Patent GB-801987-A (GB)
Title: Improvements in or relating to the treatment of proteinaceous textile materials to render them shrink-resistant
IPC: D06M15/333
Filed: 1955-03-02
Abstract: 4-Vinyl pyridine may be copolymerized with an ester of acrylic or methacrylic acid or diester of itaconic, maleic, fumaric or citraconic acid, and an alcohol having from 1 to 18 carbon atoms, the methyl, ethyl, butyl, octyl, dodecyl, cyclohexyl, cyanoethyl, benzyl or phenylethyl esters being specified; a vinyl ester of acetic, propionic or butyric acid; vinyloxyethyl acetate; ethyl, butyl or octyl vinyl ether; acrylonitrile; methacrylonitrile; acrylamide or methacrylamide, which compounds may be N-alkyl substituted; vinyltoluene; vinylnaphthalene; 4-chloro-1-vinylnaphthalene; vinyl chloride or bromide; vinylidene chloride, fluoride or cyanide; 1-chloro-1-fluoroethylene; ethylene or styrene.  The copolymer may be produced from 4-vinyl pyridine, one of the above co-monomers and acrylic, methacrylic, itaconic, maleic, fumaric or citraconic acid or mixture of such acids.  The acid component may be added as a co-monomer prior to polymerization or may be produced in the copolymer by partial hydrolysis of the ester component with an acid or an alkali.  The copolymer may be prepared by emulsifying the monomers with the aid of an anionic or non-ionic dispersing agent and adding a redox-type peroxidic free-radical catalyst, e.g. a combination of potassium persulphate and sodium metabisulphite, or of an alkali metal or ammonium persulphate or perborate, hydrogen peroxide, tert.-butyl hydroperoxide, cumene hydroperoxide or tert.-butyl perbenzoate and a thiosulphate or hydrosulphite, triethanolamine or sulphate of iron, nickel, copper or cobalt, the dispersion then being heated up to 100 DEG  C.  The dispersing agent may be sodium lauryl sulphate, an aryl or alkyl substituted phenol sulphonate, a sulphonated alkyl phenoxyethoxyethanol having 1 to 5 oxyethylene groups per molecule, di-t-octyl sodium sulphosuccinate, alkylphenoxy-polyethoxyethanols having alkyl groups of about 7 to 18 carbon atoms and 6 to 60 oxyethylene groups, polyethoxyethanol derivatives of methylene linked alkyl phenols, condensation products of ethylene oxide (6 to 60 mols.) with alkyl mercaptans or alkyl thiophenols having alkyl groups of 6 to 15 carbon atoms, ethylene oxide derivatives of lauric, myristic, palmitic or oleic acids or tall oil or of octyl, decyl, lauryl or cetyl alcohols, ethylene oxide derivatives of etherified or esterified polyhydroxy compounds such as sorbitan monostearate containing from 6 to 60 ethylene oxide groups, ethylene oxide condensates of dodecylamine, hexadecylamine, and octadecylamine containing from 6 to 60 ethylene oxide groups or block copolymers of ethylene oxide and propylene oxide comprising an hydrophobic propylene oxide section combined with one or more hydrophilic ethylene oxide sections.ALSO:Textile materials are treated with an aqueous dispersion of a water-insoluble copolymer of 3 to 15 per cent by weight of 4-vinyl pyridine and at least one other copolymerizable monoethylenically unsaturated compound.  The textile materials may be filaments, fibres, yarns, threads, plied yarns, rovings, slivers, woven, knitted or felted fabrics, sheets or cloths of wool, silk, mohair, fur, artificial protein fibres from casein, soybeans or collagen or mixtures of such proteinaceous fibres with cotton, linen, rayon, nylon or polymers of acrylonitrile.  After treatment with the aqueous dispersion the material is heated to 212 DEG  to 700 DEG  F. to bond the copolymer chemically with the fibres. The 4-vinyl pyridine may be copolymerized with an ester of acrylic or methacrylic acid or diester of itaconic, maleic, fumaric or citraconic acid, and an alcohol having from 1 to 18 carbon atoms, the methyl, ethyl, butyl, octyl, dodecyl, cyclohexyl, cyanoethyl, benzyl or phenylethyl esters being specified; a vinyl ester of acetic, propionic or butyric acid; vinyloxyethyl acetate; ethyl, butyl or octyl vinyl ether; acrylonitrile; methacrylonitrile; acrylamide or methacrylamide, which compounds may be N-alkyl substituted; vinyltoluene; vinylnaphthalene; 4-chloro-1-vinylnaphthalene; vinyl chloride or bromide; vinylidene chloride; fluoride or cyanide; 1-chloro-1-fluoroethylene; ethylene or styrene.  The dispersion may be aided with a nonionic or anionic dispersing agent, of which many are specified.  The copolymer may be produced from 4-vinyl pyridine, one of the above comonomers and acrylic, methacrylic, itaconic, maleic, fumaric or citraconic acid or mixture of such acids.  The acid component may be added as a comonomer prior to polymerization or may be produced in the copolymer by partial hydrolysis of the ester component with an acid or an alkali.  The dispersion may be applied by dipping, spraying or padding at temperatures up to the boiling point of the dispersion, and the treated material may be dried before heating.  The dispersion may also contain formic, oxalic, sulphuric or phosphoric acid, and/or formaldehyde, glyoxal, a formal, a mixture of formaldehyde with urea, thiourea, biuret, N,N-ethylene urea, N,N1-dimethyl-urea, N,N1-diethylurea, N,N1-dimethoxymethylurea, N,N-dimethoxymethylurea, N,N1-diethoxyethylurea, tetramethoxymethylurea, tetraethoxyethylurea, melamine, or precondensates such as N,N-dimethylmelamine or dimethoxymethylmonomethylolmelamine, or the fabric may be after-treated with a solution of such compounds. The treating solution may be obtained by emulsifying the copolymer or by emulsifying the monomers with the aid of an anionic or non-ionic dispersing agent and adding a redox type peroxidic free-radical catalyst, e.g. a combination of potassium persulphate and sodium metabisulphite, or of an alkali metal or ammonium persulphate or perborate, hydrogen peroxide, tert-butyl hydroperoxide, cumene hydroperoxide or tert-butyl perbenzoate and a thiosulphate or hydrosulphite, triethanolamine or sulphate of iron, nickel, copper or cobalt, the dispersion then being heated up to 100 DEG  C.  The dispersing agent may be sodium lauryl sulphate, an aryl or alkyl substituted phenol sulphonate, a sulphonated alkyl phenoxyethoxyethanol having 1 to 5 oxyethylene groups per molecule, di-t-octyl sodium sulphosuccinate, alkylphenoxy-polyethoxyethanol having alkyl groups of about 7 to 18 carbon atoms and 6 to 60 oxyethylene groups, polyethoxyethanol derivatives of methylene linked alkyl phenols, condensation products of ethylene oxide (6 to 60 mols.) with alkyl mercaptans or alkyl thiophenols having alkyl groups of 6 to 15 carbon atoms, ethylene oxide derivatives of lauric, myristic, palmitic or oleic acids or tall oil or of octyl, decyl, lauryl or cetyl alcohols, ethylene oxide derivatives of etherified or esterified polyhydroxy compounds such as sorbitan monostearate containing from 6 to 60 ethylene oxide groups, ethylene oxide condensates of dodecylamine, hexadecylamine and octadecylamine containing from 6 to 60 ethylene oxide groups or block copolymers of ethylene oxide and propylene oxide comprising a hydrophobic propylene oxide section combined with one or more hydrophilic ethylene oxide sections.