Method of applying an anti-corrosion and/or adhesion promoting coating to a metal and resulting coated metal
View Patent ↗A method of coating at least a portion of the exposed surface of a metal comprises: a) applying to said surface a curable coating composition comprising an aqueous solution of at least one partially or substantially completely hydrolyzed, and optionally partially condensed, silane possessing one or more hydroxyl groups and, optionally, one or more organonitrogen groups, said hydroxyl group(s) and optional organonitrogen group(s) being bonded to different carbon atoms of a bridging group linking such group(s) to the silicon atom of the partially or substantially completely hydrolyzed and optionally partially condensed silane; and, b) curing the curable coating composition on the surface of the metal to provide an anti-corrosion and/or adhesion promoting coating thereon.
1. Metal possessing the cured silane-based coating resulting from the method of:
a) applying to said surface a curable coating composition consisting essentially of:
(i) an aqueous solution of at least one partially or completely hydrolyzed and optionally partially condensed silane wherein the partially or completely hydrolyzed and optionally partially condensed silane is obtained from at least one hydrolyzable silane of the general Formula (1):
wherein:
each occurrence of R 1 and R 2 is independently a monovalent hydrocarbyl group of up to 20 carbon atoms, selected from an alkyl, alkenyl, arenyl, aryl, aralkyl and acyl group, optionally containing one or more etheric oxygen atoms;
each occurrence of R 3 and R 4 is independently a divalent hydrocarbylene group of up to 12 carbon atoms, selected from the group consisting of an alkylene, alkenylene, arenylene, arylene and aralkylene group;
each occurrence of R 5 is independently a divalent or polyvalent hydrocarbylene group of up to 12 carbon atoms, selected from the group consisting of an alkylene, alkenylene, arenylene, arylene and aralkylene group;
each occurrence of R 6 is independently hydrogen, a monovalent hydrocarbyl group of up to 8 carbon atoms, selected from the group consisting of an alkyl, alkenyl, arenyl, aryl or aralkyl group, an —R 3 SiR 2 a (OR 1 ) 3-a group, a —C(═O)A 1 R 5 (OH) d group and an —R 5 (OH) d group;
each occurrence of R 7 is independently hydrogen, a monovalent hydrocarbyl group of up to 8 carbon atoms, selected from the group consisting of an alkyl, alkenyl, arenyl, aryl, and aralkyl group, an —R 3 SiR 2 a (OR 1 ) 3-a group and an —R 8 (OH) f group;
each occurrence of A 1 is independently divalent oxygen (—O—) or nitrogen of the structure —NR 9 — in which wherein R 9 is hydrogen, a monovalent hydrocarbyl group of up to 8 carbon atoms, selected from the group consisting of an alkyl, alkenyl, arenyl, aryl or aralkyl group, an —R 3 SiR 2 a (OR 1 ) 3-a group and an —R 8 (OH) f group wherein each occurrence of R 8 is independently a divalent or polyvalent hydrocarbylene group selected from alkylene, alkenylene, arenylene, arylene and aralkylene groups of up to 12 carbon atoms; and
each occurrence of the subscripts a, b, c, d, e and f is independently an integer wherein a is 0 to 2; b is 0; c is 1; d is 1 to 4; e is 1; and, f is 1 to 4; and,
(ii) at least one additional component selected from the group consisting of cosolvent, surfactant, a hydrolysable silane lacking a hydroxyl group and a pH modifier; and,
b) curing the curable coating composition on the surface of the metal to provide an anti-corrosion coating thereon, wherein the curing step is carried out to provide an incompletely cured coating composition possessing a level of condensation of from 60 to 99 percent; and,
c) applying a paint to the anti-corrosion coating of step (b) to provide for a metal surface coated therewith exhibiting at least 10 percent decrease in creepage value as measured by ASTM D 1654 compared with the similarly measured creepage value of a metal surface possessing a chromium sealed zinc phosphate coating of a thickness of 0.01 to 5 micrometers and the same paint of a thickness of 0.1 to 100 micrometers.
