SILICONE HYDROGEL LENS WITH A COVALENTLY ATTACHED COATING

• US 20110134387A1
• Filed: 12/06/2010
• Published: 06/09/2011
• Est. Priority Date: 12/08/2009
• Status: Active Grant

• Current Assignee: Alcon Incorporated
• Original Assignee: Novartis Ag
• Inventors: Samuel, Newton T., Wu, Daqing
• Granted Patent: US 8,557,334 B2
• Time in Patent Office: Days
• US Class Current: 351/160.H
• CPC Class Codes: C08L 101/14 the macromolecular compounds being water soluble or water swellable, e.g. aqueous gels
• CPC Class Codes: C08L 51/085 on to polysiloxanes
• CPC Class Codes: G02B 1/043 Contact lenses

Abstract

The invention provides a cost-effective method for making a silicone hydrogel contact lens having a hydrophilic coating thereon that is covalently attached to the lens and has a good hydrophilicity, intactness and durability. The invention also provides a silicone hydrogel contact lenses having a hydrophilic coating consisting of a prime coating covalently attached to the contact lens and a top coating covalently attached to the prime coating.

Claims

1. A method of producing a silicone hydrogel contact lens having a hydrophilic coating thereon, comprising the steps of:

(a) polymerizing, in a mold, a polymerizable (or lens forming) composition comprising at least one silicone-containing vinylic monomer or macromer and an azlactone-containing vinylic monomer or macromer, thereby forming a silicone hydrogel contact lens having azlactone moieties covalently attached onto the polymer matrix of the contact lens, wherein the azlactone-containing vinylic monomer or macromer is present in an amount of about 0.5% to about 5.0% by weight in the polymerizable composition;

(b) contacting the contact lens with a solution of an anchoring hydrophilic polymer having pendant primary or secondary amino groups for a period of time sufficient to form a prime coating on the contact lens, wherein the prime coating comprises a layer of the anchoring hydrophilic polymer covalently attached to the surface of the contact lens through one or more covalent linkages each formed between one azlactone moiety at or near the surface of the contact lens and one of the pendant primary or secondary amino groups of the anchoring hydrophilic polymer;

(c) applying a top coating on top of the prime coating to form the hydrophilic coating with an increased surface hydrophilicity and/or durability with respect to the prime coating, wherein the top coating comprises at least one layer of a carboxylic acid-containing hydrophilic polymer and/or at least one layer of an azetidinium-containing polymer, wherein the layer of the carboxylic acid-containing hydrophilic polymer is formed by contacting the contact lens having the prime coating thereon with a solution of the carboxylic acid-containing hydrophilic polymer, wherein the layer of the azetidinium-containing polymer is formed by contacting the contact lens having the prime coating thereon and optionally the layer of the carboxylic acid-containing hydrophilic polymer with a solution of the azetidinium-containing polymer, wherein the layer of the carboxylic acid-containing hydrophilic polymer and/or the layer of the azetidinium-containing polymer is chemically and/or physically bound to the layer of the anchoring hydrophilic polymer.

2. The method of claim 1, wherein the azlactone-containing vinylic monomer or macromer is selected from the group consisting of azlactone-containing vinylic monomers include:

2-vinyl-4,4-dimethyl-1,3-oxazolin-5-one, 2-isopropenyl-4,4-dimethyl-1,3-oxazolin-5-one, 2-vinyl-4-methyl-4-ethyl-1,3-oxazolin-5-one, 2-isopropenyl-4-methyl-4-butyl-1,3-oxazolin-5-one, 2-vinyl-4,4-dibutyl-1,3-oxazolin-5-one, 2-isopropenyl-4-methyl-4-dodecyl-1,3-oxazolin-5-one, 2-isopropenyl-4,4-diphenyl-1,3-oxazolin-5-one, 2-isopropenyl-4,4-pentamethylene-1,3-oxazolin-5-one, 2-isopropenyl-4,4-tetramethylene-1,3-oxazolin-5-one, 2-vinyl-4,4-diethyl-1,3-oxazolin-5-one, 2-vinyl-4-methyl-4-nonyl-1,3-oxazolin-5-one, 2-isopropenyl-4-methyl-4-phenyl-1,3-oxazolin-5-one, 2-isopropenyl-4-methyl-4-benzyl-1,3-oxazolin-5-one, 2-vinyl-4,4-pentamethylene-1,3-oxazolin-5-one, 2-vinyl-4,4-dimethyl-1,3-oxazolin-6-one, and combinations thereof.

3. The method of claim 2, wherein the azlactone-containing vinylic monomer or macromer is present in an amount of from about 0.6% to about 2.5% by weight in the polymerizable composition.

4. The method of claim 3, wherein the anchoring hydrophilic polymer is selected from the group consisting of a homopolymer of C₁-C₄aminoalkyl (meth)acrylamide, a homopolymer of C₁-C₄aminoalkyl (meth)acrylate, a copolymer of C₁-C₄aminoalkyl (meth)acrylamide with at least one hydrophilic vinylic monomer, a copolymer of C₁-C₄aminoalkyl (meth)acrylate with at least one hydrophilic vinylic monomer, polyethyleneimine, polyallylamine hydrochloride homopolymer, polyallylamine hydrochloride copolymer, polyvinylalcohol with pendant primary and/or secondary amino groups, and combinations thereof.

