Patent GB-956778-A (GB)
Title: Mineral-coated paper products and methods for making them
IPC: D21H19/58
Filed: 1960-06-15
Abstract: A coating composition comprises (1) a finely-divided pigmentary material and (2) from 8 to 25 parts by weight of a binder per 100 parts by weight of the pigmentary material, which binder contains at least 25% by weight of an ammonium and/or water-soluble volatile amine salt of a copolymer of 6 to 10% by weight of acrylic and/or methacrylic acid, 6 to 30% by weight of acrylamide and/or methacrylamide, and 60 to 86% by weight of at least one C1-C4 alkyl ester of acrylic and/or methacrylic acid, at least one-fifth of the ester content of the polymer being constituted by methyl and/or ethyl esters. Preferably the pigmentary material contains a predominant proportion of clay, the binder contains at least 50% by weight of the salt, such salt being an ammonium salt of a copolymer of 60 to 86% by weight of ethyl acrylate, from 6 to 10% by weight of acrylic or methacrylic acid, and 6 to 30% by weight of methacrylamide. The copolymers have a viscosity average molecular weight between about 100,000 and one million.  In preparing the coating composition the acrylic monomers are copolymerized and the product copolymer is dissolved in an aqueous solution of ammonia or a volatile amine such as ethylamine, diethylamine, trimethylamine, ethanolamine, diethanolamine, triethanolamine, morpholine or piperidine, to form the ammonium or amine salt which serves as the pigment binder and the pigment or mineral matter is then suspended or dispersed therein. The copolymer may be combined with other binding materials such as casein, a -protein, soya-protein, starch, chlorinated starch, ethers of starch such as hydroxyethyl-starch, and emulsion copolymers, especially polyacrylate esters and synthetic rubber latices, such as butadihne-styrene copolymers. Pigments include clays, especially of the kaolin type, calcium carbonate, blanc fixe, talc, titanium dioxide, coloured lakes and toners, ochre, carbon black, graphite, aluminium powder or flake, chrome yellow, molybdate orange, toluidine red and copper phthalocyanines. According to an example, one hundred parts of fine coating kaolin and 0.2 parts of sodium hexametaphosphate were mixed in 48 parts of water, and 0.2% (on the weight of the clay) of ammonium hydroxide was added to adjust the pH to 9. The mixture thus obtained was mixed with water and an aqueous dispersion containing an emulsion copolymer having a viscosity average molecular weight of about 200,000. The copolymer dispersion was obtained by the emulsion copolymerization of a mixture of 72 parts of ethyl acrylate, 8 parts of methacrylic acid, and 20 parts of methacrylamide in about 200 parts of water in the presence of 6 parts of an emulsifier, 0.2 part of bromotrichloromethane and a catalyst. The mixed dispersion which provided a final solids concentration of about 45% in the coating composition and 12% of the copolymer salt on the weight of pigment was neutralised with ammonium hydroxide to a pH of 9.0. In other examples the copolymer included one or more of the following monomers: methyl acrylate, butyl acrylate and methyl-methacrylate. In a further example, the composition employed included a 20% ammoniacal solution of a -protein.ALSO:A mineral-coated paper product comprises a paper sheet carrying on a surface thereof a dried coating of a composition comprising (1) a finely-divided pigmentary material and (2) from 8 to 25 parts by weight of a binder per 100 parts by weight of the pigmentary material, which binder contains at least 25% by weight of an ammonium and/or water-soluble volatile amine salt of a copolymer of 6-10% by weight of acrylic and/or methacrylic acid, 6-30% by weight of acrylamide and/or methacrylamide, and 60-86% by weight of at least one C1-C4 alkyl ester of acrylic and/or methacrylic acid, at least one-fifth of the ester content of the polymer being constituted by methyl and/or ethyl esters. The term "paper" includes thin flexible paper webs or sheets and flexible or stiff boards.  Preferably the pigmentary material contains a predominant proportion of clay, the binder contains at least 50% by weight of the salt, such salt being an ammonium salt of a copolymer of 60-86% by weight of ethyl acrylate, from 6-10% by weight of acrylic or methacrylic acid, and 6-30% by weight of methacrylamide.  The paper sheet is coated on at least one side with an aqueous dispersion of 40-60% total solids concentration, having a pH of 7-9,5 and containing a finely divided pigment and 8-25% by weight based on the total weight of pigment, of a binder containing at least 25% by weight of the ammonium and/or water-soluble volatile amine salt, and the coated sheet is dried and calendered; preferably the dispersion contains 12-20% by weight of the salt based on the weight of the pigment.  The copolymers have a viscosity average molecular weight between about 100,000 and one million.  In preparing the coating composition the acrylic monomers are copolymerized and the product copolymer is dissolved in an aqueous solution of ammonia or a volatile amine such as ethylamine, diethylamine, trimethylamine, ethanolamine, diethanolamine, triethanolamine, morpholine or piperidine, to form the ammonium or amine salt which serves as the pigment binder and the pigment or mineral matter is then suspended or dispersed therein.  The copolymer may be combined with other binding materials such as casein, a -protein, soya-protein, starch, chlorinated starch, ethers of starch such as hydroxyethyl-starch, and emulsion copolymers, especially polyacrylate esters, and synthetic rubber latices, such as butadiene-styrene copolymers.  Pigments include clays, especially of the kaolin type, calcium carbonate, blanc fixe, talc, titanium dioxide, coloured lakes and toners, ochre, carbon black, graphite, aluminium powder or flake, chrome yellow, molybdate orange, toluidine red and copper phthalocyanines.  According to an example, one hundred parts of fine coating kaolin and 0,2 part of sodium hexametaphosphate were mixed in 48 parts of water, and 0,2% (on the weight of the clay) of ammonium hydroxide was added to adjust the pH to 9.  The mixture thus obtained was mixed with water and an aqueous dispersion containing an emulsion copolymer having a viscosity average molecular weight of about 200,000.  The copolymer dispersion was obtained by the emulsion copolymerization of a mixture of 72 parts of ethyl acrylate, 8 parts of methacrylic acid, and 20 parts of methacrylamide in about 200 parts of water in the presence of 6 parts of an emulsifier, 0,2 part of bromotrichloromethane and a catalyst.  The mixed dispersion which provided a final solids concentration of about 45% in the coating composition and 12% of the copolymer salt on the weight of pigment was neutralized with ammonium hydroxide to a pH of 9,0.  A dry chipboard of thickness 0,017 inch was coated with the composition to the extent of about 2 or 3 pounds of coating composition (dry weight) per 1,000 sq. ft. of the board, and the coated board was dried and calendered; the board exhibited good wet-rub and pick resistance.  In other examples the copolymer included one or more of the following monomers: methyl acrylate, butyl acrylate and methylmethacrylate.  In a further example, the composition employed included a 20% ammoniacal solution of a -protein.