Surface treatment of silicone hydrogel contact lenses comprising hydrophilic polymer chains attached to an intermediate carbon coating

• US 6,630,243 B2
• Filed: 05/20/1999
• Issued: 10/07/2003
• Est. Priority Date: 05/20/1999
• Status: Expired due to Fees

• Current Assignee: Bausch & Lomb Incorporated (Bausch Health Cos., Inc.)
• Original Assignee: Bausch & Lomb Incorporated (Bausch Health Cos., Inc.)
• Inventors: McGee, Joseph A., Grobe, George L. III, Valint, Paul L. Jr., Ammon, Daniel M. Jr., Ozark, Richard M.
• Primary Examiner(s): Beck, Shrive P.
• Assistant Examiner(s): LIGHTFOOT, ELENA TSOY
• Application Number:
  US09/315,306
• Publication Number:
  US 20020102415A1
• Time in Patent Office: 1,601 Days
• Field of Search: 428/447, 428/446, 428/421, 428/411.1, 428/420, 427/2.24, 427/533, 427/536, 427/539, 544/72, 351/160.H, 351/177, 424/422, 623/6.62
• US Class Current: 428/420
• CPC Class Codes: B29D 11/00192 Demoulding, e.g. separating lenses from mould halves
• CPC Class Codes: C08J 2383/04 Polysiloxanes
• CPC Class Codes: C08J 7/0423 with at least one layer of inorganic material and at least one layer of a composition containing a polymer binder
• CPC Class Codes: C08J 7/056 Forming hydrophilic coatings
• CPC Class Codes: C08L 83/10 Block- or graft-copolymers containing polysiloxane sequences obtained by polymerising a compound having a carbon-to-carbon double bond on to a polysiloxane C08L51/08, C08L53/00
• CPC Class Codes: G02B 1/043 Contact lenses
• CPC Class Codes: Y10T 428/249921 Web or sheet containing structurally defined element or component
• CPC Class Codes: Y10T 428/31504 Composite [nonstructural laminate]
• CPC Class Codes: Y10T 428/31536 Including interfacial reaction product of adjacent layers
• CPC Class Codes: Y10T 428/3154 Of fluorinated addition polymer from unsaturated monomers
• CPC Class Codes: Y10T 428/31663 As siloxane, silicone or silane

Abstract

The present invention provides an optically clear, hydrophilic coating upon the surface of a silicone medical device by sequentially subjecting the surface of the lens to plasma polymerization in a hydrocarbon-containing atmosphere and then covalently attaching a preformed hydrophilic polymer to the surface of the carbon coating. The invention is especially useful for forming a biocompatible coating on a silicone contact lens.

Claims

1. A method for treating the surface of a silicone medical device comprising the following steps:

(a) subjecting the surface of the silicone medical device to a plasma-polymerization reaction in a hydrocarbon-containing atmosphere to form a polymeric carbonaceous layer on the surface of the silicone medical device having a thickness of 50 to 500 Angstroms;

(b) forming reactive functionalities on the surface of the carbonaceous layer; and

(c) exposing the surface of the silicone medical device to a solution of a hydrophilic reactive polymer having complementary reactive functionalities on the carbonaceous layer, thereby forming a biocompatible surface on the silicone medical device,

wherein the silicone medical device is a silicone contact lens or silicone intraocular device.

2. The method of claim 1, wherein the silicone medical device is a silicone hydrogel, continuous-wear contact lens.

3. The method of claim 2, wherein prior to step (a), the lens is subjected to a plasma pretreatment to improve adhesion of the carbonaceous layer onto the surface of the lens.

4. The method of claim 3, wherein the plasma pretreatment comprises oxidation of the surface with a nitrogen or oxygen-containing oxidizing gas.

6. The method of claim 4, wherein the plasma pretreatment is conducted in an oxygen-containing or nitrogen-containing atmosphere, comprising a gas selected from at least one of:

ambient air, oxygen gas, ammonia, hydrogen peroxide, alcohol, and water.

