Patent GB-1061389-A (GB)
Title: Vehicles for coating compositions
IPC: C09D5/44
Filed: 1964-05-07
Abstract: A sheet of iron, steel, galvanized or phosphetized steel, zinc or aluminium is electrolytically coated from aqueous solution with a product obtained by reacting a drying or semi-drying fatty acid ester with an a : b -unsaturated dicarboxylic acid capable of forming an anhydride, the anhydride thereof, fumeric acid, or a mixture thereof which has been partially esterified with a monohydric alcohol and in which at least 10% of unesterified carboxyl groups have been neutralized. The reaction product may be mixed with an ethylenically unsaturated monomer (many specified).  The coating composition may be dispersed in tap or deionized water (e.g. using monionic and/or anionic surface-active agents) with or without a pigment (e.g. iron or lead oxide, strontium chromate, titanium dioxide, talc, barium sulphate, carbon black, phthalocyanine blue or toluidine red).  The metal to be coated is used as the anode, the applied voltage being from 1 to 500 or higher and the current density being from 0.1-15 amps/sq.ft.  Thicker coatings are obtained with higher voltages. The pH of the coating composition should be low, preferably under 8.0 (e.g. 6.0-7.5), and the water content may be from 80-99% by weight. In Examples 6 to 12, electrodeposition is effected in a polyethylene container using phosphatized steel electrodes spaced 2" apart and immersed to 6" in the coating composition.ALSO:A drying or semi-drying fatty acid ester is reacted with an a :b -ethylenically unsaturated dicarboxylic acid capable of forming an anhydride, the anhydride thereof, fumaric acid, or a mixture thereof, at least 5% of the acidic carboxyl groups being esterified with a monohydric alcohol and at least 10% of unesterified carboxyl groups being neutralized, e.g. with metal or quaternary ammonium hydroxides, ammonia amines, diamines, hydrazine, morpholine, histamine, hydroxylamine, ethanolamine, or an aminoalkylalkane diol.  Two-stage neutralization with different reagents may be effected, and heat may be applied. Esterifying alcohols specified include methanol, 1-pentanol, lower alkyl and longer chain monoethers of glycols, linseed fatty alcohol, cyclopentanol, furfuryl alcohol, and benzyl alcohol. Some of the dicarboxylic acid groups may be fully esterified. Fatty acid esters specified include linseed, perilla, walnut and sardine oils and tall oil esters, which may be modified with acids such as butyric, stearic, linoleic, or benzoic acid, phthalic acids, or rosin (abietic acid).  Di- or mono-glycerides may be formed by alcoholysis using for example glycerol, trimethylolethane or pentaerythritol) and then esterified, or oil acids may be reacted with a polyol and the product reacted with the acid.  The esters may be modified with styrene or cyclopentadiene. The ester may also be an alkyd resin derived from drying or semi-drying oils, esters of epoxides with the fatty acids, or drying or semidrying fatty acid esters of polyols (e.g. butanediol, pentaerythritol, polymers or copolymers, e.g. styrene of allyl or methallyl alcohol, or non-oil-modified alkyd resins containing free OH groups).  The reaction product of ester and acid may be mixed with an ethylenically unsaturated monomer, e.g. styrene, butadiene-1,3, a -bromostyrene, chlorobutadiene, vinyl 2-chlorobenzoate, heptyl acrylate, decyl methacrylate, methyl crotonate, isopropenyl acetate, allyl cyanide, dimethyl itaconate, decyl a -chloracrylate, dimethyl maleate, diethyl glucaconate, or ethacrylonitrile.  The coating composition may be dispersed in tap or deionized water (e.g. using nonionic and/or anionic surface-active agents), with or without a pigment (several specified), and electrodeposited or otherwise applied to a metal sheet.  The pigment: vehicle ratio is not higher than 1.5:1, preferably 1:1.  The metal (iron, steel, aluminium, zinc, or galvanized or phosphatized steel) to be coated is used as the anode, the applied voltage being from 1 to 500 or higher and the current density being from 0.1-15 amps./sq. ft.  Thicker coatings are obtained with higher voltages.  The pH of the coating composition should be low, preferably under 8.0 and the water content may be from 80-99% by weight. The coated article may be baked at 100 DEG  to 200 DEG  C.  In Example 1, a vehicle solution is prepared by reacting linseed oil and maleic anhydride at 220 DEG  C., partially esterifying the cooled product with methanol, and neutralizing with aqueous ammonia.  Some of the vehicle solution is formed into a pigment paste with red iron oxide, carbon black, strontium chromate and a dispersing agent, and more vehicle solution is added to form a pigment composition. An aqueous coating dispersion comprises still more vehicle solution plus the pigment composition and cresol as an antioxidant.  In Example 3, the linseed oil-maleic anhydride reaction product is heated with styrene in presence of di-t-butyl peroxide, esterification and neutralization are effected, and the solution is mixed with a pigment dispersion and water.