# US 5,703,215 A · Water-soluble dyes which are polymerizable containing molecules which contain a nucleophilic group and an electrophilic group > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 5,703,215 A - Document ID: US5703215A - Status: Granted - Kind: A - Application number: 08/436,822 - Filed: 1995-05-30 - Granted: 1997-12-30 - Earliest claimed: 1992-11-27 - Assignees: Zeneca Limited - Inventors: Andrew Hunter Morris Renfrew; Andrew Paul Shawcross - Web page: https://patentgrep.com/patent/US5703215A ## CPC - C09B 43/12: by acylation of amino groups - C09B 62/4401: {with two or more reactive groups at least one of them being directly attached to a heterocyclic system and at least one of them being directly attached to a non-heterocyclic system} - C09B 62/503: the reactive group being an esterified or non-esterified hydroxyalkyl sulfonyl or mercaptoalkyl sulfonyl group, a quaternised or non-quaternised aminoalkyl sulfonyl group, a heterylmercapto alkyl sulfonyl group, a vinyl sulfonyl or a substituted vinyl sulfonyl group, or a thiophene-dioxide group - C09B 69/10: Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds - D06P 1/0056: {Dyeing with polymeric dyes involving building the polymeric dyes on the fibres (dyes per se C09B)} - Y10S 8/919: Paper - C09B: ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES {, e.g. PIGMENTS}; MORDANTS; LAKES (fermentation or enzyme using processes to synthesise a desired chemical compound C12P) - D06P: DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM - Y10S: TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS ## Abstract A process for the coloration of a substrate, especially a textile, comprising the steps of: (a) applying to the substrate a mixture comprising an aqueous solvent and a water-soluble dye comprising molecules which contain a nucleophilic group and an electrophilic group; and (b) heating or basifying or heating and basifying the dye thereby causing molecules of the dye to join together. Also claimed are dyes, polymers and oligomers. ## Claims ### Claim 1 A solid water-soluble dye containing an electrophilic group and a nucleophilic group containing an --SH or .dbd.S group, which dye when heated or basified or heated and basified causes the union of molecules of the dye by formation of a covalent bond between the electrophilic group of one molecule and the nucleophilic group of another molecule of the dye. ### Claim 2 A water-soluble dye containing an electrophilic group and a nucleophilic group containing an --SH or .dbd.S group, which dye when heated or basified or heated and basified causes the union of molecules of the dye by formation of a covalent bond between the electrophilic group of one molecule and the nucleophilic group of another molecule of the dye to give a product having less than 25% of the water-solubility of the original dye. ### Claim 3 A solid water-soluble dye containing, as a nucleophilic group, an --SH or .dbd.S group and additionally containing an electrophilic group, whereby when the dye is heated or basified or heated and basified said --SH or =S group allows formation of a covalent bond between the nucleophilic group of one molecule of the dye and the electrophilic group of another molecule of the dye so as to cause the union of said molecules of the dye. ### Claim 4 A water-soluble dye containing, as a nucleophilic group, an --SH or .dbd.S group and additionally containing an electrophilic group, whereby when the dye is heated or basified or heated and basified said --SH or .dbd.S groups allows formation of a covalent bond between the nucleophilic group of one molecule of the dye and the electrophilic group of another molecule of the