Basic dye mixtures for aramid fibres

Abstract

The present invention is directed to dye mixtures comprising structures of formula and their production and their use for dyeing textiles and in particular for dyeing aramid fibres. ##STR00001##

Claims

1. A dye mixture comprising at least one dye of formula (I-1) ##STR00014## and at least one dye of the (IIa-1) ##STR00015## at least one dye of formula (III-1) ##STR00016## X is an anion, wherein the dyes of formula (I-1), (II-a) and (III-1) are present in the following amount: formula (I-1): 70 to 80 wt. %, formula (IIa-1): 10 to 15 wt. %, and formula (III-1): 10 to 15 wt, %, wherein the weight % is based of the total amount of dyes in the dye mixture.

2. The dye mixture according to claim 1, wherein the anion is selected from the group consisting of halogen, sulfate; hydrogensulfate, aminosulfate, nitrate, phosphate, dihydrogenphosphate, hydrogenphosphate, polyphosphate, hydrogencarbonate, carbonate, methosulfate, ethosulfate, cyanate, tri-chlorozincate, tetra-chlorozincate, (C.sub.1, C.sub.4)-alkylsulfonate, benzenesulfonate, naphthalinsulfonates, borate, tetraborofluorate, (C.sub.1-C.sub.4)-alkylcarboxylate, hydroxy-(C.sub.1-C.sub.4)-alkylcarboxylate, benzenecarboxylate and naphthalincarboxylate.

3. The dye mixture according to claim 1, wherein the anion is selected from the group consisting of formiate, acetate, propionate, lactate, benzoate, chloride, trichlorozincate, tetrachlorozincate, methosulfate and ethosulfate.

4. A solution for dying comprising the dye mixture according to claim 1.

5. A process for the production of the dye mixture according claim 1, comprising a) mixing the components of the dye mixture, and b) homogenizing the mixture obtained in step a).

6. A process for dyeing or printing material, comprising contacting the material with the dye mixture according to claim 1.

7. A dye mixture comprising at least one dye of formula (I) ##STR00017## at least one dye of the formula (IIc) which is selected from the group consisting of: ##STR00018## and at least one dye of the formula (III) ##STR00019## wherein independent from each other R.sup.1 is C.sub.1-C.sub.4-alkyl, R.sup.2 is (C.sub.1-C.sub.4)-alkyl, (C.sub.1-C.sub.4)-alkyl substituted by halogen, phenyl or benzyl substituted by (C.sub.1-C.sub.8)-alkyl, X.sup.−is an anion, R.sup.7 is hydrogen, (C.sub.1-C.sub.4)-alkyl or (C.sub.1-C.sub.4)-alkoxy, R.sup.8 is hydrogen or (C.sub.1-C.sub.4)-alkyl, and R.sup.9 is (C.sub.1-C.sub.4)-alkyl, (C.sub.1-C.sub.4)-alkoxy or —(CH.sub.2).sub.m—OH, wherein in is 2 to 4.

8. The dye mixture according to claim 7, wherein the anion is selected from the group consisting of halogen, sulfate, hydrogensulfate, aminosulfate, nitrate, phosphate, dihydrogenphosphate, hydrogenphosphate, polyphosphate, hydrogencarbonate, carbonate, methosulfate, ethosulfate, cyanate, tri-chlorozincate, tetra-chlorozincate, (C.sub.1-C.sub.4)-alkylsulfonate, benzenesulfonate, naphthalinsulfonates, borate, tetraborofluorate, (C.sub.1-C.sub.4)-alkylcarboxylate, hydroxy-(C.sub.1-C.sub.4)-alkylcarboxylate, benzenecarboxylate and naphthalincarboxylate.

9. The dye mixture according to claim 7, wherein the anion is selected from the group consisting of formiate, acetate, propionate, lactate, benzoate, chloride, trichlorozincate, tetrachlorozincate, methosulfate and ethosulfate.

10. A process for dyeing or printing material, comprising contacting the material with the dye mixture according to claim 7.

