DE2457800A1 - HYDRO-SOLUBLE DISAZO DYES, METHOD FOR MANUFACTURING AND USING them - Google Patents

Description

DR. BERG DIPL.-ING. STAPF

PATENT LAWYERS 8 MUNICH JO. MAUERKIÄCHEHSVR. 45

/ 4 5 / Q U ü

Lawyer file 23 337 ₍ 6 DEC.

Be / Sch

PRODUIIS GHIMIQUES UGINE KUHLMANN Paris / France

"Water-soluble disazo dyes, methods for their Manufacture and its use "

Inventor: Pierre FRANK
Andre SAILER

The present invention relates to water-soluble disazo dyes, which are particularly good for dyeing animal fibers, such as for wool and silk, and for leather and Polyamide fibers, as well as for coloring fur.

E 160 C / Dossier 126.G "-2-

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It is known that it is very difficult with the currently known dyes to dye sheepskins, for example velor lamb, and to achieve the same shade and the same color intensity on the wool and on the skin or leather. Indeed, dyes which have a good affinity for wool at moderate temperatures generally have only a low affinity for leather, while on the other hand the dyes commonly used for dyeing leather have little or no affinity for wool under the leather dyeing conditions. On the other hand, it is known that it is not possible ^{to dye sheepskins at temperatures above 60 °} C. without serious damage.

It has now been found that the dyes of the general formula

J ^r \.

SO ₂ - NH - ^ y- N - N - A ₂ (I),

wherein the radicals A ^ and A _{2 are} identical or different and are radicals of aliphatic, aromatic or heterocyclic coupling agents, at least one of the two radicals A ^ and Ao having at least one water-solubilizing group, such as sulfonic acid or carboxylic acid groups, wool dyeing at moderate temperatures (60 ^° C.), which makes it possible to use them for "double-sided" or "tone on tone" dyeing of sheepskins (velor lamb). The obtained color

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tints are on both the leather and wool side lively and very uniform, i.e. the roots of the hair are colored with the same intensity as the tips. In addition, the shades obtained are lightfast and colorfast to washing, dry cleaning and drying and wet abrasion and against sweat.

The dyes of the formula (I) are in the same way very suitable for dyeing leather of different tannings, of wool, silk and polyamides, which have vivid hues ranging from greenish yellow to purple or continue give brown shades with special fastness properties compared to the usual tests. The dyes of the formula (I) also have excellent stability and excellent fastness properties to acids on.

The dyes of the invention can be prepared thereby be that the bis-diazo derivative of a mole of 4.4 -'-diaminobenzene sulfanilide with one mole of coupling agent A ^ H and one mole of coupling agent ApH, the two the coupling agents can be the same and at least one of these coupling agents can be at least one water-solubilizing agent Group has.

Examples of the coupling agents A ^ H and ApH are to

mention: .

- the hydroxy or aminbenzene derivatives such as phenol, resorcinol,

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2-hydroxybenzoic acid, 3-amino-i-hydroxybenzene, 1,3-diaminobenzene and their sulfonic or methyl derivatives such as 2,4-diaminobenzenesulfonic acid and the 1,3-diamino-4-methylbenzene,

- the naphthalene derivatives such as the i-aminonaphthalene-4-, -5-, -6- or -7-sulfonic acids, 2-hydroxynaphthalene and their in 6- or 8-position monosulfonated derivatives or their in 3.6- or 6.8-position disulfonated derivatives, the 1-naphthol-4- or -5-sulfonic acids, 2 ~ amino-8-naphthol-6-sulfone-, 3-amino-8-naphthol-6-sulfone, i-amino-8-hydroxynaphthalene-3.6-disulfone, i-Amino-S-hydroxynaphthalene ^ .ö-disulfon-, 1-acetylamino-8-hydroxynaphthalene-3-6-disulfonic acids,

- the acetoacetanilides and in particular the 3-sulfo-N-acetylacetylaniline,

- The heterocyclic derivatives and in particular 4'-sulfo- or 5'-sulfo-1-phenyl-3-methyl-5-pyrazolone, optionally substituted on the benzene nucleus by one or two chlorine atoms, as well as the 4'-sulfo-1- phenyl ^ -pyrazolone - ^ - carboxylic acid.

The following. Examples, in which the parts given relate to weight, illustrate the invention, without restricting them.

example 1

Dissolving 26.3 parts of 4,4'-Diaminobenzolsulfanilid in 400 parts of water at 5O ⁰ C with the aid of 53 parts of a hydrochloric acid solution of 20 ⁰ Be. It is cooled to 5 ^° C. and a solution is added

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of 14 parts of sodium nitrate in 28 parts of water, stirs the mixture for one hour at 5 ° C and then destroys the light nitrous acid excess by adding some sulfamic acid.

