Patent GB-1315124-A (GB)
Title: Treatment of fibrous materials
IPC: D06M15/63
Filed: 1969-08-15
Abstract: 1315124 Treating fibrous materials CIBAGEIGY (UK) Ltd 13 Aug 1970 [15 Aug 1969 3 July 1970] 40866/69 and 32460/70 Heading DIP  A process for modifying fibrous material, which comprises treating the material with a polythiol which is a homopolymer or copolymer of butadiene or methyl butadiene having, per average molecule, more than one-SH group directly attached to C atoms of the polymer, and, optionally, with an aminoplast which is free from ethylenic unsaturation, and allowing the polythiol, and the aminoplast if used to cure on the material. The material to be treated can consist either wholly of keratinous fibres or of blends of these fibres with synthetic fibrous and filamentary material such as polyamides, polyesters, poly(acrylonitrile) and with cellulosic and regenerated cellulosic material. Preferably the polythiol contains ethylenic double bonds. The polythiol may comprise units of the formulae wherein X and Y each independently represent H or CH 3 -, Z represents -CN, -COOH, -CONH 2 , -COOR, -C 6 H 5  or -OCOR where R is an alkyl group of 1 to 8 C atoms. The average molecular weight of the polythiol is usually #500 and #50,000, preferably #1,000 and #10,000 and especially from 1,250 to 5,000. Preferably the polythiol is substantially comprised of units, in any desired sequence, of the formulae The polythiols may contain terminal units of formulae  The preferred polythiols thus contain structures of the formula wherein X 1  Y Z have the meanings previously assigned, p is a positive integer of at least one, q is zero or a positive integer and r is an integer such that the average number molecular weight of the polythiol is #500. The polythiol may contain structures of formula wherein y is either zero, in which case z is one, or y is one, in which case x is an integer of #2 and #5 and preferably 3, and 2 is an integer such that the polymer has average molecular weight of #1,000 and #10,000 and preferably between 1,250 and 5,000. The aminoplasts used in conjunction with the polythiols usually contain per molecule at least 2 groups of formula -CH 2 OR<SP>2</SP> directly attached to a N atom or atoms of an amidic nature, e.g. in urea melamine where R<SP>2</SP>=H, or a alkyl group of 1 to 4 C atoms or an acetyl group. If desired, aminoplasts containing both N- hydroxymethyl and N-alkoxymethyl or N- hydroxyethyl and N-acetoxymethyl groups may be used. The aminoplast is usually applied if desired, when a urea- or melamine-formaldehyde product is used. The polythiol may be used in conjunction with a second resin or resin-forming substance, e.g. a polymeric mercaptan, an epoxy resin, an acyclic resin or a polyisocyanate. Many of the polythiols are insoluble in water but can be applied as aqueous dispersions or emulsions but preferably they are applied from organic solvents, e.g. ketines, benzene and halogenated hydrocarbon solvents especially chlorinated and/or fluorinated hydrocarbons containing not more than 3 C atoms. From 0.5 to 15% by, weight of the polythiol is used, based on the, weight of the material treated and 0.1 to 20 % by weight of catalyst (when used) based on the weight of the polythiol is used. When an aminoplast is used, there is 1 to 10% by weight of resin-forming substance in the aminoplast based on the material treated. The catalyst, which accelerates the curing, may be a base, a siccative, an oxidative curing agent or a free radical catalyst, e.g. sulphur, a mercaptobenzothiazole, a thiocarbamate, a thiuram sulphide or a thioprea. The polythiol is cured at a temperature of 30 to 180C. Preferably the fibres and fabrics are treated at a pH>7 typically 7.5 to 12. Catalysts may be used to assist the curing of the aminoplast, examples of these catalysts are latent acid compounds, e.g. ammonium salts, amine salts and strong inorganic acids, e.g. H 2 SO 4  and HCl and contain basic substances, e.g. NaHCO 3  and Na 2 CO 3 . If strong acid catalysts are used heating is not usually required, but in other cases heating at 80 to 200C for 30 sec. to 10 min. is preferable. The polythiol and the catalyst if desired, may be applied by spraying or tumbling the garments in a solution of the polythiol. The process imparts shrink-resist and crease-resistant finish and the fabric may be 'flat set' before or after treatment with the polythiol.