11. The dye mixture according to claim 7, wherein independent from each other R.sup.1, R.sup.2 and R.sup.8 is (C.sub.1-C.sub.2)-alkyl, R.sup.7 is (C.sub.1-C.sub.2)-alkyl or (C.sub.1-C.sub.2)-alkoxy, R.sup.9 is (C.sub.1-C.sub.2)-alkyl, (C.sub.1-C.sub.2)-alkoxy or —(CH.sub.2).sub.m—OH, wherein m is 2 to 4.

12. A dye mixture consisting essentially of at least one dye of formula (I-2) ##STR00020## wherein X.sup.− is an anion, and ii. at least one dye of the formula (IIc) which is selected from the group consisting of: ##STR00021## wherein X.sup.− is an anion.

13. The dye mixture according to claim 12, wherein the anion is selected from the group consisting of halogen, sulfate, hydrogensulfate, aminosulfate, nitrate, phosphate, dihydrogenphosphate, hydrogenphosphate, polyphosphate, hydrogencarbonate, carbonate, methosulfate, ethosulfate, cyanate, tri-chlorozincate, tetra-chlorozincate, (C.sub.1-C.sub.4)-alkylsulfonate, benzenesulfonate, naphthalinsulfonates, borate, tetraborofluorate, (C.sub.1-C.sub.4)-alkylcarboxylate, hydroxy-(C.sub.1-C.sub.4)-alkylcarboxylate, benzenecarboxylate and naphthalincarboxylate.

14. The dye mixture according to claim 12, wherein the anion is selected from the group consisting of formiate, acetate, propionate, lactate, benzoate, chloride, trichlorozincate, tetrachlorozincate, methosulfate and ethosulfate.

15. A process for dyeing or printing material, comprising contacting the material with the dye mixture according to claim 12.

Description

EXAMPLES

Example A—Synthesis

(1) To 370 parts of n-Butanol and 41 parts of water 109.8 parts (0.517 mol) of Quinizarine (CAS 81-64-1) and 14.4 parts of Leuco-quinizarine (CAS 17648-03-2) were added under stirring. To this mixture 9.6 parts Boric acid (CAS 10043-35-3) and 122 parts (1.14 mol) of p-Toluidin (CAS106-49-0) were added.

(2) The reaction mixture was heated under stirring to reflux (96° C.) and kept for 20 hours under stirring.

(3) The reaction mixture was then cooled down to 50 to 60° C. and the product was filtered and washed with methanol and demineralized water.

(4) After drying under vacuum conditions 130 parts of Intermediate A were obtained.

(5) ##STR00011##

Example B—Synthesis

(6) 10 parts of Precursor A were added to 265 parts of 55% Sulfuric acid at 0 to 5° C. under stirring.

(7) The reaction mixture was then heated up to 125° C. under stirring and kept at this temperature for 11 hours.

(8) The Mixture was cooled down to 25° C. under stirring, a black suspension was observed. The mixture was filtered and washed with water.

(9) The filtered solid was re-slurried in 200 ml of demineralized water and the pH was adjusted to pH 11 with NH.sub.4OH solution and stirred for 3 hours.

(10) The reddish Brown solid product was again filtrated and washed with demineralized water and dried under vacuum conditions to deliver: 9.2 g of Intermediate B

(11) ##STR00012##

Example C—Synthesis

(12) 20 parts of dry Intermediate B (<0.5% water content) and 2 parts of MgO were added to 200 parts of dry Chlorobenzene.

(13) The mixture was stirred and heated up to 135° C. and stirred for 30 to 45 min until a solution was reached. 20 parts of Dimethylsulfate were added and the mixture was stirred for 4 h at 120 to 125° C. The reaction mixture was cooled down to 70 to 75° C. and 20 parts of water and 10 parts of diluted Hydrochloric acid were added and the mixture was stirred for 1 h.

(14) The excess of Dimethylsulfate was destroyed by cooling down the mixture to 50 to 55° C. and adding 10 parts of diluted hydrochloric acid and stirring 2 h at 50 to 55° C. Then the mixture was filtrated, washed with Chlorobenzene Methanol and water.

(15) After drying under vacuum conditions 12 g of the final dye (I-1) with X.sup.− ═CH.sub.3SO.sub.4.sup.− were obtained.

