out on a dyeing machine and treated at about 3O ⁰ C in a bath, which is prepared as follows:

a) 18 g of the diazoamino compound from diazotized! 1-Amino-2-melho \ y-4-nitrobenzene and sodium cyanamide are dissolved in about 500 ecm of water at 50 ° C.

b) 16.5 g of 1- (5'-oxy-1 ', 2', 1 ", 2"-benzocarbazole-4'-carboylamino) -4-methoxybenzene are dissolved in 66 cm of denatured ethyl alcohol and 8.25 cm of sodium hydroxide solution released from 38 "Be, 16.5 cc of 33 ⁰ / cent formaldehyde solution and 13 cc water.

The solutions a) and b) are introduced one after the other into a bath at about 27 ° C., which contains 29.5 ecm of 38 "Be sodium hydroxide solution, 50.4 g of trisodium phosphate and 6.5 g of a condensation product of oleic acid and methyl taurine in about containing 5400 cc of water. After about ³ / i hours add are added over about 3 minutes, 100 cc of 50 ^o _'() acetic acid. This raises a pH of about 5.8. one treated ¹ Z ₂ hours further, rinse thoroughly and soapy for 15 minutes at 60 ° C. and at 95 ° C. with 12 g of a condensation product of oleic acid and methyl taurine and 3 g of sodium nitrilotriacetate per liter of water, rinses and dries. A deep black coloration with very good rub fastness is obtained.

Example 13

1 kg of cotton hank is at 30 "C in a bath treated, which is manufactured as follows:

a) 24 g of 1- (6'-methoxy-2 ', 3-oxynaphthoylamino) -2,5-dimethoxy-4-chlorobenzene are dissolved in 48 ecm denatured ethyl alcohol, 12 ecm sodium hydroxide solution of 38 "Be and 48" ecm water of 60 solved up to 70 ^{J C.}

b) 36 g of the diazoamino compound from diazotized 1-amino-2-methyl-4-nitrobenzene and sodium cyanamide are dissolved in 900 ecm of water at 70 ° C.

Solutions a) and b) are introduced into a bath which contains, in 191 water, 20 g of a condensation product of oleic acid and methyl taurine, 148 ecm sodium hydroxide solution of 38 Be, 600 g of sodium chloride and 10 g of sodium äthylendtaminetetraessigsaures. After ^three and a half hours, 97 ecm of 50% acetic acid and 138 ecm of hydrochloric acid of 20 Be are added over the course of 3 to 5 minutes and treatment is continued for about half an hour at a pH of about 4.8. It is then rinsed thoroughly at 30 to 40 ° C and then cold, treated for 15 minutes each at 60 ¹ C and at the boiling point in baths which contain 40 g of a condensation product of oleic acid and methyl taurine, 5 g of sodium nitrilotriacetate and 20 g of sodium carbonate in water , rinses and dries. A red-violet dyeing with very good fastness properties is obtained.

If instead of 36 g of the diazoamino compound from diazotized! 1-amino-2-methyl-4-nitrobenzene and Cyanamidnatrtum 38.5 g of the diazoamino compound from 1-Amino ^ -melhyl ^ -nitrobenzene and cyanamide potassium are also obtained

Example 14

1 of a mixed fiber of 50 parts and 50 parts of cotton kg of a copolymer of acrylonitrile, vinylidene dichloride and N-vinyl-2-pyrrolidone at 30 ⁰ C in Flotlcnverhältnis 1: treated in an aqueous solution 20, which in

ίο liters 1.6 g 2- (2 ', 3'-oxynaphthoylamino) naphthalene, 2.2 g of the diazoamino compound from diazotized! l-amino-2-methyl-5-chlorobenzene and sodium cyanamide, 0.5 g of a condensation product of oleic acid and N-methyltaiirine, 1.6 g of sodium hydroxide and contains 33 grams of sodium chloride. Treat for 1 hour and then add over 3 to 5 minutes 7 ecm of 50% acetic acid are added. Treat for 1/2 hour at a pH of about 5.5, rinsing thoroughly hot and cold and soapy at the boil for 1/2 hour with 2 g of a condensation product of oleic acid and methyl taurine and 0.5 g of nilrilotriacetic acid Sodium per liter of water, rinses hot and cold and dries. A red coloration with very good is obtained Coverage of both fibers

Example 15

1 kg of viscose rayon is treated in a liquor ratio of 1:20 at 30 "C in a bath, which is carried out as follows will be produced:

a) 1.25 g of l- (5'-oxy-l ', 2', r.2 "-benzocarbazole-4-carboylaniino) -4-methoxybenzene are dissolved in 5 ecm of denatured ethyl alcohol, 0.63 ecm of 38 ° sodium hydroxide solution Be, 2.5 cc of water at 6O ⁰ C and 1.25 cc of 30 ° / cent formaldehyde solution dissolved.

b) 1.8 g of the diazoamino compound of diazotiertcm l-amino-2-methoxy-4-nitrobenzene and Cyanamidnatrium are dissolved in 80 cc of water at 5O ⁰ C.

