Black dye mixtures of fiber-reactive AZO dyes and use thereof for dyeing material containing hydroxy- and/or carboxamido groups

1. A black dye mixture comprising one or more reactive dyes of the general formula (I)

and one or more reactive dyes of the general formula (IIc) and/or (IId),

where

D 1 and D 2 independently represent a group of the general formula (1)

wherein

R 1 is hydrogen, (C 1 -C 4 )-alkyl, aryl or phenyl substituted by one, two or three independent groups selected from the group consisting of (C 1 -C 4 )-alkyl, (C 1 -C 4 )-alkoxy, hydroxyl, sulfo, carboxyl, amido and halogen;

R 2 and R 3 are independently hydrogen, (C 1 -C 4 )-alkyl, (C 1 -C 4 )-alkoxy, hydroxyl, sulfo, carboxyl, amido or halogen; and

A is a phenylene group of the general formula (2)

where

R 4 and R 5 are independently hydrogen, (C 1 -C 4 )-alkyl, (C 1 -C 4 )-alkoxy, hydroxyl, sulfo, carboxyl, amido or halogen; or A is a naphthylene group of the general formula (3)

where

R 6 and R 7 are independently hydrogen, (C 1 -C 4 )-alkyl, (C 1 -C 4 )-alkoxy, hydroxyl, sulfo, carboxyl, amido or halogen; or A is a polymethylene group of the general formula (4)

—(CR 8 R 9 ) k —  (4)

where

k is an integer greater than 1 and

R 8 and R 9 are independently hydrogen, (C 1 -C 4 )-alkyl, (C 1 -C 4 )-alkoxy, hydroxyl, cyano, amido, halogen or aryl; and

X 1 is hydrogen or —SO 2 -Z;

or D 1 and D 2 independently represent a phenyl group of the general formula (5)

where

R 10 and R 11 are independently hydrogen, (C 1 -C 4 )-alkyl, (C 1 -C 4 )-alkoxy, hydroxyl, sulfo, carboxyl, amido or halogen; and

X 2 has one of the meanings of X 1 ;

or D 1 and D 2 independently represent a naphthyl group of the general formula (6)

where

R 12 and R 13 are independently hydrogen, (C 1 -C 4 )-alkyl, (C 1 -C 4 )-alkoxy, hydroxyl, sulfo, carboxyl, amido or halogen;

X 3 has one of the meanings of X 1 ;

Z is —CH═CH 2 , —CH 2 CH 2 Z 1 or hydroxyl,

where

Z 1 is hydroxyl or an alkali-detachable group;

M is hydrogen or an alkali metal;

D 21 has one of the meanings of D 1 or D 2 or is a group of formula (7) or (8)

where

R 22 and R 23 have independently of one another one of the meanings of R 2 and R 3 ;

R 24 is hydrogen, (C 1 -C 4 )-alkyl, phenyl which is unsubstituted or substituted by (C 1 -C 4 )-alkyl, (C 1 -C 4 )-alkoxy, sulfo, halogen, or carboxy; and

Z 22 is a group of the general formula (9) or (10) or formula (11)

wherein

V is fluorine or chlorine;

U 1 and U 2 are independently of one another fluorine, chlorine or hydrogen; and

Q 1 and Q 2 are independently of one another chlorine, fluorine, cyanamido, hydroxy, (C 1 -C 6 )-alkoxy, phenoxy, sulfophenoxy, mercapto, (C 1 -C 6 )-alkylmercapto, pyridino, carboxypyridino, carbamoylpyridino, or a group of the general formula (12) or (13)

where

R 2′ is hydrogen, (C 1 -C 6 )-alkyl, sulfo-(C 1 -C 6 )-alkyl, phenyl which is unsubstituted or substituted by at least one of the following groups: (C 1 -C 4 )-alkyl, (C 1 -C 4 )-alkoxy, sulfo, halogen, carboxy, acetamido or ureido;

R 3′ and R 4′ have independently of one another one of the meanings of R 2′ , or form a cyclic ring system, such as —(CH 2 ) j — with j being 4 or 5, or alternatively —(CH 2 ) 2 -E-(CH 2 ) 2 — with E being oxygen, sulfur, sulfo, or —NR 5′ — with R 5′ being (C 1 -C 6 )-alkyl;