dye so as to cause the union of said molecules of the dye to give a product having less than 25% of the water-solubility of the original dye. ### Claim 5 (depends on 1, 2) A dye according to claim 1 or 2 wherein said --SH or .dbd.S group is provided by a thiourea. ### Claim 6 (depends on 1, 2) A dye according to claim 1 or 2 wherein the --SH or .dbd.S group is attached to a heterocyclic ring. ### Claim 7 (depends on 1, 2) A dye according to claim 1 or 2 wherein the number of nucleophilic groups is different from the number of electrophilic groups. ### Claim 8 (depends on 1, 2) A dye according to claim 1 or 2 wherein substantially all of the molecules unite when the dye is basified. ### Claim 9 A water-soluble dye which contains a nucleophilic group and an electrophilic group wherein: (i) the nucleophilic group is selected from --SH and .dbd.S; (ii) the electrophilic group is an activated alkene or a group capable of undergoing an elimination and addition reaction; and (iii) any sulpho groups in the dye are removable by heating or basifying the dye. ### Claim 10 (depends on 9) A dye according to claim 9 wherein the electrophilic group is a group of formula --Z.sup.1 --CR.sup.7 .dbd.CR.sup.8 R.sup.9, --CR.sup.7 .dbd.CR.sup.9 --Z.sup.2, --CZ.sup.2 .dbd.CR.sup.7 R.sup.9, --NR.sup.5 --Z.sup.1 --CR.sup.7 .dbd.CR.sup.8 R.sup.9, --Z.sup.1 --NR.sup.5 --(CR.sup.11 R.sup.11).sub.m --X.sup.2, --NR.sup.5 --Z.sup.1 --(CR.sup.11 R.sup.11).sub.m --X.sup.2, or --Z.sup.1 --(CHR.sup.11).sub.m --X.sup.2 wherein Z.sup.1 is --SO--, --SO.sub.2 -- or --CO-- and Z.sup.2 is --CN, --NO.sub.2, or an alkyl- or aryl sulphonyl group or an acyl group; R.sup.7, R.sup.8 and R.sup.9 are each independently H, C.sub.1-4 -alkyl or halo; R.sup.5 is H phenyl or C.sub.1-4 -alkyl; each R.sup.11 independently is halo, --NH.sub.2, carboxy or a group described above for R.sup.5 ; X.sup.2 is --OSO.sub.3 H, --SSO.sub.3 H, --PO.sub.3 H.sub.2, or a salt thereof, halo or acetoxy; and m is 2, 3 or 4. ### Claim 11 (depends on 9, 10) A dye according to claim 9 or 10 wherein said --SH or .dbd.S group is provided by a heterocyclic thiol or a heterocyclic thione. ### Claim 12 (depends on 9, 10) A dye according to claim 9 or 10 wherein said --SH or .dbd.S group is provided by a thiourea. ### Claim 13 (depends on 11) A dye according to claim 11 wherein the heterocyclic thiol or heterocyclic thione are of the Formula (1) or (2) or a salt thereof: ##STR135## ### Claim 14 (depends on 1) A polymer or oligomer obtainable by heating or basifying a dye according to claim 1. ### Claim 15 (depends on 14) A polymer or oligomer according to claim 14 which is free from sulpho groups. ### Claim 16 (depends on 14) A polymer or oligomer according to claim 14 which has less than 1% of the solubility of the original dye in water at 20.degree. C. ### Claim 17 (depends on 3, 4) A water-soluble dye according to claim 3 or 4 wherein the electrophilic group is of the formula: --Z.sup.1 --CR.sup.7 .dbd.CR.sup.8 R.sup.9, --CR.sup.7 .dbd.CR.sup.9 --Z.sup.2, --CZ.sup.2 .dbd.CR.sup.7 R.sup.9, --Z.sup.1 --NR.sup.5 --(CR.sup.11 R.sup.11).sub.m --X.sup.2, or --Z.sup.1 --(CHR.sup.11).sub.m --X.sup.2, wherein: Z.sup.1 is --SO--, --SO.sub.2 -- or --CO--; Z.sup.2 is --CH, --NO.sub.2, or an alkyl- or aryl sulphonyl group or and acyl group; R.sup.5 is H, C.sub.1-4 -alkyl or phenyl; R.sup.7, R.sup.8 and R.sup.9 are each independently H, C.sub.1-4 -alkyl or halo; each R.sup.11 independently is halo, --NH.sub.2, carboxy, H, C.sub.1-4 -alkyl or phenyl; and m is 2, 3, 4. ### Claim 18 (depends on 17) A water-soluble dye according to claim 17 wherein Z.sup.2 is --CN, --NO.sub.2, --SO.sub.2 --(C.sub.1-4 -alkyl), phenylsulphonyl or tosyl.