Anti-corrosive treatment for surfaces made of zinc and zinc alloys
View Patent ↗The invention refers to a process for producing an anticorrosive coating in which a surface to be treated is brought into contact with an aqueous treatment solution containing chromium(III) ions and at least one phosphate compound and an organosol. The corrosive protection of metal surfaces, in particular those containing zinc and zinciferous surfaces with conversion layers is improved. The decorative and functional properties of the surfaces are retained or improved. In addition, the well-known problems associated with the use of compounds containing chromium(VI) or with multi-stage processes are avoided in which a passivation layer containing chromium ions and a sealing are applied one after the other.
1. Process for creating a corrosion protection coating layer, comprising:
providing one or more alkoxysilanes according to formula (1)
R 4-x Si(OR 1 ) x (1)
with the residues R, identical or different from one another, representing a substituted or non-substituted hydrocarbon group with between 1 and 22 hydrocarbon atoms and x is equal to 1, 2 or 3 and R 1 stands for a substituted or non-substituted hydrocarbon group with between 1 and 8 hydrocarbon atoms;
providing an aqueous acid solution;
hydrolyzing the one or more alkoxysilanes according to formula (1) with the aqueous acid solution to form a hydrolysate;
providing one or more alkoxides according to formula (2)
Me(OR 2 ) n (2)
wherein Me stands for Ti, Zr, Hf, Al, Si and n stands for the oxidation level of Me and R 2 is selected from substituted or unsubstituted hydrocarbon groups containing between 1 and 8 carbon atoms;
combining the hydrolysate with the one or more alkoxides according to formula (2) to form an organosol;
combining the organosol with chromium(III) ions and at least one phosphate compound to form an aqueous treatment solution; and
contacting a surface to be treated with the aqueous treatment solution to form a corrosion protection layer on the surface;
wherein the aqueous treatment solution is free of inorganic or organic peroxides.
2. Process according to claim 1 wherein the molar ratio of chromium(III) ions and the at least one phosphate compound in the aqueous treatment solution (with reference to orthophosphate) is between 1:1.5 and 1:3.
3. Process according to claim 1 wherein the at least one phosphate compound in the aqueous treatment solution is selected from the group consisting of orthophosphoric acid, polyphosphoric acids, metaphosphoric acid, the salts of these acids, the esters of these acids with organic residues with up to 12 carbon atoms, and mixtures of these compounds.
4. Process according to claim 1 wherein the concentration of chromium(III) ions in the aqueous treatment solution is in the range between 0.2 g/l and 20 g/l.
5. Process according to claim 1 wherein the at least one alkoxysilane according to formula (1) is selected from the group consisting of trialkoxysilanes and dialkoxysilanes and R 1 stands for similar or different, if necessary branched and/or cyclic, hydrocarbon groups, bound to the silicon atom by a C atom, which hydrocarbon groups may be interrupted by oxygen, nitrogen or a NR 2 group, wherein R 2 is hydrogen or C 1 to C 6 alkyl and the hydrocarbon groups may be substituted by one or several substituents selected from halogens and amino, amido, carboxy, acryloxy, methacryloxy and epoxy alkyl groups.
6. Process according to claim 1 wherein the at least one alkoxysilane according to formula (1) is selected from the group consisting of 3-glycidyl-oxy-propyl-trimethoxysilane, 3-glycidyl-oxy-propyl-triethoxysilane, 3,4-epoxy-butyl-trimethoxysilane, 3,4-epoxy-butyl-triethoxysilane, 2-(3,4-epoxy-cyclohexyl)-ethyl-trimethoxysilane and 2-(3,4-epoxy-cyclohexyl)-ethyl-triethoxysilane.
7. Process according to claim 1 wherein Me is silicon in the at least one compound according to formula (2).
8. Process according to claim 1 wherein the organosol contains a solvent miscible with water with a boiling point of at least 150° C.
9. Process according to claim 1 wherein the organosol additionally contains one or more complexing agents selected from the group consisting of saturated and unsaturated carbon acids, 1,3-dicarbonyl compounds, ethanolamine, alkyl phosphates, polycarboxylic acids, hydroxycarboxylic acids, hydroxypolycarboxylic acids, amino carboxylic acids, hydroxyphosphonic acids and amino phosphonic acids.
10. Process according to claim 1 wherein the aqueous treatment solution contains at least one further complexing agent which is selected from the group consisting of acetic acid, methacrylic acid, acetylacetone, acetoacetic ester, triethanolamine, diethanolamine, butyl phosphate, citric acid, tartaric acid, lactic acid, gluconic acid, glucuronic acid, ascorbic acid, isocitric acid, gallic acid, glycolic acid, hydracrylic acid, hydroxybutyric acid, salicylic acid, nicotinic acid, lactamic acid, aminoacetic acid, aspartamic acid, aspartic acid, cysteine, glutamic acid, glutamine and lysine.
11. Process according to claim 1 wherein the treatment solution additionally contains one or more polymers soluble or dispersible in water, selected from the group consisting of polyethylene glycols, polyvinyl pyrrolidones, polyvinyl alcohols, polyitaconic acids, polyacrylates and copolymers of the particular monomers they are based on.
12. Process according to claim 1 wherein the aqueous treatment solution further contains at least one lubricant.
13. Process according to claim 1 wherein the aqueous treatment solution further contains one or more metals or metalloids, selected from the group consisting of Sc, Y, Ti, Zr, Mo, W, Mn, Fe, Co, Ni, Zn, B, Al, Si and P.
14. Process according to claim 13 wherein the metal or metalloid was added to the treatment solution in the form of one of its salts or in the form of a complex anion or of the corresponding acids of these anions, such as hexafluoroboric acid, fluosilic acid, hexafluorotitanic acid or hexafluorozirconic acid, tetrafluoroboric acid or hexafluorophosphoric acid or their salts.
15. Process according to claim 1 wherein the pH value of the aqueous treatment solution is between pH 1.5 and pH 9.
16. Process for creating a corrosion protection coating layer, comprising:
providing one or more alkoxysilanes according to formula (1)
R 4-x Si(OR 1 ) x (1)
with the residues R, identical or different from one another, representing a substituted or non-substituted hydrocarbon group with between 1 and 22 carbon atoms and x is equal to 1, 2 or 3 and R 1 stands for a substituted or non-substituted hydrocarbon group with between 1 and 8 carbon atoms;
providing an aqueous acid solution;
hydrolyzing the one or more alkoxysilanes according to formula (1) with the aqueous acid solution to form a hydrolysate;
providing one or more alkoxides according to formula (2)
Me(OR 2 ) n (2)
wherein Me stands for Ti, Zr, Hf, Al, Si and n stands for the oxidation level of Me and R 2 is selected from substituted or unsubstituted hydrocarbon groups containing between 1 and 8 carbon atoms;
combining the hydrolysate with the one or more alkoxides according to formula (2), with a complexing agent and with a water compatible solvent having a boiling point of at least 150° C. to form an organosol;
combining the organosol with chromium(III) ions and at least one phosphate compound to form an aqueous treatment solution; and
contacting a surface to be treated with the aqueous treatment solution to form a corrosion protection layer on the surface;
wherein the aqueous treatment solution is free of inorganic or organic peroxides.