W is phenylene which is unsubstituted or substituted by 1 or 2 substituents selected from the group of (C 1 -C 4 )-alkyl, (C 1 -C 4 )-alkoxy, carboxy, sulfo, chlorine and bromine; or is (C 1 -C 4 )-alkylene-arylene; or (C 2 -C 6 )-alkylene, which is optionally interrupted by oxygen, sulfur, sulfono, amino, carbonyl or carbonamido; 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 naphthylene which is unsubstituted or substituted by one or two sulfo groups; and

Z is as defined above;

R 25 , R 26 and R 27 are independently (C 1 -C 4 )-alkyl or (C 1 -C 4 )-hydroxyalkyl;

B − if is an equivalent for an anion;

R 21 has one of the meanings of R 24 ;

Z 21 is hydrogen, (C 2 -C 6 )-acyl, aroyl which is unsubstituted or substituted by (C 1 -C 4 )-alkyl, (C 1 -C 4 )-alkoxy, sulfo, carboxyl or halogen, or has one of the meanings of Z 22 ; and

n is 0 or 1;

in the general formula (I) at least one of D 1 and D 2 is a group of the general formula (1), where, if A is a group of the general formula (4), R 1 is aryl or substituted aryl and where the reactive dye of the general formula (I) contains at least one —SO 2 -Z group.

2. The mixture according to claim 1 , wherein R 3′ and R 4′ form a cyclic ring system having —(CH 2 ) j — with j being 4 or 5, or alternatively —(CH 2 ) 2 -E-(CH 2 ) 2 — with E being oxygen, sulfur, sulfo or —NR 5′ — with R 5′ being (C 1 -C 6 )-alkyl; and

B − if is hydrogensulfate, sulfate, fluoride, chloride, bromide, dihydrogenphosphate, hydrogenphosphate, phosphate, hydroxide or acetate.

3. The mixture according to claim 1 , wherein R 1 to R 5 , R 8 to R 11 , R 22 and R 24 being hydrogen, R 6 , R 7 , R 12 , R 13 , R 22 and R 23 being hydrogen or sulfo and R 25 , R 26 and R 27 being methyl.

4. The mixture according to claim 2 , wherein R 1 to R 5 , R 8 to R 11 , R 21 and R 24 being hydrogen, R 6 , R 7 , R 12 , R 13 , R 22 and R 23 being hydrogen or sulfo and R 25 , R 26 and R 27 being methyl.

5. The mixture according to claim 1 , wherein Z is vinyl, β-chloroethyl or β-sulfatoethyl.

6. The mixture according to claim 4 , wherein Z is vinyl, β-chloroethyl or β-sulfatoethyl.

7. The mixture according to claim 1 , wherein n is 0.

8. The mixture according to claim 6 , wherein n is 0.

9. The mixture according to claim 1 , which comprise one or more dyes according to the general formula (Ia)

and one or more dyes of the general formula (IIa)

wherein M, A, R 1 , Z, D 21 and Z 21 are as defined in claim 1 .

10. The mixture according to claim 9 , wherein R 1 is hydrogen, A is phenylene and Z is vinyl or β-sulfatoethyl in the general formula (Ia).

11. The mixture according to claim 1 , wherein D 21 in general formula (IIc) and/or (IId) has one of the meanings of 3-(β-sulfatoethylsulfonyl)-phenyl, 4-(β-sulfatoethylsulfonyl)-phenyl, 2-sulfo-4-(β-sulfatoethylsulfonyl)-phenyl, 2-methoxy-5-(β-sulfatoethylsulfonyl)-phenyl, 2,5-dimethoxy-4-(β-sulfatoethylsulfonyl)-phenyl, 2-methoxy-5-methyl-4-(β-sulfatoethylsulfonyl)-phenyl, 6-(β-sulfatoethylsulfonyl)-1-sulfo-naphth-2-yl, 3- or 4-vinylsulfonyl-phenyl, 4-(3-(2-sulfatoethylsulfonyl)-phenylcarbamoyl)-phenyl, 4-(4-(2-sulfatoethylsulfonyl)-phenylcarbamoyl)-phenyl, 3-(3-(2-sulfatoethylsulfonyl)-phenylcarbamoyl)-phenyl, 3-(4-(2-sulfatoethylsulfonyl)-phenylcarbamoyl)-phenyl, 1-sulfo-4-(2,4-difluoro-pyrimidin-6-yl)-amino-2-phenyl or 1-sulfo-4-(4,6-difluoro-pyrimidin-2-yl)-amino-2-phenyl, 2-sulfophenyl, 4-methyl-2-sulfophenyl or 1,5-disulfonaphth-2-yl.