A solution of 37 »6 parts of 2,4-diaminobenzenesulfonic acid in 400 parts of water and 26 parts of sodium hydroxide solution at 36 ° Be is then added to the solution of the bis-diazo derivative thus obtained. While the temperature is kept at about ^ ⁰ G , a 20 # strength aqueous sodium carbonate solution is added over the course of one hour until a pg value between 6 and 7 has been reached. The coupling is allowed to proceed and the disazo dye is then isolated by the usual methods.

He dyes leather of different tans in brown-yellow, color-fast shades compared to the usual tests.

Example 2

The solution of the bis-diazo derivative is added for 30 minutes, obtained according to the information in the first paragraph of Example 1 with 26.3 parts of 4,4'-diaminobenzenesulfanilide has, in a 5 ° C solution of 51.4 parts of 3-sulfo-N-acetylacetylaniline and 50 parts of sodium carbonate in 500 parts of water. After the coupling is complete, the Dye according to the usual procedures.

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This dye dyes leather of different tannings in greenish yellow shades with special fastness compared to the usual tests.

The dye stains the leather and wool of sheepskins in very uniform greenish yellow shades with good fastness properties compared to the usual tests; Skin or leather and wool are dyed in the same shade and with the same color intensity.

Table I below gives further examples of disazo dyes which were prepared as described in Example 2, but replacing the 3-sulfo-N-acetylacetylaniline with an equivalent amount of the coupling agent given in the second column. The dyestuffs of the formula (I) in which the radicals A. and A _{2 are} identical are obtained.

Table I.

Example color shade play coupling agent on leather

5 ^ '- sulfo-1-phenyl-3-methyl-5-pyrazolone yellow

4 2 ^l -chloro-5'-sulfo-1-phenyl-3-methyl-5-pyrazolone "

5 2 '. 5'-dichloro-4-sulfo-1-phenyl-5-methyl-5-pyrazolone "

6 i-Hydroxynaphthalene-4-sulfonic acid scarlet red

7 2-hydroxynaphthalene-8-sulfonic acid orange

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' JI

Table I (continued)

With- - 'shade

game coupling agent . on leather

8 3-Amino-8-hydro: ^ naphthalene-6-sulfone-brownish

acid orange

acidic brown-red

Ί0 1-Amino-8-hydroxynaphthalene-3 6-di-

sulfonic acid. purple-red

11 · 1-amino-8-hydroxynapht hai in-4-. 6-di-

sulfonic acid "

12 i-acetylamino-8-hydroxynaphthalene-bluish-3,6-disulfonic acid Red

13 ^ -Aminonaphthalene-4-sulfonic acid brown orange 14-i-aminonaphthalene-5-sulfonic acid brown red

Example 13

In the solution of the bis-Piazoderivats, which has been obtained ^4-1 .4- -Diaminobenzolsulfanilid according to the data of the first paragraph of Example 1 from 26.3 parts, one introduces a solution of 13.8 parts of 2-hydroxybenzoic acid and 35 parts of Sodium carbonate in 100 parts of a solution of 5 # sodium hydroxide. After monocoupling has been achieved, a solution of 10.8 parts of 1,3-diaminobenzene in 50 parts of water is added. The reaction is allowed to take place until coupling is achieved, and the disazo dye thus obtained is then isolated by the customary processes. It dyes leather of different tannings in a slightly yellowish brown shade with good fastness properties compared to the usual tests.

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57

-s-

The following Table II gives further examples of disazo dyes according to the invention, which were prepared according to the details of Example 15, but the 1,3-diaminobenzene was replaced by an equivalent amount of the coupling agent A ₀ H given in the second column.

In the state of the free acid, the dyes correspond to the formula

HOOC

_ // vS — N = N- / 7— SO ₀ - NH - (' \ -N »

N / A,

(II)

Table II

Example

Coupling agent ApH

Color tint on leather

16 1-aminonaphthalene-6-sulfonic acid

17 1-aminonaphthalene-7-sulfonic acid

18 2-Amino-8-hydroxynaphthalene-6-sulfonic acid

19 3-Amino-8-hydroxynaphthalene-6-sulfonic acid

brown-yellow

Il

brown-red

reddish brown

Example 20

In the solution of the bis-diazo derivative, which is made according to the information in the first paragraph of Example 1 from 26.3 parts 4-.4'-Diaminobenzolsulfanilid has received, one leads while-

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For 30 minutes a solution of 28.4 parts of 4'-SuIfO-I- 'phenyl-5-pyrazolone-3-carboxylic acid in 200 parts of water, to which 13 parts of a sodium hydroxide solution of 36 ^° Be were added. A solution of 20% sodium carbonate? ^ Is then added for one hour in order to achieve a p "value of 6.5. When the monocoupling has ended, a solution of 11 parts of 1,3-dihydroxybenzene in 100 parts of water and then 30 parts of sodium carbonate are added. After the coupling reaction has ended, the dye is isolated by the customary methods. He dyes leather of different tans in orange-yellow shades.

