HIGH WET FAST DISPERSE DYE MIXTURES OF N-[4-(5-FLUORO-2,4-DINITRO-PHENYLAZO)-PHENYL]-AMINE DERIVATIVES AND N-[4-(4-NITRO-PHENYLAZO)-PHENYL]-AMINE DERIVATIVES

Abstract

The present invention is directed to dye mixtures comprising dyes of formula (1) and dyes of formula (2), the process of the production and the use of the dye mixtures.

##STR00001##

Claims

1. A dye mixture comprising at least one dye of formula (1) ##STR00037## wherein independent of each other R.sup.1 is hydrogen, (C.sub.1-C.sub.4)-alkyl or C.sub.1-C.sub.4-alkoxy, R.sup.2 is hydrogen, carboxy, (C.sub.1-C.sub.4)-alkyl, halogen, acylamino, —NHCO-aryl, —NHCO-benzyl) or sulfonylamino, R.sup.3 and R.sup.4 is hydrogen, (C.sub.1-C.sub.4)-alkyl, (CH.sub.2).sub.n-phenyl, CH.sub.2—CH═CH.sub.2, (CH.sub.2).sub.n—OH, (CH.sub.2).sub.n—O—(C.sub.1-C.sub.4)-alkyl, (CH.sub.2).sub.n—O-phenyl, (CH.sub.2).sub.n—O-benzyl, (CH.sub.2).sub.n—O—(CH.sub.2).sub.m—OH, (CH.sub.2).sub.n—O—(CH.sub.2).sub.m—O—(C.sub.1-C.sub.4)-alkyl, (CH.sub.2).sub.n—O—(CH.sub.2).sub.m—O-phenyl, (CH.sub.2).sub.n—O—(CH.sub.2).sub.m—O-benzyl, (CH.sub.2).sub.n—COOH, (CH.sub.2).sub.n—COO—(C.sub.1-C.sub.4)-alkyl, (CH.sub.2).sub.n—COO-phenyl, (CH.sub.2).sub.n—COO-benzyl, (CH.sub.2).sub.n—CN, (CH.sub.2).sub.n—COO(CH.sub.2).sub.m—CO—(C.sub.1-C.sub.4)-alkyl, (CH.sub.2).sub.n—COO(CH.sub.2).sub.m—CO-phenyl, (CH.sub.2).sub.n—COO(CH.sub.2).sub.m—CO-benzyl, (CH.sub.2).sub.n—O—CO—(C.sub.1-C.sub.4)-alkyl, (CH.sub.2).sub.n—O—CO-phenyl, (CH.sub.2).sub.n—O—CO-benzyl, COO—(CH.sub.2).sub.n-2-furfuryl, (CH.sub.2).sub.m—O—(CH.sub.2).sub.n-2-furfuryl, CHR.sup.9—(CH.sub.2).sub.p—(C.sub.1-C.sub.4)-alkyl, CHR.sup.9—(CH.sub.2).sub.p phenyl, CHR.sup.9—CH═CH.sub.2, CHR.sup.9—(CH.sub.2).sub.p—OH, CHR.sup.9—(CH.sub.2).sub.p—O—(C.sub.1-C.sub.4)-alkyl, CHR.sup.9—(CH.sub.2).sub.p—O-phenyl, CHR.sup.9—(CH.sub.2).sub.p—O-benzyl, CHR.sup.9—(CH.sub.2).sub.p—O—(CH.sub.2).sub.m—OH, CHR.sup.9—(CH.sub.2).sub.p—O—(CH.sub.2).sub.m—O—(C.sub.1-C.sub.4)-alkyl, CHR.sup.9—(CH.sub.2).sub.p—O—(CH.sub.2).sub.m—O-phenyl, CHR.sup.9—(CH.sub.2).sub.p—O—(CH.sub.2).sub.m—O-benzyl, CHR.sup.9—(CH.sub.2).sub.p—COOH, CHR.sup.9—(CH.sub.2).sub.p—COO—(C.sub.1-C.sub.4)-alkyl, CHR.sup.9—(CH.sub.2).sub.p—COO-phenyl, CHR.sup.9—(CH.sub.2).sub.p—COO-benzyl, CHR.sup.9—(CH.sub.2).sub.p—CN, CHR.sup.9—(CH.sub.2).sub.p—COO(CH.sub.2).sub.m—CO—(C.sub.1-C.sub.4)-alkyl, CHR.sup.9—(CH.sub.2).sub.p—COO(CH.sub.2).sub.m—CO-phenyl, CHR.sup.9—(CH.sub.2).sub.p—COO(CH.sub.2).sub.m—CO-benzyl, CHR.sup.9—(CH.sub.2).sub.p—O—CO—(C.sub.1-C.sub.4)-alkyl, CHR.sup.9—(CH.sub.2).sub.p—O—CO-phenyl, CHR.sup.9—(CH.sub.2).sub.p—O—CO-benzyl, CHR.sup.9—(CH.sub.2).sub.p-2-furfuryl or CHR.sup.9—(CH.sub.2).sub.p—O—(CH.sub.2).sub.n-2-furfuryl, wherein R.sup.9 is (C.sub.1-C.sub.4)-alkyl or (C.sub.1-C.sub.4)-alkyl substituted by —OH or halogen, n is 1 to 4, m is 1 to 4 and p is 0 to 3, with the proviso that at least one of R.sup.3 and R.sup.4 is not hydrogen, and at least one dye of formula (2) ##STR00038## wherein independent of each other R.sup.5 and R.sup.6 is hydrogen, (C.sub.1-C.sub.4)-alkyl, (CH.sub.2).sub.n-phenyl, CH.sub.2—CH═CH.sub.2, (CH.sub.2).sub.n—OH, (CH.sub.2).sub.n—O—(C.sub.1-C.sub.4)-alkyl, (CH.sub.2).sub.n—O-phenyl, (CH.sub.2).sub.n—O-benzyl, (CH.sub.2).sub.n—O—(CH.sub.2).sub.m—OH, (CH.sub.2).sub.n—O—(CH.sub.2).sub.m—O—(C.sub.1-C.sub.4)-alkyl, (CH.sub.2).sub.n—O—(CH.sub.2).sub.m—O-phenyl, (CH.sub.2).sub.n—O—(CH.sub.2).sub.m—O-benzyl, (CH.sub.2).sub.n—COOH, (CH.sub.2).sub.n—COO—(C.sub.1-C.sub.4)-alkyl, (CH.sub.2).sub.n—COO-phenyl, (CH.sub.2).sub.n—COO-benzyl, (CH.sub.2).sub.n—CN, (CH.sub.2).sub.n—COO(CH.sub.2).sub.m—CO—(C.sub.1-C.sub.4)-alkyl, (CH.sub.2).sub.n—COO(CH.sub.2).sub.m—CO-phenyl, (CH.sub.2).sub.n—COO(CH.sub.2).sub.m—CO-benzyl, (CH.sub.2).sub.n—O—CO—(C.sub.1-C.sub.4)-alkyl, (CH.sub.2).sub.n—O—CO-phenyl, (CH.sub.2).sub.n—O—CO-benzyl, COO—(CH.sub.2).sub.n-2-furfuryl or (CH.sub.2).sub.m—O—(CH.sub.2).sub.n-2-furfuryl, wherein n is 1 to 4 and m is 1 to 4, with the proviso that at least one of R.sup.5 and R.sup.6 is not hydrogen, R.sup.10 is hydrogen, (C.sub.1-C.sub.4)-alkyl or (C.sub.1-C.sub.4)-alkoxy, R.sup.11 is hydrogen, carboxy, (C.sub.1-C.sub.4)-alkyl, halogen, acylamino, —NHCO-aryl, —NHCO-benzyl) or sulfonylamino, X.sup.5 and X.sup.6 is hydrogen, halogen, nitro or cyano, with the proviso that at least one of X.sup.5 and X.sup.6 is not hydrogen.

