Silicone hydrogel lenses with nano-textured surfaces

• US 9,244,195 B2
• Filed: 06/07/2012
• Issued: 01/26/2016
• Est. Priority Date: 06/09/2011
• Status: Active Grant

• Current Assignee: Alcon Incorporated
• Original Assignee: Novartis Ag
• Inventors: Bauman, R. Erich, Hagmann, Peter, Pruitt, John Dallas, Rappon, Joseph Michael
• Primary Examiner(s): VARGOT, MATHIEU D
• Application Number:
  US13/490,517
• Publication Number:
  US 20120314185A1
• Time in Patent Office: 1,328 Days
• US Class Current: 1/1
• CPC Class Codes: B29D 11/00038 Production of contact lenses
• CPC Class Codes: B29D 11/00326 having particular surface properties, e.g. a micropattern
• CPC Class Codes: B29D 11/00346 having nanosize structures or features, e.g. fillers
• CPC Class Codes: B29D 11/00865 Applying coatings; tinting; colouring printing, marking or copying processes B41M; identification in general G09F3/00; producing decorative effects in general B44C; positioning or marking of lenses B24B13/0055
• CPC Class Codes: G02B 1/043 Contact lenses
• CPC Class Codes: G02C 2202/16 Laminated or compound lenses
• CPC Class Codes: G02C 7/049 Contact lenses having special fitting or structural features achieved by special materials or material structures

Abstract

The invention is related to a method for making a silicone hydrogel contact lens having a nano-textured surface which mimics the surface texture of cornea of human eye. A method of the invention comprises creating a prime coating having nano-textures through controlled imbibition and/or depositions of a reactive polymeric coating material and fixing the nano-textures by crosslinking a hydrophilic polymeric material onto the prime coating to form a crosslinked polymeric coating that perserves the nano-textures of the prime coating and provides a nano-textured surface to the contact lens.

Claims

1. A method for making contact lenses having nano-textured surfaces, comprising the steps of:

(1) providing an organic-based coating solution including an organic-based solvent and a polymeric coating material dissolved in the organic-based solvent, wherein the polymeric coating material comprises multiple first reactive functional groups and multiple affinity groups or moieties, wherein the multiple first reactive functional groups are selected from the group consisting of carboxyl groups, azetidinium groups, amino groups, azlactone groups, isocyanate groups, epoxy groups, aziridine groups, thiol groups, hydroxyl groups, and combinations thereof;

(2) contacting a contact lens with the organic-based coating solution to swell the contact lens and form an intermediary coating of the polymeric coating material on the contact lens, wherein the contact lens comprises, at and near the surface of the contact lens, monomeric units and/or hydrophobic moieties and/or segments capable of interacting with the affinity groups or moieties of the polymeric coating material so as to bind the polymeric coating material, wherein the average molecular weight of the polymeric coating material is selected to be sufficient high to ensure that the polymeric coating material partially penetrate into the contact lens swollen by the organic-based solvent;

(3) contacting the swollen contact lens having the intermediary coating thereon with an aqueous solution or water to shrink the contact lens having the intermediary coating thereon to form a prime coating having nano-textures on the contact lens; and

(4) fixing the nano-textures in the prime coating by crosslinking a water-soluble and crosslinkable hydrophilic polymeric material with multiple second functional reactive functional groups onto the prime coating through the first reactive functional groups to form a crosslinked polymeric coating that preserves the nano-textures of the prime coating and provides a nano-textured surface to the contact lens, wherein the multiple second reactive functional groups of the water-soluble and crosslinkable hydrophilic polymeric material are;

carboxyl groups, azetidinium groups, amino groups, azlactone groups, isocyanate groups, epoxy groups, aziridine groups, hydroxyl groups, thiol groups, or combinations thereof, wherein one first reactive functional reactive group can react with one second reactive functional group in the presence or absence of a coupling agent to form one crosslinkage between the polymeric coating material and the water-soluble and crosslinkable hydrophilic polymeric material.

