DD283892A7 - PROCESS FOR PREPARING NEW AZOFFIN MIXTURES - Google Patents

Abstract

The invention relates to novel Azofarnstoffgemische, which are particularly suitable for dyeing leather in green color tones. They are obtained by first adding 1 equivalent of bis-diazotized 4,4'-diaminodiphenylamine-2-sulfonic acid with 0.65 to 0.95 equivalents of a diazotized 4-nitroaniline acidic acid to 1-amino-8-hydroxynaphthalene-3, And then the coupling is completed with 1.35 to 1.05 equivalents of phenol and / or acetoacetaniline. {Azo dye mixtures of triazo dyestuffs and disazo dyestuffs; 4,4'-diaminodiphenylamine-2-sulfonic acid as a disazo component; Leather, green coloring}

Description

, 'O ₃ H ^s0 3 »

SO ₃ H

= 1.8 to 19 in a molar ratio IhIII: 1, where K ^f ere group of the phenol and / or acetoacetanilide is, exist.

Field of application of the invention

The invention relates to novel azo dyes for dyeing natural hydroxy- and nitrogen-containing fiber materials, such as cellulose, cotton and wool, but especially for dyeing leather.

Characteristic of the known state of the art

From DE-AS 1046221, DE-OS 2215952 and DD-PS 108316 trisazo dyes of the general formula

H ₂ N OH

D-N = N-

-NH-

-N = N-A

in which D stands for the residues of diazo components and A stands for the residues of azo coupling components. They are primarily used for dyeing leather, with a variety of shades ranging from deep dark green, deep bluish green to reddish, greenish and bluish black. The dyeings have a consistently high level of the various fastness properties. The disadvantage is that in order to achieve a wide variety of nuances, a large number of coupling components is required and that only dull shades are obtained.

Zie. the invention

The aim of the invention are new dye mixtures that do not or only to a minor extent have the disadvantages of the dyes of the described prior art.

Explanation of the essence of the invention

It has been found that homogeneous Azofiirbstoff mixtures of trisazo dyes of the formula

H ₀ N OH

-NH- / £) X-N = N-K

and disazo dyes of the formula

aN-K

(III)

in the molar ratio 11: 111 = 1.8 to 19: 1 correspond to the task.

In the formulas, K is the remainder of the phenol and / or acetoacetanilide.

The azo dyes are obtained by first adding 1 equivalent of bis-diazotized 4,4'-diaminodiphenylamine-2-sulfonic acid with 0.65 to 0.95 equivalents of a monoazo compound diazotized by acid coupling! 4-nitroaniline is obtained on 1-amino-8-hydroxy-naphthalene-3,6-disulfonic acid, coupled and then the coupling with 1.35 to 1.05 equivalents of phenol and / or acetoacetanilide to an end. If phenol and acetoacetanilide are used together as final coupling components, this can be done in any ratio to one another.

The diazotizations and couplings are carried out in a conventional manner. The dye mixtures prepared color natural fiber materials and in particular leather green, wherein depending on the variation of the proportions of the starting components bluish to clear yellowish shades of green are to be achieved. The dyeings obtained with them have the same good fastness properties as those obtained with the dyes of the prior art according to formula I, which is surprising in that the dyes of the formula III dyeing technology are of no importance and it was assumed that they adversely affect the fastness properties ,

Relevant fastness properties of the new azo dye mixtures in comparison to commercially available dye brands are shown in the table:

properties Fiction Fiction C.I. Direct C.I. Acid fastness according to him according to him Black 155 Black 208 Amused Amused dye dye mix after mix after execution execution beiiDieli Example 2 nuance blau.'tichig yellowish greenish reddish green green black black solubility (6O ⁰ C) 5 5 5 4 fastness 3 3 2-3 2-3 perspiration hue 5 5 5 1-2 fastness to washing hue 5 5 2-3 2-3 cotton 3 3 1-2 2 Wool 5 5 3-4 4-5

embodiments

example 1

A prepared from 11.7 g of 4-nitro-1-aminobenzene, 170 ml of water, 90g of ice, 21 ml of 32% hydrochloric acid and 5.85 g of sodium nitrite at 10 ⁰ C prepared Diaioverbindung within 15 minutes in a from 27.1 g of i Amino-e-hydroxy-naphthalene-ssedisulfonic acid, 21CmL of water, 40g of ice and 17mL of 32% hydrochloric acid, and stirred overnight. The temperature is 15 ⁰ C. By careful addition of sodium carbonate solution is adjusted to a pH of 6.5, with the resulting Morioazofarbstoff completely dissolves. After 19 g of sodium carbonate and 210 g of ice have been added, a bisdiazonium compound prepared from 28 g of 4,4'-diaminodiphenylamine-2-sulfonic acid, 400 ml of water, 200 g of ice, 40 ml of 32% hydrochloric acid and 13.8 g of sodium nitrite at 10 ° C within 30 minutes. After 30 minutes no monoazo dye is detectable. The temperature is 10 ⁰ C, the pH 8. Then 11g phenol and then added 15 ml of 30% sodium hydroxide solution. The temperature provides 1O ⁰ C. After 2 hours, warmed to 20 ⁰ C and stirred overnight, with 210g sodium chloride and 50ml 32% hydrochloric acid gelallt, isolated and dried at 100 ° C. The dye colors chrome leather in bluish green tone.

Example 2

A diazo compound prepared from 11 g of 4-nitro-i-aminobenzene, 170 ml of water, 90 g of ice, 21 ml of 32% hydrochloric acid and 5.5 g of sodium nitrite at 5 ° C runs within 15 minutes in a from 25,45g i-amino -e-hydroxynaphthalene-Se-disulfonic acid, 200ml of water, 40g of ice and 15ml of 32% hydrochloric acid slurry and stirred overnight. After adding sodium carbonate solution to pH 6.5, the coupling quantitatively dissolves. This coupling solution then passes to a bisdiazonium compound of 28 g of 4,4'-diaminodiphenylamine-2-sulfonic acid prepared analogously to Example 1. The pH is then brought to 6.5-6.8 within 60 minutes by adding sodium carbonate solution. It is then left to stir for 30 minutes at 10 ⁰ C and then brings first 1.8 g of phenol. After completion of the unilateral coupling, 18 g of acetoacetanilide, dissolved in 120 ml of water and 15 ml of 30% strength sodium hydroxide solution, are added. The mixture is stirred overnight, the temperature of 1O ⁰ C to about 2O ⁰ C increases. By adding 200g of rock salt and 50 ml of 32% hydrochloric acid, the dye is precipitated and can then be isolated and dried

 The dyestuff thus produced dyes chrome leather in a clear yellowish hue.

Claims (1)

Claim: Novel azo dye mixtures, characterized in that they consist of trisazo dyes of the formula HJT OH (II) O ₃ N-ZqA-N = N- and disazo dyes of the formula (III) K-Ii = N- (q \ -NH- -N = N- -NH-