(16) ##STR00013##

Example D—Powder Formulation

(17) 36 parts of dye (I-2), with X.sup.− ═CH.sub.3SO.sub.4.sup.− and 14 parts of dye (IIc-1), with X.sup.− ═ZnCl.sub.3.sup.− and 4 parts white oil 90 as a dedusting agent and 1 part of Avolan® IW as a wetting agent and 45 parts of Dextrin as a cutting agent were homogeneously mixed and milled with a Bauermeister type of mill using a 2 mm size sieve. This delivered 97 parts of a black powder that dyes m-Aramid fibres in deep black shades.

(18) Other dedusting-agents, wetting-agents and also cutting-agents, like sodiumsulfate, sodium-chloride, rice starch, maize starch amidosulfonic acid can be used to formulate powder products.

(19) Liquid formulations have advantages in some applications of the claimed dyes. Those liquid formulations can be prepared by special synthesis procedures directly delivering a liquid formulation or by dissolving the isolated final product in water-soluble organic solvents or mixtures of those solvents with water.

Example E—Liquid Formulation

(20) 8.25 parts of dye (I-1), with X.sup.− ═CH.sub.3SO.sub.4.sup.− and 4.8 parts of dye (IIa-1), with X.sup.−═Cl.sup.− and 2.2 parts of dye (III-1), with X.sup.− ═Cl.sup.− were added under stirring to 85 parts of ethylene glycol at room temperature. The mixture was stirred for 3 hours until a clear solution was reached. The solution was filtrated to remove possible insoluble parts and delivered then deep Black dyeings on m-Aramid fibres.

(21) The dye samples were synthesized as outlined above. The dye mixtures were then prepared as in the following examples.

Example 1—Dye Mixture

(22) 72 parts of the green basic dye of the formula (I-2) (with X.sup.− ═ZnCl.sub.3.sup.−) and 28 parts of the red basic dye of the formula (IIc-1) (with X.sup.− ═ZnCl.sub.3.sup.−), were prepared according to Example D. The resultant dye mixture of the invention provides grey and black dyeings and prints, on meta-aramid, under the dyeing conditions previously described.

Example 2—Dye Mixture

(23) 76 parts of the green basic dye of the formula (I-2) (with X.sup.− ═CH.sub.3CH.sub.2SO.sub.4.sup.−), 14 parts of the red basic dye of the formula (IIa-1) (with X.sup.− ═Cl.sup.−) and 10 parts of the blue basic dye of the formula (III-1) (with X.sup.− ═ZnCl.sub.3.sup.−), were prepared according to Example D

(24) The resultant dye mixture of the invention provides grey and black dyeings and prints, on meta-aramid, under the dyeing conditions previously described.

Example 3—Dye Mixture

(25) 85 parts of the green basic dye of the formula (I-1) (with X.sup.− ═Cl.sup.−), 9 parts of the red basic dye of the formula (IIc-1) (with X.sup.− ═ZnCl.sub.3.sup.−) and 6 parts of the blue basic dye of the formula (III-1) (with X.sup.− ═Cl.sup.−), were prepared according to Example D.

(26) The resultant dye mixture of the invention provides olive dyeings and prints, on meta-aramid, under the dyeing conditions previously described.

(27) Further mixtures listed in the table below provide dyeing's with Olive, Brown, Grey & Black shades.

