Dye mixtures of fiber-reactive azo dyes, their preparation and their use

1. A reactive dye mixture which comprise from 10 to 90% by weight of one or more dyes of the formula (I-a)

and from 10 to 90% by weight of one or more dyes of the formula (lI-a)

wherein

D 1 is a group of the formula (1)

 wherein

R 1 is hydrogen;

R 2 is sulfo;

X 1 is a group of the formula —SO 2 -Z;

where

Z is —CH═CH 2 or β-sulfatoethyl;

D 2 is a group of the formula (1′)

 wherein

R 1′ is (C 1 -C 4 )-alkyl;

R 2′ is (C 1 -C 4 )-alkoxy;

X 1 is defined above;

D 3 is a naphthyl group of the formula (2)

 where

R 3 and R 4 are sulfo; and

X 2 is hydrogen;

R 0 is a group of the formula (5)

 where

Q 1 is chlorine; and

Q 2 is a group of the formula (7)

 wherein

R 8 is hydrogen;

W is phenylene, which is unsubstituted; and

Z is —CH═CH 2 or β-sulfatoethyl;

R* is hydrogen;

f is 1; and

M is hydrogen, an alkali metal or one equivalent of an alkaline earth metal.

2. The reactive dye mixture as claimed in claim 1 , further comprising one or more monoazo dyes of the general formulae (15) to (16), each in an amount of 0-10% by weight

wherein

M is hydrogen, an alkali metal or one equivalent of an alkaline earth metal;

R* is hydrogen;

D 1 is a group of the formula (1)

 wherein

R 1 is hydrogen,

R 2 is sulfo,

X 1 is a group of the formula —SO 2 -Z,

where

Z is —CH═CH 2 or β-sulfatoethyl; and

R** is hydrogen, (C 1 -C 4 )-alkyl or a group of the formula (14)

—CH 2 —SO 3 M  (14)

 with at least one dye of the formula (15) or (16) being present.

3. The reactive dye mixture as claimed in claim 1 , further comprising, as a further blending or shading component, at least one dye conforming to the hereinbelow indicated and defined general formulae (Ga)-(Gf)

wherein

D 5 , D 6 , D 7 , D 8 and D 9 have one of the meanings of D 1 , D 2 or D 3 , wherein D 5 , when R 31 is not a group of the general formula (4) or (5), and also D 6 or D 7 and D 9 and contain at least one fiber-reactive group of the formula —SO 2 Z or Z 2 ;

Z 2 is a group of the formula (4), (5) or (6)

 wherein

V 11 is fluorine or chlorine;

U 111 and U 211 are independently fluorine, chlorine or hydrogen;

and

Q 111 and Q 211 are independently chlorine, fluorine, cyanamido, hydroxyl, (C 1 -C 6 )-alkoxy, phenoxy, sulfophenoxy, mercapto, (C 1 -C 6 )-alkylmercapto, pyridino, carboxypyridino, carbamoylpyridino or a group of the formula (7-2) or (8-2)

 where

R 81 is hydrogen or (C 1 -C 6 )-alkyl, sulfo-(C 1 -C 6 )-alkyl or phenyl which is unsubstituted or substituted by (C 1 -C 4 )-alkyl, (C 1 -C 4 -alkoxy, sulfo, halogen, carboxyl, acetamido, ureido;

R 91 and R 101 independently have one of the meanings of R 81 or combine to form a cyclic ring system of the formula —(CH 2 ) j —, wherein j is 4 or 5, or alternatively —(CH 2 ) 2 -E-(CH 2 ) 2 —, wherein E is oxygen, sulfur, sulfonyl, —NR 11 where R 11 =(C 1 -C 6 )-alkyl;

W 11 is phenylene, which is unsubstituted or substituted by 1 or 2 substituents, which are (C 1 -C 4 )-alkyl, (C 1 -C 4 )-alkoxy, carboxyl, sulfo, chlorine, bromine, or are (C 1 -C 4 )-alkylenearylene or (C 2 -C 6 )-alkylene, which may be interrupted by oxygen, sulfur, sulfonyl, amino, carbonyl, carboxamido, or are phenylene-CONH-phenylene which is unsubstituted or substituted by (C 1 -C 4 )-alkyl, (C 1 -C 4 )-alkoxy, hydroxyl, sulfo, carboxyl, amido, ureido or halogen, or are naphthylene which is unsubstituted or substituted by one or two sulfo groups;

R 31 is hydrogen, acetyl, carbamoyl, sulfomethyl or a group of the general formula (4-1) or (5-1)

where

V 1 is fluorine or chlorine;