2. The dye mixture according to claim 1, wherein independent of each other in the at least one dye of formula (1) R.sup.1 is hydrogen, methyl or methoxy, R.sup.2 is hydrogen, hydroxy, COOH, COO—(C.sub.1-C.sub.2)-alkyl, (C.sub.1-C.sub.2)-alkyl, —NHCO—(C.sub.1-C.sub.2)-alkyl, —NHCO-aryl, —NHCO-benzyl or —NHSO.sub.2—(C.sub.1-C.sub.2)-alkyl, R.sup.3 and R.sup.4 is hydrogen, (C.sub.1-C.sub.2)-alkyl, (CH.sub.2)-phenyl, CH.sub.2—CH═CH.sub.2, (CH.sub.2).sub.2—O—(C.sub.1-C.sub.2)-alkyl, (CH.sub.2).sub.2—O-phenyl, (CH.sub.2).sub.2—O-benzyl, (CH.sub.2).sub.2—O—(CH.sub.2).sub.m—O—(C.sub.1-C.sub.2)-alkyl, (CH.sub.2).sub.2—O—(CH.sub.2).sub.m—O-phenyl, (CH.sub.2).sub.2—O—(CH.sub.2).sub.m—O-benzyl, (CH.sub.2).sub.n—COO—(C.sub.1-C.sub.2)-alkyl, (CH.sub.2).sub.n—COO-phenyl, (CH.sub.2).sub.n—COO-benzyl, (CH.sub.2).sub.n—CN, (CH.sub.2).sub.n—COO(CH.sub.2).sub.m—CO—(C.sub.1-C.sub.2)-alkyl, (CH.sub.2).sub.n—COO(CH.sub.2).sub.m—CO-phenyl, (CH.sub.2).sub.n—COO(CH.sub.2).sub.m—CO-benzyl, (CH.sub.2).sub.n—O—CO—(C.sub.1-C.sub.2)-alkyl, (CH.sub.2).sub.n—O—CO-phenyl, (CH.sub.2).sub.n—O—CO-benzyl, COO—(CH.sub.2).sub.n-2-furfuryl, (CH.sub.2).sub.m—O—(CH.sub.2).sub.n-2-furfuryl, CHR.sup.9—CH═CH.sub.2, CHR.sup.9—(CH.sub.2).sub.p—O—(C.sub.1-C.sub.2)-alkyl, CHR.sup.9—(CH.sub.2).sub.p—O-phenyl, CHR.sup.9—(CH.sub.2).sub.p—O-benzyl, CHR.sup.9—(CH.sub.2).sub.p—O—(CH.sub.2).sub.m—O—(C.sub.1-C.sub.2)-alkyl, CHR.sup.9—(CH.sub.2).sub.p—O—(CH.sub.2).sub.m—O-phenyl, CHR.sup.9—(CH.sub.2).sub.p—O—(CH.sub.2).sub.m—O-benzyl, CHR.sup.9—(CH.sub.2).sub.p—COO—(C.sub.1-C.sub.2)-alkyl, CHR.sup.9—(CH.sub.2).sub.p—COO-phenyl, CHR.sup.9—(CH.sub.2).sub.p—COO-benzyl, CHR.sup.9—(CH.sub.2).sub.p—CN, CHR.sup.9—(CH.sub.2).sub.p—COO(CH.sub.2).sub.m—CO—(C.sub.1-C.sub.2)-alkyl, CHR.sup.9—(CH.sub.2).sub.p—COO(CH.sub.2).sub.m—CO-phenyl, CHR.sup.9—(CH.sub.2).sub.p—COO(CH.sub.2).sub.m—CO-benzyl, CHR.sup.9—(CH.sub.2).sub.p—O—CO—(C.sub.1-C.sub.2)-alkyl, CHR.sup.9—(CH.sub.2).sub.p—O—CO-phenyl or CHR.sup.9—(CH.sub.2).sub.p—O—CO-benzyl, wherein R.sup.9 is (C.sub.1-C.sub.4)-alkyl or (C.sub.1-C.sub.4)-alkyl substituted by —OH or halogen, n is 1 or 2, m is 1 or 2 and p is 0 or 1, with the proviso that at least one of R.sup.3 and R.sup.4 is not hydrogen.

