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

Abstract

The present invention relates to dye mixtures comprising one or more dye(s) of: formula (I) ##STR00001## and one or more dye(s) of: formula (II) and/or formula (III) ##STR00002## and optionally one or more dye(s) of: formula (IV) ##STR00003## to processes for their preparation and to their use for dyeing and printing hydroxyl- and carboxamido-containing materials.

Claims

1. A dye mixture comprising one or more dye(s) of formula (I) ##STR00053## and one or more dye(s) of formula (II) and/or formula (III) ##STR00054## and optionally one or more dye(s) of: formula (IV) ##STR00055## wherein D.sup.1 and D.sup.2 independent of one another is group of formula (1) ##STR00056## wherein R.sup.1 and R.sup.2 independent of one another is hydrogen, (C.sub.1-C.sub.4)-alkyl, (C.sub.1-C.sub.4)-alkoxy, sulfo, carboxyl, amido or ureido, X.sup.1 is hydrogen or SO.sub.2CHCH.sub.2, D.sup.3 and D.sup.4 independent of one another is a group of formula (1) wherein R.sup.1 and R.sup.2 independent of one another is hydrogen, (C.sub.1-C.sub.4)-alkyl, (C.sub.1-C.sub.4)-alkoxy, sulfo, carboxyl, amido or ureido, X.sup.1 is hydrogen or a group of the formula: SO.sub.2Z, wherein Z is hydroxyl, CHCH.sub.2 or CH.sub.2CH.sub.2Z.sup.1, wherein Z.sup.1 is hydroxyl or a group which can be eliminated under the action of alkali, R.sup.200 and R.sup.201 independent of one another is i) hydrogen, ii) C.sub.1-C.sub.6-alkyl, which is linear or branched and is unsubstituted or substituted by amino, (C.sub.1-C.sub.4)-alkylamino, hydroxyl, (C.sub.1-C.sub.4)-alkoxy, sulfo, halogen, carboxyl, acetamido or ureido; iii) phenyl which is unsubstituted or substituted by (C.sub.1-C.sub.4)-alkyl, (C.sub.1-C.sub.4)-alkoxy, sulfo, halogen, carboxyl, acetamido or ureido; (iv) amino, (C.sub.1-C.sub.4)-alkylamino, hydroxyl, (C.sub.1-C.sub.4)-alkoxy, sulfo, carboxyl, cyano, halogen, nitro, amido or ureido, R* and R** independent of one another is hydrogen, (C.sub.1-C.sub.4)-alkyl, CO-(C.sub.1-C.sub.4-alkyl) or CH.sub.2SO.sub.3M, 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), (III) 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: ##STR00057## wherein D.sup.1 to D.sup.4 and R* are as defined in claim 1 and R.sup.105 .sup.108 independent of one another is hydrogen, C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-alkoxy, sulfo, carboxy, CN, COOR.sup.1 or CONR.sup.2R.sup.3, wherein R.sup.1 is M or (C.sub.1-C.sub.4)-alkyl, R.sup.2 and R.sup.3 independent of one another is H or (C.sub.1-C.sub.4)-alkyl, R.sup.200 and R.sup.201 independent of one another is hydroxyl, (C.sub.1-C.sub.4)-alkoxy, sulfo, halogen, carboxyl, acetamido, ureido, amino, (C.sub.1-C.sub.4)-alkylamino or phenyl, which phenyl is unsubstituted or substituted by a substituent selected from the group consisting of (C.sub.1-C.sub.4)-alkyl, (C.sub.1-C.sub.4)-alkoxy, sulfo, halogen, carboxyl, acetamido and ureido, G and G.sup.1 is SO.sub.2Z or hydrogen, with the proviso that not both G and G1 are hydrogen, Z is vinyl, -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: ##STR00058## wherein R.sup.101 R.sup.112 independent of one another is hydrogen, carboxy, sulfo, (C.sub.1-C.sub.4)-alkyl or (C.sub.1-C.sub.4)-alkoxy, R.sup.200 and R.sup.201 independent of one another is hydrogen, carboxy, sulfo or amino, G and G.sup.1 are SO.sub.2Z or hydrogen with the proviso that not both G and G1 are hydrogen, Z is vinyl, -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: ##STR00059## wherein R.sup.101 and R.sup.102 independent of one another is hydrogen or sulfo, R.sup.103 and R.sup.104 independent of one another is hydrogen, sulfo or carboxy, R.sup.201 is hydrogen or sulfo, G and G.sup.1 is SO.sub.2Z or hydrogen with the proviso that not both G and G1 are hydrogen, Z is vinyl, -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.

