Carboxylic acid type water-soluble sulfur dye

Patent metadata

Field	Value
Publication number	US-9193696-B2
Application number	US-201214368092-A
Country	US
Kind code	B2
Filing date	Nov 30, 2012
Priority date	Dec 23, 2011
Publication date	Nov 24, 2015
Grant date	Nov 24, 2015

Abstract

The present invention provides a group of water-soluble sulfur dye having carboxyl groups. For the kind of dye, a sulfur dye is first reduced to a leuco compound by sodium sulfide, and the leuco compound reacts with an active compound containing carboxyl groups to obtain a water-soluble sulfur dye containing the carboxyl group. The water-soluble sulfur dye provided by the present invention is applicable to dying of cotton, wool, silk, and leather. Being both water-soluble and carboxyl group reactive, the product has a simple application process and desirable color fastness, thereby having broad application prospects.

First claim

The invention claimed is:

1. A carboxylic acid type water-soluble sulfur dye comprising a parent compound and a number of carboxyl groups of formula I attached to the parent compound,

wherein R 1 and R 2 are each independently selected from the group consisting of Cl, F, OH, formula Ia, formula Ib, and formula Ic, with the proviso that R 1 and R 2 are not simultaneously Cl, F, or OH;

R 3 is selected form the group consisting of H, CH 3 , (CH 3 ) 2 CH, CH 3 CH(CH 3 )CH 2 , CH 3 CH 2 CH(CH 3 ), CH 2 OH, HSCH 2 , CH 3 SCH 2 CH 2 , C 5 H 6 CH 2 , CH 2 COOH, and CH 2 CH 2 COOH; R 4 is selected from the group consisting of H, Cl, Br, CH 3 , OH, NH 2 , NO 2 , and COOH;
R 5 is selected from the group consisting of —CH 2 —, —CH 2 CH 2 —, —CH(CH 3 )—, —CH(CH 2 CH 3 )—, and —CH(CH(SH)COOH)—; and
X is selected from the group consisting of NH and O,
wherein the parent compound is one selected from the group consisting of C.I. Sulphur Black 1, 2, 5, 6, 7, 10, 11, and 12; or one selected from the group consisting of C.I. Sulphur Yellow 2, 9, 16, 19, and 20; or one selected from the group consisting of C.I. Sulphur Orange 1 and 3; or one selected from the group consisting of C.I. Sulphur Brown 8, 10, 12, 15, 16, 21, 51, 52, 63, 88, and 90; or one selected from the group consisting of C.I. Sulphur Blue 2, 3, 5, 7, 9, 11, 13, 15, and 19; or one selected from the group consisting of C.I. Sulphur Red 2, 6, 7, 10, 11, 12, 13, and 14; or one selected from the group consisting of C.I. Sulphur Green 1, 2, 3, 6, 9, 19, 22, 25, 27, 31, 36, and 37.

2. The carboxylic acid type water-soluble sulfur dye according to claim 1 , further comprising at least a carboxyl group chosen from formula II or formula III attached to the parent compound,

wherein a number of water soluble carboxyl groups of the formula II is m, and a number of water soluble carboxyl groups of the formula III is p;
wherein R 6 is selected from the group consisting of H, CH 3 CH═CH—, COOH, CH 2 COOH, HOOCCH(OH)CH 2 —, HOOCCH(Cl)CH 2 —, HOOCCH(Cl)CH 2 CH 2 , HOOCCH(Cl)CH 2 CH 2 CH 2 —, and HOOCCH 2 CH 2 —;
R 11 is selected from the group consisting of IIIa, IIIb, and IIIc;

R 7 is selected from the group consisting of H, CH 3 , (CH 3 ) 2 CH, CH 3 CH(CH 3 )CH 2 , CH 3 CH 2 CH(CH 3 ), CH 2 OH, HSCH 2 , CH 3 SCH 2 CH 2 , C 5 H 6 CH 2 , CH 2 COOH, and CH 2 CH 2 COOH;
R 8 is selected from the group consisting of H, Cl, Br, CH 3 , OH, NH 2 , NO 2 , and COOH;
R 9 is selected from the group consisting of —CH 2 —, —CH 2 CH 2 —, —CH(CH 3 )—, —CH(CH 2 CH 3 )—, and —CH(CH(SH)COOH)—;
Z is selected from the group consisting of NH and O; and
Y is selected from the group consisting of H, CH 3 —, —COOH and C 6 H 5 CH 2 .

3. The carboxylic acid type water-soluble sulfur dye according to claim 2 , wherein the parent compound comprises a sulfhydryl group, an amino group, or a hydroxyl group, where the carboxyl group of formula I, II or III is connected to the S atom of the sulfhydryl group, the N atom of the amino group, or the O atom of the hydroxyl group of parent A.

4. The carboxylic acid type water-soluble sulfur dye according to claim 1 , wherein the carboxylic acid type water-soluble sulfur dye contains 1 to 30% by weight of carboxyl groups of formula I, wherein the weight of carboxyl groups is measured by back titration.

5. The carboxylic acid type water-soluble sulfur dye according to claim 1 , wherein the number of carboxyl groups is an integer from 1 to 10.

6. The carboxylic acid type water-soluble sulfur dye according to claim 2 , wherein m is an integer from 0 to 10 and p is an integer from 0 to 10, wherein m and p are not simultaneously zero.

Assignees

• Univ Dalian Tech

Inventors

• Tang Bingtao
• Zhang Shufen
• Ma Wei

Classifications

• D06P1/30

  using sulfur dyes · CPC title

• C07D251/50 Primary

  with a halogen atom attached to the third ring carbon atom · CPC title

• C07D251/44

  with halogen atoms attached to the two other ring carbon atoms · CPC title

• C07D251/38

  Sulfur atoms · CPC title

• C09B49/00

  Sulfur dyes · CPC title