Surface treatment of silicone medical devices with reactive hydrophilic polymers

• US 6,440,571 B1
• Filed: 05/20/1999
• Issued: 08/27/2002
• 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: Ozark, Ricahrd M., McGee, Joseph A., Salamone, Joseph C., Valint, Paul L. Jr.
• Primary Examiner(s): Moore, Margaret G.
• Application Number:
  US09/315,620
• Time in Patent Office: 1,195 Days
• Field of Search: 428/447, 351/160.R, 351/160.H
• US Class Current: 428/447
• CPC Class Codes: A61L 27/34 Macromolecular materials
• CPC Class Codes: C08J 2383/04 Polysiloxanes
• 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: 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 428/31663 As siloxane, silicone or silane

Abstract

The present invention is directed toward the surface treatment of silicone medical devices such as contact lenses and medical implants. In particular, the present invention is directed to a method of modifying the surface of a medical device to increase its biocompatibility or hydrophilicity by coating the device with a hydrophilic polymer by means of reaction between reactive functionalities on the hydrophilic polymer which functionalities are complementary to reactive functionalities on or near the surface of the medical device. The present invention is also directed to a contact lens or other medical device having such a surface coating.

Claims

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

(a) forming a medical device from a silicone material, wherein the silicone material comprises monomeric units having reactive functionalities selected from the group consisting of azlactone, carboxylic acid, amine, hydroxy and epoxy functionalities, and combinations thereof;

(b) forming a hydrophilic reactive polymer having complementary reactive functionalities along the polymer chain selected from the group consisting of azlactone, isocyanate, acid anhydride, epoxy, hydroxy, primary and secondary amine, carboxylic acid functionalities, and combinations thereof, wherein in the case of the hydroxy or amine complementary reactive functionalities, the silicone material comprises azlactone reactive functionalities and in the case of the carboxylic acid complementary functionality, the silicone material comprises epoxy reactive functionalities; and

(c) reacting the hydrophilic reactive polymer of (b) having complementary reactive functionalities along the polymer chain with said reactive functionalities on or near the surface of the medical device of (a), thus forming a biocompatible surface on the medical device, wherein the polymer comprises the reaction product of 50 to 95 mole percent of hydrophilic monomers selected from the group consisting of acrylamides, lactones, poly(alkyleneoxy)methacrylates, methacrylic acid and hydroxyalkyl methacrylates and 5 to 50 mole percent of azlactone, isocyanate, acid anhydride, epoxy, hydroxy, primary amine, secondary amine or carboxylic acid containing monomers, wherein the alkyl or alkylene groups have 1 to 6 carbon atoms.

2. The method of claim 1, wherein the medical device is a silicone contact lens or intraocular lens that further comprises an uncolored coating.

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

4. The method of claim 1, wherein the hydrophilic monomers are selected from the group consisting of dimethylacrylamide, acrylamide, and N-vinyl pyrrolidinone.

5. The method of claim 1, wherein the hydrophilic reactive polymer comprises 0 to 35 mole percent monomeric units derived from hydrophobic monomers.

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

wherein R³ and R⁴ independently are selected from the group consisting of 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; and

an arenyl group having 6 to 26 carbon atoms; and

contain 0 to 3 heteroatoms selected from the group consisting of S, N, and nonperoxidic O;

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

7. The method of claim 6, 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.

8. The method of claim 7, 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;

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

2-vinyl-4,4-dimethyl-2-oxazol in-5-one.

9. The method of claim 6, wherein the medical device is dipped in a solution comprising at least one hydrophilic reactive polymer in the absence of a coloring substance.

10. A silicone medical device including a hydrophilic surface comprising:

a medical device made from a silicone material, wherein the silicone material comprises monomeric units having reactive functionalities selected from the group consisting of azlactone, carboxylic acid, amine, hydroxy, and epoxy functionalities, and compatible combinations thereof; and

hydrophilic polymers attached to the medical device wherein the points of attachment are the result of the reaction of isocyanate, hydroxy, amine, carboxylic acid, or ring-opening complementary reactive functionalities or compatible combinations thereof in monomeric units along the hydrophilic reactive polymers with said functionalities on or near the surface of the medical device wherein in the case of the hydroxy or amine complementary reactive functionalities, the silicone material comprises azlactone reactive functionalities and in the case of the carboxylic acid complementary functionality, the silicone material comprises epoxy reactive functionalities, thereby producing a clear, transparent biocompatible coating comprising a polymer comprising the reaction product of from 50 to 95 mole percent of hydrophilic monomers selected from the group consisting of acrylamides, lactones, poly(alkyleneoxy)methacrylates, methacrylic acid and hydroxyalkyl methacrylates and 5 to 50 mole percent of azlactone, carboxylic acid, amine, hydroxy or epoxy-containing monomers, wherein the alkyl or alkylene groups have 1 to 6 carbon atoms.

11. The medical device of claim 10, wherein the medical device is a silicone contact lens or intraocular device.

12. The medical device of claim 10, wherein the medical device is a silicone hydrogel continuous-wear lens.

13. The medical device of claim 10, wherein the hydrophilic polymer comprises moieties along the chain having the following formula:

wherein R³ and R⁴ independently are selected from the group consisting of 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; and

an arenyl group having 6 to 26 carbon atoms; and

contain 0 to 3 heteroatoms selected from the group consisting of S, N, and nonperoxidic O;

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

14. The medical device claim 10, wherein the hydrophilic polymer comprises moieties along the chain represented by the general formula:

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

15. The medical device claim 10, wherein hydrophilic polymer chains attached to the surface of the medical device 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 surface of the medical device and, in addition, (b) a second hydrophilic reactive polymer having supplemental reactive functionalities that are reactive with the first hydrophilic reactive polymer.

16. The medical device of claim 15, 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.

17. The medical device of claim 10, wherein the coating consists essentially of the reaction product of an epoxy-functional hydrophilic reactive polymer.

18. The medical device of claim 10, wherein the hydrophilic surface comprises azlactone-functional monomeric units that have been coverted to acid groups near or on the surface.

19. A method for treating the surface of a silicone medical device comprising:

(a) forming a medical device from a silicone material, wherein the silicone material comprises monomeric units having reactive functionalities selected from the group consisting of azlactone, carboxylic acid, amine, hydroxy and epoxy functionalities, and combinations thereof and;

(b) forming a hydrophilic reactive polymer having complementary reactive functionalities along the polymer chain which functionalities are selected from the group consisting of azlactone, isocyanate, acid anhydride, epoxy, amine, carboxylic acid, and acid functionalities and compatible combinations thereof, which hydrophilic reactive polymer comprises the reaction product of 5 to 50 mole percent of azlactone, isocyanate, acid anhydride, epoxy, amine, carboxylic acid or acid functionality-containing monomers, or combinations thereof, and 0.5 to 20 mole percent of hydrophobic monomers, wherein if the hydrophilic reactive polymer comprises hydroxy or amine complementary reactive functionalities, the silicone material comprises azlactone reactive functionalities and if the hydrophilic reactive polymer comprises a carboxylic acid complementary functionality, the silicone material comprises epoxy reactive functionalities;

(c) reacting the hydrophilic reactive polymer of (b) having complementary reactive functionalities along the polymer chain with said reactive functionalities on or near the surface of the medical device of (a) in the absence of a coloring substance, thus forming a biocompatible surface on the medical device.