Patent GB-787032-A (GB)
Title: Improvements in the production of pigmented prints, impregnations and coatings on fibrous materials
Inventor: COOPER ALBERT CHARLES
IPC: D06M13/11
Filed: 1954-12-24
Abstract: Pigmented prints, impregnations and/or glazed coatings are provided on fibrous materials by coating them with an aqueous mixture comprising (1) an epoxide having functionality greater than one; (2) a synthetic polymer containing active -OH, -COOH or COOH salt groups; (3) a basic catalyst for the polymerization and hardening of the epoxide and condensation with the polymer, and heating the fibres to produce an insoluble coating thereon. There are specified as: (1) poly-epoxides-di- or polyepoxides, e.g. 1:2-3:4-diepoxy butane, methyl di-(2,3-epoxypropyl) acetate; 1:4-divinylbenzene diepoxide; di-(2:3-epoxypropyl) ether and glycidyl ethers of alcohols and phenols, e.g. glycerol tri-(2:3-epoxypropyl) ether, m- and p-di - (2:3 - epoxypropoxy) - benzene; glycidyl amines, e.g. N:N-di-(2:3-epoxypropyl)-aniline or -anisidine, glycidyl esters of polybasic acids, e.g. di-(2:3-epoxypropyl) sebacate, tri-(2:3-epoxypropyl) trimesate: polymeric epoxides-obtained by reacting polyhydric alcohols or phenols with epichlorhydrin in presence of alkali; by polymerizing through the double bond unsaturated epoxides such as 3:4-epoxy-1-butene or 2:3-epoxypropyl allylether or methacrylate; polymers and copolymers with monoepoxides as obtained from 4-vinylcyclohexene di-epoxide in presence of boron trifluoride. The non-polymeric epoxides may be pre-reacted with a minor amount of polyfunctional compounds having at least two groups reactive to epoxide groups, e.g. polyamines; (2) polymers-polyesters from adipic acid, ethyleneglycol and glycerol as described in Specification 690,706, [Group VIII]; copolymers of b -ethoxyethylmethacrylate with 1 per cent methacrylic acid as described in Specification 478,323, [Group IV]; polyvinyl alcohols, polyglyceryl methacrylate, cellulose ethers; vinyl copolymers containing COOH groups in minor amount.  Instead of employing (1) and (2) separately they may be combined, by copolymerization, within the same molecule, e.g. polymers of 2:3-epoxy-propyl methacrylate, and from methacrylic acid and other copolymerisable components, e.g. vinyl chloride, vinyl acetate and acrylic and methacrylic esters; (3) catalysts-2:4:6:-tri-(dimethylaminomethylphenol); condensation products of biguanides with polyalkylene polyamines; diethylenetriamine, 2:5 - di - (dimethylaminomethyl) - quinol, N:N - dimethyl benzylamine N:N: N1:N1-tetramethylhexamethylenediamine, 2 - (dimethylaminomethyl)-cyclohexanone, phenyl 2-(dimethylamino) ethylketone, di-[2-(di-ethylamino) ethyl] adipate, N-ethylhexamethyleneimine, hexamethyleneimine, N-methylbenzylamine; quaternary ammonium hydroxides; alkali metal hydroxides.  In examples: (1) 4 parts of 2,2-di-[4-(2,3-epoxypropoxy)-phenyl] propane having an epoxide equivalent of 234 are stirred with 16 parts of a 24 per cent aqueous solution of a 90:10 interpolymer of methacrylic acid and beta-ethoxyethyl methacrylate in which 80 per cent of the carboxyl groups are neutralized with NaOH.  A smooth emulsion is obtained which is mixed with 0.5 parts 2 : 4 : 6-tris-(dimethylaminomethyl)-phenol and 5 parts of a 20 per cent aqueous paste of copper phthalocyanine and used to impregnate a piece of cotton printer's cloth; a coloured pattern fast to washing is obtained; (2) polyvinyl alcohol is substituted for the copolymer of Example 1; (3) the copolymer employed is a 40 per cent butadiene/acrylonitrile polymer emulsified in kerosene with cetyl alcohol/ethylene oxide/polyvinyl alcohol copolymer and is mixed with an emulsion of 2 : 2-di-[4-(2 : 3-epoxypropyl]-phenyl)-propane and polyvinyl alcohol made by stirring diglycide ether in xylene with polyvinyl alcohol and an alkylphenol-ethylene oxide condensate.  In Examples (5)-(7) a copolymer latex prepared from butadiene, methylmethacrylate and methacrylic acid and emulsified in kerosene is used.  The pigment used is obtained by coupling diazotized O-anisidine-p-sulphondiethylamide with 2 : 3-hydroxynaphthoic-5-chloro-2 : 4-dimethoxyanilide; (10) a viscous liquid polymer obtained by blowing air through 2 : 3-epoxypropyl allyether at its boiling-point and then distilling out excess monomer and having an epoxide equivalent of 139.7 is emulsified with water and polyvinyl alcohol and used as a polymer.