3. The dye mixture according to claim 1, wherein independent of each other in the at least one dye of formula (1) R.sup.1 is hydrogen or methoxy, R.sup.2 is hydrogen, methyl or —NHCO—(C.sub.1-C.sub.2)-alkyl, R.sup.3 and R.sup.4 is hydrogen, (C.sub.1-C.sub.2)-alkyl, (CH.sub.2)-phenyl, CH.sub.2—CH═CH.sub.2, (CH.sub.2).sub.2—O—(C.sub.1-C.sub.2)-alkyl, (CH.sub.2).sub.2—O-phenyl, (CH.sub.2).sub.2—O-benzyl, (CH.sub.2).sub.2—O—(CH.sub.2).sub.m—O—(C.sub.1-C.sub.2)-alkyl, (CH.sub.2).sub.n—COO—(C.sub.1-C.sub.2)-alkyl, (CH.sub.2).sub.n—COO-phenyl, (CH.sub.2).sub.n—COO-benzyl, (CH.sub.2).sub.n—CN, (CH.sub.2).sub.n—COO(CH.sub.2).sub.m—CO—(C.sub.1-C.sub.2)-alkyl, (CH.sub.2).sub.n—COO(CH.sub.2).sub.m—CO-phenyl, (CH.sub.2).sub.n—COO(CH.sub.2).sub.m—CO-benzyl, (CH.sub.2).sub.n—O—CO—(C.sub.1-C.sub.2)-alkyl, (CH.sub.2).sub.n—O—CO-phenyl, COO—(CH.sub.2).sub.n-2-furfuryl or (CH.sub.2).sub.m—O—(CH.sub.2).sub.n-2-furfuryl, CHR.sup.9—(CH.sub.2).sub.p—COO—(C.sub.1-C.sub.2)-alkyl, wherein R.sup.9 is (C.sub.1-C.sub.4)-alkyl, n is 1 or 2, m is 1 or 2 and with the proviso that at least one of R.sup.3 and R.sup.4 is not hydrogen.

4. The dye mixture according to claim 1, wherein the at least one dye of formula (1) is a dye of formula (1a) ##STR00039## wherein independent from each other R.sup.3 and R.sup.4 is hydrogen, (C.sub.1-C.sub.2)-alkyl, (CH.sub.2)-phenyl, CH.sub.2—CH═CH.sub.2, (CH.sub.2).sub.2—O—(C.sub.1-C.sub.2)-alkyl, (CH.sub.2).sub.2—O-phenyl, (CH.sub.2).sub.2—O-benzyl, (CH.sub.2).sub.2—O—(CH.sub.2).sub.m—O—(C.sub.1-C.sub.2)-alkyl, (CH.sub.2).sub.n—COO—(C.sub.1-C.sub.2)-alkyl, (CH.sub.2).sub.n—COO-phenyl, (CH.sub.2).sub.n—COO-benzyl, (CH.sub.2).sub.n—CN, (CH.sub.2).sub.n—COO(CH.sub.2).sub.m—CO—(C.sub.1-C.sub.2)-alkyl, (CH.sub.2).sub.n—COO(CH.sub.2).sub.m—CO-phenyl, (CH.sub.2).sub.n—COO(CH.sub.2).sub.m—CO-benzyl, (CH.sub.2).sub.n—O—CO—(C.sub.1-C.sub.2)-alkyl, (CH.sub.2).sub.n—O—CO-phenyl, COO—(CH.sub.2).sub.n-2-furfuryl, (CH.sub.2).sub.m—O—(CH.sub.2).sub.n-2-furfuryl or CHR.sup.9—(CH.sub.2).sub.p—COO—(C.sub.1-C.sub.2)-alkyl, wherein R.sup.9 is (C.sub.1-C.sub.4)-alkyl, n is 1 or 2, m is 1 or 2 and p is 0 or 1, with the proviso that at least one of R.sup.3 and R.sup.4 is not hydrogen and R.sup.7 and R.sup.8 is ethyl or methyl.

5. The dye mixture according to claim 1, wherein the at least one dye of formula (1) is a dye of formula (1b) ##STR00040## wherein independent from each other R.sup.3 and R.sup.4 is hydrogen, (C.sub.1-C.sub.2)-alkyl, (CH.sub.2)-phenyl, CH.sub.2—CH═CH.sub.2, (CH.sub.2).sub.2—O—(C.sub.1-C.sub.2)-alkyl, (CH.sub.2).sub.2—O-phenyl, (CH.sub.2).sub.2—O-benzyl, (CH.sub.2).sub.2—O—(CH.sub.2).sub.m—O—(C.sub.1-C.sub.2)-alkyl, (CH.sub.2).sub.n—COO—(C.sub.1-C.sub.2)-alkyl, (CH.sub.2).sub.n—COO-phenyl, (CH.sub.2).sub.n—COO-benzyl, (CH.sub.2).sub.n—CN, (CH.sub.2).sub.n—COO(CH.sub.2).sub.m—CO—(C.sub.1-C.sub.2)-alkyl, (CH.sub.2).sub.n—COO(CH.sub.2).sub.m—CO-phenyl, (CH.sub.2).sub.n—COO(CH.sub.2).sub.m—CO-benzyl, (CH.sub.2).sub.n—O—CO—(C.sub.1-C.sub.2)-alkyl, (CH.sub.2).sub.n—O—CO-phenyl, COO—(CH.sub.2).sub.n-2-furfuryl, (CH.sub.2).sub.m—O—(CH.sub.2).sub.n-2-furfuryl or CHR.sup.9—(CH.sub.2).sub.p—COO—(C.sub.1-C.sub.2)-alkyl, wherein R.sup.9 is (C.sub.1-C.sub.4)-alkyl, n is 1 or 2 and m is 1 or 2, p is 0 or 1, with the proviso that at least one of R.sup.3 and R.sup.4 is not hydrogen and R.sup.7 is ethyl or methyl.

