Patent GB-1333465-A (GB)
Title: Coating compositions containing vinyl fluoride or vinylidene  fluoride polymers
IPC: C25D13/10
Filed: 1971-04-19
Abstract: 1333465 Vinyl fluoride or vinylidene fluoride polymer compositions DAIKIN KOGYO CO Ltd 19 April 1971 [19 March 1970] 24740/71 Headings C3P C3B and C3R [Also in Division C7] A polymeric composition comprises (i) polyvinyl fluoride or polyvinylidene fluoride containing at least 75% by weight homopolymer units and having particle size 0À01-100microns; (ii) a mixture of 20-90% by weight of an organic solvent or solvent mixture capable of dissolving the polymer at a temperature below its boiling point and 80-10% of water; and (iii) 0À1- 30% by weight of the polymer of a watersoluble resin which dissociates in water. The polymers may be copolymers with ethylene, propylene, isobutylene, styrene, vinyl chloride, vinylidene chloride, difluoro chloroethylene, trifluorochloroethylene, tetrafluoroethylene, trifuoropropylene, hexafluoropropylene, vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, methyl methacrylate, allyl methacrylate, acrylonitrile, N-butylmethacrylamide, allylacetate, isopropenyl acetate, acrylic acid or an acrylic acid salt. Generally the amount of polymer in the composition is 1-30% by weight and preferably it is 5-15%. Suitable solvents which may be used alone are dimethylformamide, dimethylacetamide, 2-pyrrolidone, N-methyl-2-pyrrolidone, γ-butyrolactone, ethyleneglycol monobutyl ether, diethyleneglycol monomethyl ether, diethyleneglycol monoethyl ether, diethyleneglycol diethyl ether, diethylene glycol monoethyl ether acetate, diethyleneglycol monobutyl ether and triethyleneglycol monomethyl ether. Solvents which may not be used alone but which may be used in combination with the aforementioned solvents are dimethyl. adipate, dioctyl adipate, dimethyl sebacate, isophorone, dimethyl phthalate, diethyl phthalate, dibutyl phthalate, quinoline, ethyleneglycol monophenyl ether or its acetate, diethylene glycol monobutyl ether acetate and diethyleneglycol dibutyl ether; these may also be used in combination with water-soluble solvents that are not solvents for the polymers, e.g. butylalcohol or an aminoalcohol. Suitable dissociating resins are acrylic acid resins, alkyd resins and acrylic amide resins, particularly ammonium salts of copolymers of acrylic acid or methacrylic acid with alkyl esters of α,#- ethylenically unsaturated carboxylic acids and salts of sulphonated copolymers of alkyl esters of acrylic or methacrylic acid with vinyl toluenes. In preparing the compositions the polymer may be first dispersed in a mixture of the organic solvent and water and then the resin added thereto, or the polymer may be added to water, the organic solvent added and then the resin incorporated. The compositions may also contain surfactants such as alkylbenzene sulphonates, alkylnaphthalene sulphonates and dialkyl sulphosuccinates, and pigments such as carbon black, titanium dioxide, cyanine green, cyanine blue, cadmium red, cadmium yellow and red iron oxide. The compositions are used for electro-deposition coating of metal substrates. In examples coatings prepared from the compositions of the invention are compared with coatings prepared from compositions containing no water-soluble dissociating resin or containing a water-insoluble resin, e.g. an insoluble acrylic resin, or a watersoluble but non-ionizable resin, e.g. polyvinyl alcohol or a melamine resin. Also described are the preparation of (a) a thermosettting acrylic resin solution from acrylamide, acrylic acid, butyl acrylate, acrylonitrile, paraformaldehyde, dodecylmercaptan, ethyleneglycol monoethyl ether, aq. sodium hyposulphite and ammonium persulphate by refluxing and subsequently neutralizing with ammonia; (b) an acrylic resin solution by refluxing dioxan, ethyl acrylate, acrylic acid, butylmercaptan and cumene hydroperoxide and adding aq. ammonia; (c) an alkyd resin solution by heating to 200‹ C. linseed oil fatty acid, pentaerythritol and phthalic anhydride and dissolving the product in triethylamine and water; (c) an alkyd resin solution by heating linseed oil, maleic anhydride, ethyleneglycol and glycerol and dissolving the product in dimethylaminoethanol and water; (d) an alkyd resin solution by heating trimellitic acid, propyleneglycol, adipic acid and tall oil fatty acid and adding the product to isobutanol, triethylamine and water; (e) an acrylic resin solution by heating to 50‹ C. methacrylamide, methacrylic acid, styrene, ethylacrylate, isopropanol, t-butanol, paraformaldehyde, aq. sodium hyposulphite and aq. ammonium persulphate and neutralizing the product with aqueous ammonia; and (f) an epoxy resin solution by heating an epoxy resin "Epikote" (Registered Trade Mark), dehydrated castor oil fatty acid, rosin, hempseed oil fatty acid and xylene, and adding the product to butanol and neutralizing with aqueous ammonia.