Method for treating metallic surfaces with an acidic aqueous composition and a post rinsing composition to improve corrosion resistance
Described herein is a method for treatment of a metallic surface, including the step of (A) contacting the metallic surface with a first aqueous composition, and a subsequent step of (B) contacting the metallic surface subsequent to step (A) with a second aqueous composition. Also described herein is a kit-of-parts including the first and second aqueous composition and a kit-of-parts including master-batches of the first and second aqueous compostions. Also described is a method of using the kit-of-parts for treating a metallic surface and substrates including the thus treated metallic surfaces.
1. A method for treatment of a metallic surface, comprising the step
(A) of contacting the metallic surface with a first aqueous composition, the first aqueous composition being an acidic aqueous composition comprising
(a) one or more metal compounds (M) selected from the group consisting of titanium compounds, zirconium compounds and hafnium compounds; and
(b) one or more hydrolysable organosilane compounds (S) or their hydrolysis products (HS) and/or condensation products (CS);
and a subsequent step
(B) of contacting the metallic surface subsequent to step (A) with a second aqueous composition, the second aqueous composition comprising
(c) one or more linear polymers (P), prepared by controlled radical polymerization, containing
(m1) N,N-dimethyl (meth)acryl amide, and
(m2) vinylphosphonic acid,
in form of their polymerized monomeric units,
with the proviso that 85 to 95 mol-% of the polymerized monomeric units are polymerized monomeric units of the N,N-dimethyl (meth)acryl amide, and the rest of the polymerized monomeric units are polymerized monomeric units of the vinylphosphonic acid, and
the one or more linear polymers (P) are being comprised in the second aqueous composition in an amount of 10 to 500 ppm based on the total weight of the second aqueous composition.
2. The method according to claim 1 , characterized in that the metallic surface contains or consists of one or more metals or alloys selected from the group consisting of zinc, steel, cold rolled steel, hot rolled steel, galvanized steel, hot-dip galvanized steel, aluminum, magnesium and zinc-magnesium alloys.
3. The method according to claim 1 , characterized in that the first aqueous composition has a pH in the range of 0.5 to 5.5.
4. The method according to claim 1 , characterized in that the one or more metal compounds (M) are the fluoro metallates of said metals and/or the one or more metal compounds (M) are comprised in the first aqueous composition in a concentration in the range of 20 to 1600 ppm.
5. The method according to claim 1 , characterized in that the one or more linear polymers (P) are comprised in the second aqueous composition in a concentration in the range of 20 to 250 ppm.
6. The method according to claim 1 , characterized in that the one or more hydrolysable organosilane compounds (S) or their hydrolysis products (HS) and/or condensation products (CS) are selected from the group consisting of organoalkoxysilanes, organosilanoles, polyorganosilanoles, organosiloxanes and polyorganosiloxanes and/or that the one or more hydrolysable organosilane compounds (S) or their hydrolysis products (HS) and/or condensation products (CS) are comprised in the first aqueous composition in a concentration in the range of 1 to 750 ppm.
7. The method according to claim 6 , characterized in that the hydrolysable organosilane compounds (S) or their hydrolysis products (HS) comprise at least one of the groups selected from the group consisting of amino groups, urea groups, imido groups, imino groups and ureidos group, and the one or more condensation products (CS) of the hydrolysable silane compounds (S) comprises the same number of the before mentioned groups per condensed unit of the hydrolysable silane compound (S) or its hydrolysis product (HS).
8. The method according to claim 1 , characterized in that the first aqueous composition further comprises (d) at least one kind of metal cation selected from the group consisting of metal cations of metals comprised in the 1 st , 2 nd , 3 rd , 5 th , 6 th , 7 th or 8 th subgroup of the periodic table of the elements including lanthanides, the metal cations of metal comprised in the 2nd main group of the periodic table of the elements, lithium, bismuth and tin.
9. The method according to claim 8 , characterized in that the (d) at least one kind of metal cation is selected from the group consisting of the cations of zinc, copper, cerium and molybdenum and/or the (d) at least one kind of metal cation is comprised in the first aqueous composition in a concentration in the range of 5 to 5000 ppm.
10. The method according to claim 1 , characterized in that the first aqueous composition further comprises e) a water-soluble fluorine compound.
11. The method according to claim 10 , characterized in that the water-soluble fluorine compound is a water-soluble fluoride having free fluoride ions (F) and a concentration of free fluoride in the first aqueous composition is in the range of 15 to 150 ppm.
12. A kit-of-parts, comprising
i. a first aqueous composition, the first aqueous composition being an acidic aqueous composition comprising
one or more metal compounds (M) selected from the group consisting of titanium compounds, zirconium compounds and hafnium compounds; and
one or more hydrolysable organosilane compounds (S) or their hydrolysis products (HS) and/or condensation products (CS); and
ii. a second aqueous composition, the second aqueous composition comprising
(c) one or more linear polymers (P), prepared by controlled radical polymerization, containing
(m1) N,N-dimethyl (meth)acryl amide, and
(m2) vinylphosphonic acid,
in form of their polymerized monomeric units,
with the proviso that 85 to 95 mol-% of the polymerized monomeric units are polymerized monomeric units of the N,N-dimethyl (meth)acryl amide, and the rest of the polymerized monomeric units are polymerized monomeric units of the vinylphosphonic acid, and
the one or more linear polymers (P) are being comprised in the second aqueous composition in an amount of 10 to 500 ppm based on the total weight of the second aqueous composition.
13. A kit-of-parts, comprising
i. a first master batch to produce a first aqueous composition by diluting the first master batch with water and if applicable adjusting the pH value, the first aqueous composition being an acidic aqueous composition comprising
one or more metal compounds (M) selected from the group consisting of titanium compounds, zirconium compounds and hafnium compounds; and
one or more hydrolysable organosilane compounds (S) or their hydrolysis products (HS) and/or condensation products (CS); and
ii. a second master batch to produce a second aqueous composition by diluting the second master batch with water and if applicable adjusting the pH value, the second aqueous composition being an aqueous composition comprising
(c) one or more linear polymers (P), prepared by controlled radical polymerization, containing
(m1) N,N-dimethyl (meth)acryl amide, and
(m2) vinylphosphonic acid,
in form of their polymerized monomeric units,
with the proviso that 85 to 95 mol-% of the polymerized monomeric units are polymerized monomeric units of the N,N-dimethyl (meth)acryl amide, and the rest of the polymerized monomeric units are polymerized monomeric units of the vinylphosphonic acid, and
the one or more linear polymers (P) are being comprised in the second aqueous composition in an amount of 10 to 500 ppm based on the total weight of the second aqueous composition.
14. The method according to claim 1 , characterized in that the method provides corrosion protection to the metallic surface and/or provides an increased adhesion of further coatings applied onto the thus treated metallic surface.
15. A substrate comprising a metallic surface, treated according to the method as defined in claim 1 , the substrate being selected from the group consisting of parts of motor vehicles, rail vehicles, aircrafts, spacecrafts, parts of apparatus and machines, furniture parts, parts used in the construction field, to produce guard railing, lamps, profiles, cover panels or small parts, autobodies and parts thereof, single or separate components, pre-assembled elements, for the manufacture of apparatus and constructions, for household aids, control units, testing equipment and construction elements.
16. The kit-of-parts according to claim 13 , wherein the first master batch and/or the second master batch are diluted with water and/or an aqueous solution in a ratio of 1:5,000 to 1:10.