Heavy metal free, blue and navy fibre-reactive dye mixtures

Abstract

The invention relates to mixtures of fiber-reactive Triphendioxazine dyes with other fiber-reactive azo dyes and their use for the dyeing of hydroxyl- and especially carboxamide-containing material in blue and navy shades.

Claims

1. A dye mixture comprising at least one dye of formula (I) ##STR00011## and at least one dye (II) selected from the group consisting of: ##STR00012## wherein independent of each other A is OH and B is NH.sub.2 or A is NH.sub.2 and B is OH, D is (C.sub.1-C.sub.4)-alkyl or Cl, R.sup.1 is hydrogen or (C.sub.1-C.sub.4)-alkyl, R.sup.2 is hydrogen, (C.sub.1-C.sub.4)-alkyl, (C.sub.1-C.sub.4)-alkoxy or sulfo, Z.sup.1 is CHCH.sub.2, CH.sub.2CH.sub.2G or hydroxyl, wherein G is hydroxyl; halogen; ester groups of organic carboxylic and sulfonic acids; or acidic ester groups of inorganic acids; X is Cl or F, and M is hydrogen, an alkali metal or one equivalent of an alkaline earth metal and.

2. The dye mixture according to claim 1, comprising at least one dye of formula (Ia) ##STR00013## wherein R.sup.1 is hydrogen, methyl or ethyl, R.sup.2 is hydrogen, (C.sub.1-C.sub.2)-alkyl, (C.sub.1-C.sub.2)-alkoxy or sulfo, Z.sup.1 is CHCH.sub.2, CH.sub.2CH.sub.2G or hydroxyl, wherein G is hydroxyl; halogen; ester groups of organic carboxylic and sulfonic acids; or acidic ester groups of inorganic acids; and M is hydrogen, an alkali metal or one equivalent of an alkaline earth metal.

3. The dye mixture according to claim 1 comprising at least one dye of formula (Ib) ##STR00014## wherein R.sup.1 is hydrogen, methyl or ethyl, Z.sup.1 is CHCH.sub.2, CH.sub.2CH.sub.2G or hydroxyl, wherein G is hydroxyl; halogen; ester groups of organic carboxylic and sulfonic acids; or acidic ester groups of inorganic acids; and M is hydrogen, an alkali metal or one equivalent of an alkaline earth metal.

4. The dye mixture according to claim 1, comprising at least one dye selected from the group consisting of: ##STR00015## ##STR00016##

5. The dye mixture according to claim 1, with a weight ratio of (I) 80 to 20% and (II) 20 to 80%.

6. The dye mixture according to claim 5, with a weight ratio of (I) 70 to 30% and (II) 30 to 70%.

7. A process for dyeing a carboxamido-containing material which comprises contacting the material with a dye mixture comprising at least one dye of formula (I) ##STR00017## and at least one dye of formula (II) ##STR00018## wherein independent of each other A is OH and B is NH.sub.2 or A is NH.sub.2 and B is OH, D is (C-C.sub.4)-alkyl or CI, R.sup.1 is hydrogen or (C.sub.1-C.sub.4)-alkyl, R.sup.2 is hydrogen, (C.sub.1-C.sub.4)-alkyl, (C.sub.1-C.sub.4)-alkoxy or sulfo, Z.sup.1 is CHCH.sub.2, CH.sub.2CH.sub.2G or hydroxyl, wherein G is hydroxyl; halogen; ester groups of organic carboxylic and sulfonic acids; or acidic ester groups of inorganic acids; X is Cl or F, n is 2 or 3 and M is hydrogen, an alkali metal or one equivalent of an alkaline earth metal and with the proviso that formula (II) is not of the formula (II-2) ##STR00019##

8. The process as claimed in claim 7, wherein in the material is wool.

9. A dye mixture comprising at least one dye of formula (I) which is selected from the group consisting of (I-1)-(I-10) ##STR00020## ##STR00021## ##STR00022## and at least one dye of formula (II) which is selected from the group consisting of (II-1), (II-2) and (II-3) ##STR00023## wherein independent of each other M is hydrogen, an alkali metal or one equivalent of an alkaline earth metal.

10. The dye mixture according to claim 9, wherein the dye of formula (II) is a dye of formula (II-1) or (II-3).

11. The dye mixture according to claim 9, wherein the dye of formula (II) is a dye of formula (I-1), (I-3), (I-4), (I-6), (I-7), (I-8), (I-9) or (I-10).

12. The dye mixture according to claim 10, wherein the dye of formula (II) is a dye of formula (I-1), (I-3), (I-4), (I-6), (I-7), (I-8), (I-9) or (I-10).