U 11 and U 21 are independently fluorine, chlorine or hydrogen;

and

Q 11 and Q 21 are independently chlorine, fluorine, cyanamido, hydroxyl, (C 1 -C 6 )-alkoxy, phenoxy, sulfophenoxy, mercapto, (C 1 -C 6 )-alkylmercapto, pyridino, carboxypyridino, carbamoylpyridino or a group of the general formula (7-1) or (8-1)

 where

R 81 is hydrogen or (C 1 -C 6 )-alkyl, sulfo-(C 1 -C 6 )-alkyl or phenyl which is unsubstituted or substituted by (C 1 -C 4 )-alkyl, (C 1 -C 4 )-alkoxy, sulfo, halogen, carboxyl, acetamido, ureido;

R 91 and R 100 independently have one of the meanings of R 81 or combine to form a cyclic ring system of the formula —(CH 2 ) j —, wherein j is 4 or 5, or alternatively —(CH 2 ) 2 -E-(CH 2 ) 2 —, wherein E is oxygen, sulfur, sulfonyl, —NR 11 where R 11 =(C 1 -C 6 )-alkyl;

W 1 is phenylene, which is unsubstituted or substituted by 1 or 2 substituents, wherein the 1 or 2 substituents are (C 1 -C 4 )-alkyl, (C 1 -C 4 )-alkoxy, carboxyl, sulfo, chlorine, bromine, or is (C 1 -C 4 )-alkylenearylene or (C 2 -C 6 )-alkylene, which may be interrupted by oxygen, sulfur, sulfonyl, amino, carbonyl, carboxamido, or is phenylene-CONH-phenylene which is unsubstituted or substituted by (C 1 -C 4 )-alkyl, (C 1 -C 4 )-alkoxy, hydroxyl, sulfo, carboxyl, amido, ureido or halogen, or is naphthylene which is unsubstituted or substituted by one or two sulfo groups; and

Z is —CH═CH 2 or β-sulfatoethyl;

R 32 is hydrogen or sulfomethyl;

R 33 is methyl, carboxyl or carboxyalkyl with C 1 - to C 4 -alkyl;

R 34 is hydrogen or methyl;

R 35 is hydrogen, cyano, carbamoyl, carboxyl or sulfomethyl;

R 36 is methyl, ethyl or β-sulfoethyl;

R 37 is methyl, carboxyl or carboxyalkyl with C 1 - to C 4 -alkyl;

R 38 is acetamido, ureido or methyl;

R 39 is hydrogen, methyl or methoxy;

m is 0 or 1;

n is 1, 2 or 3;

Z 3 has one of the meanings of Z 2 , and M is hydrogen, an alkali metal or one equivalent of an alkaline earth metal.

4. The reactive dye mixture as claimed in claim 2 further comprising as a further blending or shading component, at least one dye conforming to the hereinbelow indicated and defined general formulae (Ga)-(Gf)

wherein

D 5 , D 6 , D 7 , D 8 and D 9 have one of the meanings of D 1 , D 2 or D 3 , wherein D 5 , when R 31 is not a group of the general formula (4) or (5), and also D 6 or D 7 and D 9 and contain at least one fiber-reactive group of the formula —SO 2 Z or Z 2 ;

R 31 is hydrogen, acetyl, carbamoyl, sulfomethyl or a group of the general formula (4-1) or (5-1)

 where

V 1 is fluorine or chlorine;

U 11 and U 21 are independently fluorine, chlorine or hydrogen;

and

Q 11 and Q 021 are independently chlorine, fluorine, cyanamido, hydroxyl, (C 1 -C 6 )-alkoxy, phenoxy, sulfophenoxy, mercapto, (C 1 -C 6 )-alkylmercapto, pyridino, carboxypyridino, carbamoylpyridino or a group of the formula (7-1) or (8-1)

 where

R 81 is hydrogen or (C 1 -C 6 )-alkyl, sulfo-(C 1 -C 6 )-alkyl or phenyl which is unsubstituted or substituted by (C 1 -C 4 )-alkyl, (C 1 -C 4 )-alkoxy, sulfo, halogen, carboxyl, acetamido, ureido;

R 91 and R 100 independently have one of the meanings of R 81 or combine to form a cyclic ring system of the formula —(CH 2 ) j —, wherein j is 4 or 5, or alternatively —(CH 2 ) 2 -E-(CH 2 ) 2 —, wherein E is oxygen, sulfur, sulfonyl, —NR 11 where R 11 =(C 1 -C 6 )-alkyl;

