Coatings on ophthalmic lenses

• US 20070122540A1
• Filed: 11/27/2006
• Published: 05/31/2007
• Est. Priority Date: 11/29/2005
• Status: Abandoned Application

• Current Assignee: Bausch & Lomb Incorporated (Bausch Health Cos., Inc.)
• Original Assignee: Bausch & Lomb Incorporated (Bausch Health Cos., Inc.)
• Inventors: Kunzler, Jay, Ammon, Daniel, Linhardt, Jeffrey, Hook, Daniel, Salamone, Joseph
• Application Number:
  US11/604,635
• Publication Number:
  US 20070122540A1
• Time in Patent Office: Days
• US Class Current: 427/2.240
• CPC Class Codes: A61L 27/10 Ceramics or glasses
• CPC Class Codes: A61L 27/34 Macromolecular materials
• CPC Class Codes: A61L 29/085 Macromolecular materials
• CPC Class Codes: C08J 7/12 Chemical modification
• CPC Class Codes: C08L 43/04 Homopolymers or copolymers of monomers containing silicon
• CPC Class Codes: C08L 83/04 Polysiloxanes
• CPC Class Codes: G02B 1/043 Contact lenses
• CPC Class Codes: G02B 1/10 Optical coatings produced by application to, or surface treatment of, optical elements G02B1/08 takes precedence
• CPC Class Codes: G02B 1/12 by surface treatment, e.g. by irradiation

Abstract

This invention is directed toward surface treatment of a device. The surface treatment comprises the attachment of terminal functionalized surfactants to the surface of the substrate by means of reactive functionalities of the terminal functionalized surfactant material reacting with complementary surface reactive functionalities in monomeric units along the polymer substrate. The present invention is also directed to a surface modified medical device, examples of which include contact lenses, intraocular lenses, vascular stents, phakic intraocular lenses, aphakic intraocular lenses, corneal implants, catheters, implants, and the like, comprising a surface made by such a method.

Claims

1. A method of forming a surface modified medical device, the method comprising:

providing a medical device made of a copolymer that is the polymerization product of a monomer mixture comprising a monomer that has at least one group providing surface functionality to at least one surface of the medical device;

providing a surface modifying agent comprising a terminal functionalized surfactant having functionalized reactivity that is complimentary to the at least one group providing surface functionality of the medical device;

contacting the at least one surface having reactive functionality of the medical device with the surface modifying agent, and;

subjecting the device surface and surface modifying agent to reaction conditions suitable for forming a covalent bond between the device surface and the surface modifying agent to form a surface modified medical device.

2. The method of claim 1 wherein the monomer mixture comprises a silicon containing monomer.

3. The method of claim 2 wherein the silicon containing monomer comprises a silicon containing monomer selected from the group consisting of silicon containing vinyl carbonates, silicon containing vinyl carbamates, polyurethane-polysiloxanes having one or more hard-soft-hard blocks and end-capped with a hydrophilic monomer, fumarate containing silicon containing monomers, poly(organosiloxanes) capped with an unsaturated group at two or more ends of the molecule, polyurethane-polysiloxane macromonomers and mixtures thereof.

4. The method of claim 1 wherein the copolymer in the bulk monomer mixture that is to be copolymerized comprises 5 to 50 percent by weight of one or more silicon containing macromonomers, 5 to 75 percent by weight of one or more polysiloxanylalkyl (meth)acrylic monomers, and 10 to 50 percent by weight of a hydrophilic monomer.

5. The method of claim 1 wherein the copolymer in the bulk monomer mixture that is to be copolymerized comprises 10 to 25 percent by weight of one or more silicon containing macromonomers, 30 to 60 percent by weight of one or more polysiloxanylalkyl (meth)acrylic monomers, and 20 to 40 percent by weight of a hydrophilic monomer.

6. The method of claim 1 wherein the medical device comprises hydrogel materials.

7. The method of claim 1 wherein the medical device comprises silicon containing hydrogel materials.

8. The method of claim 1 wherein the medical device comprises vinyl functionalized polydimethylsiloxanes copolymerized with hydrophilic monomers.

9. The method of claim 1 wherein the medical device comprises fluorinated monomers.

10. The method of claim 1 wherein the medical device comprises methacrylate functionalized fluorinated polyethylene oxides copolymerized with hydrophilic monomers.

11. The method of claim 1 wherein the medical device is selected from the group consisting of heart valves, intraocular lenses, contact lenses, intrauterine devices, vessel substitutes, artificial ureters, vascular stents, phakic intraocular lenses, aphakic intraocular lenses, corneal implants, catheters, implants, and artificial breast tissue.

