Mixtures of fiber-reactive azo dyes, their preparation and their use

1. A dye mixture comprising

one or more dye(s) of: formula (I)

and

one or more dye(s) of: formula (II)

and optionally

one or more dye(s) of: formula (IV)

wherein

D 1 and D 2 independent of one another is group of formula (1)

wherein

R 1 and R 2 independent of one another is hydrogen, (C 1 -C 4 )-alkyl, (C 1 -C 4 )-alkoxy, sulfo, carboxyl, amido or ureido,

X 1 is hydrogen or —SO 2 —CH═CH 2 ,

D 3 and D 4 independent of one another is a group of formula (1)

wherein

R 1 and R 2 independent of one another is hydrogen, (C 1 -C 4 )-alkyl, (C 1 -C 4 )-alkoxy, sulfo, carboxyl, amido or ureido,

X 1 is hydrogen or a group of the formula: —SO 2 —Z, wherein

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

Z 1 is hydroxyl or a group which can be eliminated under the action of alkali,

R 200 is

i) hydrogen,

ii) C 1 -C 6 -alkyl, which is linear or branched and is unsubstituted or substituted by amino, (C 1 -C 4 )-alkylamino, hydroxyl, (C 1 -C 4 )-alkoxy, sulfo, halogen, carboxyl, acetamido or ureido,

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

iv) amino, (C 1 -C 4 )-alkylamino, hydroxyl, (C 1 -C 4 )-alkoxy, sulfo, carboxyl, cyano, halogen, nitro, amido or ureido,

R 201 is a group of the formula: —N═N-D 3 ,

R* and R** independent of one another is hydrogen, (C 1 -C 4 )-alkyl, CO—(C 1 -C 4 -alkyl) or —CH 2 —SO 3 M,

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

and wherein the sum of weights of all dyes of formula (I) that are present in the dye mixture is at least 40% of the weight of the dye mixture—calculated on the basis of the sum of weights of all dyes according to formulae (I), (II) and (IV) that are present in the dye mixture.

2. The dye mixture according to claim 1 , wherein one or more dye(s) of formula (I) to (IV) independent from each other is/are:

wherein D 1 to D 4 and R* are as defined in claim 1 and

R 105 to R 108 independent of one another is hydrogen, C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, sulfo, carboxy, —CN, —COOR 1 or —CONR 2 R 3 , wherein

R 1 is M or (C 1 -C 4 )-alkyl,

R 2 and R 3 independent of one another is H or (C 1 -C 4 )-alkyl,

R 200 is hydroxyl, (C 1 -C 4 )-alkoxy, sulfo, halogen, carboxyl, acetamido, ureido, amino, (C 1 -C 4 )-alkylamino or phenyl, which phenyl is unsubstituted or substituted by a substituent selected from the group consisting of (C 1 -C 4 )-alkyl, (C 1 -C 4 )-alkoxy, sulfo, halogen, carboxyl, acetamido and ureido,

R 201 is a group of the formula: —N═N-Phenyl, which —N═N-Phenyl group is substituted by —SO 2 Z and —R 109 ,

R 109 is hydrogen, C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, sulfo, carboxy, —CN, —COOR 1 or —CONR 2 R 3 , wherein

R 1 is M or (C 1 -C 4 )-alkyl,

R 2 and R 3 independent of one another is H or (C 1 -C 4 )-alkyl,

G and G 1 is SO 2 Z or hydrogen, with the proviso that not both G and G1 are hydrogen,

Z is vinyl, β-sulfatoethyl or hydroxyl and

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

3. The dye mixture according to claim 1 , wherein one or more dye(s) of formula (I) to (IV) independent from each other is:

wherein

R 101 to R 112 independent of one another is hydrogen, carboxy, sulfo, (C 1 -C 4 )-alkyl or (C 1 -C 4 )-alkoxy,

R 200 is hydrogen, carboxy, sulfo or amino,

R 201 is a group of the formula: —N═N-Phenyl, which —N═N-Phenyl group is subsituted by —SO 2 Z and —R 109 ,

G and G 1 are SO 2 Z or hydrogen with the proviso that not both G and G1 are hydrogen,

Z is vinyl, β-sulfatoethyl or hydroxyl and

M is hydrogen or an alkali metal.

4. The dye mixture according to claim 1 , wherein one or more dye(s) of formula (I) to (IV) independent from each other is:

wherein

R 101 and R 102 independent of one another is hydrogen or sulfo,

R 103 and R 104 independent of one another is hydrogen, sulfo or carboxy,

R 201 is is a group of the formula: —N═N-Phenyl, which —N═N-Phenyl group is substituted by —SO 2 Z and —R 109 ,

R 109 is hydrogen, carboxy, sulfo, (C 1 -C 4 )-alkyl or (C 1 -C 4 )-alkoxy,

G and G 1 is SO 2 Z or hydrogen with the proviso that not both G and G1 are hydrogen,

Z is vinyl, β-sulfatoethyl or hydroxyl and

M is hydrogen or an alkali metal.

5. An ink comprising the dye mixture according to claim 1 .

6. A process for dyeing or printing hydroxyl- and/or carboxamido-containing material which comprises contacting the material with the dye mixture according to claim 1 .

7. A bound fiber comprising a fiber and the dye mixture according to claim 1 in chemically and/or physically bound form wherein the fiber is selected from the group consisting of synthetic fiber materials, nylon materials, nylon-6, nylon-6.6, aramid fiber, vegetable fiber, seed fiber, cotton, organic cotton, kapok, coir from coconut husk, bast fiber, flax, hemp, jute, kenaf, ramie, rattan, leaf fiber, sisal, henequen, banana, stalk fiber, bamboo, fiber from animals, wool, organic wool, silk, cashmere wool, alpaca fiber, mohair, Angora fiber, fur, leather materials; manufactured, regenerated and recycled fiber, cellulosic fiber, paper fiber, cellulosic regenerated fiber, viscose rayon fiber, acetate and triacetate fiber and Lyocell fiber.

8. A blend comprising a fiber and the dye mixture according to claim 1 in chemically and/or physically bound form wherein the fiber is selected from the group consisting of synthetic fiber materials, nylon materials, nylon-6, nylon-6.6, aramid fiber, vegetable fiber, seed fiber, cotton, organic cotton, kapok, coir from coconut husk, bast fiber, flax, hemp, jute, kenaf, ramie, rattan, leaf fiber, sisal, henequen, banana, stalk fiber, bamboo, fiber from animals, wool, organic wool, silk, cashmere wool, alpaca fiber, mohair, Angora fiber, fur, leather materials; manufactured, regenerated and recycled fiber, cellulosic fiber, paper fiber, cellulosic regenerated fiber, viscose rayon fiber, acetate and triacetate fiber and Lyocell fiber.