6. The dye mixture according to claim 1, wherein the at least one dye of formula (1) is a dye of formula (1c) ##STR00041## wherein independent from each other R.sup.3 and R.sup.4 is hydrogen, (C.sub.1-C.sub.2)-alkyl, (CH.sub.2)-phenyl, CH.sub.2—CH═CH.sub.2, (CH.sub.2).sub.2—O—(C.sub.1-C.sub.2)-alkyl, (CH.sub.2).sub.2—O-phenyl, (CH.sub.2).sub.2—O-benzyl, (CH.sub.2).sub.2—O—(CH.sub.2).sub.m—O—(C.sub.1-C.sub.2)-alkyl, (CH.sub.2).sub.n—COO—(C.sub.1-C.sub.2)-alkyl, (CH.sub.2).sub.n—COO-phenyl, (CH.sub.2).sub.n—COO-benzyl, (CH.sub.2).sub.n—CN, (CH.sub.2).sub.n—COO(CH.sub.2).sub.m—CO—(C.sub.1-C.sub.2)-alkyl, (CH.sub.2).sub.n—COO(CH.sub.2).sub.m—CO-phenyl, (CH.sub.2).sub.n—COO(CH.sub.2).sub.m—CO-benzyl, (CH.sub.2).sub.n—O—CO—(C.sub.1-C.sub.2)-alkyl, (CH.sub.2).sub.n—O—CO-phenyl, COO—(CH.sub.2).sub.n-2-furfuryl, (CH.sub.2).sub.m—O—(CH.sub.2).sub.n-2-furfuryl or CHR.sup.9—(CH.sub.2).sub.p—COO—(C.sub.1-C.sub.2)-alkyl, wherein R.sup.9 is (C.sub.1-C.sub.4)-alkyl, n is 1 or 2, m is 1 or 2 and p is 0 or 1, with the proviso that at least one of R.sup.3 and R.sup.4 is not hydrogen.

7. The dye mixture according to claim 1, wherein the at least one dye of formula (1) is selected from the group consisting of ##STR00042## ##STR00043## ##STR00044## ##STR00045## ##STR00046## ##STR00047## ##STR00048## ##STR00049## ##STR00050## ##STR00051## ##STR00052## ##STR00053## ##STR00054##

8. The dye mixture according to claim 1, wherein independent of each other in the at least one dye of formula (2) R.sup.5 and R.sup.6 is hydrogen, (C.sub.1-C.sub.2)-alkyl, (CH.sub.2)-phenyl, CH.sub.2—CH═CH.sub.2, (CH.sub.2).sub.2—O—(C.sub.1-C.sub.2)-alkyl, (CH.sub.2).sub.2—O-phenyl, (CH.sub.2).sub.2—O-benzyl, (CH.sub.2).sub.2—O—(CH.sub.2).sub.m—O—(C.sub.1-C.sub.2)-alkyl, (CH.sub.2).sub.2—O—(CH.sub.2).sub.m—O-phenyl, (CH.sub.2).sub.2—O—(CH.sub.2).sub.m—O-benzyl, (CH.sub.2).sub.n—COO—(C.sub.1-C.sub.2)-alkyl, (CH.sub.2).sub.n—COO-phenyl, (CH.sub.2).sub.n—COO-benzyl, (CH.sub.2).sub.n—CN, (CH.sub.2).sub.n—COO(CH.sub.2).sub.m—CO—(C.sub.1-C.sub.2)-alkyl, (CH.sub.2).sub.n—COO(CH.sub.2).sub.m—CO-phenyl, (CH.sub.2).sub.n—COO(CH.sub.2).sub.m—CO-benzyl, (CH.sub.2).sub.n—O—CO—(C.sub.1-C.sub.2)-alkyl, (CH.sub.2).sub.n—O—CO-phenyl, (CH.sub.2).sub.n—O—CO-benzyl, COO—(CH.sub.2).sub.n-2-furfuryl or (CH.sub.2).sub.m—O—(CH.sub.2).sub.n-2-furfuryl, wherein n is 1 or 2 and m is 1 or 2, with the proviso that at least one of R.sup.5 and R.sup.6 is not hydrogen, R.sup.10 is hydrogen, methyl or methoxy, R.sup.11 is hydrogen, hydroxy, COOH, COO—(C.sub.1-C.sub.2)-alkyl, (C.sub.1-C.sub.2)-alkyl, —NHCO—(C.sub.1-C.sub.2)-alkyl, —NHCO-aryl, —NHCO-benzyl or —NHSO.sub.2—(C.sub.1-C.sub.2)-alkyl and X.sup.5 and X.sup.6 is hydrogen, chloro, bromo, nitro or cyano, with the proviso that at least one of X.sup.5 and X.sup.6 is not hydrogen.