Description

EXAMPLES

A. Examples of Compounds of Formula (I)

Example A-1

(1) 10 parts 2-[(4-Aminophenyl)sulfonyl]ethyl sodium sulfate (Parabase-ester) were mixed with 9 parts water, 3 parts ice and 3.9 parts hydrochloric acide 30% at 4 to 6 C. The mixture was diazotized with 4.8 parts of 40.5%ic sodium nitrit solution. To this parabase-ester diazotation 5.7 parts 1-amino-3,6-disulfo-8-hydroxy-naphthalene (H-acid) were added in potions. The product of the 1.sup.st coupling reaction was transferred to a vessel containing 7 parts of water. During this transfer the pH was kept between pH 4.8 and 5.5 using 1.9 parts of sodium carbonate. After the 2.sup.nd coupling the pH was adjusted to pH 8 to 9 and the mixture was stirred until vinylisation was completed. Then the product was isolated via filtration.

(2) The resulting product has the following structure:

(3) ##STR00034##
and dyes cotton in navy blue shades.

Examples A2-A5

(4) The following compounds of formula (I) can be prepared accordingly using the corresponding diazo components:

Example A-2

(5) ##STR00035##

(6) Dyes cotton in reddish blue shades.

Example A-3

(7) ##STR00036##

(8) Dyes cotton in greenish blue shades

Example A-4

(9) ##STR00037##

(10) Dyes cotton in navy blue shades.

Example A-5

(11) ##STR00038##

(12) Dyes cotton in greenish blue shades

(13) The dyes of formulae (II), (Ill) and (IV) can be synthesized according to the literature given above.

B. Examples of Mixtures of the Invention

Example B-1

(14) 60 parts dye of the formula (A-1)

(15) ##STR00039##
were mixed with 25 parts of a dye of the formula (II-1)

(16) ##STR00040##
and mixed with 15 parts of a dye powder of the formula (IV-1)

(17) ##STR00041##

(18) The resulting dye mixture of the invention was dried under reduced pressure or can be dryed via spray drying and gives very deep black dyeings and prints, on cotton for example, under the dyeing conditions typical for reactive dyes.

(19) Thus the inventive dye mixture offers a high build up to very deep black shades as well as an excellent polyamide staining and a very good white dischargability.

Example B-2

(20) 54 parts dye of the formula (A-1)

(21) ##STR00042##
were mixed with 20 parts of a dye of the formula (III-1)

(22) ##STR00043##
and mixed with 26 parts of a dye powder of the formula (IV-2)

(23) ##STR00044##

(24) The resulting dye mixture of the invention was dried via spray drying or can be dryed under reduced pressure and gives very deep black dyeing and prints, on cotton for example, under the dyeing conditions typical for reactive dyes.

Example B-3

(25) 65 parts dye of the formula (A-4)

(26) ##STR00045##
were mixed with 28 parts of a dye of the formula (II-2)

(27) ##STR00046##
and mixed with 7 parts of a dye powder of the formula (IV-3)

(28) ##STR00047##

(29) The resulting dye mixture was dried under reduced pressure or can be dryed via spray drying and gives very deep black dyeings and prints, on cotton for example, under the dyeing conditions typical for reactive dyes.