7. The method of claim 1, wherein the plasma polymerization reaction of step (b) is conducted in an atmosphere comprising hydrocarbons having between 1 to 10 carbon atoms.

8. The method of claim 7, wherein the hydrocarbons are aliphatic or olefinic and comprise 4 to 8 carbon atoms.

9. The method of claim 8, wherein the hydrocarbons comprise at least one of:

butane, isoprene, isobutylene, and 1,3-butadiene.

11. The method of claim 1, wherein the hydrophilic reactive polymer comprises 0 to 99 mole percent of monomeric units that are derived from non-reactive hydrophilic monomers.

12. The method of claim 11, wherein the polymer comprises 50 to 95 mole percent of monomeric units derived from non-reactive hydrophilic monomers selected from the group consisting of acrylamides, lactones, poly(alkyleneoxy)methacrylates, methacrylic acid or hydroxyalkyl methacrylates, and 5 to 50 percent of monomeric units derived from compatible functionally reactive monomers selected from the group consisting of isocyanate, epoxy, azlactone, and anhydride containing monomers, and combinations thereof, wherein the alkyl or alkylene groups have 1 to 6 carbon atoms.

13. The method of claim 11, wherein the hydrophilic monomers are selected from the group consisting of dimethylacrylamide, acrylamide, hydroxyethyl methacrylate, and N-vinyl pyrrolidinone.

14. The method of claim 1, wherein the hydrophilic reactive polymer comprises 0 to 20 mole percent monomeric units derived from hydrophobic monomers.

15. The method of claim 1, wherein the hydrophilic reactive polymer comprises oxazolinone moieties having the following formula:

wherein R³ and R⁴ independently can be an alkyl group having 1 to 14 carbon atoms;

a cycloalkyl group having 3 to 14 carbon atoms;

an aryl group having 5 to 12 ring atoms;

an arenyl group having 6 to 26 carbon atoms; and

0 to 3 heteroatoms selected from S, N, and nonperoxidic O;

or

R³ and R⁴ taken together with the carbon to which they are joined can form a carbocyclic ring containing 4 to 12 ring atoms, and n is an integer 0 or 1.

16. The method of claim 15, wherein the polymer comprises the reaction product of a mixture of monomers comprising the monomer represented by the general formula:

where R¹ and R² independently denote a hydrogen atom or a lower alkyl radical with one to six carbon atoms, and R³ and R⁴ independently denote alkyl radicals with one to six carbon atoms or a cycloalkyl radicals with 5 or 6 carbon atoms.

17. The method of claim 16, wherein the monomer is selected from the group consisting of 2-vinyl-4,4-dimethyl-2-oxazolin-5-one;

2-isopropenyl-4,4-dimethyl-2-oxazolin-5-one; and

2-vinyl-4,4-dimethyl-2-oxazolin-5-one.

18. The method of claim 1, wherein the medical device is dipped in a solution comprising at least one hydrophilic reactive polymer.

19. The method of claim 1, wherein the carbon layer is subjected to a plasma treatment with a gas comprising ammonia or an alkyl amine.

30. The method of claim 11, wherein the hydrophilic monomers are selected from the group consisting of dimethylacrylamide, acrylamide, hydroxyethyl methacrylate, and N-vinyl pyrrolidinone.

5. The method of claim 5, wherein the plasma pretreatment is conducted at 10 to 1000 watts for a period of 1 to 10 minutes at a pressure of 0.1 to 1.0 torr.

10. A method for treating the surface of a silicone medical device comprising the following steps:

(a) subjecting the surface of the silicone medical device to a plasma-polymerization reaction in a hydrocarbon-containing atmosphere to form a polymeric carbonaceous layer on the surface of the silicone medical device having a thickness of 50 to 500 Angstroms;

(b) forming reactive functionalities on the surface of the carbonaceous layer by plasma treatment with a nitrogen-containing gas or gaseous mixture; and

(c) exposing the surface of the silicone medical device to a solution of a hydrophilic reactive polymer having complementary reactive functionalities on the carbonaceous layer, thereby forming a biocompatible surface on the silicone medical device.