12. The mixture according to claim 8 , wherein D 21 in general formula (IIc) and/or (IId) has one of the meanings of 3-(β-sulfatoethylsulfonyl)-phenyl, 4-(β-sulfatoethylsulfonyl)-phenyl, 2-sulfo-4-(β-sulfatoethylsulfonyl)-phenyl, 2-methoxy-5-(β-sulfatoethylsulfonyl)-phenyl, 2,5-dimethoxy-4-(β-sulfatoethylsulfonyl)-phenyl, 2-methoxy-5-methyl-4-(β-sulfatoethylsulfonyl)-phenyl, 6-(β-sulfatoethylsulfonyl)-1-sulfo-naphth-2-yl, 3- or 4-vinylsulfonyl-phenyl, 4-(3-(2-sulfatoethylsulfonyl)-phenylcarbamoyl)-phenyl, 4-(4-(2-sulfatoethylsulfonyl)-phenylcarbamoyl)-phenyl, 3-(3-(2-sulfatoethylsulfonyl)-phenylcarbamoyl)-phenyl, 3-(4-(2-sulfatoethylsulfonyl)-phenylcarbamoyl)-phenyl, 1 -sulfo-4-(2,4-difluoro-pyrimidin-6-yl)-amino-2-phenyl or 1-sulfo-4-(4,6-difluoro-pyrimidin-2-yl)-amino-2-phenyl, 2-sulfophenyl, 4-methyl-2-sulfophenyl or 1,5-disulfonaphth-2-yl.

13. The mixture according to claim 1 , wherein Z 21 in general formula (IIc) and/or (IId) has one of the meanings of 2,4-dichloro-1,3,5-triazin-6-yl, 2-chloro-4-morpholino-1,3,5-triazin-6-yl, 2-chloro-4-(3-sulfophenylamino)-1,3,5-triazin-6-yl, 2-chloro-4-(4-sulfophenylamino)-1,3,5-triazin-6-yl, 2-chloro-4-cyanamido-1,3,5-triazin-6-yl, 2-chloro-4-(3-(2-sulfatoethylsulfonyl)-phenylamino)-1,3,5-triazin-6-yl, 2-chloro-4-(4-(2-sulfatoethylsulfonyl)-phenylamino)-1,3,5-triazin-6-yl, 2-chloro-4-(3-(vinylsulfonyl)-phenylamino)-1,3,5-triazin-6-yl, 2-chloro-4-(4-(vinylsulfonyl)-phenylamino)-1,3,5-triazin-6-yl, 2-chloro-4-(N-methyl-N-(2-(2-sulfatoethylsulfonyl)-ethyl)-amino)-1,3,5-triazin-6-yl, 2-chloro-4-(N-phenyl-N-(2-(2-sulfatoethylsulfonyl)-ethyl)-amino)-1,3,5-triazin-6-yl, 2-fluoro-4-morpholino-1,3,5-triazin-6-yl, 2-fluoro-4-(2-sulfophenylamino)-1,3,5-triazin-6-yl, 2-fluoro-4-(3-sulfophenylamino)-1,3,5-triazin-6-yl, 2-fluoro-4-(4-sulfophenylamino)-1,3,5-triazin-6-yl, 2-fluoro-4-(3-trimethylammoniumphenylamino)-1,3,5-triazin-6-yl, 2-fluoro-4-(4-trimethylammoniumphenylamino)-1,3,5-triazin-6-yl, 2-fluoro-4-(3-(2-sulfatoethylsulfonyl)-phenylamino)-1,3,5-triazin-6-yl, 2-fluoro-4-(4-(2-sulfatoethylsulfonyl)-phenylamino)-1,3,5-triazin-6-yl, 2-fluoro-4-(3-(vinylsulfonyl)-phenylamino)-1,3,5-triazin-6-yl, 2-fluoro-4-(4-(vinylsulfonyl)-phenylamino)-1,3,5-triazin-6-yl, 2-fluoro-4-(N-methyl-N-(2-(2-sulfatoethylsulfonyl)-ethyl)-amino)-1,3,5-triazin-6-yl, 2-fluoro-4-(N-phenyl-N-(2-(2-sulfatoethylsulfonyl)-ethyl)-amino)-1,3,5-triazin-6-yl, 2,4-difluoro-pyrimidin-6-yl, 4,6-difluoro-pyrimidin-2-yl, 5 -chloro-2,4-difluoro-pyrimidin-6-yl, 5-chloro-4,6-difluoro-pyrimidin-2-yl, 2,3-dichlorochinoxalin-6-carbonyl or acetyl.