(28) TABLE-US-00001 Component I Component II Component III Example Structure X.sup.− % Structure X.sup.− % Structure X.sup.− % 4 I-1 CH.sub.3SO.sub.4.sup.− 86 IIa-1 Cl.sup.− 8 III-1 Cl.sup.− 6 5 I-1 CH.sub.3SO.sub.4.sup.− 71 IIa-1 Cl.sup.− 17 III-1 Cl.sup.− 12 6 I-1 CH.sub.3SO.sub.4.sup.− 66 IIa-1 Cl.sup.− 18 III-1 Cl.sup.− 16 7 I-1 CH.sub.3SO.sub.4.sup.− 60 IIa-1 Cl.sup.− 19 III-1 Cl.sup.− 21 8 I-1 Cl.sup.− 63 IIa-1 ZnCl.sub.3.sup.− 22 III-1 Cl.sup.− 15 9 I-1 CH.sub.3SO.sub.4.sup.− 50 IIa-1 Cl.sup.− 42 III-1 Cl.sup.− 8 10 I-1 ZnCl.sub.3.sup.− 82 IIa-2 Cl.sup.− 13 III-1 ZnCl.sub.3.sup.− 5 11 I-1 CH.sub.3SO.sub.4.sup.− 71 IIa-2 CH.sub.3SO.sub.4.sup.− 16 III-1 Cl.sup.− 13 12 I-1 CH.sub.3SO.sub.4.sup.− 59 IIa-2 Cl.sup.− 22 III-1 Cl.sup.− 19 13 I-1 CH.sub.3SO.sub.4.sup.− 48 IIa-2 ZnCl.sub.3.sup.− 40 III-1 Cl.sup.− 12 14 I-1 CH.sub.3SO.sub.4.sup.− 87 IIa-1 Cl.sup.− 9 III-3 Cl.sup.− 4 15 I-1 CH.sub.3SO.sub.4.sup.− 75 IIa-1 Cl.sup.− 15 III-3 CH.sub.3SO.sub.4.sup.− 10 16 I-1 CH.sub.3SO.sub.4.sup.− 63 IIa-1 Cl.sup.− 22 III-3 Cl.sup.− 15 17 I-1 CH.sub.3SO.sub.4.sup.− 85 IIa-2 CH.sub.3SO.sub.4.sup.− 9 III-3 Cl.sup.− 6 18 I-1 CH.sub.3SO.sub.4.sup.− 74 IIa-2 Cl.sup.− 16 III-3 Cl.sup.− 10 19 I-1 CH.sub.3SO.sub.4.sup.− 60 IIa-2 Cl.sup.− 24 III-3 Cl.sup.− 16 20 I-1 Cl.sup.− 82 IIa-1 Cl.sup.− 18 — — — 21 I-1 CH.sub.3SO.sub.4.sup.− 73 IIa-1 Cl.sup.− 27 — — — 22 I-1 CH.sub.3SO.sub.4.sup.− 60 IIa-1 CH.sub.3SO.sub.4.sup.− 40 — — — 23 I-1 Cl.sup.− 85 IIa-2 Cl.sup.− 15 — — — 24 I-1 CH.sub.3SO.sub.4.sup.− 76 IIa-2 Cl.sup.− 24 — — — 25 I-1 CH.sub.3SO.sub.4.sup.− 55 IIa-2 ZnCl.sub.3.sup.− 45 — — — 26 I-2 Cl .sup.− 82 IIa-1 Cl.sup.− 13 III-1 Cl.sup.− 5 27 I-2 CH.sub.3CH.sub.2SO.sub.4 .sup.− 71 IIa-1 Cl.sup.− 17 III-1 Cl.sup.− 12 28 I-2 CH.sub.3CH.sub.2SO.sub.4 .sup.− 85 IIa-2 Cl.sup.− 12 III-1 CH.sub.3SO.sub.4.sup.− 3 29 I-2 CH.sub.3CH.sub.2SO.sub.4 .sup.− 75 IIa-2 Cl.sup.− 15 III-1 Cl.sup.− 10 30 I-3 CH.sub.3SO.sub.4.sup.− 80 IIa-2 Cl.sup.− 12 III-1 Cl.sup.− 8 31 I-4 ZnCl.sub.3 .sup.− 75 IIa-2 Cl.sup.− 15 III-1 ZnCl.sub.3.sup.− 10 32 I-2 CH.sub.3CH.sub.2SO.sub.4 .sup.