Examples B4 to B53

(30) The tabular examples herein below describe further inventive mixtures of the dyes of the general formulae (I)-(IV), each recited in the form of the sodium salts. The mixing proportions are indicated in percent by weight. The dye mixtures provide deep black dyeings and prints, on cotton for example, by the dyeing methods customary for reactive dyes.

(31) Dye mixtures in accordance with Examples B1-B3 or without dyes of formula (IV).

(32) All Radicals that are not defined in blow Table are equal to Hydrogen.

(33) TABLE-US-00001 Dye of Dye of Dye of for- for- for- Ratio mula mula mula (I):(II)/ Expl. (I) (II)/(III) (IV) (III):(IV) B4 (A-1) Formula (IIa) with: Formula (IVb) with: 68:22:10 R.sup.201: SO.sub.3H R.sup.109: o-SO.sub.3Na R.sup.200: H R.sup.111: H R.sup.105: H SO.sub.2Z: para R.sup.107: H Z: -sulfatoethyl G: p-SO.sub.2Z, Z: - sulfatoethyl G.sub.1: p-SO.sub.2Z; Z: - sulfatoethyl B5 (A-1) Formula (IIa) with: Formula (IVb) with: 65:23:12 R.sup.201: SO.sub.3Na R.sup.110: o-SO.sub.3Na R.sup.200: H R.sup.112: H R.sup.106: H SO.sub.2Z: para R.sup.108: p-COOH Z: -sulfatoethyl G: p-SO.sub.2Z; Z: - sulfatoethyl G.sub.1: H B6 (A-1) Formula (IIa) with: Formula (IVb) with: 57:27:16 R.sup.201: SO.sub.3Na R.sup.109: H R.sup.200: H R.sup.111: o-SO.sub.3Na R.sup.106: H SO.sub.2Z: para R.sup.108: p-COOH Z: -sulfatoethyl G: p-SO.sub.2Z; Z: - sulfatoethyl G.sub.1: H B7 (A-1) Formula (IIa) with: Formula (IVb) with: 61:23:16 R.sup.201: SO.sub.3Na R.sup.110: o-SO.sub.3Na R.sup.200: H R.sup.112: H R.sup.106: H SO.sub.2Z: para R.sup.108: p-COOH Z: -sulfatoethyl G: m-SO.sub.2Z; Z: - sulfatoethyl G.sub.1: H B8 (A-1) Formula (IIa) with: Formula (IVb) with: 72:18:10 R.sup.201: SO.sub.3H R.sup.109: o-SO.sub.3Na R.sup.200: H R.sup.111: H R.sup.105: H SO.sub.2Z: para R.sup.107: p-COOH Z: -sulfatoethyl G: m-SO.sub.2Z; Z: - sulfatoethyl G.sub.1: H B9 (A-1) Formula (IIa) with: Formula (IVb) with: 70:15:15 R.sup.201: COOH R.sup.110: o-SO.sub.3Na R.sup.200: H R.sup.112: o-SO.sub.3Na R.sup.106: H SO.sub.2Z: para R.sup.108: p-COOH Z: -sulfatoethyl G: p-SO.sub.2Z; Z: - sulfatoethyl G.sub.1: H B10 (A-1) Formula (IIa) with: Formula (IVb) with: 70:20:10 R.sup.201: SO.sub.3Na R.sup.109: o-SO.sub.3Na R.sup.200: H R.sup.111: o-SO.sub.3Na R.sup.106: H SO.sub.2Z: para R.sup.108: p-COOH Z: -sulfatoethyl G: p-SO.sub.2Z; Z: - sulfatoethyl G.sub.1: H B11 (A-1) Formula (IIa) with: Formula (IVb) with: 67:22:11 R.sup.201: SO.sub.3H R.sup.109: o-SO.sub.3Na