Patent GB-1078496-A (GB)
Title: Bonded fibrous substrates and processes
IPC: D04H1/64
Filed: 1963-12-12
Abstract: The fibres of a fibrous substrate are bonded to one another by a bonding agent comprising a modified copolymer of ethylene and an alkyl acrylate.  This copolymer contains 0.01 to 0.5 mol of acrylate units per mol of ethylene units and has an emulsification-inducing proportion of the acrylate units in hydrophilic form, so that it can form a stable aqueous emulsion without emulsifying agents but is water-insoluble.  The same binder may serve also to bond pigments to the substrate.  The bonding agent is formed by treating a copolymer of ethylene and an alkyl acrylate or methacrylate, with a caustic alkali to hydrolyse some or all of the ester groups.  Ammonia or an amine may also be present to convert some of the ester groups to amide groups, and some ester groups to amide groups, and some ester groups may remain unchanged.  A tertiary amine, such as choline can be used to provide a quaternary ammonium salt. Alternatively, the copolymer can be reacted with: an aminoaliphatic carboxylic acid (e.g. glycine) or an aminosulphonic acid (e.g. sulphanilic acid) to give a substituted amide with an acid group in the side chain; an unsaturated amine or alcohol (e.g. allylamine or allyl alcohol) to give an ester or amide with an unsaturated side chain, which can then be further reacted to give e.g. a salt of a sulphate half-ester; a diamine (e.g. ethylendiamine) to give an amide with an amino-substituted side chain; a polyether (e.g. a polyethylene oxide) to give a half-ester of the polyether, which may then be treated to give a sulphate half-ester salt.  The emulsion may also contain methanol, ethanol or isopropanol.  When used to bond a pigment, it may also include thickening agents, such as gum tragacanth, alginates, methylcellulose, hydroxyethylcellulose, aqueous gasoline or aqueous oil emulsions, protective colloids, catalysts, stabilizers or thermosetting resins such as urea- or melamine-aldehyde, or may be a water-in-oil emulsion of pasty consistency, which may be applied by printing.  The copolymer can be cross-linked by using such agents as aldehydes, or by the interaction of carboxylate and amide groups if both be present. Catalysts that can be used are ammonium chloride and ammonium hydroxide.  The substrate may be of staple fibres, yarn, filament, card sliver or twisted continuous filaments and may be woven, knitted, felted or fused or may be a pile fabric or a paper fabric.  The fibres may be natural e.g. cotton, flax, hemp, jute, ramie, sisal, abaca, phormium, silk, wool, fur, hair, animal bristles or straw, or synthetic, e.g. of polyamide, polyester, polyacrylonitrile, copolymers of acrylonitrile with vinyl acetate, vinyl chloride, methyl acrylate, vinylpyridine or sodium styrenesulphonate, terpolymer of acrylonitrile, methyl acrylate and sodium styrensulphonate, vinyl or vinylidene polymer or copolymer, polycarbonate, polyurethane, polyesteramide, polyethylene, polypropylene, polytetrafluorethylene, celluse acetate or triacetate, composite filament, e.g. a sheath of polyamide around a core of polyester, self-crimped composite filaments, e.g. two acrylonitrile polymers differing in ionizable-group content spun as sheath and core, regenerated cellulose, fibres made from casein or peanut protein, glass, asbestos, rock wool or silica.  They may be crimped, drawn or bulked; blends of two or more fibres may be used.  Pigments referred to are carbon black, phthalo-cyanine blue, phthalocyanine green, azo pigments, vat pigments of the indigoid and anthraquinone types, chromium oxide, and titanium oxide.ALSO:The fibres of a fibrous substrate are bonded to one another by a bonding agent comprising a modified copolymer of ethylene and an alkyl acrylate. This copolymer contains 0.01 to 0.5 mol of acrylate units per mol of ethylene units and has an emulsification-inducing proportion of the acrylate units in hydrophilic form, so that it can form a stable aqueous emulsion without emulsifying agents but is water-insoluble. The same binder may serve also to bond pigments to the substrate. The bonding agent is formed by treating a copolymer of ethylene and an alkyl acrylate or methacrylate, with a caustic alkali to hydrolyse some or all of the ester groups.  Ammonia or an amine may also be present to convert some of the ester groups to amide groups, and some ester groups may remain unchanged.  A tertiary amine, such as choline can be used to provide a quaternary ammonium salt.  Alternatively, the copolymer can be reacted with: an aminoaliphatic carboxylic acid (e.g. glycine) or an aminosulphonic acid (e.g. sulphanilic acid) to give a substituted amide with an acid group in the side chain; an unsaturated amine or alcohol (e.g. allylamine or allyl alcohol) to give an ester or amide with an unsaturated side chain, which can then be further reacted to give e.g. a salt of a sulphate half-ester; a diamine (e.g. ethylendiamine) to give an amide with an amino-substituted side chain; a polyether (e.g. a polyethylene oxide) to give a half-ester of the polyether, which may then be treated to give a sulphate half-ester salt.  The emulsion may also contain methanol, ethanol or isopropanol.  When used to bond a pigment, it may also include thickening agents, such as gum tragacanth, alginates, methylcellulose, hydroxyethylcellulose, aqueous gasoline or aqueous oil emulsions, protective colloids, catalysts, stabilizers or thermosetting resins such as urea- or melamine-aldehyde, or may be a water-in-oil emulsion of pasty consistency, which may be applied by printing.  The copolymer can be cross-linked by using such agents as aldehydes, or by the interaction of carboxylate and amide groups if both be present. Catalysts that can be used are ammonium chloride and ammonium hydroxide.  The substrate may be of staple fibres, yarn, filament, card sliver or twisted continuous filaments and may be woven, knitted, felted or fused or may be a pile fabric or a paper fabric.  The fibres may be natural e.g. cotton, flax, hemp, jute, ramie, sisal, abaca, phormium, silk, wool, fur, hair, animal bristles or straw, or synthetic, e.g. of polyamide, polyester, polyacrylonitrile, copolymers of acrylonitrile with vinyl acetate, vinyl chloride, methyl acrylate, vinylpyridine or sodium styrenesulphonate, terpolymer of acrylonitrile, methyl acrylate and sodium styrensulphonate, vinyl or vinylidene polymer or copolymer, polycarbonate, polyurethane, polyesteramide, polyethylene, polypropylene, polytetrafluorethylene, celluse acetate or triacetate, composite filament, e.g. a sheath of polyamide around a core of polyester, self-crimped composite filaments, e.g. two acrylonitrile polymers differing in ionizable-group content spun as sheath and core, regenerated cellulose, fibres made from casein or peanut protein, glass, asbestos, rock wool or silica.  They may be crimped, drawn or bulked; blends of two or more fibres may be used.  Pigments referred to are carbon black, phthalo-cyanine blue, phthalocyanine green, azo pigments, vat pigments of the indigoid and anthraquinone types, chromium oxide, and titanium oxide.