12. The method of claim 11 wherein the medical device formed is a soft contact lens.

13. The method of claim 12 wherein the medical device is a silicon containing hydrogel contact lens material.

14. The method of claim 1 wherein the medical device has at least one surface functionality selected from the group consisting of epoxides, carboxylic acids, anhydrides, oxazolinones, lactams, lactones, amines, hydroxys, hydrazines, hydrazides, thiols, nucleophilic groups, electrophilic groups, carboxylic esters, imide esters, orthoesters, carbonates, isocyanates, isothiocyanates, aldehydes, ketones, thiones, alkenyls, acrylates, methacrylates, acrylamides, sulfones, maleimides, disulfides, iodos, sulfonates, thiosulfonates, silanes, alkoxysilanes, halosilanes, phosphoramidate and alcohol functionality.

15. The method of claim 14 wherein the surface functionality is selected from the group consisting of aldehyde hydrates, hemiacetals, acetals, ketone hydrates, hemiketals, ketals, thioketals, and thioacetals.

16. The method of claim 14 wherein the surface functionality is selected from the group consisting of succinimidyl carbonate, succinimidyl ester, maleimide, benzotriazole carbonate, glycidyl ether, imidazoyl ester, p-nitrophenyl carbonate, acrylate, tresylate, aldehyde, and orthopyridyl disulfide.

17. The method of claim 1 wherein the surface modifying agent has at least one functionalized terminal selected from the group consisting of epoxides, carboxylic acids, anhydrides, oxazolinones, lactams, lactones, amines, hydroxys, hydrazines, hydrazides, thiols, nucleophilic groups, electrophilic groups, carboxylic esters, imide esters, orthoesters, carbonates, isocyanates, isothiocyanates, aldehydes, ketones, thiones, alkenyls, acrylates, methacrylates, acrylamides, sulfones, maleimides, disulfides, iodos, sulfonates, thiosulfonates, silanes, alkoxysilanes, halosilanes, phosphoramidate and alcohol functionality.

18. The method of claim 17 wherein the surface modifying agent has at least one functionalized terminal selected from the group consisting of aldehyde hydrates, hemiacetals, acetals, ketone hydrates, hemiketals, ketals, thioketals, and thioacetals.

19. The method of claim 17 wherein the surface modifying agent has at least one functionalized terminal selected from the group consisting of succinimidyl carbonate, succinimidyl ester, maleimide, benzotriazole carbonate, glycidyl ether, imidazoyl ester, p-nitrophenyl carbonate, acrylate, tresylate, aldehyde, and orthopyridyl disulfide.

20. The method of claim 17 wherein the surface modifying agent has at least one functionalized terminal selected from the group consisting of succinimidyl carbonate, succinimidyl ester, maleimide, benzotriazole carbonate, glycidyl ether, imidazoyl ester, p-nitrophenyl carbonate, acrylate, tresylate, aldehyde, and orthopyridyl disulfide.

42. The method of claim 1 wherein the step of subjecting the device surface and surface modifying agent to reaction conditions suitable for forming a covalent bond between the device surface and the surface modifying agent to form a surface modified medical device occurs under autoclave conditions.

43. The method of claim 42 further comprising the step of applying a lid stock to a package containing the device and the surface modifying agent prior to subjecting it to the step of autoclaving.

44. The method of claim 43 further comprising the steps of removing the surface modifying agent after autoclaving, rinsing the coated device, providing a storage solution and further autoclaving the device to sterilize the device.

48. A method of inhibiting the attachment of bacteria to a medical device, the method comprising the method of claim 1.

49. A method of inhibiting the attachment of bacteria to a device, the method comprising the method of claim 1.

52. The method of claim 1 wherein the monomer mixture comprises vinal acid, N-vinyl pyrollidinone, vinyl carbonate terminated PDMS, 3-[tris(trimethylsiloxy)silyl]propylvinyl carbamate.

53. The method of claim 1 wherein the monomer mixture comprises diluent, vinal acid, N-vinyl pyrollidinone, fluorine containing vinyl carbonate terminated PDMS, 3-[tris(trimethylsiloxy)silyl]propylvinyl carbamate.

54. The method of claim 1 wherein the monomer mixture comprises methacrylic acid, neopentyl glycol dimethacrylate, methyl methacrylate, N-vinyl pyrollidinone, methacrylate terminated PDMS, 3-[tris(trimethylsiloxy)silyl]propyl methacrylate, bis-hexafluoroitaconate and hexafluoroisopropyl methacrylate.