R.sup.200: H R.sup.111: H R.sup.105: SO.sub.3H SO.sub.2Z: para R.sup.107: SO.sub.3H Z: -sulfatoethyl G: p-SO.sub.2Z, Z: - sulfatoethyl G.sub.1: p-SO.sub.2Z; Z: - sulfatoethyl B12 (A-1) Formula (IIa) with: Formula (IVb) with: 68:18:14 R.sup.201: SO.sub.3H R.sup.109: o-SO.sub.3Na R.sup.200: H R.sup.111: o-SO.sub.3Na R.sup.105: o-SO.sub.3Na SO.sub.2Z: para R.sup.107: H Z: -sulfatoethyl G: p-SO.sub.2Z, Z: - sulfatoethyl G.sub.1: p-SO.sub.2Z; Z: - sulfatoethyl B13 (A-1) Formula (IIa) with: Formula (IVb) with: 66:22:12 R.sup.201: SO.sub.3H R.sup.109: o-SO.sub.3Na R.sup.200: H R.sup.111: o-SO.sub.3Na R.sup.105: o-SO.sub.3Na SO.sub.2Z: para R.sup.107: o-SO.sub.3Na Z: -vinyl G: p-SO.sub.2Z, Z: vinyl G.sub.1: p-SO.sub.2Z; Z: vinyl B14 (A-1) Formula (IIa) with: Formula (IVb) with: 67:22:11 R.sup.201: SO.sub.3Na R.sup.110: o-SO.sub.3Na R.sup.200: CH.sub.3 R.sup.112: H R.sup.106: H SO.sub.2Z: para R.sup.108: p-COOH Z: -sulfatoethyl G: p-SO.sub.2Z; Z: - sulfatoethyl G.sub.1: H B15 (A-1) Formula (IIa) with: Formula (IVb) with: 65:20:15 R.sup.201: SO.sub.3Na R.sup.109: H R.sup.200: CH.sub.3 R.sup.111: o-SO.sub.3Na R.sup.106: H SO.sub.2Z: para R.sup.108: p-COOH Z: -sulfatoethyl G: p-SO.sub.2Z; Z: - sulfatoethyl G.sub.1: H B16 (A-1) Formula (IIa) with: Formula (IVb) with: 66:18:16 R.sup.201: SO.sub.3Na R.sup.109: H R.sup.200: CH.sub.3 R.sup.111: o-SO.sub.3Na R.sup.106: H SO.sub.2Z: para R.sup.108: H Z: -sulfatoethyl G: p-SO.sub.2Z; Z: - sulfatoethyl G.sub.1: p-SO.sub.2Z; Z: - sulfatoethyl B17 (A-1) Formula (IIa) with: Formula (IVa) with: 67:22:11 R.sup.201: SO.sub.3Na R.sup.110: o-SO.sub.3Na R.sup.200: H R.sup.112: H R.sup.106: H SO.sub.2Z: para R.sup.108: H Z: -sulfatoethyl G: p-SO.sub.2Z; Z: - R*: CH.sub.3 sulfatoethyl G.sub.1: p-SO.sub.2Z; Z: - sulfatoethyl B18 (A-1) Formula (IIa) with: Formula (IVa) with: 65:22:13 R.sup.201: SO.sub.3Na R.sup.109: H R.sup.200: H R.sup.111: o-SO.sub.3Na R.sup.106: H SO.sub.2Z: para R.sup.108: H Z: -sulfatoethyl G: p-SO.sub.2Z; Z: - R*: CH.sub.3 sulfatoethyl G.sub.1: p-SO.sub.2Z; Z: - sulfatoethyl B19 (A-1) Formula (IIa) with: Formula (IVa) with: 68:20:12 R.sup.201: SO.sub.3Na R.sup.110: o-SO.sub.3Na R.sup.200: H R.sup.112: H R.sup.106: H SO.sub.2Z: para R.sup.108: p-COOH Z: -sulfatoethyl G: p-SO.sub.2Z; Z: - R*: CH.sub.3 sulfatoethyl G.sub.1: H B20 (A-1) Formula (IIIa) with: Formula (IVb) with: 65:20:15 R.sup.200: H R.sup.110: o-SO.sub.3Na R.sup.105: SO.sub.3Na R.sup.112: H R.sup.107: SO.sub.3Na SO.sub.2Z: para G: p-SO.sub.2Z Z: -sulfatoethyl G.sub.1: p-SO.sub.2Z Z: -sulfatoethyl B21 (A-1) Formula (IIIa) with: Formula (IVb) with: 70:20:10 R.sup.200: H R.sup.109: H R.sup.105: o-SO.sub.3Na R.sup.111: o-SO.sub.3Na R.sup.107: o-SO.sub.3Na SO.sub.2Z: para G: p-SO.sub.2Z Z: -sulfatoethyl G.sub.1: p-SO.sub.2Z Z: -sulfatoethyl B22 (A-1) Formula (IIIa) with: Formula (IVb) with: 67:20:13 R.sup.200: H R.sup.110: o-SO.sub.3Na R.sup.105: o-SO.sub.3Na R.sup.112: H R.sup.107: H SO.sub.2Z: para G: p-SO.sub.2Z Z: -sulfatoethyl G.sub.1: p-SO.sub.2Z Z: -sulfatoethyl B23 (A-1) Formula (IIIa) with: Formula (IVb) with: 69:20:11 R.sup.200: SO.sub.3Na R.sup.109: H R.sup.105: H R.sup.111: o-SO.sub.3Na R.sup.107: H SO.sub.2Z: para G: p-SO.sub.2Z Z: -sulfatoethyl G.sub.1: p-SO.sub.2Z Z: -sulfatoethyl B24 (A-1) Formula (IIIa) with: Formula (IVb) with: 64:20:16 R.sup.200: COOH R.sup.109: H R.sup.105: H R.sup.111: o-SO.sub.3Na R.sup.107: H SO.sub.2Z: para G: p-SO.sub.2Z Z: -sulfatoethyl G.sub.1: p-SO.sub.2Z Z: -sulfatoethyl B25 (A-1) Formula (IIIa) with: Formula (IVb) with: 65:18:17 R.sup.200: CH.sub.3 R.sup.109: o-SO.sub.3Na R.sup.105: H R.sup.111: o-SO.sub.3Na R.sup.107: H SO.sub.2Z: para G: p-SO.sub.2Z Z: -sulfatoethyl G.sub.1: p-SO.sub.2Z Z: -sulfatoethyl B26 (A-1) Formula (IIIa) with: Formula (IVb) with: 67:22:11 R.sup.200: CH.sub.3 R.sup.109: H R.sup.201: CH.sub.3 R.sup.111: o-SO.sub.3H R.sup.105: H SO.sub.2Z: para R.sup.107: H Z: -sulfatoethyl G: p-SO.sub.2Z G.sub.1: p-SO.sub.2Z Z: -sulfatoethyl B27 (A-1) Formula (IIIa) with: Formula (IVb) with: 68:21:11 R.sup.200: COOH R.sup.109: o-SO.sub.3Na R.sup.201: CH.sub.3 R.sup.111: o-SO.sub.3Na R.sup.105: H SO.sub.2Z: para R.sup.107: H Z: -sulfatoethyl G: p-SO.sub.2Z G.sub.1: p-SO.sub.2Z Z: -sulfatoethyl B28 (A-1) Formula (IIIa) with: Formula (IVb) with: 68:20:12 R.sup.200: SO.sub.3Na R.sup.109: H R.sup.201: CH.sub.3 R.sup.111: o-SO.sub.3Na R.sup.105: H SO.sub.2Z: para R.sup.107: H Z: -sulfatoethyl G: p-SO.sub.2Z G.sub.1: p-SO.sub.2Z Z: -sulfatoethyl B29 (A-2) Formula (IIa) with: Formula (IVb) with: 65:18:17 R.sup.201: SO.sub.3Na R.sup.110: o-SO.sub.3H R.sup.200: H R.sup.112: H R.sup.106: H SO.sub.2Z: para R.sup.108: p-COOH Z: -sulfatoethyl G: p-SO.sub.2Z; Z: - sulfatoethyl G.sub.1: H B30 (A-2) Formula (IIa) with: Formula (IVb) with: 70:15:15 R.sup.201: SO.sub.3Na R.sup.109: H R.sup.200: H R.sup.111: o-SO.sub.3H R.sup.106: H SO.sub.2Z: para R.sup.108: p-COOH Z: -sulfatoethyl G: p-SO.sub.2Z; Z: - sulfatoethyl G.sub.1: H B31 (A-2) Formula (IIa) with: Formula (IVb) with: 65:20:15 R.sup.201: SO.sub.3Na R.sup.109: H R.sup.200: H R.sup.111: o-SO.sub.3H R.sup.106: o-SO.sub.3Na SO.sub.2Z: para R.sup.108: H Z: -sulfatoethyl G: p-SO.sub.2Z; Z: - sulfatoethyl G.sub.1: p-SO.sub.2Z; Z: - sulfatoethyl B32 (A-1) Formula (IIa) with: Formula (IVb) with: 64:18:18 R.sup.201: SO.sub.3Na R.sup.110: o-SO.sub.3Na R.sup.200: H R.sup.112: H R.sup.106: H SO.sub.2Z: para R.sup.108: p-SO.sub.3Na Z: -sulfatoethyl G: p-SO.sub.2Z; Z: - sulfatoethyl G.sub.1: H B33 (A-1) Formula (IIa) with: Formula (IVb) with: 75:10:15 R.sup.201: SO.sub.3Na R.sup.109: H R.sup.200: H R.sup.111: o-SO.sub.3Na R.sup.106: H SO.sub.2Z: para R.sup.108: m-COOH Z: -sulfatoethyl G: p-SO.sub.2Z; Z: - sulfatoethyl G.sub.1: H B34 (A-3) Formula (IIa) with: Formula (IVb) with: 70:15:15 R.sup.201: SO.sub.3Na R.sup.110: o-SO.sub.3H R.sup.200: H R.sup.112: H R.sup.106: H SO.sub.2Z: para R.sup.108: p-COOH Z: -sulfatoethyl G: p-SO.sub.2Z; Z: - sulfatoethyl G.sub.1: H B35 (A-3) Formula (IIa) with: Formula (IVb) with: 65:23:12 R.sup.201: SO.sub.3Na R.sup.109: H R.sup.200: H R.sup.111: o-SO.sub.3H R.sup.106: o-SO.sub.3Na SO.sub.2Z: para R.sup.108: H Z: -sulfatoethyl G: p-SO.sub.2Z; Z: - sulfatoethyl G.sub.1: p-SO.sub.2Z; Z: - sulfatoethyl B36 (A-3) Formula (IIa) with: Formula (IVb) with: 64:24:12 R.sup.201: SO.sub.3Na R.sup.109: H R.sup.200: H R.sup.111: o-SO.sub.3H R.sup.106: H SO.sub.2Z: para R.sup.108: p-COOH Z: -sulfatoethyl G: p-SO.sub.2Z; Z: - sulfatoethyl G.sub.1: H B37 (A-4) Formula (IIa) with: Formula (IVb) with: 65:20:15 R.sup.201: SO.sub.3Na R.sup.110: o-SO.sub.3H R.sup.200: H R.sup.112: H R.sup.106: H SO.sub.2Z: para R.sup.108: p-COOH Z: -sulfatoethyl G: p-SO.sub.2Z; Z: - sulfatoethyl G.sub.1: H B38 (A-4) Formula (IIa) with: Formula (IVb) with: 64:22:14 R.sup.201: SO.sub.3Na R.sup.109: H R.sup.200: H R.sup.111: o-SO.sub.3H R.sup.106: H SO.sub.2Z: para R.sup.108: p-COOH Z: -sulfatoethyl G: p-SO.sub.2Z; Z: - sulfatoethyl G.sub.1: H B39 (A-4) Formula (IIa) with: Formula (IVb) with: R.sup.201: SO.sub.3Na R.sup.110: o-SO.sub.3Na R.sup.200: H R.sup.112: H R.sup.106: o-SO.sub.3Na SO.sub.2Z: para R.sup.108: H Z: -sulfatoethyl G: p-SO.sub.2Z; Z: - sulfatoethyl G.sub.1: p-SO.sub.2Z; Z: - sulfatoethyl B40 (A-1) Formula (IIa) with: 70:30:0 R.sup.201: SO.sub.3Na R.sup.200: H R.sup.106: H R.sup.108: p-COOH G: p-SO.sub.2Z; Z: - sulfatoethyl G1: H B41 (A-1) Formula (IIa) with: 67:33:0 R.sup.201: SO.sub.3Na R.sup.200: H R.sup.105: o-SO.sub.3Na R.sup.107: H