9. The dye mixture according to claim 1, wherein independent of each other in the at least one dye of formula (2) R.sup.5 and R.sup.6 is hydrogen, (C.sub.1-C.sub.2)-alkyl, (CH.sub.2)-phenyl, CH.sub.2—CH═CH.sub.2, (CH.sub.2).sub.2—O—(C.sub.1-C.sub.2)-alkyl, (CH.sub.2).sub.2—O-phenyl, (CH.sub.2).sub.2—O-benzyl, (CH.sub.2).sub.2—O—(CH.sub.2).sub.m—O—(C.sub.1-C.sub.2)-alkyl, (CH.sub.2).sub.n—COO—(C.sub.1-C.sub.2)-alkyl, (CH.sub.2).sub.n—COO-phenyl, (CH.sub.2).sub.n—COO-benzyl, (CH.sub.2).sub.n—CN, (CH.sub.2).sub.n—COO(CH.sub.2).sub.m—CO—(C.sub.1-C.sub.2)-alkyl, (CH.sub.2).sub.n—COO(CH.sub.2).sub.m—CO-phenyl, (CH.sub.2).sub.n—COO(CH.sub.2).sub.m—CO-benzyl, (CH.sub.2).sub.n—O—CO—(C.sub.1-C.sub.2)-alkyl, (CH.sub.2).sub.n—O—CO-phenyl, COO—(CH.sub.2).sub.n-2-furfuryl or (CH.sub.2).sub.m—O—(CH.sub.2).sub.n-2-furfuryl, wherein n is 1 or 2 and m is 1 or 2, with the proviso that at least one of R.sup.5 and R.sup.6 is not hydrogen, R.sup.10 is hydrogen or methoxy, R.sup.11 is hydrogen, methyl or —NHCO—(C.sub.1-C.sub.2)-alkyl and X.sup.5 and X.sup.6 is hydrogen, bromo, chloro, nitro or cyano, with the proviso that at least one of X.sup.5 and X.sup.6 is not hydrogen.

10. The dye mixture according to claim 1, wherein the at least one dye of formula (2) is a dye of formula (2a) ##STR00055## wherein independent from each other R.sup.5 and R.sup.6 are hydrogen, (C.sub.1-C.sub.2)-alkyl, (CH.sub.2)-phenyl, CH.sub.2—CH═CH.sub.2, (CH.sub.2).sub.2—O—(C.sub.1-C.sub.2)-alkyl, (CH.sub.2).sub.2—O-phenyl, (CH.sub.2).sub.2—O-benzyl, (CH.sub.2).sub.2—O—(CH.sub.2).sub.m—O—(C.sub.1-C.sub.2)-alkyl, (CH.sub.2).sub.n—COO—(C.sub.1-C.sub.2)-alkyl, (CH.sub.2).sub.n—COO-phenyl, (CH.sub.2).sub.n—COO-benzyl, (CH.sub.2).sub.n—CN, (CH.sub.2).sub.n—COO(CH.sub.2).sub.m—CO—(C.sub.1-C.sub.2)-alkyl, (CH.sub.2).sub.n—COO(CH.sub.2).sub.m—CO-phenyl, (CH.sub.2).sub.n—COO(CH.sub.2).sub.m—CO-benzyl, (CH.sub.2).sub.n—O—CO—(C.sub.1-C.sub.2)-alkyl, (CH.sub.2).sub.n—O—CO-phenyl, COO—(CH.sub.2).sub.n-2-furfuryl or (CH.sub.2).sub.m—O—(CH.sub.2).sub.n-2-furfuryl, wherein n is 1 or 2 and m is 1 or 2, with the proviso that at least one of R.sup.5 and R.sup.6 is not hydrogen, R.sup.7 and R.sup.8 is ethyl or methyl, X.sup.5 is hydrogen, bromo, chloro, nitro or cyano and X.sup.6 is nitro or cyano, with the proviso that X.sup.5 and X.sup.6 are not both nitro.

11. The dye mixture according to claim 1, wherein the at least one dye of formula (2) is a dye of formula (2b) ##STR00056## R.sup.5 and R.sup.6 are hydrogen, (C.sub.1-C.sub.2)-alkyl, (CH.sub.2)-phenyl, CH.sub.2—CH═CH.sub.2, (CH.sub.2).sub.2—O—(C.sub.1-C.sub.2)-alkyl, (CH.sub.2).sub.2—O-phenyl, (CH.sub.2).sub.2—O-benzyl, (CH.sub.2).sub.2—O—(CH.sub.2).sub.m—O—(C.sub.1-C.sub.2)-alkyl, (CH.sub.2).sub.n—COO—(C.sub.1-C.sub.2)-alkyl, (CH.sub.2).sub.n—COO-phenyl, (CH.sub.2).sub.n—COO-benzyl, (CH.sub.2).sub.n—CN, (CH.sub.2).sub.n—COO(CH.sub.2).sub.m—CO—(C.sub.1-C.sub.2)-alkyl, (CH.sub.2).sub.n—COO(CH.sub.2).sub.m—CO-phenyl, (CH.sub.2).sub.n—COO(CH.sub.2).sub.m—CO-benzyl, (CH.sub.2).sub.n—O—CO—(C.sub.1-C.sub.2)-alkyl, (CH.sub.2).sub.n—O—CO-phenyl, COO—(CH.sub.2).sub.n-2-furfuryl or (CH.sub.2).sub.m—O—(CH.sub.2).sub.n-2-furfuryl, wherein n is 1 or 2 and m is 1 or 2, with the proviso that at least one of R.sup.5 and R.sup.6 is not hydrogen, R.sup.7 is ethyl or methyl and X.sup.5 is bromo, chloro, nitro or cyano and X.sup.6 is nitro or cyano, with the proviso that X.sup.5 and X.sup.6 are not both nitro.