2. The method of claim 1, wherein the organic-based solvent is a solvent system which consists of one or more organic solvents and optionally about 30% or less by weight of water relative to the weight of the solvent system, wherein the one or more organic solvents are selected from the group consisting of tripropylene glycol methyl ether, dipropylene glycol methyl ether, ethylene glycol n-butyl ether, acetone, methyl ethyl ketone, diethylene glycol n-butyl ether, diethylene glycol methyl ether, ethylene glycol phenyl ether, propylene glycol methyl ether, propylene glycol methyl ether acetate, dipropylene glycol methyl ether acetate, propylene glycol n-propyl ether, dipropylene glycol n-propyl ether, tripropylene glycol n-butyl ether, propylene glycol n-butyl ether, dipropylene glycol n-butyl ether, tripropylene glycol n-butyl ether, propylene glycol phenyl ether dipropylene glycol dimetyl ether, polyethylene glycols, polypropylene glycols, ethyl acetate, butyl acetate, amyl acetate, methyl lactate, ethyl lactate, i-propyl lactate, a C₁-C₁₂ alcohol, 1-methyl-2-pyrrolidone, N,N-dimethylpropionamide, dimethyl formamide, dimethyl acetamide, dimethyl propionamide, N-methyl pyrrolidinone, 1,2-propylene glycol, polyethyleneglycol having a molecular weight of about 200 or less, tetrahydrofuran, methylene chloride, and combinations thereof.

3. The method of claim 2, wherein the contact lens is swollen by the organic-based coating solution by at least about 50%.

4. The method of claim 1, wherein the affinity groups or moieties are either identical to or different from the first reactive functional groups and are selected from the group consisting of carboxyl groups, ammonium groups, hydrophobic moieties, hydrophobic segments, and combinations thereof.

5. The method of claim 4, wherein the polymeric coating material is:

(1) a homopolymer of an ammonium-containing vinylic monomer or a carboxyl containing vinylic monomer;

(2) a copolymer of one or more ammonium-containing and/or carboxyl-containing vinylic monomers;

(3) a copolymer of one or more ammonium-containing and/or carboxyl-containing vinylic monomers with a non-reactive vinylic monomer selected from the group consisting of (meth)acrylamide, N,N-dimethyl (meth)acrylamide, N-vinylpyrrolidone (NVP), N,N-dimethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylamide, glycerol methacrylate, 3-acryloylamino-1-propanol, N-hydroxyethyl acrylamide, N-[tris(hydroxymethyl)methyl]-acrylamide, N-methyl -3-methylene-2-pyrrolidone, 1-ethyl-3-methylene-2-pyrrolidone, 1-methyl-5-methylene-2-pyrrolidone, 1-ethyl-5-methylene-2-pyrrolidone, 5-methyl-3-methylene-2-pyrrolidone, 5-ethyl-3-methylene-2-pyrrolidone, 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, C₁ , C₄-alkoxy polyethylene glycol (meth)acrylate having a weight average molecular weight of up to 1500 Daltons, N-vinyl formamide, N-vinyl acetamide, N-vinyl isopropylamide, N-vinyl-N-methyl acetamide, allyl alcohol, vinyl alcohol (hydrolyzed form of vinyl acetate in the copolymer), a phosphorylcholine-containing vinylic monomer, and combinations thereof and optionally with one or more reactive vinylic monomer having a reactive functional group selected from the group consisting of azetidinium group, azlactone groups, isocyanate groups, epoxy groups, aziridine groups, and combinations thereof;

(4) polyethyleneimine (PEI);

(5) polyvinylalcohol with pendant primary and/or secondary amino groups;

(6) a block copolymer including at least one hydrophobic segments and polymeric segments having reactive functional groups selected from the group consisting of azetidinium groups, azlactone groups, isocyanate groups, epoxy groups, aziridine groups, thiol groups, and combinations thereof;

or (7) a combination thereof.

6. The method of claim 4, wherein the polymeric coating material is a polymer or copolymer comprising at least about 70% by mole of monomeric units of one or more carboxyl-containing vinylic monomers, wherein the one or more carboxyl-containing vinylic monomers are selected from the group consisting of acrylic acid, a C₁-C₄ alkylacrylic acid, N,N-2-acrylamidoglycolic acid, beta methyl-acrylic acid, alpha-phenyl acrylic acid, beta-acryloxy propionic acid, sorbic acid, angelic acid, cinnamic acid, 1-carobxy-4-phenyl butadiene-1,3, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, aconitic acid, maleic acid, fumaric acid, and combination thereof.

