Inorganic composite coatings comprising novel functionalized acrylics

Patent metadata

Field	Value
Publication number	US-9963786-B2
Application number	US-201313833675-A
Country	US
Kind code	B2
Filing date	Mar 15, 2013
Priority date	Mar 15, 2013
Publication date	May 8, 2018
Grant date	May 8, 2018

Abstract

Disclosed is a sol-gel coating composition comprising: one or more silane hydrolysis promoting acids; at least one silanol precursor; and an acrylic-based co-polymer comprising nitrogen-containing organic functional groups, and methods of making and using same, as well as metals coated using the compositions.

First claim

What is claimed is:

1. A sol-gel coating composition comprising:
a) one or more silane hydrolysis promoting acids;
b) at least one silanol precursor; and
c) 10 to 35% by weight of an acrylic-based co-polymer formed by copolymerization of a combination of monomers consisting of a monomer bearing a nitrogen-containing organic functional group and one or more co-monomers and comprising nitrogen-containing organic functional groups, based on a total weight of the sol-gel composition excluding water and solvents, wherein the acrylic-based co-polymer has a glass transition temperature of from 0 to 50° C.;

wherein the nitrogen-containing organic functional groups are selected from the group consisting of thiourea, thiazole and combinations thereof;
and
wherein the co-monomers co-polymerized with the monomer bearing a nitrogen-containing organic group to form the acrylic-based co-polymer are selected from the group consisting of methyl methacrylate, 2-ethylhexyl acrylate, n-butyl methacrylate, butyl acrylate, styrene, alpha-methylstyrene, acrylamide, acrylonitrile, methacrylonitrile, methylenebutyrolactone, vinylpyrrolidone, vinyl acetate and combinations thereof.

2. The sol-gel coating composition of claim 1 further comprising a source of vanadium.

3. The sol-gel coating composition of claim 1 wherein the nitrogen-containing organic functional groups are present in an amount of about 0.5-15% by weight based on a total weight of the acrylic-based co-polymer on a dry-solids basis.

4. The sol-gel coating composition of claim 1 wherein the at least one silanol precursor comprises at least one of tetraethylorthosilicate, methyltriethoxysilane, 3-glycidyloxypropyltriethoxysilane, and aminoethylaminopropyltrimethoxysilane.

5. The sol-gel coating composition of claim 1 wherein the sol-gel coating composition further comprises a surfactant and the co-monomers co-polymerized to form the acrylic-based co-polymer are selected from the group consisting of n-butyl methacrylate, styrene, methyl methacrylate, 2 ethylhexyl acrylate and combinations thereof.

6. The sol-gel coating composition of claim 1 , wherein the monomer bearing a nitrogen-containing organic functional group is selected from the group consisting of N-allyl thiourea and 4-methyl-5-vinylthiazole and the co-monomers co-polymerized with the monomer bearing a nitrogen-containing organic group to form the acrylic-based co-polymer are a combination of methyl methacrylate, 2-ethylhexyl acrylate, n-butyl methacrylate and styrene.

7. A coated metal substrate comprising:
a. at least one metal surface;
b. deposited on and chemically adhered to said at least one metal surface an organic-inorganic composite coating comprising reaction products of the composition of claim 1 with the metal surface and products of condensation of the sol-gel.

8. The coated metal substrate according to claim 7 , wherein the organic-inorganic composite coating on the coated metal substrate further comprises vanadium.

9. An article of manufacture comprising the coated metal substrate according to claim 7 , said article of manufacture being selected from a component of a vehicle, an architectural element, a household appliance and an electronic device.

10. The coated metal substrate according to claim 7 , wherein said at least one metal surface comprises galvanized metal.

11. A coated metal substrate comprising:
a. a metal substrate having at least one metal surface comprising aluminum or an alloy thereof, at least a portion of said surface comprising a metal oxide chemically adhered thereto;
b. deposited on and chemically adhered to said metal substrate an organic-inorganic composite coating comprising products of condensation of the sol-gel composition of claim 1 .

12. The coated metal substrate according to claim 11 , wherein the organic-inorganic composite coating comprises reaction products of said sol-gel composition with one or more of the metal surface and the metal oxide.

13. The coated metal substrate according to claim 11 , wherein said metal oxide comprises titanium dioxide and/or zirconium dioxide.

14. A method of coating a metal surface comprising:
a. optionally, cleaning a metal substrate having at least one metal surface, at least a portion of said surface optionally comprising a metal oxide chemically adhered thereto;
b. contacting the at least one metal surface with a sol-gel coating composition according to claim 1 ;
c. drying said sol-gel coating composition in place on the at least one metal surface, such that the sol-gel coating composition reacts with said metal surface thereby forming a chemically adhered organic-inorganic composite coating on the metal surface, the organic-inorganic composite coating comprising silicon-based polymer chains and acrylic-based polymer chains.

15. The method of coating a metal surface according to claim 14 , wherein the sol-gel coating composition is applied in a continuous process.

16. The method of coating a metal surface according to claim 14 , wherein the contacting step immediately follows a galvanizing treatment and the metal surface being contacted comprises galvanized metal.

17. The method of coating a metal surface according to claim 14 , wherein the metal oxide is present on the metal substrate, said metal substrate comprising aluminum or an alloy thereof and said metal oxide comprising titanium dioxide and/or zirconium dioxide.

18. The method of coating a metal surface according to claim 14 , wherein during at least a portion of drying step c., the metal surface has a peak metal temperature ranging from about 40° C. to about 150° C.

19. A sol-gel coating composition comprising:
a) one or more silane hydrolysis promoting acids;
b) at least one silanol precursor; and
c) 10 to 35% by weight of an acrylic-based co-polymer comprising nitrogen-containing organic functional groups, based on a total weight of the sol-gel composition excluding the weight of water and solvents, wherein the nitrogen-containing organic functional groups comprise thiourea and the nitrogen-containing organic functional groups are present in an amount of 2 to 6% by weight based on a total weight of the acrylic-based co-polymer on a dry-solids basis wherein the acrylic-based co-polymer has a glass transition temperature of from 0 to 50° C.

20. The sol-gel coating composition of claim 19 further comprising a source of vanadium.

21. The sol-gel coating composition of claim 19 wherein the nitrogen-containing organic functional groups further comprise one or more of a thiazole and an imidazole.

22. The sol-gel coating composition of claim 19 wherein the at least one silanol precursor is selected from the group consisting of silicic acid esters, alkylalkoxysilanes, and organofunctionalsilanes.

23. A sol-gel coating composition consisting of:
a) one or more silane hydrolysis promoting inorganic acids;
b) about 55 to about 85 wt % of at least one silanol precursor, based on a total weight of the sol-gel coating composition excluding the weight of water and solvents;
c) 10 to 35% by weight of an acrylic-based co-polymer comprising nitrogen-containing organic functional groups, based on a total weight of the sol-gel coating composition excluding the weight of water and solvents wherein the nitrogen-containing organic functional groups are selected from the group consisting of thiourea, thiazole and combinations thereof, and wherein the acrylic-based co-polymer has a glass transition t

Assignees

• Henkel Ag & Co Kgaa

Inventors

• Bammel Brian D
• Mcgee John D
• Donaldson Gregory T

Classifications

• C09D5/08

  Anti-corrosive paints · CPC title

• C09D139/04

  Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member · CPC title

• Y10T428/31663

  As siloxane, silicone or silane · CPC title

• C09D133/10

  Homopolymers or copolymers of methacrylic acid esters · CPC title

• C09D133/12

  Homopolymers or copolymers of methyl methacrylate · CPC title