Patent GB-973357-A (GB)
Title: Improvements in or relating to the dyeing of textile materials with sulphur dyestuffs
IPC: C09B69/00
Filed: 1961-01-17
Abstract: Dyes of formula D-B-S-R, where D is a chromophoric group-containing residue, B is -SO2NHAr-, -CONHAr-, -CH2Ar- or <FORM:0973357/C4-C5/1> where Ar is an o-, m- or p-phenylene group optionally substituted with from 1 to 4 substituents and Y is Hlg, OH, NH2, OCH3, NHC6H5, NHD or SR and R is H, or an alkali metal atom, are made for use in conjunction with an epoxy or amino resin, or resin intermediate, and heat treatment to dye textile materials (see Division D1).  The dyes are made in conventional fashion from appropriate amino-group containing dyes and triazine halides, or appropriate dyes and amines, the products being treated, e.g. by diazotization and reaction, with sodium sulphide, to form the SR group. The group -S-R may be formed in situ by treating an aqueous solution of a compound of formula D-B-S-R1, where R1 is <FORM:0973357/C4-C5/2> (R11 being H, Me or Et), -CSOR111 (R111 being Me or Et) or CN, with an alkali, e.g. sodium hydroxide and/or a reducing agent, e.g. sodium sulphide.  The azoic dyes may also be made by diazotizing and coupling from appropriate components containing the B-S-R group. Cotton, linen, wool, silk, viscose, polyvinyl-acetal, polyamide, polyester, acetylcellulose and polyacrylonitrile textiles may be coloured. Examples show (1) copper phthalocyanine disulphochloride (1 mol.) reacted with p-phenylene diamine (2 mols.) at 10-15 DEG  C., the resultant anilide being tetrazotized and treated with excess thiourea at 5-20 DEG  C.; (2) the dye benzidine\sQ a -naphthylamine is treated with cyanuric halide and the product with sodium sulphide in the presence of sodium hydroxide, and other dyes used to colour textiles in a variety of shades being <FORM:0973357/C4-C5/3> <FORM:0973357/C4-C5/4> \sM5 chloro-2-methoxyaniline (formed on fibre) <FORM:0973357/C4-C5/5> <FORM:0973357/C4-C5/6> <FORM:0973357/C4-C5/7>ALSO:Natural or man-made textile materials are dyed by impregnation with an aqueous system comprising a dye of formula D-B-S-R where D is a chromophoric group containing residue, B is -SO2NHAr-, -CONHAr-, -CH2Ar- or <FORM:0973357/D1-D2/1> where Ar is an o, m or p-phenylene group, optionally substituted with 1-4 substituents, and Y is Hlg or OH, NH2, OCH3, NHC6H5, NHD or SR and R is H or an alkali metal atom and a water-soluble epoxy or amino resin or resin intermediate, the epoxy resin, or resin intermediate, having at least two epoxy groups per molecule and the amino resin or resin intermediate having at least two methylol groups per molecule and thereafter heating the impregnated textile material at 80 DEG -200 DEG C.  Indicated materials are cotton, linen, wool, silk, viscose, polyvinylacetate, polyamides, acetycellulose, polyesters and polyacrylonitrile and its copolymers.  The group SR may be formed in the aqueous solution by dissolving in an aqueous solution of an alkali e.g. sodium hydroxide, and/or a reducing agent e.g. sodium sulphide, a compound of formula D-B-S-R1 where R1 is <FORM:0973357/D1-D2/2> (R11 being H, Me or Et), -CSOR111 (R111 being Me or Et) and -CN, so that -SR1 is a group which forms a mercapto group on treatment with the alkali or reducing agent. 0.1-20% by weight of dye and 1-20% by weight of resin, or intermediate, are used based on the total weight of textile material to be coloured.  The material to be coloured is dipped in, or padded with, the solution or printed with a paste prepared thereform.  The two solutions may be mixed before the textile is treated or the textile may be first treated with the dye solution and then the resin solution.  The dye may be formed on the material from appropriate azoic components before, or after, impregnation with the resinous component.  The heat treatment is effected at a temperature appropriate to the material used e.g. 80-200 DEG C. for linen and cellulose, 80-160 DEG C. for silk, wool and polyesters, 80-130 DEG C for acetylcellulose, polyamides and acrylonitriles and 80-100 DEG C. for polyvinylacetals.  A preferred epoxy resinous component is the initial adduct of bisphenol and epichlorohydrin.  Preferred amino resinous components are dimethylol urea, di-or tri-methylol melamine, dimethylol glyoxal monoureine and di-and tetramethylol glyoxal diureine or O-methyl derivatives of the methylol compounds which from the methylol compounds or solution, and water-soluble condensation products of the above compounds.  Catalysts e.g. zinc fluoborate, diethylene triamine, p-phenylene diamine, phthalic anhydride, secondary ammonium phosphate and ammonium chloride may be used with the resinous component.  Examples are provided of the colouring of textiles in a variety of shades the dyes used being of the phthalocyanine, mono-and dis-azo and anthraquinone series.