7. The method of claim 6, wherein the polymeric coating material is:

a linear or branched polyacrylic acid;

a linear or branched polymethacrylic acid;

a linear or branched poly(acrylic acid-co-acrylamide) having at least about 70% by mole;

a linear or branched poly(methacrylic acid-co-acrylamide) having at least about 70% by mole of methacrylic acid;

a linear or branched poly(acrylic acid-co-vinylpyrrolidone) having at least about 70% by mole of acrylic acid;

a linear or branched poly(methacrylic acid-co-vinylpyrrolidone) having at least about 70% by mole of methacrylic acid, or combination thereof.

8. The method of claim 4, wherein the contact lens is a silicone hydrogel contact lens obtained by polymerization of a lens formulation comprising at least one components selected from the group consisting of a silicone-containing vinylic monomer, a silicone-containing vinylic macromer, a silicone-containing prepolymer, a hydrophilic vinylic monomer, a hydrophobic vinylic monomer, a crosslinking agent, a free-radical initiator, a hydrophilic vinylic macromer/prepolymer, a UV-absorbing agent, a visibility tinting agent, antimicrobial agents, a bioactive agent, a leachable lubricant, a leachable tear-stabilizing agent, and combination thereof.

9. The method of claim 4, wherein the second reactive functional groups are thermally-crosslinkable groups.

10. The method of claim 4, wherein the water-soluble and crosslinkable hydrophilic polymeric material is a partially-crosslinked hydrophilic polymeric material that comprises a three-dimensional network and the second reactive functional groups within the network.

11. The method of claim 10, wherein the water-soluble and crosslinkable hydrophilic polymeric material comprises:

(i) from about 20% to about 95% by weight of first polymer chains derived from an epichlorohydrin-functionalized polyamine or polyamidoamine, (ii) from about 5% to about 80% by weight of hydrophilic moieties or second polymer chains derived from at least one hydrophilicity-enhancing agent having at least one reactive functional group selected from the group consisting of amino group, carboxyl group, thiol group, and combination thereof, wherein the hydrophilic moieties or second polymer chains are covalently attached to the first polymer chains through one or more covalent linkages each formed between one azetidinium group of the epichlorohydrin-functionalized polyamine or polyamidoamine and one amino, carboxyl or thiol group of the hydrophilicity-enhancing agent, and (iii) azetidinium groups which are parts of the first polymer chains or pendant or terminal groups covalently attached to the first polymer chains.

12. The method of claim 11, wherein the hydrophilicity-enhancing agent is:

an amino-, carboxyl- or thiol-containing monosaccharide;

an amino-, carboxyl- or thiol-containing disaccharide;

an amino-, carboxyl- or thiol-containing oligosaccharide;

or a combinations thereof.

13. The method of claim 11, wherein the hydrophilicity-enhancing agent is:

carboxymethylcellulose having a carboxyl content of about 40% or less which is estimated based on the composition of repeating units, —

[C₆H_10-mO₅(CH₂CO₂H)_m]—

in which m is 1 to

     3);

carboxyethylcellulose having a carboxyl content of about 36% or less which is estimated based on the composition of repeating units, —

[C₆H_10-mO₅(C₂H₄CO₂H)_m]—

in which m is 1 to 3;

carboxypropylcellulose having a carboxyl content of about 32% or less which is estimated based on the composition of repeating units, —

[C₆H_10-mO₅(C₃H₆CO₂H)_m]—

, in which m is 1 to 3;

hyaluronic acid having a carboxyl content of about 11% which is estimated based on the composition of repeating units, —

(C₁₃H₂₀O₉NCO₂H)—

);

chondroitin sulfate having a carboxyl content of about 9.8% which is estimated based on the composition of repeating units, —

(C₁₂H₁₈O₁₃NS CO₂H)—

);

or a combination thereof.