− 82 IIa-1 Cl.sup.− 13 III-3 Cl.sup.− 5 33 I-2 CH.sub.3CH.sub.2SO.sub.4 .sup.− 71 IIa-1 Cl.sup.− 17 III-3 Cl.sup.− 12 34 I-2 CH.sub.3CH.sub.2SO.sub.4 .sup.− 85 IIa-2 Cl.sup.− 12 III-3 Cl.sup.− 3 35 I-3 CH.sub.3SO.sub.4.sup.− 75 IIa-2 Cl.sup.− 15 III-3 Cl.sup.− 10 36 I-4 Cl .sup.− 80 IIa-2 Cl.sup.− 12 III-3 Cl.sup.− 8 37 I-2 CH.sub.3CH.sub.2SO.sub.4 .sup.− 75 IIa-2 Cl.sup.− 15 III-3 Cl.sup.− 10 38 I-2 ZnCl.sub.3 .sup.− 81 IIa-1 Cl.sup.− 19 — — — 39 I-2 CH.sub.3CH.sub.2SO.sub.4 .sup.− 74 IIa-1 Cl.sup.− 26 — — — 40 I-2 CH.sub.3CH.sub.2SO.sub.4 .sup.− 55 IIa-1 Cl.sup.− 45 — — — 41 I-2 CH.sub.3CH.sub.2SO.sub.4 .sup.− 80 IIa-2 ZnCl.sub.3.sup.− 20 — — — 42 I-2 CH.sub.3CH.sub.2SO.sub.4 .sup.− 65 IIa-2 Cl.sup.− 35 — — — 43 I-3 CH.sub.3SO.sub.4.sup.− 60 IIa-1 Cl.sup.− 40 — — — 44 I-4 CH.sub.3CH.sub.2SO.sub.4 .sup.− 57 IIa-1 Cl.sup.− 43 — — — 45 I-1 CH.sub.3SO.sub.4.sup.− 74 IIb-2 Cl.sup.− 17 III-1 Cl.sup.− 9 46 I-1 CH.sub.3SO.sub.4.sup.− 55 IIb-2 Cl.sup.− 25 III-1 Cl.sup.− 20 47 I-1 CH.sub.3SO.sub.4.sup.− 85 IIb-3 CH.sub.3SO.sub.4.sup.− 10 III-1 Cl.sup.− 5 48 I-1 CH.sub.3SO.sub.4.sup.− 70 IIb-3 CH.sub.3SO.sub.4.sup.− 20 III-1 Cl.sup.− 10 49 I-1 ZnCl.sub.3.sup.− 80 IIb-1 Cl.sup.− 15 III-1 Cl.sup.− 5 50 I-1 CH.sub.3SO.sub.4.sup.− 72 IIb-1 Cl.sup.− 18 III-1 Cl.sup.− 10 51 I-1 CH.sub.3SO.sub.4.sup.− 85 IIc-2 ZnCl.sub.3.sup.− 10 III-1 Cl.sup.− 5 52 I-1 Cl.sup.− 75 IIc-2 ZnCl.sub.3.sup.− 15 III-1 Cl.sup.− 10 53 I-1 CH.sub.3SO.sub.4.sup.− 79 IIa-3 Cl.sup.− 13 III-1 Cl.sup.− 8 54 I-1 CH.sub.3SO.sub.4.sup.− 66 IIc-3 ZnCl.sub.3.sup.− 21 III-1 Cl.sup.− 13 55 I-1 CH.sub.3SO.sub.4.sup.− 86 IIa-1 Cl.sup.− 8 III-2 Cl.sup.− 6 56 I-1 ZnCl.sub.3.sup.− 73 IIa-1 Cl.sup.− 17 III-4 Cl.sup.− 10 57 I-1 CH.sub.3SO.sub.4.sup.− 75 IIa-1 Cl.sup.− 15 III-5 Cl.sup.− 10 58 I-1 CH.sub.3SO.sub.4.sup.− 76 IIa-1 CH.sub.3COO.sup.− 14 III-1 CH.sub.3COO.sup.− 10 59 I-1 CH.sub.3SO.sub.4.sup.− 65 IIa-1 Cl.sup.− 15 III-1 Cl.sup.− 20 60 I-1 CH.sub.3SO.sub.4.sup.− 60 IIa-1 Cl.sup.− 15 III-1 Cl.sup.− 25 61 I-1 CH.sub.3SO.sub.4.sup.− 60 IIa-1 Cl.sup.− 10 III-1 Cl.sup.− 30