Dye mixtures of fiber-reactive AZO dyes, their preparation and their use
View Patent ↗Reactive dye mixtures which comprise one or more dyes of the indicated general formula (i) and one or more dyes of the hereinbelow indicated and defined general formula (II) where D 1 , D 2 , D 3 , R 0 , R*, R**, T, b, f, v and M are each as defined in claim 1, the dyes of the general formulae (I) and (II) containing at least one fiber-reactive group of the formula —SO 2 -Z or Z 2 , their preparation and their use for dyeing and printing hydroxyl- and/or carboxamido-containing fiber material.
1. A reactive dye mixture 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)
wherein
D 1 is a group of the formula (I)
wherein
R 1 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 hydrogen or,
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 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 a group of the formula (14)
—CH 2 —SO 3 M (14);
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 formulae (15) to (16), each in an amount of 0-10% by weight
where M, R*, R** and D 1 are each as defined in claim 1 , 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 formulae (Ga)-(Gf)
where 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 formula (4) or (5), and also D 6 or D 7 and D 9 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 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 as defined in claim 1 ,
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 and Z are each as defined in claim 1 .
4. Aqueous liquid product comprising a dye mixture according to claim 1 having a total dye content of 5-50% by weight.
5. Aqueous printing inks for textile printing by the inkjet process, comprising 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 inks.
6. A process for dyeing, printing and also inkjet printing textile fiber materials, which comprises utilizing dye mixtures as claimed in claim 1 .
7. 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 formulae (Ga)-(Gf)
where
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 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 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 vinyl, β-chloroethyl 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 .
8. The process as claimed in claim 6 , wherein the fiber materials are hydroxyl- and/or carboxamido-containing fiber materials.
9. The reactive dye mixture as claimed in claim 1 , wherein
Z is β-sulfatoethyl,
M is hydrogen or sodium,
R 1′ is hydrogen or methyl, and
R 2′ is methoxy.
10. 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).