Aqueous crosslinkable coating compositions based on vinyl fluoropolymer

• US 7,247,671 B2
• Filed: 07/22/2002
• Issued: 07/24/2007
• Est. Priority Date: 08/14/2001
• Status: Expired due to Fees

• Current Assignee: DSM IP Assets BV (DSM-Firmenich AG)
• Original Assignee: DSM IP Assets BV (DSM-Firmenich AG)
• Inventors: Overbeek, Gerardus Cornelis, Scheerder, Jurgen, Nabuurs, Tijs
• Primary Examiner(s): Smith; Duane
• Assistant Examiner(s): WU, IVES J
• Application Number:
  US10/485,572
• Publication Number:
  US 20050004300A1
• Time in Patent Office: 1,828 Days
• Field of Search: 524/544, 525/326.2
• US Class Current: 524/544
• CPC Class Codes: C08G 18/4833 Polyethers containing oxyethylene units
• CPC Class Codes: C08G 18/6279 containing fluorine atoms
• CPC Class Codes: C08G 18/706 the liquid medium being water
• CPC Class Codes: C08L 2666/14 Macromolecular compounds according to C08L59/00 - C08L87/00; Derivatives thereof
• CPC Class Codes: C08L 61/20 Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen with aminophenols C08L61/04
• CPC Class Codes: C09D 133/16 Homopolymers or copolymers of esters containing halogen atoms
• CPC Class Codes: C09D 175/04 Polyurethanes

Abstract

Aqueous crosslinkable coating composition suitable for anti-graffiti and heavy duty applications comprising: (A) an aqueous polymer emulsion comprising at least one vinyl fluoropolymer which comprises as a polymerized constituent monomer thereof (i) a fluoromonomer(s) having the formula (1) wherein R¹ is CH₃ or H, R² is a per-fluorinated C_1-5 alkyl group and n is 1, 2, 3 or 4, (ii) a hydroxyl functional monomer(s) and (iii) a carboxylic acid-functional monomer(s) where the vinyl fluoropolymer has a glass transition temperature Tg within the range of from −50 to 90° C. and (B) at least one hydroxyl-reactive crosslinker material

Claims

1. Aqueous crosslinkable coating composition suitable for anti-graffiti and heavy duty applications comprising:

(A) an aqueous polymer emulsion comprising at least one vinyl fluoropolymer in which;

(i) said at least one vinyl fluoropolymer comprises as a polymerised constituent monomer thereof a fluoromonomer(s) having the formula;

2. Composition according to claim 1 wherein the amount of fluoromonomer(s) of formula (1) used to prepare said at least one fluoropolymer of component (A) is within the range of from 5 to 50 weight % based on the total amount of monomers employed.

3. Composition according to claim 1 wherein the fluoromonomer of formula (1) is 2,2,2-trifluoroethyl methacrylate (TFEMA) or 2,2,2,-trifluoroethyl acrylate (TFEA).

4. Composition according to claim 1 wherein the hydroxyl value of said at least one fluoropolymer of component (A) is within the range of from 20 to 175 mg KOH/g of solid polymer.

5. Composition according to claim 1 wherein said hydroxy functional monomer(s) of (ii) is selected from one or more of 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxy-n-propyl methacrylate, 2-hydroxy-n-propyl acrylate, 3-hydroxy-n-propyl methacrylate, 3-hydroxy-n-propyl acrylate and 4-hydroxy-n-butyl acrylate.

6. Composition according to claim 1 wherein the acid value of said at least one fluoropolymer of component (A) is within the range of from 4 to 55 mg KOH/g of solid polymer.

7. Composition according to claim 1 wherein said carboxylic acid functional monomer(s) of (iii) is selected from one or more of acrylic acid, methacrylic acid, beta-carboxyethyl acrylate, itaconic acid, crotonic acid, fumaric acid, maleic acid and maleic anhydride.

8. Composition according to claim 1 wherein said non-fluoro, non-hydroxyl, non-acid vinyl monomer(s) of component (A) is selected from one or more esters of acrylic acid and methacrylic acids of formula

CH₂═

CR⁴CO₂R⁵

wherein R⁴ is H or methyl and R⁵ is optionally substituted alkyl of 1 to 20 carbon atoms or cycloalkyl of 5 to 12 ring carbon atoms but which exclude fluorine-containing, acid-containing and hydroxy containing groups;

styrene; and

α

-methyl styrene.

9. Composition according to claim 1 wherein said at least one vinyl fluoropolymer of component (A) is made using an aqueous emulsion polymerisation process.

10. Composition according to claim 1 wherein the Tg of said at least one vinyl fluoropolymer of component (A) is within the range of from 0 to 60°

C.

11. Composition according to claim 1 wherein the average particle size of said at least one vinyl fluoropolymer of component (A) is within the range of from 20 to 500 nm.

12. Composition according to claim 1 wherein the weight average molecular weight of said at least one vinyl fluoropolymer of component (A) is within the range of from 5,000 to 5,000,000 Daltons.

13. Composition according to claim 1 wherein said at least one hydroxyl-reactive crosslinker material(s) of component (B) is selected from organic polyisocyanates, organic blocked polyisocyanates, organic isothiocyanates and melamine-based resins.

14. Composition according to claim 1 wherein the aqueous polymer emulsion of component (A) further comprises a non-fluoropolymer(s).

15. Composition according to claim 14 wherein said non-fluoropolymer is hydroxyl-functional.

16. Composition according to claim 14 wherein said non-fluoropolymer is acid-functional.

17. Composition according to claim 14 wherein said non-fluoropolymer(s) has an average particle size within the range of from 30 to 600 nm.

19. Composition according to claim 14 wherein the Tg of the non-fluoropolymer(s) is in the range of from −

50 to 90°

C.

20. Composition according claim 14 wherein said non-fluoropolymer(s) of component (A) is derived from a monomer system which comprises 32 to 100 weight % of a non-fluoro, non-acid, non-hydroxyl monomer(s);

0 to 58 weight % of a non-fluoro, non-acid, hydroxyl functional monomer(s) and 0 to 10 weight % of a non-fluoro, non-hydroxy, carboxylic acid-functional monomer(s) wherein all weight % values are based on the total weight of monomers used for the polymerisation.

21. Composition according to claim 14 wherein the weight ratio of fluoropolymer(s)/non-fluoropolymer(s) is within the range of from 99/1 to 10/90.

22. Method of coating a substrate which comprises applying a coating composition according to claim 1 to a substrate, causing or allowing the aqueous carrier medium of the composition to be removed, and developing crosslinking of the coating that has been applied to the substrate.

23. A crosslinked coating derived from a coating composition according to claim 1.

24. Coated substrate which has been prepared using a method according to claim 22.

18. Aqueous crosslinkable coating composition suitable for anti-graffiti and heavy duty applications comprising:

(A) an aqueous polymer emulsion comprising at least one vinyl fluoropolymer in which;

(i) said at least one vinyl fluoropolymer comprises as a polymerised constituent monomer thereof a fluoromonomer(s) having the formula;

25. Aqueous crosslinkable coating composition suitable for anti-graffiti and heavy duty applications comprising:

(A) an aqueous polymer emulsion comprising at least one vinyl fluoropolymer in which;

(i) said at least one vinyl fluoropolymer comprises as a polymerised constituent monomer thereof a fluoromonomer(s) having the formula;