Patent GB-900795-A (GB)
Title: Copolymer emulsions
IPC: C08F2/22
Filed: 1958-10-16
Abstract: Coating compositions are based upon aqueous film-forming emulsions comprising (1) in the continuous phase, water and from 2 to 35% of a film-forming oxidizable emulsifier comprising at least one water-soluble ammonia or amine salt of a resin-modified drying oil, fatty or resin acid modified alkyd resin, a copolymer thereof or of a drying oil with unsaturated aliphatic, cycloaliphatic or vinyl aromatic monomers; such a product modified with a -b -unsaturated dibasic acid or anhydride; or a drying or semi-drying oil modified with a -b  unsaturated dibasic acids or anhydrides and (2) in the dispersed phase a polymerization product formed in situ in the presence of the emulsifier of 5 to 40% of an emulsion polymerizable vinyl monomer and 3 to 35% of an emulsion polymerizable long chain fatty ester or ether monomer, said ester or ether containing at least one double bond capable of reacting with the vinyl monomer.  The latter is an esterification product formed of a drying or semi-drying oil or long chain fatty acid or alcohol ester derivative thereof modified with a polyhydroxy alcohol and an a -b  unsaturated mono or di-basic carboxylic acid or anhydride thereof or mixtures thereof, a vinyl ester or ether of a drying oil fatty acid or alcohol, or an esterification product derived from a drying or semi-drying oil fatty acid, and an amino alcohol, and formaldehyde or a formaldehyde release agent.  The emulsifier (1) is exemplified by (a) an ammonium salt of a linseed oil, pentaerythritol rosin ester reacted with isopropyl acid maleate, (b) a dimethylethanolamine salt of a soya, adipic, benzoic acid glycerol alkyd (c) an ammonium salt of a linseed oil, isophthalic and maleic acid, glycerol alkyd, (c) an ammonium salt of a linseed oil, isophthalic and maleic acid, glycerol alkyd and (d) linseed oil-cyclopentadiene copolymer reacted with maleic acid and neutralized with ammonia or triethylamine and also soyabean oil with maleic anhydride with or without pentaerythritol neutralized with ammonia, a linseed oil with methallyl acid maleate neutralized with morpholine, linseed oil with maleic anhydride esterified with pentaerythritol or ethyl alcohol and neutralized with ammonia.  The vinyl monomers in the dispersed phase (2) may be styrene, a -methyl styrene vinyl toluene, divinyl benzene, methyl, ethyl, and butyl acrylate and methacrylate, acrylonitrile, vinyl acetate and N-vinyl-2-pyrrolidone and preferably a vinyl toluene-methacrylate ester.  The emulsions may include a water-soluble thickening agent, a pigment, a pigment dispersant, and a watermiscible solvent and are prepared by mixing the vinyl monomer and long chain fatty ester or ether monomer in the presence of an aqueous solution of the emulsifier, adding a catalyst and agitating and heating the mixture at between 135 DEG  F. and 205 DEG  F.  Anionic and non-ionic surface active agents such as sodium alkylaryl polyether sulphonates and sulphates, sodium tetradecyl and dodecyl benzene sulphonates, sodium dioctyl and dihexyl sulphosuccinates and n-octadecyl disodium sulphosuccinamate and nonyl and iso-octyl phenoxy polyoxyethylene ethanol, polyethylene glycol mono laurate and rosin ester, alkyl phenyl polyethylene glycol ether, ditertiary acetylenic glycols, polyoxypropylene polyoxyethylene condensates, ethylene and propylene oxide adducts of fatty alcohols.  Examples describe (1) a flat paint based on an aqueous emulsion containing hydroxy cellulose, diethylene glycol monoethyl ether, hexylene glycol, lecithin, an alkyl phenyl polyethylene glycol ether, phenyl mercuric acetate, mineral spirits, titanium dioxide, calcium carbonate magnesium silicate, water dispersible cobalt (6%) and an emulsion based upon a linseed oil cyclopentadiene copolymer with maleic anhydride neutralized with ammonia, soyabean oil alcoholized with pentaerythritol and reacted with maleic anhydride, and vinyl toluene, and (2) a gloss paint based on a casein solution containing monoethyl ether of ethylene glycol, lecithin, an alkyl phenyl polyethylene glycol ether, phenyl mercuric acetate and titanium dioxide and an emulsion similar to (1) above with a vinyl toluene-methyl methacrylate copolymer.  