G: p-SO.sub.2Z, Z: - sulfatoethyl G1: p-SO.sub.2Z; Z: - sulfatoethyl B42 (A-1) Formula (IIa) with: 68:32:0 R.sup.201: H R.sup.200: COOH R.sup.105: o-SO.sub.3Na R.sup.107: H G: p-SO.sub.2Z, Z: - sulfatoethyl G1: p-SO.sub.2Z; Z: - sulfatoethyl B43 (A-1) Formula (IIa) with: 66:34:0 R.sup.201: SO.sub.3H R.sup.200: H R.sup.105: o-SO.sub.3Na R.sup.107: o-SO.sub.3Na G: p-SO.sub.2Z, Z; vinyl G1: p-SO.sub.2Z; Z: vinyl B45 (A-1) Formula (IIa) with: 66:34:0 R.sup.201: SO.sub.3Na R.sup.200: CH.sub.3 R.sup.106: H R.sup.108: H G: p-SO.sub.2Z; Z: - sulfatoethyl G1: p-SO.sub.2Z; Z: - sulfatoethyl B46 (A-1) Formula (IIa) with: 62:38:0 R.sup.201: SO.sub.3Na R.sup.200: H R.sup.106: H R.sup.108: H G: p-SO.sub.2Z; Z: - sulfatoethyl G1: p-SO.sub.2Z; Z: - sulfatoethyl B47 (A-1) Formula (IIIa) with: 65:35:0 R.sup.200: H R.sup.105: o-SO.sub.3Na R.sup.107: o-SO.sub.3Na G: p-SO.sub.2Z G1: p-SO.sub.2Z Z: -sulfatoethyl B48 (A-1) Formula (IIIa) with: 64:36:0 R.sup.200: COOH R.sup.105: H R.sup.107: H G: p-SO.sub.2Z G1: p-SO.sub.2Z Z: -sulfatoethyl B49 (A-1) Formula (IIIa) with: 65:35:0 R.sup.200: CH.sub.3 R.sup.105: H R.sup.107: H G: p-SO.sub.2Z G1: p-SO.sub.2Z Z: -sulfatoethyl B50 (A-1) Formula (IIa) with: Formula (IV) with: 63:27:10 R.sup.201: SO.sub.3Na D4: formula (1) with R.sup.200: H X: m-SO.sub.2Z R.sup.106: H Z: -sulfatoethyl R.sup.108: p-COOH and R.sup.1: o-methoxy G: p-SO.sub.2Z; Z: - D3: formula (1) with sulfatoethyl X: p-SO.sub.2Z G.sub.1: H Z: -sulfatoethyl and R.sup.1: o-SO.sub.3Na R*: CH.sub.2SO.sub.3Na B51 (A-1) Formula (IIa) with: Formula (IV) with: 58:20:22 R.sup.201: SO.sub.3Na D4: formula (1) with R.sup.200: H X: p-SO.sub.2Z R.sup.106: H Z: -sulfatoethyl R.sup.108: p-COOH D3 = formula (1) with G: p-SO.sub.2Z; Z: - X: p-SO.sub.2Z sulfatoethyl R1: o-SO.sub.3Na G.sub.1: H Z: -sulfatoethyl R*: CH.sub.2SO.sub.3Na B52 (A-1) Formula (IIa) with: Formula (IV) with: 62:22:16 R.sup.201: SO.sub.3Na D4: formula (1) with R.sup.200: H X: p-SO.sub.2Z R.sup.105: o-SO.sub.3Na Z: -sulfatoethyl R.sup.107: H D3: formula (1) with G: p-SO.sub.2Z, Z: - X: p-SO.sub.2Z sulfatoethyl Z: -sulfatoethyl G.sub.1: p-SO.sub.2Z; Z: - R*: CH.sub.2SO.sub.3Na sulfatoethyl B53 (A-1) Formula (IIa) with: Formula (IV) with: 67:22:11 R.sup.201: SO.sub.3Na D4: formula (1) with R.sup.200: H X: p-SO.sub.2Z R.sup.106: H Z: -sulfatoethyl R.sup.108: H D3: formula (1) with G: p-SO.sub.2Z; Z: - X: p-SO.sub.2Z sulfatoethyl Z: -sulfatoethyl G.sub.1: p-SO.sub.2Z; Z: - R*: CH.sub.2SO.sub.3Na sulfatoethyl