14. The mixture according to claim 12 , wherein Z 21 in general formula (IIc) and/or (IId) has one of the meanings of 2,4-dichloro-1,3,5-triazin-6-yl, 2-chloro-4-morpholino-1,3,5-triazin-6-yl, 2-chloro-4-(3-sulfophenylamino)-1,3,5-triazin-6-yl, 2-chloro-4-(4-sulfophenylamino)-1,3,5-triazin-6-yl, 2-chloro-4-cyanamido-1,3,5-triazin-6-yl, 2-chloro-4-(3-(2-sulfatoethylsulfonyl)-phenylamino)-1,3,5-triazin-6-yl, 2-chloro-4-(4-(2-sulfatoethylsulfonyl)-phenylamino)-1,3,5-triazin-6-yl, 2-chloro-4-(3-(vinylsulfonyl)-phenylamino)-1,3,5-triazin-6-yl, 2-chloro-4-(4-(vinylsulfonyl)-phenylamino)-1,3,5-triazin-6-yl, 2-chloro-4-(N-methyl-N-(2-(2-sulfatoethylsulfonyl)-ethyl)-amino)-1,3,5-triazin-6-yl, 2-chloro-4-(N-phenyl-N-(2-(2-sulfatoethylsulfonyl)-ethyl)-amino)-1,3,5-triazin-6-yl, 2-fluoro-4-morpholino-1,3,5-triazin-6-yl, 2-fluoro-4-(2-sulfophenylamino)-1,3,5-triazin-6-yl, 2-fluoro-4-(3-sulfophenylamino)-1,3,5-triazin-6-yl, 2-fluoro-4-(4-sulfophenylamino)-1,3,5-triazin-6-yl, 2-fluoro-4-(3-trimethylammoniumphenylamino)-1,3,5-triazin-6-yl, 2-fluoro-4-(4-trimethylammoniumphenylamino)-1,3,5-triazin-6-yl, 2-fluoro-4-(3-(2-sulfatoethylsulfonyl)-phenylamino)-1,3,5-triazin-6-yl, 2-fluoro-4-(4-(2-sulfatoethylsulfonyl)-phenylamino)-1,3,5-triazin-6-yl, 2-fluoro-4-(3-(vinylsulfonyl)-phenylamino)-1,3,5-triazin-6-yl, 2-fluoro-4-(4-(vinylsulfonyl)-phenylamino)-1,3,5-triazin-6-yl, 2-fluoro-4-(N-methyl-N-(2-(2-sulfatoethylsulfonyl)-ethyl)-amino)-1,3,5-triazin-6-yl, 2-fluoro-4-(N-phenyl-N-(2-(2-sulfatoethylsulfonyl)-ethyl)-amino)-1,3,5-triazin-6-yl, 2,4-difluoro-pyrimidin-6-yl, 4,6-difluoro-pyrimidin-2-yl, 5-chloro-2,4-difluoro-pyrimidin-6-yl, 5-chloro-4,6-difluoro-pyrimidin-2-yl, 2,3-dichlorochinoxalin-6-carbonyl or acetyl.

15. The mixture according to claim 1 , wherein a dye of formula (I) is present in the mixture in an amount of from 30 to 95% by weight; a dye of the formula (IIc) and/or (IId) is present in the mixture in an amount of from 5 to 70% by weight.

16. The mixture according to claim 14 , wherein a dye of formula (I) is present in the mixture in an amount of from 30 to 95% by weight; a dye of the formula (IIc) and/or (IId) is present in the mixture in an amount of from 5 to 70% by weight.