The paints are prepared by conventional mixing methods and air-drying with high water resistance and adhesion.ALSO:An aqueous film-forming emulsion suitable for use in a coating composition, comprises (1) in the continuous phase, water and from 2 to 35% of a film-forming oxidizable emulsifier comprising at least one water soluble ammonia or amine salt of a resin-modified drying oil, fatty or resin acid modified alkyd resin, a copolymer thereof, or of a drying oil with unsaturated aliphatic, cycloaliphatic or vinyl aromatic monomers; such a product modified with a -b  unsaturated dibasic acid or anhydride; or a drying or semi-drying oil modified with a -b unsaturated dibasic acids or anhydrides and (2) in the dispersed phase a polymerization product formed in situ in the presence of the emulsifier of 5 to 40% of an emulsion polymerizable vinyl monomer and 3 to 35% of an emulsion polymerizable long chain fatty ester or ether monomer, said ester or ether containing at least one double bond capable of reacting with the vinyl monomer.  The latter is an esterification product formed of a drying or semi-drying oil or long chain fatty acid or alcohol ester derivative thereof modified with a polyhydroxy alcohol and an a -b  unsaturated mono- or di-basic carboxylic acid or anhydride thereof or mixtures thereof, a vinyl ester or ether of a drying oil fatty acid or alcohol, or an esterification product dervied from a drying or semi-drying oil fatty acid, an aminoalcohol, and formaldehyde or a formaldehyde release agent.  The emulsifier (1) is exemplified by (a) an ammonium salt of a linseed oil, pentaerythritol rosin ester reacted with isopropyl acid maleate (b) a dimethylethanolamine salt of a soya, adipic, benzoic acid-glycerol alkyd, (c) an ammonium salt of a linseed oil, isophthalic and maleic acid, glycerol alkyd and (d) linseed oil-cyclopentadiene copolymer reacted with maleic acid and neutralized with ammonia or triethylamine and also soyabean oil with maleic anhydride with or without pentaerythritol neutralized with ammonia, or linseed oil with methallyl acid maleate neutralized with morpholine, linseed oil with maleic anhydride esterified with pentaerythritol or ethyl alcohol and neutralized with ammonia.  The vinyl monomers in the dispersed phase (2) may be styrene, a -methyl styrene, vinyl toluene, divinyl benzene, methyl, ethyl and butyl acrylate and methacrylate, acrylonitrile, vinyl acetate and N-vinyl-2-pyrrolidone and preferably a vinyl toluene-methacrylate ester.  The emulsions may include a water-soluble thickening agent, a pigment, a pigment dispersant, and a water-miscible solvent and are prepared by mixing the vinyl monomer and long chain fatty ester or ether monomer in the presence of an aqueous solution of the emulsifier, adding a catalyst such as potassium and ammonium persulphates, hydrogen, benzoyl and methyl ketone peroxides and cumene hydroperoxide, and a combination of water and monomer soluble catalysts is preferred, agitating and heating the mixture at between 135 DEG F. and 205 DEG F. or in stages with the portionwise addition of the catalyst, to polymerize the mixture. Anionic and non-anionic surface-active agents may be present and conventional types are listed, and the pH of the emulsion is preferably maintained at 8,2 to 8,6 by continuous addition of bases.  Ferric-ferrous chloride and sodium bisulphite accelerators and t-mercaptan chain stoppers may also be present.  Examples describe the preparation of emulsions with emulsifiers comprising linseed oil-cyclopentadiene copolymer with maleic anhydride, a linseed fatty acid, phthalic anhydride, pentaerythritol alkyd, a linseed oil, pentaerythritol rosin esterisopropyl acid maleate all neutralized with ammonia, and fatty ester monomers reacted with vinyl toluene, alone or with methyl methacrylate, ethyl acrylate, butyl methacrylate or styrene alone. The emulsions are air-drying to form tough chemical resistant adherent films and coating compositions with improved gloss are described based on the emulsions. Specifications 564,504, 564,506 and U.S.A. Specifications 2,188,882, 2,188,890, 2,559,440 and 2,887,194 are referred to.