Example B 54

(34) 60 parts of a dye of formula (A-1)

(35) ##STR00048##
were mixed with 13 parts of a dye of formula (II-1)

(36) ##STR00049##
and mixed with 12 parts of a dye of the formula (III-1)

(37) ##STR00050##
and mixed with 15 parts of a dye powder of the formula (IV-1)

(38) ##STR00051##

(39) The resulting inventive dye mixture was dried under reduced pressure. (Alternatively it could be dried via spray drying.) It gives very deep black dyeings and prints, e.g. on cotton, under the dyeing conditions typical for reactive dyes.

Performance-Examples C1 to C2

(40) C1

(41) The dye from example A1 of this invention was compared with the corresponding non-inventive dye (Ia) wherein D.sup.1 and D.sup.2 is p-Sulfatoethyl sulfonyl-anilin:

(42) ##STR00052##

(43) Remazol Black B 133%, in exhaust dyeing (liquor ratio 1:10, soda ash 20 g/l, 70 g/l NaCl, unbleached cotton knit) at 40 C., 50 C. and 60 C.

(44) The resulting color strengths (in %) were measured in a full black relative to dyeings performed at 60 C.:

(45) TABLE-US-00002 Temperature in C. 40 50 60 Sample from A1 95.7 99.9 100 Remazol Black B 133% 90.8 102 100

(46) It can be seen clearly that the product from example Al has a significant lower sensibility to variations in the temperature during the dying process, which makes the dying process much more predictable and allows for more temperature variability in the dyeing process when using the inventive dye mixture as compared to known mixtures.

(47) C2

(48) Inventive new dye mixtures Remazol Midnight Black RGB and Remazol Onyx RGB wer dyed on cotton knit with a liqueur ratio 10:1, at 60 C., Soda ash 5 g/l, caustic soda 50% 2 ml/l, 80 g/l Salt (NaCl) and their colour strength in a deep black shade was set to be 100%.

(49) Then cotton knit was dyed using the same dying conditions but using the non-inventive state of the art deep black dyes listed below.

(50) Their colour strength relative to the inventive products is: Novacron Black WAE=90% Bezaktiv Cosmos S-MAX=95% Remazol Deep Black RGB=92% Jakazol Black JNN=95% Novacron Black CNN=95%

(51) It can be seen from C2 that the colour strength of a dye mixture according to the present invention is even higher than that of state of the art products. The combination with the high temperature tolerance during the dying process as shown in C1 allows the dyer more freedom in performing the process and reduces the amounts of dye required to achieve the same dyeing result as with other dyes.