2. Metal of claim 1 wherein each R 1 O— group is independently a hydrolyzable alkyloxy, acyloxy, alkoxyalkyloxy, alkoxyaryloxy, acyloxyalkyloxy, acyloxyaryloxy or aryloxy group.
3. Metal of claim 1 wherein each R 3 and R 4 group possesses from 1 to 12 carbon atoms and is independently a linear, branched or cyclic alkylene group.
4. Metal of claim 1 wherein the partially or completely hydrolyzed and optionally partially condensed silane is obtained from at least one hydrolyzable silane containing at least one hydroxyl group and is derived from a ureidoalkoxysilane.
5. Metal of claim 1 wherein the partially or completely hydrolyzed hydrolyzed and optionally partially condensed silane is obtained by hydrolysis of a mixture of hydrolyzable silanes at least one of which is a hydroxyl-containing hydrolyzable silane and at least one other of which is a hydrolyzable silane lacking a hydroxyl group.
6. Metal of claim 1 wherein the partially or completely hydrolyzed and optionally partially condensed silane is obtained from a hydrolyzable silane having a solubility of up to full miscibility with water.
7. Metal of claim 1 wherein curing step (b) is carried out to provide an underlying incompletely cured silane-based coating possessing a level of condensation of from 65 to 95 percent.
8. Metal of claim 1 wherein at least one component of the paint possesses groups that form covalent bonds and/or hydrogen bonds with hydroxyl groups of silane-based component(s) of the underlying incompletely cured coating.
9. Metal of claim 1 wherein the paint is selected from epoxies, enamels, latexes, primers, basecoats, clearcoats, lacquers, varnishes, shellacs and polyurethane finishes.
10. Metal of claim 1 wherein the metal possesses a form selected from the group consisting of sheet, bar, rod, wire or foil, the metal being selected from the group consisting of copper, silver, brass, titanium, titanium alloy, gold, tin, nickel, chromium, tantalum, iron, surface cold-rolled steel, galvanized steel, hot dip galvanized steel, aluminum aluminum alloy, and steel coated with at least one of zinc, zinc alloy or aluminum.
11. Metal of claim 1 wherein the aqueous solution has a stability of at least 3 months.
12. Metal of claim 1 wherein an amount of curable coating composition is applied to the metal surface so as to provide upon curing a coating thickness of from 0.01 to 5 micrometers.
13. Metal of claim 1 wherein an amount of curable coating composition is applied to the metal surface so as to provide upon curing a coating thickness of from 0.1 to 1 micrometer.
14. Metal of claim 1 wherein the partially or completely hydrolyzed and optionally partially condensed silane is obtained from at least one hydrolyzable silane selected from the group consisting of (N-3-trimethoxysilylpropyl-N′,N′-bis(2-hydroxyethyl) urea), N-3-triethoxysilylproply-N′,N′-bis(2- hydroxyethyl) urea and N-(3-trimethoxysilanyl-propyl)-carbamic acid 2-hydroxy-ethyl ester.
15. Metal of claim 1 wherein the aqueous solution contains a cosolvent selected from the group consisting of 3-{2-[2-(2-methoxy-ethoxy)-ethoxy]-ethoxy}-propan-1-ol, 3-[2-(2-butoxy-propoxy)-propoxy]-propan-1-ol, acetone, methyl ethyl ketone, hexylene glycol, 2-methyl-1,3-butanediol and acetic acid 3-[2-(2-butoxy-propoxy)-propoxy]-propyl ester.
16. Metal of claim 1 wherein the aqueous coating includes a surfactant selected from the group consisting of polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester fatty acid salt, alkyl sulfate ester salt, alkyl benzene sulfonate, alkyl phosphate, alkylallyl sulfate ester salt, polyoxyethylene alkylphosphate ester, quaternary ammonium salt, long chain alkyl trimethylammonium salt, long chain alkyl benzyl dimethyl ammonium salt, di(long chain alkyl) dimethyl ammonium salt, ethoxylated nonyl phenol and polyvinyl alcohol.