Solutions a) and b) are stirred into a solution of 1 g of a condensation product of oleic acid and methyl taurine, 3 ecm of sodium hydroxide solution at 38 ° Be and 20 g of sodium chloride in 920 ecm of water at 30 ° C. After 1 hour treatment, the mixture is added slowly 8 ecm 5O ° / o acetic acid are added and further treated at a pH of about 5.5 '/ 2 hour. Then rinsed luke warm and cold and soaped per 15 minutes at 6O ⁰ C and at the boiling temperature with 1 g of Kondensationsprodukles from Oleic acid and methyltaurine and 0.5 g of sodium nitrilotriacetate per liter of water, rinsed and dried, giving a true black coloration.

Example 16

A cheese with 500 g of not genetztem, raw cotton is treated in a dyeing preparation with about 6 1 content under circulation with alternating liquor direction at 6O ⁰ C with a solution containing soft in 6 1 water 12 g purified sulphite cellulose waste liquor, 7.5 g of a condensation product of formaldehyde and / 5-naphthalenesulfonic acid, 12 g hexametaphosphate, 48 cc of 32 ^u / o sodium hydroxide solution, 7.5 g of 2- (2 ', 3'-oxynaphthoylamino) -naphthalene (dissolved by boiling) and 24 cc of 33 ° / o formaldehyde contains. After 15 minutes, 120 g of common salt are added and circulation is continued. After the coil is completely wetted, 10.4 g of the diazoamino compound are removed in dissolved form

Claims (1)

diazotized! l-Amino ^ -methyl-S-chlorobenzene and sodium cyanamide and 3 g of a condensation product of oleic acid and methyl taurine were added, the dyebath was ^{cooled to about 20 to 30 °} C. and allowed to circulate at this temperature for a further 15 minutes. 190 g of monosodium phosphate are then added in dissolved form, as a result of which dye formation occurs. After 30 minutes circulation is allowed from the bath, rinsed carefully, soaped for 15 minutes at 6O ⁰ C with 16.5 g of a mixture of 63% perchlorethylene, 17% of an action of the product of about 10 moles of ethylene oxide to 1 mole of nonylphenol, 20 ¹ Yo isopropyl and 12 g of a 25% solution of nitrolotriacetic acid sodium in 61 water, rinsed hot, soaped for 20 minutes at boiling temperature with 6 g of a condensation product of oleic acid and methyl taurine and 18 g soda in 6 l water, rinsed and dried. A full red coloration with good fastness characteristics is obtained. The table below contains a number of further diazoamino compounds which can be used according to the invention as well as the shades of the using 1.1 g / 12- (2 ', 3'-oxynaphthoylamino) -3-melhoxydiphenylene oxide azo dyes produced as the azo component on cellulose fiber. Diazoamino compound from cyanamide sodium and diazotized! l-Amino-2-phenoxy-5-chlorobenzene ... l-amino-2-chlorobenzene 1-Amino-2-trifluoromethyl-4-chlorobenzene I-amino-2-nitrobenzoI l-Amino-2-methoxybenzene-5-sulfonic acid diethylamide l- \ rnino-2-methylbenzene-5-sulfonic acid dimethylamide l-amino-2- (4'-chloro) -phenoxy-5-chlorobenzene l-Amino ^ -methyl-S-nitrobenzene .... ·. 1-amino-3-nitrobenzene l-Amino-2-methoxy-5-nitrobenzene ... Process for the production of water-insoluble azo dyes on textile material made of cellulose or protein fibers, characterized in that the textile material is treated in an alkaline bath, since it is an azo component and a diazoamino ^ "or tetrazoamino compound of the formula Liquor ratio 20th PH value hue Red 20th during the brownish red 1 : 20th coupling brownish red 1.49 1 20th 4.5 Red-brown 1.02 1 20th 4.5 Red . 1.35 1 20th 3.5 Red 1.08 1 20th 4th Red 1.68 1 20th 5 bluish red 1.65 ' 1 : 20 5 to 6 brownish red 1.70 1 20th 4.5 Bordo 1.15 1 4 to 5 1.08 1 4th 1.23 Claim 4 to 5 Me = N-N-CN where R is the radical of an aromatic or heterocyclic amine, Me is an alkali or alkaline earth metal and η is 1 or 2, as well as a wetting or dispersing agent and optionally an inorganic salt, and then by treatment with acidic agents below 40 ⁰ C the dye formation brings about. Considered publications:
German patent specification No. 1,057,061. When the application was announced, two coloring tables with explanations were displayed. (09 5U / 636 3.6 »© Bundesdruckcrei Berlin