Patent GB-1019864-A (GB)
Title: Hydrofluorocarbon polymer film-forming composition
IPC: C08L33/06
Filed: 1964-06-25
Abstract: Film-forming coating compositions comprise a dispersion in a volatile liquid of a hydrofluorocarbon polymer and an inorganic pigment having adsorbed on its surface a layer of a polymer which is free from fluorine atoms and epoxide groups.  The hydrofluorocarbon polymer may be a polymer of vinyl and/or vinylidene fluoride, optionally together with an alkyl acrylate or methacrylate, or bis (2-chlorethyl) vinyl phosphonate. Specified pigments are titanium dioxide, silica, iron oxides, lead titanate, talc, diatomaceous earth, asbestos, mica, clay, basic lead silicate, zinc oxide, zinc sulphide, antimony oxide, zirconium oxide, white lead, lithopone, carbon black, lead chromate, metals, calcium carbonate and barium sulphate.  Organic pigments, e.g. phthalocyanines may also be present.  The adsorbed polymer may be a polymer of an alkyl acrylate and/or methacrylate, or an alkyd resin, polyglycol, polyvinyl ester or acetal, polyvinyl alcohol, polyacrolein, polyvinyl ketone or ether, a copolymer of an unsaturated acid with an olefin or styrene, an ethylene/carbon monoxide copolymer, a styrene/allyl alcohol copolymer, a hydrolysed ethylene/vinyl acetate copolymer or a polymer of an unsaturated acid amide.  The liquid medium may be water or an organic liquid which is a solvent or latent solvent for the hydrofluorocarbon polymer.  An extensive list of suitable solvents including amides, sulphones, nitro compounds, amines, phenols, alcohols, esters, cyclic carbonates, lactones, ketones and heterocyclic nitrogen compounds, is given.  The compositions may be used for casting unsupported films, and for coating wood, masonry, wall boards, leather, plastics, paper and fabrics. Examples describe compositions comprising a methyl methacrylate/ethyl acrylate/methacrylic acid copolymer, titanium dioxide, ethoxyethyl acetate and aromatic hydrocarbons mixed with (1 to 3) polyvinylidene fluoride, dimethyl orthophthalate and diisobutyl ketone; (4) a vinylidene fluoride/tetrafluoroethylene/bis (2-chlorethyl) vinyl phosphonate copolymer, dimethyl orthophthalate and methyl ethyl ketone, together with (5) phthalocyanine pigment; (6) polyvinyl fluoride, titanium dioxide, gamma butyrolactone and dimethyl acetamide; (11) polyvinylidene fluoride, silica, dimethyl orthophthalate and diisobutyl ketone; and (12) a vinylidene fluoride/tetrafluoroethylene copolymer, magnesium silicate and butyrolactone; compositions comprising polyvinylidene fluoride, titanium dioxide and dimethyl orthophthalate mixed with (7) polymethyl methacrylate and xylene; and (8) polyethyl acrylate and xylene; polyethylene ether glycol; coconut oil modified glycerol phthalate alkyd; an ethylene/carbon monoxide copolymer and xylene; polyvinyl acetate and xylene; a styrene/acrylamide copolymer; or a styrene/itaconic acid copolymer; and compositions comprising (9) a methyl methacrylate/ethyl acrylate copolymer, dimethyl acetamide, titanium dioxide, phthalocyanine blue and polyvinyl fluoride; and (10) an ammoniated glycidyl methacrylate/methyl methacrylate copolymer, toluene, isopropanol, xylene, butyl benzyl phthalate, titanium dioxide, hydrogenated castor oil, methyl ethyl ketone and a vinylidene fluoride/tetrafluoroethylene/bis (2 - chlorethyl) vinyl phosphonate copolymer.ALSO:Substrates may be coated with compositions comprising a dispersion in a volatile liquid of a hydrofluorocarbon polymer and an inorganic pigment having adsorbed on the surface thereof a layer of a polymer free from fluorine atoms and epoxy groups. Specified substrates are leather, paper, nonwoven and woven fabrics, masonry, composition wall boards, plastics and particularly metals.  The hydrofluorocarbon polymer may be a polymer of vinyl and/or vinylidene fluoride, optionally together with an alkyl acrylate or methacrylate or bis(2-chlorethyl) vinyl phosphonate. Specified pigments are titanium dioxide, silica, iron oxide, lead titanate, talc, diatomaceous earth, asbestos, mica, clay, basic lead silicate, zinc oxide, zinc sulphide, antimony oxide, zirconium oxide, white lead, lithopone, carbon black, lead chromate, metals, calcium carbonate and barium sulphate.  Organic pigments, e.g. phthalo-cyanines, may also be present.  The adsorbed polymer may be a polymer of an alkyl acrylate or methacrylate, or an alkyd resin, polyglycol, polyvinyl ester, acetal or alcohol, polyacrolein, polyvinyl ketone or ether, a copolymer of an unsaturated acid with styrene or an olefin, an ethylene/carbon monoxide copolymer, a styrene/allyl alcohol copolymer, a hydrolysed ethylene/vinyl acetate copolymer or a polymer of an unsaturated amide.  The liquid may be water or an organic solvent or latent solvent for the hydrofluorocarbon polymer.  Examples describe the coating of aluminium sheets with compositions comprising dispersions of titanium dioxide and (1) polyvinylidene fluoride and an ethyl acrylate/methyl methacrylate/methacrylic acid copolymer, (6) polyvinyl fluoride and an ethyl acrylate/methyl methacrylate/methacrylic acid copolymer, (7) polyvinylidene fluoride and polymethyl methacrylate, and (8) polyvinylidene fluoride and polyethyl acrylate, polyethylene ether glycol, coconut oil-modified glyceryl phthalate alkyd, an ethylene/carbon monoxide copolymer or polyvinyl acetate; the coating of galvanized steel sheets with compositions comprising dispersions of titanium dioxide, and (2) polyvinylidene fluoride and an ethyl acrylate/methyl methacrylate/methacrylic acid copolymer; the coating of aluminium and galvanized steel sheets with compositions comprising dispersions of (4) a vinylidene fluoride/tetrafluoroethylene/bis(2-chlorethyl) vinyl phosphonate copolymer, an ethyl acrylate/methyl methacrylate/methacrylic acid copolymer and titanium dioxide together with (5) phthalocyanine blue; and the coating of metal articles with compositions comprising dispersions of polyvinylidene fluoride, titanium dioxide and (3) an ethyl acrylate/methyl methacrylate/methacrylic acid copolymer and (10) an ammoniated methyl methacrylate/glycidyl methacrylate copolymer.