Patent GB-1073906-A (GB)
Title: Method of manufacturing resinoids
Inventor: TANAKA SHIGEYOSHI
IPC: C09D151/08
Filed: 1964-10-09
Abstract: Resins are made by solution copolymerization of two "vinyl" components (1) 4 to 40 parts by weight of a mixture of 2 to 20 parts by weight a ,b -unsaturated monocarboxylic acid and 2 to 20 parts by weight of one or more a ,b -unsaturated monocarboxylic amide or N-C1- 4 alkyl derivatives thereof and (2) 30 to 80 parts by weight of other "vinyl" compounds, in the presence of 3 to 35 parts by weight of epoxide having an epoxy equivalent of 50 to 4000, and a polymerization catalyst, component (1) providing 0.5 to 4.0 functional group equivalents per epoxy equivalent.  Suitable epoxides are condensates of epichlorohydrin with bisphenol-A, ethylene glycol or glycerol, epoxidized vegetable oils, the 3,4-epoxy-6-methylcyclohexylmethyl ester of 3,4-epoxy-6-methylcyclohexane carboxylic acid and the 3,4-epoxycyclohexyl methyl ester of 3,4-epoxycyclohexane carboxylic acid.  Specified acids are acrylic and methacrylic acid.  Specified amides are acrylamide, methacrylamide and the N-methyl, N-ethyl, N-n-propyl and N-n-butyl derivatives thereof. Other vinyl compounds are styrene, a -methyl styrene, vinyl toluene, acrylonitrile, methacrylonitrile, vinyl acetate, alkyl vinyl ethers and C1- 12 alkyl acrylates and methacrylates. Specified catalysts are benzoyl peroxide, di-t.-butyl peroxide, cumene hydroperoxide and azodiisobutyronitrile.  Specified solvents are alcohols, toluene, xylene, methylethylketone, butoxyethanol, dioxane and mixtures. The products are useful in heat curable coating compositions, and may be compounded with pigments, e.g. titanium dioxide; and alkyletherified amine/aldehyde and phenol/aldehyde resins, e.g. methylated methylolurea, methylol - N,N1 - ethyleneurea, methyloldicyandiamide, methylolmelamine and methylolbenzoguanamine; butylated methylol-N,N1-ethyleneurea, methyloldicyandiamide and methylolbenzoguanamine; and butylated methylol p-octylphenol, methylol p-t.-butyl phenol, methylol p-cyclohexylphenol, methylol bisphenol-A, methylol o-cresol, methylol m-cresol and methylol p-cresol.  In examples resins are prepared by polymerizing acrylamide with (1) styrene, ethyl acrylate and methacrylic acid, (2) methyl methacrylate, ethyl acrylate and methacrylic acid and (3) vinyl toluene, n-butyl acrylate and acrylic acid, in the presence of epichlorohydrin/bisphenol-A condensates.  Coating compositions are prepared from (4) resin (1), butylated methylol melamine and titanium dioxide; (5) resin (1), butylated methylol melamine, butylated methylol urea and titanium dioxide; (6) resin (2), methylated methylol benzoguanamine and titanium dioxide; (7) resin (3), butylated methylol melamine and titanium dioxide; resin (1) and (8) butylated methylol bisphenol-A or (9) butylated methylol p-t.-butyl phenol; resin (2) and (10) butylated methylol m-cresol or (11) butylated methylol bisphenol-A; (12) resin (1), butylated methylol melamine and butylated methylol bisphenol-A; (13) resin (2), butylated methylol benzoguanamine and butylated methylol bisphenol-A; and (14) resin 3, butylated methylol urea and butylated methylol p-cresol.ALSO:Metal substrates may be coated with heat curable compositions comprising resins made by solution copolymerisation of two "vinyl" components (1) 4 to 40 parts by weight of a mixture of 2 to 20 parts by weight of a , b -unsaturated monocarboxylic acid and 2 to 20 parts by weight of a , b -unsaturated monocarboxylic amide or N-C1-4 alkyl derivatives thereof and (2) 30 to 80 parts by weight of other "vinyl" compounds, in the presence of 3 to 35 parts by weight of an epoxide having an epoxy equivalent of 50 to 4,000, and a polymerisation catalyst, component (1) providing 0.5 to 4.0 functional group equivalents per epoxy equivalent.  The compositions may also comprise pigments, e.g. titanium dioxide, and alkyletherified amine/aldehyde and phenol-aldehyde resins.  The substrate may be steel.  Specified resin precursors are:- condensates of epichloro-hydrin with bisphenol-A, ethylene glycol or glycerol, epoxidised vegetable oils, the 3,4-epoxy-6-methylcyclo-hexylmethyl ester of 3,4-epoxy-6-methylcyclohexane carboxylic acid and the 3,4-epoxycyclohexylmethyl ester of 3,4-epoxycyclohexane carboxylic acid; acrylic and methacrylic acids; the amides and N-methyl, N-ethyl, N-n-propyl and N-n-butyl derivatives of acrylic and methacrylic acids; styrene, a -methylstyrene, vinyltoluene, acrylonitrile, methacrylonitrile, vinyl acetate, alkyl vinyl ethers, and C1-12 alkyl acrylates and methacrylates. Specified amine and phenol resins are condensates of formaldehyde with urea, N,N\sv-ethylene urea, dicyandiamide, melamine, benzoguanamine, p-octylphenol, p-t-butylphenol, p-cyclohexylphenol, cresols, xylenol and bisphenol-A, etherified with C1-6 alcohols.  Examples describe the preparation of resins from epichlorohydrin/bisphenol-A condensates and acryl-amide together with (1) styrene, ethyl acrylate and methacrylic acid, (2) methyl methacrylate, ethyl acrylate and methacrylic acid and (3) vinyl toluene, n-butyl acrylate and acrylic acid, in xylene/butanol solvent; and the coating of steel panels with compositions comprising (4) resin (1), butylated methylol melamine and titanium dioxide; (5) resin (1), butylated methylol melamine, butylated methylol urea and titanium dioxide; (6) resin (2), methylated methylol benzoguanamine and titanium dioxide; (7) resin (3), butylated methylol melamine and titanium dioxide; resin (1) and (8) butylated methylol bisphenol-A or (9) butylated methylol p-t-butylphenol; resin (2) and (10) butylated methylol m-cresol or (11) butylated methylol bisphenol-A; (12) resin (1), butylated methylol melamine and butylated methylol bisphenol-A; (13) resin (2), butylated methylol benzoguanamine and butylated methylol bisphenol-A; and (14) resin (3), butylated methylol urea and butylated methylol p-cresol.