Patent GB-1315820-A (GB)
Title: Keratinous textiles and fibres
IPC: D06M101/00
Filed: 1969-12-05
Abstract: 1315820 Modifying textiles and fibres CIBAGEIGY (UK) Ltd 12 Nov 1970 [5 Dec 1969] 59661/69 Heading DIP A process for modifying keratinous material comprises treating the material with an ester containing at least 2 mercaptan (-SH) groups per molecule, obtained by the reaction of (a) a monomer captodicarboxylic acid, or its anhydride, (b) a substance containing at least 2 alcoholic hydroxyl groups or one 1,2-epoxide group, and allowing the ester to cure on the material. The ester may be left on the material in a still curable state. The material to be treated can consist either wholly or keratinous fibres or of blends of these fibres with synthetic material such as polyamides, polyesters, and poly(acrylonitrile) and with cellulosic and regenerated cellulosic material. Preferred polymercaptans are those esters having a molecular weight of between 400 and 40,000. Component (a) may be a monomercaptodicarboxylic acid and (b) a compound containing at least two but not more than six hydroxyl groups. The ester may be obtainable by reaction of components (a) and (b) with (c) per molecule, a substance containing at least one mercaptan group which is a monocarboxylic acid or a monohydric alcohol. The ester is also obtainable by the reaction of components (a) and (b) and optionally (c) with a compound which is (a) a dicarboxylic acid containing no mercaptan group, or an anhydride of such an acid or (e) a monocarboxylic acid or (f) a monohydric alcohol. The monomercaptodicarboxylic acid (a) is usually of formula HOOC-R- | SH COOH where R represents a trivalent aliphatic or alicyclic radical and preferably R denotes -CH-CH 2 -. Preferred polymercaptan esters | are represented by wherein a and b present zero or 1, but a#b, q = 0 to 5, p = 1 to 6, such that (p+q) is #2 and #6 when a = 0, a group of formula -CO-R-CO- or -CO-R<SP>2</SP>-CO is | SH attached to R<SP>4</SP> through the indicated oxygen atoms, and when a = 1, a group of formula -O-R<SP>3</SP>-O is attached to R<SP>4</SP>. Through the indicated carboxyl gp., c, d, f and g are the same or different are zero or a integer, e represents an integer the values of c, d, e, f and g being such that c is in the range (d-1) to (d+1) and f is in the range (e+g-1) to (e+g+1), f groups alternate with e groups (and/or g groups, and c groups alternate with d groups, such that no group is directly linked to an identical group and e and g groups are not linked directly to each other, R is as above, R<SP>2</SP> represents a divalent aliphatic, aromatic or alicyclic residue and R<SP>3</SP> represents a divalent aliphatic or alicyclic residue derived from a substance containing two hydroxy groups or one 1,2 epoxy group by removal of the two hydroxy groups on the one 1,2 epoxy group respectively, Y, when attached to a group of formula -OR<SP>3</SP>- or, represents H or -COR<SP>5</SP> and, when attached to -CO-R-CO or | SH -CO-R<SP>2</SP>-CO, represents OH or -OR<SP>5</SP>, Z, when attached to -O-R<SP>3</SP>-O, or when a, c and d each represent zero, denotes H or -COR<SP>5</SP> and when attached to -CO-R-CO | SH or -CO-R<SP>2</SP>-CO, or when b, c and d each represent zero, Z denotes OH or -OR<SP>5</SP>, R<SP>4</SP> represents an aliphatic or alicyclic residue derived from substance containing (p+q) (p+q) hydroxyl groups, or -epoxy groups, 2 or (p+q) carboxyl groups by removal of these hydroxyl, epoxy or carboxy groups and R<SP>5</SP> represents an alkyl, aryl, or cycloalkyl group which may be substituted by mercaptan groups and/or alkoxy groups with the proviso that, when e and p both represent one then (i) Y and/or Z contain the group R<SP>5</SP> and (ii) R<SP>5</SP> contains at least one mercaptan group. The preferred polymercaptan esters have the general formula  wherein R<SP>2</SP>, R<SP>3</SP>, R<SP>4</SP>, Y, Z, a, b, c, d, e, f, g, p and q are as above, and preferably a, q and g = 0 and R<SP>4</SP> is derived from a substance containing 2 -OH gps. or one 1,2 epoxy gp. by removal of the 2 -OH gps. or of the one 1,2 epoxy gp., i.e. The polymercaptans may be used alone or in association with other resins or with resinforming substances, e.g. aminoplasts, epoxy resins, acrylic resins and polyisocyanates. The polymercaptans are applied as aqueous dispersions or emulsions, but preferably they are applied to fabrics and garments from organic solvents, e.g. alcohols, ketones, benzene and halogenated hydrocarbon solvents, especially chlorinated and/or fluorinated hydrocarbons containing #3 C atoms. For the purpose of shrink resistance and crease setting from 0.5 to 15% by weight of polymercaptan based on the material treated is preferred. The polymercaptan may be cured at elevated temp., e.g. 30 to 180C, preferably in the presence of a catalyst. Examples of the catalyst, which is used in an amount from 0.1 to 20% by weight based on the weight of polymercaptan, are bases, siccatives, oxidative curing agents, free radical catalysts, sulphur, a mercapto-benzothiazole, a dithiocarbamate, a thiuram sulphide, a salt of a heavy metal with an acid having an acid strength below 5, or a chelate of a heavy metal. Various methods for carrying out the process of shrink-resist and durable press treatment are given. The composition may also contain antisoiling, antistatic, bacteriostatic, rot-proofing, flame-proofing, wetting agents, water-repellants and fluorescent brightening agents.