13. The dye mixture according to claim 10, with a weight ratio of (I) 80 to 20% and (II) 20 to 80%.

14. The dye mixture according to claim 10, with a weight ratio of (I) 70 to 30% and (II) 30 to 70%.

15. The dye mixture according to claim 9, comprising at least one dye selected from the group consisting of dyes (I-2), (I-5) and (I-10) with at least one dye selected from the group consisting of dyes (II-2), (II-3).

Description

EXAMPLE 1

(1) 70 parts of an electrolyte-containing dye powder containing the navy azo dye of formula (I-2) in a 75% fraction (i.e. having a dye content of 75%), and 30 parts of an electrolyte-containing dye powder containing the bright blue triphendioxazine dye of formula (II-2) in an 80% fraction, were mixed mechanically with one another.

(2) The resultant inventive dye mixture provides navy dyeings on wool, under the dyeing conditions customary for reactive dyes.

EXAMPLE 2

(3) 50 parts of an electrolyte-containing dye powder containing the navy azo dye of formula (I-2) in a 75% fraction, and 50 parts of an electrolyte-containing dye powder containing the blue triphendioxazine dye of formula (II-2) in an 80% fraction were mixed mechanically with one another.

(4) The resultant inventive dye mixture provides reddish navy dyeings on wool under the dyeing conditions customary for reactive dyes.

(5) TABLE-US-00001 % % Example No. Component 1 (pure dye) Component 2 (pure dye) 3 I-2 65 II-2 35 4 I-2 80 II-2 20 5 I-2 30 II-2 70 6 I-2 60 II-3 40 7 I-2 65 II-1 35 8 I-5 50 II-1 50 9 I-5 65 II-2 35 10 I-5 80 II-3 20 11 I-10 60 II-1 40 12 I-10 60 II-2 40 13 I-10 60 II-3 40 14 I-1 50 II-1 50 15 I-1 70 II-2 30 16 I-1 60 II-3 40 17 I-3 55 II-1 45 18 I-3 65 II-2 35 19 I-3 70 II-3 30 20 I-4 80 II-1 20 21 I-4 60 II-2 40 22 I-4 60 II-3 40 23 I-5 70 II-1 30 24 I-5 50 II-2 50 25 I-5 60 II-3 40 26 I-6 75 II-1 25 27 I-6 50 II-2 50 28 I-6 40 II-3 60 29 I-7 70 II-1 30 30 I-7 65 II-2 35 31 I-7 55 II-3 45 32 I-8 80 II-1 20 33 I-8 80 II-2 20 34 I-8 75 II-3 25 35 I-9 50 II-1 50 36 I-9 45 II-2 55 37 I-9 60 II-3 40 38 I-9 20 II-3 80

EXAMPLES 39 TO 42 DYEING AND BLEACH TESTS

(6) Inventive mixtures of dyes as well as mixtures based on known mixtures were dyed on cotton and the retention of depths after bleach treatment was measured.

(7) TABLE-US-00002 C.I. Reactive Structure Structure Recipe Black 5 I-2 II-2 39 0.66 0.34 40 0.66 0.34 41 0.38 0.62 42 0.38 0.62

(8) C.I. Reactive Black 5 has the following structure:

(9) ##STR00010##

(10) The mixtures were dyed on a 100% cotton interlock substrate at a liquor ratio of 10:1 and at a temperature of 60 C. All recipes included 25 g/l common salt and 5 g/l soda ash. The substrate was subsequently rinsed, soaped and dried. The measurement of dyeing yield was done by spectrophotometer.

(11) After treatment with oxidizing agents the following data was obtained:

(12) TABLE-US-00003 Integ of Hypochlorite bleach ISO 105-E03 Recipe original DIN 54034 20 mg chlorine 39 12.81 2.95 4.92 40 8.46 5.96 5.70 41 11.77 4.23 4.36 42 8.85 6.30 4.70

(13) This translates into the following Retention of depth of dyeing after treatment with oxidizing agents

(14) TABLE-US-00004 Hypochlorite bleach ISO 105-E03 Recipe Original mild DIN 54034 20 mg/l active chlorine 39 100% 23% 38% 40 100% 70% 67% 41 100% 36% 37% 42 100% 71% 53%

(15) It can thus be summarized that the stability of the dye mixture according to the present invention (Examples 40 and 42) against oxidizing agents is significantly better than the stability of a comparative mixture of reactive dyes (Examples 39 and 41). It goes without saying that the absence of heavy metals is the other mayor advantage of the inventive dye mixtures shown above as compared to mordant type dyes.