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) ##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) ##STR00025## and one or more dye(s) of: formula (II) ##STR00026## and optionally one or more dye(s) of: formula (IV) ##STR00027## wherein D.sup.1 and D.sup.2 independent of one another is group of formula (1) ##STR00028## 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 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.sup.201 is a group of the formula: NN-D.sup.3, 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 mixturecalculated 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: ##STR00029## wherein D.sup.1 to D.sup.4 and R* are as defined in claim 1 and R.sup.105 to R.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 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, R.sup.201 is a group of the formula: NN-Phenyl, which NN-Phenyl group is substituted by SO.sub.2Z and R.sup.109, R.sup.109 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, 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: ##STR00030## wherein R.sup.101 to 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 is hydrogen, carboxy, sulfo or amino, R.sup.201 is a group of the formula: NN-Phenyl, which NN-Phenyl group is subsituted by SO.sub.2Z and R.sup.109, 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: ##STR00031## 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 is a group of the formula: NN-Phenyl, which NN-Phenyl group is substituted by SO.sub.2Z and R.sup.109, R.sup.109 is hydrogen, carboxy, sulfo, (C.sub.1-C.sub.4)-alkyl or (C.sub.1-C.sub.4)-alkoxy, 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) ##STR00011##

(4) and dyes cotton in navy blue shades.

Examples A2-A5

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

Example A-2

(6) ##STR00012##

(7) Dyes cotton in reddish blue shades.

Example A-3

(8) ##STR00013##

(9) Dyes cotton in greenish blue shades

Example A-4

(10) ##STR00014##

(11) Dyes cotton in navy blue shades.

Example A-5

(12) ##STR00015##

(13) Dyes cotton in greenish blue shades

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

B. Examples of Mixtures of the Invention

Example B-1

(15) 60 parts dye of the formula (A-1)

(16) ##STR00016##

(17) were mixed with 25 parts of dye of the formula (II-1)

(18) ##STR00017##

(19) and mixed with 15 parts of a dye powder containing the dye of the formula (IV-1)

(20) ##STR00018##

(21) 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.

(22) 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

(23) 54 parts dye of the formula (A-1)

(24) ##STR00019##

(25) were mixed with 20 parts of a dye of the formula (II-2)

(26) ##STR00020##

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

(28) ##STR00021##

(29) The resulting dye mixture of the invention was dried via spray drying and can be dryed also 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

(30) 65 parts dye of the formula (A-4)

(31) ##STR00022##

(32) were mixed with 28 parts of a dye of the formula (II-3)

(33) ##STR00023##

(34) and mixed with 7 parts of a dye of the formula (IV-3)

(35) ##STR00024##

(36) 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 B16

(37) 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.

(38) Dye mixtures in accordance with Examples B1-B3.

(39) All Radicals that are not defined in below table are equal to Hydrogen.

