Surface coating of polymer objects

• US 5,135,297 A
• Filed: 11/27/1990
• Issued: 08/04/1992
• Est. Priority Date: 11/27/1990
• Status: Expired due to Term

• Current Assignee: Bausch & Lomb Incorporated (Bausch Health Cos., Inc.)
• Original Assignee: Bausch & Lomb Incorporated (Bausch Health Cos., Inc.)
• Inventors: Valint, Paul L. Jr.
• Primary Examiner(s): BELL, JANYCE A
• Application Number:
  US07/618,441
• Time in Patent Office: 616 Days
• Field of Search: 427/54.1, 427/164, 427/430.1, 428/500, 428/514, 351/160 R, 351/166
• US Class Current: 351/160.00R
• CPC Class Codes: C08F 220/22 Esters containing halogen
• CPC Class Codes: C08F 290/04 Polymers provided for in subclasses C08C or C08F
• CPC Class Codes: C08F 299/00 Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
• CPC Class Codes: C08J 7/0427 with only one layer of a composition containing a polymer binder with more layers C08J7/042
• CPC Class Codes: C08J 7/056 Forming hydrophilic coatings
• CPC Class Codes: C09D 155/005 Homopolymers or copolymers obtained by polymerisation of macromolecular compounds terminated by a carbon-to-carbon double bond
• CPC Class Codes: G02B 1/043 Contact lenses
• CPC Class Codes: Y10T 428/31855 Of addition polymer from unsaturated monomers
• CPC Class Codes: Y10T 428/31906 Ester, halide or nitrile of addition polymer

Abstract

A method of modifying surfaces of polymeric objects which comprises immersing the polymeric object in an aqueous dispersion of a polymerizable surfactant, a cross-linking agent, and a free radical initiator and exposing the immersant to ultraviolet light to form a permanent, cross-linked surface coating on the object. Also disclosed are coated objects prepared by this method, which is particularly suited for coating contact lenses.

Claims

1. A method of modifying the surface of a polymeric object which comprises immersing the polymeric object in an aqueous dispersion of a surface active macromer described by the formula:

DC wherein A is at least one ethylenically unsaturated hydrophobic monomer, B is at least one ethylenically unsaturated hydrophilic monomer, C is a functional chain transfer agent, D is an ethylenically unsaturated end group, y is within the range from about 0.1 to about 0.9, and x+y=1, a hydrophobic cross-linking agent, and a free radical initiator and exposing the immersed polymeric object to ultraviolet light to form a permanent, cross-linked surface coating on the polymeric object.

2. The method of claim 1 wherein the aqueous dispersion contains a surface active macromer at a molar concentration of about 0.1 to 0.001, from about 1 to about 10^-4 parts by weight of a cross-linking agent, and from about 0.1 to about 10^-4 parts by weight of a free radical initiator.

3. The method of claim 1 wherein A is selected from the group consisting of ethylenically unsaturated polyoxyalkylenes, polyacrylamides, polyvinylpyrrolidones, polyvinyl alcohols, poly (HEMA), and N-alkyl-N-vinyl acetamide.

4. The method of claim 1 wherein A is an ethylenically unsaturated polyoxyalkylene selected from the group consisting of (meth)acrylated polyoxyalkylenes, (meth)acrylamido polyoxyalkylenes, styrenyl polyoxyalkylenes, alkenyl polyoxyalkylenes, vinyl carbonate polyoxyalkylenes and vinyl carbamate polyoxyalkylenes.

5. The method of claim 4 wherein the polyoxyalkylene is polyethylene oxide.

6. The method of claim 1 wherein A is (meth)acrylated polyethylene oxide.

7. The method of claim 6 wherein A is methoxy polyethylene glycol methacrylate.

8. The method of claim 3 wherein A is a methacrylate endcapped poly-N-vinylpyrrolidinone.

9. The method of claim 3 wherein A is a methaorylate endcapped poly-N,N-dimethylacrylamide.

10. The method of claim 1 wherein B is selected from the group consisting of alkyl (meth)acrylates, N-alkyl (meth)acrylamides, alkyl vinylcarbonates, alkyl vinylcarbamates, fluoroalkyl (meth)acrylates, N-fluoroalkyl (meth)acrylamides, N-fluoroalkyl vinylcarbonates, N-fluoroalkyl vinylcarbamates, silicone-containing (meth)acrylates, (meth)acrylamides, vinyl carbonates, vinyl carbamates, styrenic monomers and polyoxypropylene (meth)acrylates.

11. The method of claim 10 wherein the styrenic monomers are selected from the group consisting of styrene, alpha-methyl styrene, paramethyl styrene, para-t-butyl monochloro styrene, and para-t-butyl dichloro styrene.

12. The method of claim 10 wherein B is 1-H,1-H,5-H-octafluoropentyl methacrylate.

13. The method of claim 1 wherein C is selected from the group consisting of mercapto carboxylic acids, mercapto alcohols, and aminomercaptans.

14. The method of claim 13 wherein C is thioglycolic acid.

15. The method of claim 13 wherein C is 2-mercaptoethanol.

16. The method of claim 13 wherein C is 2-aminoethane thiol.

17. The method of claim 14 wherein D is a (meth)acrylated hydroxy ester moiety derived from glycidyl (meth)acrylate.

18. The method of claim 15 wherein D is a (meth)acrylated ester moiety derived from (meth)acryloyl chloride.

19. The method of claim 15 wherein D is a (meth)acrylated urethane moiety derived from (meth)acrylated isocyanate.

20. The method of claim 16 wherein D is a (meth)acrylated urea moiety derived from (meth)acrylated isocyanate.

21. The method of claim 15 wherein D is a vinylcarbonate moiety derived from vinyl chloroformate.

22. The method of claim 16 wherein D is a (meth)acrylated amide moiety derived from (meth)acryloyl chloride.

23. The method of claim 16 wherein D is a vinylcarbamate moiety derived from vinyl chloroformate.

24. The method of claim 1 wherein the polymeric object is a contact lens.

25. The method of claim 24 wherein the contact lens is a hydrogel contact lens.

26. The method of claim 24 wherein the contact lens is a rigid gas permeable lens.

27. The method of claim 24 wherein the contact lens is a silicone elastomer contact lens.

28. The method of claim 1 wherein the cross-linking agent is selected from the group consisting of hydrophobic molecules having two or more polymerizable groups.

29. The method of claim 28 wherein the cross-linking agent is selected from the group consisting of hydrophobic molecules having two or more (meth)acrylate groups.

30. The method of claim 28 wherein the cross-linking agent is selected from the group consisting of hydrophobic molecules having two or more (meth)acrylamide groups.

31. The method of claim 28 wherein the cross-linking agent is neopentyl glycol dimethacrylate.

32. A surface-modified polymeric object prepared by immersing the polymeric object in an aqueous dispersion of a surface active macromer described by the formula:

DC wherein A is at least one ethylenically unsaturated hydrophobic monomer, B is at least one ethylenically unsaturated hydrophilic monomer, C is a functional claim transfer agent, D is an ethylenically unsaturated end group, y is within the range from about 0.1 to about 0.9, and x+y=1, a hydrophobic cross-linking agent, and a free radical initiator and exposing the immersed polymeric object to ultraviolet light to form a permanent, cross-linked surface coating on the polymeric object.

33. The surface-modified polymeric object of claim 32 wherein the object is a contact lens.