5. The method of claim 4, wherein the anchoring hydrophilic polymer is polyethyleneimine, polyallylamine hydrochloride homopolymer, polyallylamine hydrochloride copolymer, or mixtures thereof.

6. The method of claim 4, wherein the anchoring hydrophilic polymer is a polyhydroxyl polymer which is a derivative of a poly(vinyl alcohol) and has from about 0.5% to about 80%, based on the number of hydroxyl groups in the poly(vinyl alcohol), of units of the formula I

7. The method of claim 4, wherein the anchoring hydrophilic polymer has a molecular weight of from about 500,000 to 5,000,000 Daltons.

8. The method of claim 4, wherein the solution of the anchoring hydrophilic polymer is prepared by dissolving the anchoring hydrophilic polymer in a mixture of water and one or more organic solvents, an organic solvent, or a mixture of one or more organic solvent.

9. The method of claim 4, wherein the top coating comprises at least one layer of a carboxylic acid-containing hydrophilic polymer and is formed by contacting the contact lens with the prime coating thereon with a solution of a carboxylic acid-containing hydrophilic polymer.

10. The method of claim 9, wherein the carboxylic acid-containing hydrophilic polymer contains further aldehyde groups.

11. The method of claim 9, wherein the carboxylic acid-containing hydrophilic polymer is carboxymethyl cellulose, hyaluronic acid aldehyde, a linear polyacrylic acid, a branched polyacrylic acid, a polymethacrylic acid, a copolymer of (meth)acrylic acid with at least one hydrophilic vinylic monomer, a maleic or fumaric acid copolymer, or combinations thereof.

12. The method of claim 9, wherein the carboxylic acid-containing hydrophilic polymer is carboxymethyl cellulose, hyaluronic acid aldehyde, or combinations thereof.

13. The method of claim 1, wherein the top coating comprises at least one layer of an azetidinium-containing polymer.

14. The method of claim 13, wherein the top coating comprises at least one bilayer consisting of one layer of one carboxylic acid-containing hydrophilic polymer and one layer of an azetidinium-containing polymer.

15. The method of claim 1, comprising a step of applying a final layer of a carboxylic acid-containing hydrophilic polymer or azetidinium-containing polymer onto the contact lens in a lens package which is sealed and autoclave at a temperature of about 115°

C. to about 125°

C. for a period of from about 15 minutes to about 90 minutes.

16. A silicone hydrogel contact lens, comprising:

a core silicone hydrogel material and a hydrophilic coating, wherein the core silicone hydrogel material comprises azlactone moieties directly derived from an azlactone-containing vinylic monomer or macromer contained in a lens forming material for making the core silicone hydrogel material, wherein the hydrophilic coating comprises a prime coating and a top coating which is covalently attached to the prime coating, wherein the prime coating is a layer of an anchoring hydrophilic polymer having primary or secondary groups or thiol groups and is covalently attached directly to the core silicone hydrogel material through covalent linkages each formed between one azlactone moiety at or near the surface of the contact lens and one primary or secondary amino group or thiol group of the anchoring hydrophilic polymer, wherein the top coating comprises at least one layer of a carboxylic acid-containing hydrophilic polymer and/or at least one layer of an azetidinium-containing polymer, wherein the layer of the carboxylic acid-containing hydrophilic polymer and/or the layer of the azetidinium-containing polymer is chemically and/or physically bound to the layer of the anchoring hydrophilic polymer, wherein the silicone hydrogel contact lens has an oxygen permeability of at least 40 barrers, a surface wettability characterized by a water contact angle of about 100 degrees or less, and a good coating durability characterized by surviving a digital rubbing test.

17. The contact lens of claim 16, wherein the anchoring hydrophilic polymer is selected from the group consisting of a homopolymer of C₁-C₄aminoalkyl (meth)acrylamide, a homopolymer of C₁-C₄aminoalkyl (meth)acrylate, a copolymer of C₁-C₄aminoalkyl (meth)acrylamide with at least one hydrophilic vinylic monomer, a copolymer of C₁-C₄aminoalkyl (meth)acrylate with at least one hydrophilic vinylic monomer, polyethyleneimine, polyallylamine hydrochloride homopolymer, polyallylamine hydrochloride copolymer, polyvinylalcohol with pendant primary and/or secondary amino groups, and combinations thereof, wherein the top coating comprises at least one layer of a carboxylic acid-containing hydrophilic polymer and/or at least one layer of an azetidinium-containing polymer.

18. The contact lens of claim 17, wherein the carboxylic acid-containing hydrophilic polymer contains further aldehyde groups.

19. The contact lens of claim 17, wherein the carboxylic acid-containing hydrophilic polymer is carboxymethyl cellulose, hyaluronic acid aldehyde, a linear polyacrylic acid, a branched polyacrylic acid, a polymethacrylic acid, a copolymer of (meth)acrylic acid with at least one hydrophilic vinylic monomer, a maleic or fumaric acid copolymer, or combinations thereof.

20. The contact lens of claim 17, wherein the top coating further comprising an outmost final layer of a carboxylic acid-containing hydrophilic polymer or a azetidinium-containing polymer, wherein the outmost final layer is formed in a lens package which contains a solution of the carboxylic acid-containing hydrophilic polymer or azetidinium-containing polymer, is sealed and autoclave at a temperature of from about 115°

C. to 125°

C. for a period of from about 15 minutes to about 90 minutes.