(40) TABLE-US-00001 Ratio Expl. Dye of formula (I) Dye of formula (II) Dye of formula (IV) (I):(II):(IV) B4 (A-1) Formula (IIa) with: Formula (IVb) with: 65:22:13 R.sup.201: N = N-Phenyl, R.sup.109: o-SO.sub.3Na Phenyl substituted with SO.sub.2Z R.sup.111: H and SO.sub.2Z: para R.sup.109: o-SO.sub.3Na Z: -sulfatoethyl R.sup.200: H R.sup.105: o-SO.sub.3Na R.sup.106: p-methoxy R.sup.107: o-SO.sub.3Na G: H G.sub.1: p-SO.sub.2Z; Z: -sulfatoethyl B5 (A-1) Formula (IIa) with: Formula (IVb) with: 61:27:12 R.sup.201: N = N-Phenyl, R.sup.109: H Phenyl substituted with SO.sub.2Z R.sup.111: o-SO.sub.3Na and SO.sub.2Z: para R.sup.109: o-SO.sub.3Na Z: -sulfatoethyl R.sup.200: COOH R.sup.105: o-SO.sub.3Na R.sup.107: o-SO.sub.3Na G: p-SO.sub.2Z; Z: -sulfatoethyl G.sub.1: p-SO.sub.2Z; Z: -sulfatoethyl B6 (A-1) Formula (IIa) with: Formula (IVb) with: 55:27:18 R.sup.201: N = N-Phenyl, R.sup.109: o-SO.sub.3Na Phenyl substituted with SO.sub.2Z R.sup.111: o-SO.sub.3Na and SO.sub.2Z: para R.sup.109: H Z: -sulfatoethyl R.sup.200: COOH R.sup.105: o-SO.sub.3Na R.sup.107: o-SO.sub.3Na G: p-SO.sub.2Z; Z: -sulfatoethyl G.sub.1: p-SO.sub.2Z; Z: -sulfatoethyl B7 (A-1) Formula (IIa) with: Formula (IVb) with: 60:23:17 R.sup.201: N = N-Phenyl, R.sup.109: H Phenyl substituted with SO.sub.2Z R.sup.111: o-SO.sub.3Na and SO.sub.2Z: para R.sup.109: o-SO.sub.3Na Z: -sulfatoethyl R.sup.200: H R.sup.105: o-SO.sub.3Na R.sup.107: o-SO.sub.3Na G: p-SO.sub.2Z; Z: -sulfatoethyl G.sub.1: p-SO.sub.2Z; Z: -sulfatoethyl B8 (A-1) Formula (IIa) with: Formula (IVb) with: 70:18:12 R.sup.201: N = N-Phenyl, R.sup.109: H Phenyl substituted with SO.sub.2Z R.sup.111: H and SO.sub.2Z: para R.sup.109: H Z: -sulfatoethyl R.sup.200: H R.sup.105: o-SO.sub.3Na R.sup.107: o-SO.sub.3Na G: p-SO.sub.2Z; Z: -sulfatoethyl G.sub.1: p-SO.sub.2Z; Z: -sulfatoethyl B9 (A-1) Formula (IIa) with: 66:34:0 R.sup.201: N = N-Phenyl, Phenyl substituted with SO.sub.2Z and R.sup.109: o-SO.sub.3Na R.sup.200: H R.sup.105: o-SO.sub.3Na R.sup.106: p-methoxy R.sup.107: o-SO.sub.3Na G: H G1: p-SO.sub.2Z; Z: -sulfatoethyl B10 (A-1) Formula (IIa) with: 63:37:0 R.sup.201: N = N-Phenyl, Phenyl substituted with SO.sub.2Z and R.sup.109: o-SO.sub.3Na R.sup.200: COOH R.sup.105: o-SO.sub.3Na R.sup.107: o-SO.sub.3Na G: p-SO.sub.2Z; Z: -sulfatoethyl G1: p-SO.sub.2Z; Z: -sulfatoethyl B11 (A-1) Formula (IIa) with: 65:35:0 R.sup.201: N = N-Phenyl, Phenyl substituted with SO.sub.2Z and R.sup.109: H R.sup.200: COOH R.sup.105: o-SO.sub.3Na R.sup.107: o-SO.sub.3Na G: p-SO.sub.2Z; Z: -sulfatoethyl G1: p-SO.sub.2Z; Z: -sulfatoethyl B12 (A-1) Formula (IIa) with: 67:33:0 R.sup.201: N = N-Phenyl, Phenyl substituted with SO.sub.2Z and R.sup.109: o-SO.sub.3Na R.sup.200: H R.sup.105: o-SO.sub.3Na R.sup.107: o-SO.sub.3Na G: p-SO.sub.2Z; Z: -sulfatoethyl G1: p-SO.sub.2Z; Z: -sulfatoethyl B13 (A-1) Formula (IIa) with: 70:30:0 R.sup.201: N = N-Phenyl, Phenyl substituted with SO.sub.2Z and R.sup.109: H R.sup.200: H R.sup.105: o-SO.sub.3Na R.sup.107: o-SO.sub.3Na G: p-SO.sub.2Z; Z: -sulfatoethyl G1: p-SO.sub.2Z; Z: -sulfatoethyl B14 (A-1) Formula (IIa) with: Formula (IV) with: 65:23:12 R.sup.201: N = N-Phenyl, D4: formula (1) Phenyl substituted with SO.sub.2Z with and X: p-SO.sub.2Z R.sup.109: o-SO.sub.3Na Z: -sulfatoethyl R.sup.200: H D3: formula (1) R.sup.105: o-SO.sub.3Na with R.sup.106: p-methoxy X: p-SO.sub.2Z and R.sup.107: o-SO.sub.3Na R1: o-SO.sub.3Na G: H Z: -sulfatoethyl G1: p-SO.sub.2Z; Z: -sulfatoethyl R*: CH.sub.2SO.sub.3Na B15 (A-1) Formula (IIa) with: Formula (IV) with: 60:31:9 R.sup.201: N = N-Phenyl, D4: formula (1) Phenyl substituted with SO.sub.2Z with and X: p-SO.sub.2Z R.sup.109: o-SO.sub.3Na Z: -sulfatoethyl R.sup.200: COOH D3: formula (1) R.sup.105: o-SO.sub.3Na with R.sup.107: o-SO.sub.3Na X: p-SO.sub.2Z G: p-SO.sub.2Z; Z: -sulfatoethyl Z: -sulfatoethyl G1: p-SO.sub.2Z; Z: -sulfatoethyl R*: CH.sub.2SO.sub.3Na B16 (A-1) Formula (IIa) with: Formula (IV) with: 58:27:15 R.sup.201: N = N-Phenyl, D4: formula (1) Phenyl substituted with SO.sub.2Z with and X: p-SO.sub.2Z R.sup.109: H Z: -sulfatoethyl R.sup.200: COOH D3: formula (1) R.sup.105: o-SO.sub.3Na with R.sup.107: o-SO.sub.3Na X: p-SO.sub.2Z G: p-SO.sub.2Z; Z: -sulfatoethyl Z: -sulfatoethyl G1: p-SO.sub.2Z; Z: -sulfatoethyl R*: CH.sub.2SO.sub.3Na