W 11 is phenylene, which is unsubstituted or substituted by 1 or 2 substituents, wherein the 1 or 2 substituents are (C 1 -C 4 )-alkyl, (C 1 -C 4 )-alkoxy, carboxyl, sulfo, chlorine, bromine, or is (C 1 -C 4 )-alkylenearylene or (C 2 -C 6 )-alkylene, which may be interrupted by oxygen, sulfur, sulfonyl, amino, carbonyl, carboxamido, or is phenylene-CONH-phenylene which is unsubstituted or substituted by (C 1 -C 4 )-alkyl, (C-C 4 )-alkoxy, hydroxyl, sulfo, carboxyl, amido, ureido or halogen, or is naphthylene which is unsubstituted or substituted by one or two sulfo groups; and

Z is —CH═CH 2 or β-sulfatoethyl,

Z 2 is a group of the formula (4), (5) or (6)

 wherein

V 11 is fluorine or chlorine;

U 111 and U 211 are independently fluorine, chlorine or hydrogen;

and

Q 111 and Q 211 are independently chlorine, fluorine, cyanamido, hydroxyl, (C 1 -C 6 )-alkoxy, phenoxy, sulfophenoxy, mercapto, (C 1 -C 6 )-alkylmercapto, pyridino, carboxypyridino, carbamoylpyridino or a group of the formula (7-2) or (8-2)

 where

R 81 is hydrogen or (C 1 -C 6 )-alkyl, sulfo-(C 1 -C 6 )-alkyl or phenyl which is unsubstituted or substituted by (C 1 -C 4 )-alkyl, (C 1 -C 4 )-alkoxy, sulfo, halogen, carboxyl, acetamido, ureido;

R 91 and R 101 independently have one of the meanings of R 81 or combine to form a cyclic ring system of the formula —(CH 2 ) j —, wherein j is 4 or 5, or alternatively —(CH 2 ) 2 -E-(CH 2 ) 2 —, wherein E is oxygen, sulfur, sulfonyl, —NR 11 where R 11 =(C 1 -C 6 )-alkyl;

W 11 is phenylene, which is unsubstituted or substituted by 1 or 2 substituents, which are (C 1 -C 4 )-alkyl, (C 1 -C 4 )-alkoxy, carboxyl, sulfo, chlorine, bromine, or are (C 1 -C 4 )-alkylenearylene or (C 2 -C 6 )-alkylene, which may be interrupted by oxygen, sulfur, sulfonyl, amino, carbonyl, carboxamido, or are phenylene-CONH-phenylene which is unsubstituted or substituted by (C 1 -C 4 )-alkyl, (C 1 -C 4 )-alkoxy, hydroxyl, sulfo, carboxyl, amido, ureido or halogen, or are naphthylene which is unsubstituted or substituted by one or two sulfo groups;

R 32 is hydrogen or sulfomethyl;

R 33 is methyl, carboxyl or carboxyalkyl with C 1 - to C 4 -alkyl;

R 34 is hydrogen or methyl;

R 35 is hydrogen, cyano, carbamoyl, carboxyl or sulfomethyl;

R 36 is methyl, ethyl or β-sulfoethyl;

R 37 is methyl, carboxyl or carboxyalkyl with C 1 - to C 4 -alkyl;

R 38 is acetamido, ureido or methyl;

R 39 is hydrogen, methyl or methoxy;

m is 0 or 1;

n is 1, 2 or 3;

Z 3 has one of the meanings of Z 2 , and

M is hydrogen, an alkali metal or one equivalent of an alkaline earth metal.

5. A process for dyeing, printing and also inkjet printing textile fiber materials, which comprises utilizing the dye mixture as claimed in claim 1 .

6. The reactive dye mixture as claimed in claim 1 wherein

Z is β-sulfatoethyl;

M is hydrogen or sodium;

R 1′ is methyl; and

R 2′ is methoxy.

7. The reactive dye mixture as claimed in claim 1 which comprise from 25 to 75% by weight of one or more dyes of the formula (I-a) and from 25 to 75% by weight of one or more dyes of the formula (II-a).

8. The reactive dye mixture as claimed in claim 1 which comprise from 20 to 80% by weight of one or more dyes of the formula (I-a) and from 20 to 80% by weight of one or more dyes of the formula (II-a).

9. An aqueous liquid product comprising the dye mixture according to claim 1 having a total dye content of 5-50% by weight.

10. An aqueous printing ink for textile printing by the inkjet process, comprising the dye mixtures as claimed in claim 1 in amounts from 0.01% by weight to 40% by weight based on the total weight of the ink.

11. The process as claimed in claim 5 , wherein the fiber materials are hydroxyl- and/or carboxamido-containing fiber materials.