17. The mixture according to claim 1 , further comprising a monoazo dye of formula (14) in a total amount of 0.5 to 6.0% by weight and/or a monoazo dye of formula (15) in a total amount of 0.5 to 6.0% by weight

wherein D 2 and M are as defined in claim 1 .

18. The dye mixture according to claim 1 , wherein said at least one dye of general formula (I) is present in an amount up to 95% by weight.

19. A process for the preparation of the dye mixture according to claim 1 , which comprises mechanically mixing the individual dyes of the formulae (I) and (IIc) and/or (IId) in solid form or in form of aqueous solutions.

20. A process for the preparation of the dye mixture according to claim 1 , which comprises diazotizing an amine of the general formula (16)

D 2 -NH 2   (16),

wherein D 2 is defined below, in a strongly acidic medium and then carrying out the coupling reaction of the 1-amino-8-napthol-3,6-disulfonic acid or 1-amino-8-napthol-4,6-disulfonic acid with the diazo component at a pH below 2 to form the red compound (14) followed by diazotation of an amine of the general formula (17)

D 1 -NH 2   (17),

wherein D 1 is defined below, in a strongly acidic medium and then carrying out the second coupling reaction with the monoazo dye product (14) to form the disazo dye conforming to the formula (I) at a pH between 4 and 8 and followed by addition of an aqueous solution of the optionally N-substituted 2-Amino-7-sulfo-5-naphthol or 2-Amino-6-sulfo-8-naphthol to the coupling reaction to form the dye conforming to the formula (IIc) and/or (IId) which is carried out in the same pH-range between 4 and 7.5 followed by isolation of the dyestuff mixture from the solution and D 1 and D 2 independently represent a group of the general formula (1)

wherein

R 1 is hydrogen, (C 1 -C 4 )-alkyl, aryl or phenyl substituted by on, two or three independent groups selected from the group consisting of (C 1 -C 4 )-alkyl, (C 1 -C 4 )-alkoxy, hydroxyl, sulfo, carboxyl, amido and halogen;

R 2 and R 3 are independently hydrogen, (C 1 -C 4 )-alkyl, (C 1 -C 4 )-alkoxy, hydroxyl, sulfo, carboxyl, amido or halogen; and

A is a phenylene group of the general formula (2)

where

R 4 and R 5 are independently hydrogen, (C 1 -C 4 )-alkyl, (C 1 -C 4 )-alkoxy, hydroxyl, sulfo, carboxyl, amido or halogen; or A is a naphthylene group of the general formula (3)

where

R 6 and R 7 are independently hydrogen, (C 1 -C 4 -alkyl, (C 1 -C 4 )-alkoxy, hydroxyl, sulfo, carboxyl, amido or halogen; or A is a polymethylene group of the general formula (4)

—(CR 8 R 9 ) k —  (4)

where

k is an integer greater than 1 and

R 8 and R 9 are independently hydrogen, (C 1 -C 4 )-alkyl, (C 1 -C 4 )-alkoxy, hydroxyl, cyano, amido, halogen or aryl; and

X 1 is hydrogen or —SO 2 -Z;

or D 1 and D 2 each represent a phenyl group of the general formula (5)

where

R 10 and R 11 are independently hydrogen, (C 1 -C 4 )-alkyl, (C 1 -C 4 )-alkoxy, hydroxyl, sulfo, carboxyl, amido or halogen; and

X 2 has one of the meanings of X 1 ;

or D 1 and D 2 each represent a naphthyl group of the general formula (6)

where

R 12 and R 13 are independently hydrogen, (C 1 -C 4 )-alkyl, (C 1 -C 4 )-alkoxy, hydroxyl, sulfo, carboxyl, amido or halogen;

3 has one of the meanings of X 1 ;

Z is —CH═CH 2 , —CH 2 CH 2 Z 1 or hydroxyl,

where

Z 1 is hydroxyl or an alkali-detachable group;

M is hydrogen or an alkali metal;

and with the proviso that D 1 and D 21 in the general formulae (I) and formula (IIc) and/or (IId) have the same meaning.

21. A process for dyeing hydroxy- and/or carboxamido-containing fiber material, which comprises applying the dye mixture as claimed in claim 1 to the material and the dyes are fixed to the material by means of

(a) heat

(b) with the aid of an alkali or

(c) heat and with the aid of an alkali.