Black dye mixtures of fiber-reactive azo dyes, methods for their preparation and use thereof for dyeing hydroxy-and/or carboxamido-containing fiber material

The disazo dyes of the general formula (2-1),

• 48
• wherein
• M is hydrogen or an alkali metal;
• R5, R6 is hydrogen, methyl, methoxy, sulfo, cyano, or chloro;
• R11 is hydrogen or alkyl or phenyl, which may be mono- or di-substituted by an alkyl, alkoxy, ester, ureido, carboxamido, hydroxy, chloro, cyano or sulfo group;
• L3 is a fiber-reactive group of the formulae (5a-d):
• 49
• wherein:
• R12 has one of the meanings of R11;
• Y is in each instance, independently of one another, vinyl or is ethyl which is substituted in the β-position by a substituent which can be eliminated by the action of an alkali, forming the vinyl group, such as chlorine, thiosulfato, sulfato, alkanoyloxy of 2 to 5 carbon atoms, such as acetyloxy, phosphate, sulfobenzoyloxy and p-toluylsulfonyloxy;
• *—denotes the bond to the aromatic ring;
• X denotes chloro or fluoro and
• Z has one of the meanings of X or is hydrogen or cyano;
• Q is chloro, fluoro, cyanamide, hydroxy, alkoxy of 1 to 4 carbon atoms, pyridino, carboxypyridino, carbamoylpyridino a group of the general formula W or is a group of the general formulae (6a) or (6b),
• 50
• in which
• R13 is hydrogen, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, sulfoalkyl of 1 to 4 carbon atoms, phenyl unsubstituted or substituted by 1 to 2 substituents selected from the group of substituents consisting of chlorine, bromine, methyl, ethyl, methoxy, sulfo, acetamido, ureido and carboxy;
• R14 has on of the meanings given for R13;
• R15 has one of the meanings given for R3, or
• R13 and R14 form a cyclic ringsystem of the general formulae (6c) or (6d)
• 51
• wherein
• Ro is a heterogroup such as O, S, SO2 or NR12 or is a methylene group;
• G is arylene, C1-C6-alkylene or alkylene-arylene, each unsubstituted or substituted, or being of 2 to 6 carbon atoms, if interrupted by a hetero group, such as O, S, NH, SO2, CO, CO—NH, NH—CO, arylene being phenylene or naphthylene, the substituents of phenylene being selected from the group consisting of alkyl of 1 to 4 carbon atoms, such as methyl and ethyl, alkoxy of 1 to 4 carbon atoms, such as methoxy and ethoxy, carboxy, sulfo and chlorine;
• W1 is a phenyl group of the general formula (3) or naphtyl group of the general formula (4)
• 52
• in which
• M is defined as above;
• * denotes the bond to the diazo group;
• R7, R8, R9, R10 are hydrogen, methyl, methoxy, sulfo, cyano, or chloro;
• n is in each case independently 0 or 1 and
• L4, L5 have one of the meanings of L3.

A process for the preparation of disazo dyes of the general formula (2-1) by diazotizing the aromatic amine having the structure

• W1—NH2
• wherein W1 is as defined above and coupling the resulting diazo-compound to the naphtylamine of the following formula
• 53
• wherein M, R11 and n are defined as above and then acetoacetylating the intermediate followed by subsequent coupling with a second diazo compound at the 1,3-diketo-moiety.

The disazo dyes of the general formula (2-2),

• 54
• wherein
• M is hydrogen or an alkali metal;
• R5, R6 is hydrogen, methyl, methoxy, sulfo, cyano, or chloro;
• R11 is hydrogen or alkyl or phenyl, which may be mono- or di-substituted by an alkyl, alkoxy, ester, ureido, carboxamido, hydroxy, chloro, cyano or sulfo group;
• L3 is a fiber-reactive group of the formulae (5a-d):
• 55
• wherein:
• R12 has one of the meanings of R11;
• Y is in each instance, independently of one another, vinyl or is ethyl which is substituted in the 1-position by a substituent which can be eliminated by the action of an alkali, forming the vinyl group, such as chlorine, thiosulfato, sulfato, alkanoyloxy of 2 to 5 carbon atoms, such as acetyloxy, phosphate, sulfobenzoyloxy and p-toluylsulfonyloxy;
• *—denotes the bond to the aromatic ring;
• X denotes chloro or fluoro and
• Z has one of the meanings of X or is hydrogen or cyano;
• Q is chloro, fluoro, cyanamide, hydroxy, alkoxy of 1 to 4 carbon atoms, pyridino, carboxypyridino, carbamoylpyridino a group of the general formula W or is a group of the general formulae (6a) or (6b),
• 56
• in which
• R13 is hydrogen, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, sulfoalkyl of 1 to 4 carbon atoms, phenyl unsubstituted or substituted by 1 to 2 substituents selected from the group of substituents consisting of chlorine, bromine, methyl, ethyl, methoxy, sulfo, acetamido, ureido and carboxy;
• R14 has one of the meanings given for R13;
• R15 has one of the meanings given for R13, or
• R13 and R14 form a cyclic ringsystem of the general formulae (6c) or (6d)
• 57
• wherein
• Ro is a heterogroup such as O, S, SO2 or NR2 or is a methylene group;
• G is arylene, C1-C6-alkylene or alkylene-arylene, each unsubstituted or substituted, or being of 2 to 6 carbon atoms, if interrupted by a hetero group, such as O, S, NH, SO2, CO, CO—NH, NH—CO, arylene being phenylene or naphthylene, the substituents of phenylene being selected from the group consisting of alkyl of 1 to 4 carbon atoms, such as methyl and ethyl, alkoxy of 1 to 4 carbon atoms, such as methoxy and ethoxy, carboxy, sulfo and chlorine;
• W2 is a phenyl group of the general formula (3′) or naphtyl group of the general formula (4′)
• 58
• M is defined as above;
• * denotes the bond to the diazo group;
• R7′, R8′ are hydrogen, methoxy, methyl
• R9′, R10′ is hydrogen methyl, methoxy, sulfo, cyano;
• n is in each case independently 0 or 1 and
• L4, L5 have one of the meanings of L3.

A process for the preparation of disazodyes of the general formula (2-2) by diazotizing the aromatic amine having the structure

• W2—NH2
• wherein W2 is as defined above and coupling the resulting diazo-compound to the naphtylamine of the following formula
• 59
• wherein M, R11 and n are defined as above and then acetoacetylating the intermediate followed by the subsequent coupling with a second diazo at the 1,3-diketo moiety.