12. The dye mixture according to claim 1, wherein the at least one dye of formula (2) is a dye of formula (2c) ##STR00057## wherein independent from each other R.sup.2 is hydrogen or —NHCO—(C.sub.1-C.sub.2)-alkyl, R.sup.5 and R.sup.6 is hydrogen, (C.sub.1-C.sub.2)-alkyl, (CH.sub.2)-phenyl, CH.sub.2—CH═CH.sub.2, (CH.sub.2).sub.2—O—(C.sub.1-C.sub.2)-alkyl, (CH.sub.2).sub.2—O-phenyl, (CH.sub.2).sub.2—O-benzyl, (CH.sub.2).sub.2—O—(CH.sub.2).sub.m—O—(C.sub.1-C.sub.2)-alkyl, (CH.sub.2).sub.n—COO—(C.sub.1-C.sub.2)-alkyl, (CH.sub.2).sub.n—COO-phenyl, (CH.sub.2).sub.n—COO-benzyl, (CH.sub.2).sub.n—CN, (CH.sub.2).sub.n—COO(CH.sub.2).sub.m—CO—(C.sub.1-C.sub.2)-alkyl, (CH.sub.2).sub.n—COO(CH.sub.2).sub.m—CO-phenyl, (CH.sub.2).sub.n—COO(CH.sub.2).sub.m—CO-benzyl, (CH.sub.2).sub.n—O—CO—(C.sub.1-C.sub.2)-alkyl, (CH.sub.2).sub.n—O—CO-phenyl, COO—(CH.sub.2).sub.n-2-furfuryl or (CH.sub.2).sub.m—O—(CH.sub.2).sub.n-2-furfuryl, wherein n is 1 or 2 and m is 1 or 2 with the proviso that at least one of R.sup.5 and R.sup.6 is not hydrogen, X.sup.5 and X.sup.6 is bromo or chloro.

13. The dye mixture according to claim 1, wherein the at least one dye of formula (2) is a dye of formula (2d) ##STR00058## wherein independent from each other R.sup.5 and R.sup.6 is hydrogen, (C.sub.1-C.sub.2)-alkyl, (CH.sub.2)-phenyl, CH.sub.2—CH═CH.sub.2, (CH.sub.2).sub.2—O—(C.sub.1-C.sub.2)-alkyl, (CH.sub.2).sub.2—O-phenyl, (CH.sub.2).sub.2—O-benzyl, (CH.sub.2).sub.2—O—(CH.sub.2).sub.m—O—(C.sub.1-C.sub.2)-alkyl, (CH.sub.2).sub.n—COO—(C.sub.1-C.sub.2)-alkyl, (CH.sub.2).sub.n—COO-phenyl, (CH.sub.2).sub.n—COO-benzyl, (CH.sub.2).sub.n—CN, (CH.sub.2).sub.n—COO(CH.sub.2).sub.m—CO—(C.sub.1-C.sub.2)-alkyl, (CH.sub.2).sub.n—COO(CH.sub.2).sub.m—CO-phenyl, (CH.sub.2).sub.n—COO(CH.sub.2).sub.m—CO-benzyl, (CH.sub.2).sub.n—O—CO—(C.sub.1-C.sub.2)-alkyl, (CH.sub.2).sub.n—O—CO-phenyl, COO—(CH.sub.2).sub.n-2-furfuryl or (CH.sub.2).sub.m—O—(CH.sub.2).sub.n-2-furfuryl, wherein n is 1 or 2 and m is 1 or 2 with the proviso that at least one of R.sup.5 and R.sup.6 is not hydrogen, R.sup.7 is ethyl or methyl and X.sup.6 is chloro, bromo, nitro or cyano.

14. The dye mixture according to claim 1, wherein the at least one dye of formula (2) is selected from the group consisting of ##STR00059## ##STR00060## ##STR00061## ##STR00062## ##STR00063## ##STR00064## ##STR00065## ##STR00066##

Description

EXAMPLES

Example 1

[0108] a) 55 parts of a dye having formula (1-14) were mixed with 45 parts of a dye of the formula (2-4). The resulting dye mixture of the invention was mixed intensively with 100 parts of a lignin sulfonate dispersing agent (Reax 85A) and 300 parts of water. The pH of the mixture is adjusted with diluted Sulfuric acid to 5, 5+/−0, 2 and the milled in a glass bead mill (0.4-0.7 mm glass beads) for 4-6 hours to a size magnitude of 0.3-5 micrometres. The milled dye mixture slurry was filtrated from the glass beads and spray dried in a lab spray dryer (Buchi) at 120° C. inlet and 60-70° C. outlet temperature. [0109] b) 1 g of the dye mixture obtained as per a) are dispersed in 100 ml of water at 40-50° C. A dyebath is prepared from 11.5 ml of this aqueous dispersion, 57.5 ml of deionized water and 1.2 ml of buffering solution (pH 4.5) and entered with a 5 g piece of polyester. The dyebath is heated to 130° C. and maintained at 130° C. for 45 minutes in a Werner Mathis high temperature dyeing machine. After rinsing with water and reduction clearing, the polyester material has a gives blue/navy dyeing with a good build up to deep shades, good light- and very good wet-fastness.

Example 2

[0110] 30 parts dye of formula (1-33) were mixed with 30 parts of a dye of formula (1-31) and with parts of a dye powder of the formula (2-23).

[0111] The resulting dye mixture of the invention was formulated using dispersing agent and dried via spray drying according to Example 1a) and gives blue/navy dyeing's on polyester or polyester blends under the dyeing conditions according to 1b) with a good light- and very good wet-fastness.

Example 3

[0112] 54 parts dye of formula (1-1) were mixed with 22 parts of a dye of formula (2-24) and mixed with 24 parts of a dye powder of the formula (2-21)

[0113] The resulting dye mixture of the invention was formulated using dispersing agent and dried via spray drying according to Example 1a) and gives blue/navy dyeing's on polyester or polyester blends under the dyeing conditions according to 1b) with a good light- and very good wet-fastness.

Example 4

[0114] 38 parts dye of formula (1-7) were mixed with 53 parts of a dye of formula (2-1) and 9 parts of a dye of formula (2-28).

