Coating processes – With post-treatment of coating or coating material – Heating or drying
Reexamination Certificate
1999-07-19
2004-12-07
La Villa, Michael (Department: 1775)
Coating processes
With post-treatment of coating or coating material
Heating or drying
C427S388100, C427S409000
Reexamination Certificate
active
06827981
ABSTRACT:
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to silane coatings for metals. More particularly, the present invention provides coatings which include a vinyl silane and a bis-silyl aminosilane, and are particularly useful for preventing corrosion. Solutions for applying such coatings, as well as methods of treating metal surfaces, are also provided.
2. Description of Related Art
Most metals are susceptible to corrosion, including the formation of various types of rust. Such corrosion will significantly affect the quality of such metals, as well as that of the products produced therefrom. Although rust and the like may often be removed, such steps are costly and may further diminish the strength of the metal. In addition, when polymer coatings such as paints, adhesives or rubbers are applied to the metals, corrosion may cause a loss of adhesion between the polymer coating and the metal.
By way of example, metallic coated steel sheet such as galvanized steel is used in many industries, including the automotive, construction and appliance industries. In most cases, the galvanized steel is painted or otherwise coated with a polymer layer to achieve a durable and aesthetically-pleasing product. Galvanized steel, particularly hot-dipped galvanized steel, however, often develops “white rust” during storage and shipment.
White rust (also called “wet-storage stain”) is typically caused by moisture condensation on the surface of galvanized steel which reacts with the zinc coating. On products such as GALVALUME®, the wet-storage stain is black in color (“black rust”). White rust (as well as black rust) is aesthetically unappealing and impairs the ability of the galvanized steel to be painted or otherwise coated with a polymer. Thus, prior to such coating, the surface of the galvanized steel must be pretreated in order to remove the white rust and prevent its reformation beneath the polymer layer. Various methods are currently employed to not only prevent the formation of white rust during shipment and storage, but also to prevent the formation of white rust beneath a polymer coating (e.g., paint).
In order to prevent white rust on hot-dipped galvanized steel during storage and shipping, the surface of the steel is often passivated by forming a thin chromate film on the surface of the steel. While such chromate coatings do provide resistance to the formation of white rust, chromium is highly toxic and environmentally undesirable. It is also known to employ a phosphate conversion coating in conjunction with a chromate rinse in order to improve paint adherence and provide corrosion protection. It is believed that the chromate rinse covers the pores in the phosphate coating, thereby improving the corrosion resistance and adhesion performance. Once again, however, it is highly desirable to eliminate the use of chromate altogether. Unfortunately, however, the phosphate conversion coating is generally not very effective without the chromate rinse.
Recently, various techniques for eliminating the use of chromate have been proposed. These include coating the galvanized steel with an inorganic silicate followed by treating the silicate coating with an organofunctional silane (U.S. Pat. No. 5,108,793). U.S. Pat. No. 5,292,549 teaches the rinsing of metallic coated steel sheet with a solution containing an organic silane and a crosslinking agent. Various other techniques for preventing the formation of white rust on galvanized steel, as well as preventing corrosion on other types of metals, have also been proposed. Many of these proposed techniques, however, are ineffective, or require time-consuming, energy-inefficient, multi-step processes. Thus, there is a need for a simple, low-cost technique for preventing corrosion on the surface of metal.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide a treatment method for metal surfaces, especially to prevent corrosion.
It is another object of the present invention to provide a treatment solution useful in preventing corrosion of metal surfaces, particularly zinc, zinc alloys, and other metals having a zinc-containing coating thereon.
It is yet another object of the present invention to provide a metal surface having improved corrosion resistance.
The foregoing objects can be accomplished, in accordance with one aspect of the present invention, by a method of treating a metal surface, comprising the steps of:
(a) providing a metal surface, said metal surface chosen from the group consisting of:
a metal surface having a zinc-containing coating;
zinc; and
zinc alloy;
and
(b) applying a silane solution to said metal surface, said silane solution having at least one vinyl silane and at least one bis-silyl aminosilane, wherein said at least one vinyl silane and said at least one bis-silyl aminosilane have been at least partially hydrolyzed.
The vinyl silane(s) may have a trisubstituted silyl group, wherein the substituents are individually chosen from the group consisting of hydroxy, alkoxy, aryloxy and acyloxy. Preferably, the vinyl silane comprises:
wherein:
each R
1
is individually chosen from the group consisting of: hydrogen, C
1
-C
24
alkyl and C
2
-C
24
acyl;
X
1
is chosen from the group consisting of: a C—Si bond, substituted aliphatic groups, unsubstituted aliphatic groups, substituted aromatic groups, and unsubstituted aromatic groups; and
each R
2
is individually chosen from the group consisting of: hydrogen, C
1
-C
6
alkyl, C
1
-C
6
alkyl substituted with at least one amino group, C
1
-C
6
alkenyl, C
1
-C
6
alkenyl substituted with at least one amino group, arylene, and alkylarylene.
The bis-silyl aminosilane(s) may comprise an aminosilane having two trisubstituted silyl groups, wherein the substituents are individually chosen from the group consisting of hydroxy, alkoxy, aryloxy and acyloxy. Preferably, the bis-silyl aminosilane comprises:
wherein:
each R
1
is individually chosen from the group consisting of: hydrogen, C
1
-C
24
alkyl and C
2
-C
24
acyl;
each R
3
is individually chosen from the group consisting of: substituted aliphatic groups, unsubstituted aliphatic groups, substituted aromatic groups, and unsubstituted aromatic groups; and
X
2
is either:
wherein each R
4
is individually chosen from the group consisting of: hydrogen, substituted and unsubstituted aliphatic groups, and substituted and unsubstituted aromatic groups; and
R
5
is chosen from the group consisting of: substituted and unsubstituted aliphatic groups, and substituted and unsubstituted aromatic groups.
The present invention also provides a solution (preferably aqueous) comprising at least one vinyl silane and at least one bis-silyl aminosilane, wherein the at least one vinyl silane and the at least one bis-silyl aminosilane are at least partially hydrolyzed. A metal surface having improved corrosion resistance is also provided.
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van Ooij Wim J.
Yuan Wei
Dinsmore & Shohl LLP
La Villa Michael
The University of Cincinnati
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