14. The method of claim 11, wherein the hydrophilicity-enhancing agent is:

PEG-NH₂;

PEG-SH;

PEG-COOH;

H₂N-PEG-NH₂;

HOOC-PEG-COOH;

HS-PEG-SH;

H₂N-PEG-COOH;

HOOC-PEG-SH;

H₂N-PEG-SH;

multi-arm PEG with one or more amino, carboxyl or thiol groups;

PEG dendrimers with one or more amino, carboxyl or thiol groups;

a monoamino-, monocarboxyl-, diamino- or dicarboxyl-terminated homo- or copolymer of a non-reactive hydrophilic vinylic monomer selected from the group consisting of acryamide (AAm), N,N-dimethylacrylamide (DMA), N-vinylpyrrolidone (NVP), N-vinyl-N-methyl acetamide, glycerol (meth)acrylate, hydroxyethyl (meth)acrylate, N-hydroxyethyl (meth)acrylamide, C₁-C₄-alkoxy polyethylene glycol (meth)acrylate having a weight average molecular weight of up to 400 Daltons, vinyl alcohol, N-methyl-3-methylene-2-pyrrolidone, 1-methyl-5-methylene-2-pyrrolidone, 5-methyl-3-methylene-2-pyrrolidone, N,N-dimethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (metha)crylamide, (meth)acryloyloxyethyl phosphorylcholine, and combinations thereof;

a copolymer which is a polymerization product of a composition comprising (1 ) from about 0.1% to about 30% by weight of (meth)acrylic acid, allylamine and/or amino-C₂-C₄ alkyl (meth)acrylate, and (2) at least one non-reactive hydrophilic vinylic monomer selected from the group consisting of acryamide, N,N-dimethylacrylamide, N-vinylpyrrolidone, (meth)acryloyloxyethyl phosphorylcholine, N-vinyl-N-methyl acetamide, glycerol (meth)acrylate, hydroxyethyl (meth)acrylate, N-hydroxyethyl (meth)acrylamide, C₁-C₄-alkoxy polyethylene glycol (meth)acrylate having a weight average molecular weight of up to 400 Daltons, vinyl alcohol, and a combination thereof;

or a combination thereof.

15. The method of claim 11, wherein the hydrophilicity-enhancing agent is:

PEG-NH₂;

PEG-SH;

PEG-COOH;

monoamino-, monocarboxyl-, diamino- or dicarboxyl-terminated polyvinylpyrrolidone;

monoamino-, monocarboxyl-, diamino- or dicarboxyl-terminated polyacrylamide;

monoamino-, monocarboxyl-, diamino- or dicarboxyl-terminated poly(DMA);

monoamino- or monocarboxyl-, diamino- or dicarboxyl-terminated poly(DMA-co-NVP);

monoamino-, monocarboxyl-, diamino- or dicarboxyl-terminated poly(NVP-co-N,N-dimethylaminoethyl (meth)acrylate));

monoamino-, monocarboxyl-, diamino- or dicarboxyl-terminated poly(vinylalcohol);

monoamino-, monocarboxyl-, diamino- or dicarboxyl-terminated poly[(meth)acryloyloxyethyl phosphrylcholine] homopolymer or copolymer;

monoamino-, monocarboxyl-, diamino- or dicarboxyl-terminated poly(NVP-co-vinyl alcohol);

monoamino-, monocarboxyl-, diamino- or dicarboxyl-terminated poly(DMA-co-vinyl alcohol);

poly[(meth)acrylic acid-co-acrylamide] with from about 0.1% to about 30% by weight of (meth)acrylic acid;

poly[(meth)acrylic acid-co-NVP) with from about 0.1% to about 30% by weight of (meth)acrylic acid;

a copolymer which is a polymerization product of a composition comprising (1) (meth)acryloyloxyethyl phosphorylcholine and (2 ) from about 0.1% to about 30% by weight of (meth)acrylic acid, allylamine and/or amino-C₂ C₄alkyl (meth)acrylate; and

combination thereof;

or a combination thereof.

16. The method of claim 4, wherein the step of fixing the nano-textures in the prime coating is performed by autoclaving the contact lens that comprises the prime coating including nano-textures and is immersed in a packaging solution including the water-soluble crosslinkable hydrophilic polymeric material in a sealed lens package at a temperature of from about 118°

C. to about 125°

C. for approximately 2090minutes, wherein the second reactive functional groups of the water-soluble crosslinkabe hydrophilic polymeric material are azetidinium groups and/or epoxy groups.