[0115] The resulting dye mixture of the invention was formulated using dispersing agent and dried via spray drying according to Example 1a) and gives blue/navy dyeing's on polyester or polyester blends under the dyeing conditions according to 1b) with good light- and very good wet-fastness.

[0116] All examples of the following tables are prepared as formulations as explained above.

TABLE-US-00001 Dye of 2.sup.nd Dye of Dye of 2.sup.nd Dye of formula formula formula formula Ratio Shade on Example (1) (1) (2) (2) (1):(1):(2):(2) Polyester 5 (1-8) — (2-1)  — 85:—:15:— Blue 6  (1-11) — (2-1)  — 28:—:72:— Blue 7 (1-1) — (2-24) — 75:—:25:— Blue 8 (1-5) — (2-24) — 15:—:85:— Blue 9 (1-7) — (2-41) — 50:—:50:— Blue 10 (1-3) — (2-35) — 57:—:43:— Blue 11  (1-19) — (2-37) — 34:—:66:— Blue 12  (1-12) — (2-36) — 90:—:10:— Blue 13 (1-7) — (2-35) — 40:—:60:— Blue 14  (1-11) — (2-36) — 73:—:27:— Blue 15  (1-11) — (2-15) — 15:—:85:— Blue 16 (1-7) — (2-36) — 55:—:45:— Blue 17 (1-7) — (2-40) — 74:—:26:— Blue 18  (1-20) — (2-41) — 25:—:75:— Blue 19  (1-35) — (2-23) — 44:—:56:— Blue 20  (1-14) — (2-2)  — 87:—:13:— Blue 21  (1-22) — (2-35) — 60:—:40:— Blue 22 (1-8) (1-11) (2-29) — 50:40:10:— Navy 23 (1-3) — (2-24) (2-28) 60:—:22:18 Red. Navy 24 (1-3) — (2-15) (2-30) 53:—:31:16 Red. Navy 25  (1-16) — (2-1)  (2-32) 53:—:42:5 Red. Navy 26 (1-8) — (2-1)  (2-31) 51:—:41:8 Red. Navy 27  (1-11) — (2-2)  (2-33) 36:—:55:9 Red. Navy 28 (1-7) (1-11) (2-1)  (2-29) 28:28:34:10 Red. Navy 29 (1-3) — (2-29) — 76:—:24:— Bl. Violet 30  (1-24) — (2-28) — 66:—:34:— Violet 31  (1-33) — (2-32) — 83:—:17:— Red. Navy 32  (1-27) — (2-33) — 74:—:26:— Violet 33  (1-29) — (2-31) — 69:—:31:— Violet 34  (1-11) — (2-42) — 60:—:40:— Violet 35 (1-7) — (2-42) — 50:—:50:— Violet 36 (1-3) — (2-43) — 57:—:43:— Black 37 (1-8) (1-11) (2-44) — 20:40:40:— Black 38 (1-3) — (2-15) (2-43) 40:—:31:29 Black 39 (1-8) — (2-1)  (2-45) 36:—:29:35 Black 40  (1-11) — (2-1)  (2-46) 35:—:31:34 Black 41 (1-7) (1-11) (2-1)  (2-44) 28:28:14:30 Black 42 (1-7) (2-1)  (2-28) (2-44) 39:25:12:24 Black 43  (1-11) (2-1)  (2-28) (2-46) 35:30:9:26 Black Dye of 2.sup.nd Dye of Dye of 2.sup.nd Dye of Dye of Dye of Dye of formula formula formula formula formula formula formula Ratio Shade on Example (1) (1) (2) (2) (3) (4) (5) (1):(1):(2):(2):(3):(4):(5) Polyester 44 (1-16) — (2-2) — (3-1) (4-1) (5-2) 40:—:25:—:12:12:11 Black 45 (1-20) —  (2-11) — (3-3) (4-1) (5-1) 14:—:51:—:9:12:14 Black 46 (1-24) — (2-3) — (3-4) (4-2) (5-1) 59:—:18:—:7:8:8 Black 47 (1-31) —  (2-18) — (3-2) (4-1) (5-1) 38:—:36:—:6:11:9 Black 48 (1-33) —  (2-22) — (3-1) (4-2) (5-2) 45:—:20:—:15:8:12 Black 49 (1-7)  — (2-1) (2-28) (3-1) — (5-1) 38:—:26:12:11:—:13 Black 50 (1-11) — (2-1) (2-28) (3-1) — (5-1) 38:—:26:12:12:—:12 Black 51 (1-7)  (1-11) (2-1) (2-28) (3-1) — (5-1) 25:23:22:9:13:—:8 Black 52 (1-7)  — (2-2) — (3-1) — (5-1) 56:—:18:—:17:—:9 Black 53 (1-11) — (2-2) — (3-3) — (5-1) 13:—:53:—:26:—:8 Black 54 (1-29) (1-49) (2-1) — (3-2) — (5-1) 38:15:16:—:18:—:13 Black 55 (1-7)  —  (2-46) — (3-1) — (5-1) 52:—:15:—:21:—:12 Black 56 (1-11) —  (2-44) — — — (5-1) 62:—:25:—:—:—:13 Black 57 (1-7)  —  (2-43) — (3-1) — — 54:—:35:—:11:—:— Black

[0117] When the dye mixture of the present invention is used in dyeing, the dye mixture is dispersed in an aqueous medium by means of a dispersing agent and wetting agent in the usual way to prepare a dye bath for dyeing or a printing of hydrophobic textile-fibres.

[0118] And also the use of a dye mixture as described above for dying fibres, as well as blends of such fibres forms an aspect of the present invention.