20. A method for treating the surface of a silicone medical device comprising the following steps:

(a) subjecting the surface of the silicone medical device to a plasma-polymerization reaction in a hydrocarbon-containing atmosphere to form a polymeric carbonaceous layer on the surface of the lens having a thickness of 50 to 500 Angstroms;

(b) forming reactive functionalities on the surface of the carbonaceous layer; and

exposing the surface of the silicone medical device to a solution of a hydrophilic reactive polymer selected from the group consisting of glycidyl methacrylate, maleic anhydride, itaconic anhydride, and isocyanotmethacrylate having complementary reactive functionalities along the polymer chain in order to covalently bond with said reactive functionalities on the carbonaceous layer, thereby forming a biocompatible surface on the silicone medical device.

31. The method of claim 20, wherein the reactive functionalities are formed by plasma treatment with a nitrogen-containing gas or gaseous mixture.

32. The method of claim 20, wherein the hydrophilic reactive polymer comprises 0 to 99 mole percent of monomeric units that are derived from non-reactive hydrophilic monomers.

21. A silicone medical device including a hydrophilic surface, wherein said surface comprises:

(a) a carbonaceous layer on the surface of the medical device; and

(b) hydrophilic polymer chains attached to the carbonaceous layer wherein the points of attachment are the result of the reaction of complementary reactive functionalities in monomeric units along the hydrophilic polymers with reactive functionalities on the carbonaceous layer wherein hydrophilic polymer chains attached to the carbonaceous layer are the result of the reaction of a mixture of polymers comprising (a) a first hydrophilic reactive polymer having reactive functionalities in monomeric units along the hydrophilic polymers complementary to reactive functionalities on the carbonaceous layer and, in addition, (b) a second hydrophilic reactive polymer having supplemental reactive functionalities that are reactive with the first hydrophilic reactive polymer and wherein the first hydrophilic reactive polymer is an epoxy-functional polymer and the second hydrophilic reactive polymer is an acid-functional polymer, either simultaneously or sequentially applied to the substrate to be coated.

22. The medical device of claim 21, wherein the medical device is a silicone contact lens or an intraocular lens.

23. The medical device of claim 21, wherein the medical device is a silicone hydrogel, continuous-wear lens.

24. The medical device of claim 21, wherein the hydrophilic polymer chains attached to the medical device are the result of the reaction of isocyanate or ring-opening reactive functionalities in monomeric units along the hydrophilic reactive polymers with said reactive functionalities on the surface of the medical device.

25. The medical device of claim 21, wherein the hydrophilic polymer chains comprise 1 to 100 mole percent of monomeric units having reacted reactive functionalities and 0 to 99 mole percent of monomeric units that are derived from non-reactive hydrophilic monomers.

26. The medical device of claim 21, wherein the reactive functionalities are derived from monomers containing one or more of the following groups:

glycidyl, azlactone, isocyanate, and acid anhydride.

27. The medical device of claim 21, wherein the hydrophilic monomeric units are derived from monomers selected from the group consisting of acrylamides, lactams, poly(alkyleneoxy)methacrylates, methacrylic acid or hydroxyalkyl methacrylates.

28. The medical device of claim 21, wherein the hydrophilic polymer chains comprise moieties along the chain having the following formula:

wherein R³ and R⁴ independently can be an alkyl group having 1 to 14 carbon atoms;

a cycloalkyl group having 3 to 14 carbon atoms;

an aryl group having 5 to 12 ring atoms;

an arenyl group having 6 to 26 carbon atoms; and

0 to 3 heteroatoms selected from S, N, and nonperoxidic 0;

or

R¹ and R² taken together with the carbon to which they are joined can form a carbocyclic ring containing 4 to 12 ring atoms, and n is an integer 0 or 1.

29. The medical device claim 21, wherein the hydrophilic polymer chains comprise moieties along the chain represented by the general formula:

where R³ and R⁴ independently denote a hydrogen atom or a lower alkyl radical with one to six carbon atoms, and R³ and R⁴ independently denote alkyl radicals with one to six carbon atoms or a cycloalkyl radicals with 5 or 6 carbon atoms.