Example 21

If, in the previous example, instead of 1,3-dihydroxybenzene If 9 ^ parts of phenol are used, a dye is obtained that can be used in leather of various advertisements a slightly yellowish shade.

The following table III gives further examples of Dyes according to the invention which are in the free acid state of the formula

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2457

N = N

N = N-A,

(III)

correspond.

It is produced by following the procedure in Example 20
works, but the 4'-SuIfo-i-phenyl - ^ - pyrazolon - ^ - carboxylic acid by 25.4 parts of 4'-SuIfo-i-phenyl ^ -methyl ^ -pyrazolon and the 1,3-dihydroxybenzene by an equivalent
Amount of the coupling agent AoH given in the second column.

example

Table III

Coupling agent

Color tint on leather

22 1,3-diaminobenzene

23 1-aminonaphthalene-6-sulfonic acid

24 2-Amino-8-hydroxynaphthalene-6-sulfonic acid

25 1-Amino-8-hydroxynaphthalene-3,6-disulfonic acid

brownish orange

Brown

violet

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Example 26

In the solution of the bis-diazo derivative, which, according to the information in the first paragraph of Example 1, was obtained from 26.3 parts of ^. ^ '- diaminobenzenesulfanilide, a solution of 3 ^, 1 parts of the monosodium salt of the i- Amino-e-hydroxynaphthalene ^ .ö-disulfonic acid in 200 parts of water, which were added in 13 parts of sodium hydroxide solution of 36 Be. An aqueous solution of sodium carbonate 20 # are then added over one hour to a p _H ~ to reach a value of 3 ». 5 The mixture is allowed to react until the monocoupling is reached, which takes about 5 hours, then a solution of 25.4 parts of Λ'-sulfoiphenyl-3-methyl-5-pyrazolone in 100 parts of water and 13 parts of sodium hydroxide solution of 36 is added Be to. 30 parts of sodium carbonate are then added, the mixture is allowed to react until the formation of the disazo dye has ended and the dye is isolated by the customary processes. He dyes leather of different tans in orange shades.

Table IV below summarizes further examples of the dyes of the invention, which as in Example 26 with the coupling agent ApH indicated in the second column and those in the free acid state of the formula

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24578

SO ₂ -NH

N - N-A,

(IV)

correspond.

example

Table IV

Coupling agent

Color tint on leather

27 1-Hydroxynaphthalene-5-sulfonic acid

28 2-Hydroxynaphthalene-6-sulfonic acid

29 2-Hydroxynaphthalene-6.8-disulfonic acid

30 2-hydroxynaphthalene-3,6-disulfonic acid

Red

bluish red bluish red violet red

Example 31

100 parts of chrome-tanned lambskin are soaked in the presence of a little ammonia and a wetting agent based on ethoxylated fatty alcohol. This coat is added in a fulling mill containing a solution of 5 parts of the dye of Example 3 and 2 parts of acetic acid in 2000 parts of water of 60 ⁰ C. After drumming for 30 minutes at 6O ⁰ G, then 3 parts 85 $ formic acid solution and drumming continued at 60 ⁰ C for one hour. The dye is rinsed, dried and subjected to the usual treatments. The result is a lambskin that is

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Uniformly colored is yellow with a special shade Authenticity compared to the usual tests.

-Patent claims-

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Claims (10)

Patent application: 1. Disazo dye of the general formula -N = N- / ' ^N V- SO ₂ -NH- (') - N - N - k _o (I), wherein the radicals A ^ and A _{2 are} identical or different and are radicals of aliphatic, aromatic or heterocyclic coupling agents, at least one of the radicals A ^ and Ap having at least one water-solubilizing group. 2. Dyestuffs according to Claim 1, characterized in that at least one of the radicals A ^ and A _{2 is} the radical of an amine and / or hydroxy-benzene coupling agent. 3. Dyestuffs according to Claim 1, characterized in that at least one of the radicals A- and A _{2 is} the radical of a naphthalene coupling agent. 4 ·· Dyestuffs according to Claim 1, characterized in that at least one of the radicals A- and A _{2 is} the radical of an acetoacetanil oxide. 5- dyes according to claim 1, characterized in that that at least one of the leftovers -15-509827 / 08U .'and A _{2 is} the remainder of a pyrazolone. 6. Process for the preparation of disazo dyes according to Claim 1, characterized in that that the bis-diazo derivative of a mole of 4,4'-diaminobenzene sulfanilide with one mole of a coupling agent A ^ H ... and one mole of a coupling agent ApH, the the two coupling agents can be the same and at least one of them has at least one water-solubilizing group having. 7. Use of the dyes according to one of claims 1 up to 5 for coloring animal and polyamide fibers. 8. Use of the dyes according to any one of claims 1 to 5 for dyeing pelts, in particular lambskins. 9. Use of the dyes according to any one of claims 1 up to 5 for coloring leather. 10. Objects, provided they are colored with a dye according to any one of claims 1 to 5. 509827 / 08U