[0119] The synthetic textile material may preferably be selected from aromatic polyester, especially polyethylene terephthalate, polyamide, especially polyhexamethylene adipamide, secondary cellulose acetate, cellulose triacetate, and natural textile materials, especially cellulosic materials and wool. An especially preferred textile material is an aromatic polyester or fibre blend thereof with fibres of any of the above mentioned textile materials. Especially preferred fibre blends include those of polyester-cellulose, such as polyester-cotton, and polyester-wool. The textile materials or blends thereof may be in the form of filaments, loose fibres, yarn or woven or knitted fabrics.

[0120] Particularly, among polyester fibres, not only ordinary polyester fibres (regular denier fibres) but also microfibres (fine denier fibres, which are less than 0.6 denier) may be used as fibres which can successfully be dyed with the dye mixture of the present invention.

[0121] In general all kinds of fibres can be dyed and therefore fibre and blends containing such fibre selected from the group consisting of synthetic fibre materials, nylon materials, nylon-6, nylon-6.6 and aramid fibres, vegetable fibres, seed fibres, cotton, organic cotton, kapok, coir from coconut husk; bast fibres, flax, hemp, jute, kenaf, ramie, rattan; leaf fibres, sisal, henequen, banana; stalk fibres, bamboo; fibres from animals, wool, organic wool, silk, cashmere wool, alpaca fibre, mohair, Angora fibre as well as fur and leather materials; manufactured, regenerated and recycled fibres, cellulosic fibres; paper fibres, cellulosic regenerated fibres, viscose rayon fibres, acetate and triacetate fibres, and Lyocell fibres comprising a dye mixture as described above either in chemically and/or physically bound form forms/form another aspect of the present invention.

[0122] Typical examples of dispersing agent are lignosulphonates, naphthalene sulphonic acid/formaldehyde condensates and phenol/cresol/sulphanilic acid/formaldehyde condensates, typical examples of wetting agent are alkyl aryl ethoxylates which may be sulphonated or phosphated and typical example of other ingredients which may be present are inorganic salts, de-dusting agents such as mineral oil or nonanol, organic liquids and buffers. Dispersing agents may be present at from 30 to 500% based on the weight of the dye mixture. Dedusting agents may be used at from 0 to 5% based on the weight of the dye mixture.

[0123] A process for dyeing or printing carboxamido- and/or hydroxyl-containing material, comprising contacting the carboxamido- and/or hydroxyl-containing material with a dye mixture as described above and/or an aqueous solution as described above forms yet another aspect of the present invention.

[0124] For example, in the case of dyeing polyester fibres and fibre mixture products such as blended yarn fabrics of union cloth product comprising polyester fibres can be dyed with good colour fastness by common dyeing methods, such as a high temperature dyeing method, a carrier dyeing method and a thermosol dyeing method. In some cases, the addition of an acid substance to the dye bath may result in even more successful dyeing.

[0125] Suitable process conditions may be selected from the following [0126] (i) exhaust dyeing at a pH of from 4 to 8.5, at a temperature of from 125 to 140° C. for from to 120 minutes and under a pressure of from 1 to 2 bar, a sequestrant optionally being added; [0127] (ii) continuous dyeing at a pH of from 4 to 8.5, at a temperature of from 190 to 225° C. for from 15 seconds to 5 minutes, a migration inhibitor optionally being added; [0128] (iii) direct printing at a pH of from 4 to 6.5, at a temperature of from 160 to 185° C. for from 4 to 15 minutes for high temperature steaming, or at a temperature of from 190 to 225° C. for from 15 seconds to 5 minutes for bake fixation with dry heat or at a temperature of from 120 to 140° C. and 1 to 2 bar for from 10 to 45 minutes for pressure steaming, wetting agents and thickeners (such as alginates) of from 5 to 100% by weight of the dye optionally being added; [0129] (iv) discharge printing (by padding the dye on to the textile material, drying and overprinting) at a pH of from 4 to 6.5, migration inhibitors and thickeners optionally being added; [0130] (v) carrier dyeing at a pH of from 4 to 7.5, at a temperature of from 95 to 100° C. using a carrier such as methylnaphthalene, diphenylamine or 2-phenylphenol, sequestrants optionally being added; and [0131] (vi) atmospheric dyeing of acetate, triacetate and nylon at a pH of from 4 to 7.5, at a temperature of about 85° C. for acetate or at a temperature of about 90° C. for triacetate and nylon for from 15 to 90 minutes, sequestrants optionally being added.

[0132] In all the above processes, the dye mixture is applied as a dispersion comprising from 0.001 to 20 wt. %, preferably from 0.005 to 16 wt. %, of the dye mixture in an aqueous medium.

[0133] In addition to the above-mentioned application processes, the dye mixture may be applied to synthetic textile materials and fibre blends by ink-jet printing, the substrates optionally having been pre-treated to aid printing.

[0134] An ink for digital textile printing, comprising a dye mixture as described above is another aspect of the present invention.

[0135] For ink-jet applications, the application medium may comprise water and a water-soluble organic solvent, preferably in a weight ratio of 1:99 to 99:1, more preferably 1:95 to 50:50 and especially in the range 10:90 to 40:60. The water-soluble organic solvent preferably comprises a C.sub.1-C.sub.4-alkanol, especially methanol or ethanol, a ketone, especially acetone or methyl ethyl ketone, 2-pyrrolidone or N-methylpyrrolidone, a glycol, especially ethylene glycol, propylene glycol, trimethylene glycol, butane-2,3-diol, thiodiglycol or diethylene glycol, a glycol ether, especially ethylene glycol monomethyl ether, propylene glycol monomethyl ether or diethylene glycol monomethyl ether, urea, a sulphone, especially bis-(2-hydroxyethyl) sulphone or mixtures thereof.

[0136] The dyestuff may also be applied to textile materials using supercritical carbon dioxide, in which case the dye formulating agents may optionally be omitted.