21. A method of forming a surface modified medical device, the method comprising:

providing a medical device made of a copolymer that is the polymerization product of a monomer mixture wherein the polymerized monomer mixture does not contain a surface functionality;

providing a surface functionality to at least one surface of the medical device;

providing a surface modifying agent comprising a terminal functionalized surfactant having functionalized reactivity that is complimentary to the at least one group providing surface functionality of the medical device;

contacting the at least one surface having reactive functionality of the medical device with the surface modifying agent, and;

subjecting the device surface and surface modifying agent to reaction conditions suitable for forming a covalent bond between the device surface and the surface modifying agent to form a surface modified medical device.

22. The method of claim 21 wherein the surface functionality is provided by a plasma treatment selected from the group consisting of gaseous plasma treatment, atmospheric plasma treatment, corona treatment and UV/ozone treatment.

23. The method of claim 22 wherein the gaseous plasma treatment comprises at least one defluorinating plasma treatment selected from the group consisting of oxygen plasma treatments, hydrogen-ammonia treatments, ammonia-butadiene-ammonia (ABA) treatments, hydrogen-ammonia-butadiene-ammonia (HABA) treatments and combinations thereof.

24. The method of claim 22 wherein the step of plasma treatment is conducted in the presence of a gas or mixture of gases.

25. The method of claim 24 wherein the gas or mixture of gases is selected from hydrogen, hydrogen in an inert gas, hydrogen in argon and mixtures thereof.

26. The method of claim 22 wherein the plasma treatment utilizes an electric discharge frequency of about 13.56 MHz between about 100-1000 watts at a pressure of about 0.1 -1.0 torr.

27. The method of claim 22 wherein the plasma treatment utilizes an electric discharge frequency of about 13.56 MHz between about 200 to 800 watts.

28. The method of claim 21 further comprising the step of flipping the medical device over to better treat both sides of the lens.

29. The method of claim 22 wherein the plasma-treatment gas is suitably provided at a flow rate of 50 to 500 sccm.

30. The method of claim 22 wherein the plasma-treatment gas is suitably provided at a flow rate of 100 to 300 sccm.

31. The method of claim 21 wherein the medical device is supported within a vessel on a support device designed to adjust the position of the medical devices.

32. The method of claim 21 wherein the medical devices may be provided the surface functionality by placing them, in their unhydrated state, within an electric glow discharge reaction vessel.

33. The method of claim 22 wherein the medical device comprises a hydrogen-plasma treated fluorinated polymeric surface which is subsequently oxidized by an oxidizing plasma.

34. The method of claim 33 wherein the oxidizing plasma is selected from the group consisting of oxygen gas, water, peroxide, air, ammonia, methanol, acetone, alkylamines and mixtures thereof.

35. The method of claim 21 wherein the medical device formed is selected from the group consisting of heart valves, intraocular lenses, contact lenses, intrauterine devices, vessel substitutes, artificial ureters and artificial breast tissue.

36. The method of claim 35 wherein the medical device formed is a contact lens.

37. The method of claim 36 wherein the medical device formed is a soft contact lens.

45. The method of claim 21 wherein the step of subjecting the device surface and surface modifying agent to reaction conditions suitable for forming a covalent bond between the device surface and the surface modifying agent to form a surface modified medical device occurs under autoclave conditions.

46. The method of claim 45 further comprising the step of applying a lid stock to a package containing the device and the surface modifying agent prior to subjecting it to the step of autoclaving.

47. The method of claim 45 further comprising the steps of removing the surface modifying agent after autoclaving, rinsing the coated device, providing a storage solution and further autoclaving the device to sterilize the device.

50. A method of inhibiting the attachment of bacteria to a device, the method comprising the method of claim 21.

38. A surface modified medical device comprising:

a medical device manufactured from a monomer mixture conprising surface functionality after polymerization of the monomer mixture; and

one or more reactive terminal functionalized surfactants applied to the surface of the medical device;

whereby a chemical reaction between the surface functionality of the medical device and the one or more reactive terminal functionalized surfactants forms covalent bonds there between.

39. The surface modified medical device of claim 38 wherein the medical device is a contact lens.

40. The surface modified medical device of claim 38 wherein the medical device is a hydrophilic contact lens.

41. The surface modified medical device of claim 38 wherein the medical device is a hydrogel contact lens.

51. The surface modified device of claim 38 wherein the device is resistant to the attachment of bacteria.