Method for applying stable coating on silicone hydrogel contact lenses

• US 10,449,740 B2
• Filed: 12/13/2016
• Issued: 10/22/2019
• Est. Priority Date: 12/15/2015
• Status: Active Grant

• Current Assignee: Alcon Incorporated
• Original Assignee: Novartis Ag
• Inventors: Qian, Xinming, Nelson, Jared, Tucker, Robert Carey, Zhang, Steve Yun, Wu, Daqing, Muya, Leroy Wainaina, Patel, Dharmesh, Munoz, Zach, Qiu, Yongxing, Chiang, Chung-Yuan, Shrestha, Ritu, Tallau, Kelly Kayi
• Primary Examiner(s): Vargot, Mathieu D
• Application Number:
  US15/376,708
• Publication Number:
  US 20170165932A1
• Time in Patent Office: 1,043 Days
• CPC Class Codes: B29D 11/00038 Production of contact lenses
• CPC Class Codes: B29D 11/00144 wherein the lens material is not fully polymerized, e.g. by leaving an unpolymerized volume
• CPC Class Codes: B29D 11/0025 Removing impurities from contact lenses, e.g. leaching
• 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: B29K 2083/00 Use of polymers having silicon, with or without sulfur, nitrogen, oxygen, or carbon only, in the main chain, as moulding material
• CPC Class Codes: B29K 2105/0002 monomers or prepolymers
• CPC Class Codes: B29K 2105/0061 Gel or sol
• CPC Class Codes: B29K 2995/0092 hydrophilic
• 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 present invention generally relates to a method for producing silicone hydrogel contact lenses having a stable lubricious coating thereon without involving use of organic solvent in post-curing processes.

Claims

1. A method for producing coated silicone hydrogel contact lenses each having a durable crosslinked hydrophilic coating thereon, comprising the steps of:

(1) introducing a polymerizable composition into a lens mold, wherein the polymerizable composition comprises

(a) at least silicone-containing polymerizable component which is at least one siloxane-containing vinylic monomer, at least one silicone-containing vinylic macromer, or a combination thereof,

(b) at least one vinylic crosslinking agent,

(c) a blending vinylic monomer, wherein the blending vinylic monomer is a C₁-C₁₀ alkyl (meth)acrylate, cyclopentylacrylate, cyclohexylmethacrylate, cyclohexylacrylate, isobornyl (meth)acrylate, styrene, 4,6-trimethylstyrene (TMS), t-butyl styrene (TBS), trifluoroethyl (meth)acrylate, hexafluoro-isopropyl (meth)acrylate, hexafluorobutyl (meth)acrylate, or combinations thereof, (d) from about 30% to about 60% by weight of at least one N-vinyl amide monomer relative to the total amount of polymerizable components, wherein said at least one N-vinyl amide monomer is N-vinylpyrrolidone, N-vinyl-N-methyl acetamide, N-vinyl acetamide, N-vinyl formamide, N-vinyl isopropylamide, or a mixture thereof, and

(e) at least one free-radical initiator;

(2) curing thermally or actinically the polymerizable composition in the lens mold to form a silicone hydrogel contact lens;

(3) forming a stable base coating on the formed silicone hydrogel contact lens according to a water-based coating process which comprises

(i) a substep of immersing the formed silicone hydrogel contact lens in an aqueous solution of a polyanionic polymer having carboxyl groups and a number average molecular weight of at least about 100000 Daltons for a time period of from about 60 minutes to about 240 minutes, wherein the aqueous solution has a pH of from about 0 to about 3.5, and

(ii) a substep of rinsing the silicone hydrogel contact lens having the base coating thereon with a buffered saline having a pH from about 6.5 to about 9.5; and

(4) heating the rinsed silicone hydrogel contact lens having the stable base coating thereon in a packaging solution including a water-soluble, thermally-crosslinkable hydrophilic polymeric material at a temperature from about 60°

C. to about 140°

C. to form the durable crosslinked hydrophilic coating, wherein the packaging solution has a pH from about 6.8 to about 7.6 and a tonicity of from about 200 to about 450 milliosmol (mOsm), wherein the durable crosslinked hydrophilic coating exhibits a water-break-up-time (WBUT) of at least about 5 seconds, a friction rating of about 3 or lower, and a coating durability characterized by surviving a digital rubbing test,

provided that after step (2) the silicone hydrogel contact lens is not in contact with any organic solvent other than propylene glycol and polyethylene glycol having a molecular weight of 400 Daltons or less to remove unpolymerized polymerizable components.

2. The method of claim 1, wherein the polymerizable composition comprises from about 35% to about 56% by weight of N-vinylpyrrolidone relative to the total amount of polymerizable components.

3. The method of claim 1, wherein the polymerizable composition is a solution of all used components dissolved in propylene glycol or a polyethylene glycol having a molecular weight of about 400 Daltons or less.

4. The method of claim 1, wherein the polymerizable composition is free of any organic solvent.

5. The method of claim 1, wherein the step of curing is carried out thermally for a time period of at least about 60 minutes, wherein the polymerizable composition comprises at least one thermal free-radical initiator.

6. The method of claim 1, wherein the step of curing is carried out by UV/visible irradiation, wherein the polymerizable composition comprises at least one free-radical photoinitiator.

7. The method of claim 1, wherein the polyanionic polymer is polyacrylic acid, polymethacrylic acid, poly(2-ethylacrylic acid), poly(acrylic acid-co-methacrylic acid), poly(acrylic acid-co-ethacrylic acid), poly(methacrylic acid-co-ethacrylic acid), or a mixture thereof.

8. The method of claim 7, wherein the aqueous solution of the polyanionic polymer has a pH of about 0 to about 2.5, wherein the concentration of the polyanionic polymer is from about 0.01% by weight to about 10% by weight.

9. The method of claim 7, wherein the aqueous solution of the polyanionic polymer has a temperature of from about 35°

C. to about 90°

C.

10. The method of claim 7, wherein the silicone hydrogel contact lens is immersed in the aqueous solution of the polyanionic polymer for a time period of from about 60 minutes to about 240 minutes.

11. The method of claim 7, wherein the silicone hydrogel contact lens having the base coating thereon is rinsed with a buffered saline having a pH from about 6.8 to about 8.

12. The method of claim 7, wherein the silicone hydrogel contact lens having the base coating thereon is rinsed with a buffered saline having a temperature of from about 22°

C. to about 28°

C.

13. The method of claim 7, further comprising a step of immersing the silicone hydrogel contact lens in a buffered saline before the step of forming the base coating.

14. The method of claim 7, further comprising a step of immersing the silicone hydrogel contact lens in water before the step of forming the base coating.

15. The method of claim 7, further comprising a step of immersing the silicone hydrogel contact lens in a water with pH adjusted by oxidative acid or non-oxidative acid before the step of forming the base coating.

16. The method of claim 7, wherein the step of heating is carried out directly in a sealed lens package containing a packaging solution including the water-soluble, thermally crosslinkable hydrophilic polymeric material during sterilization by autoclave at a temperature from about 115°

C. to about 125°

C. for at least about 20 minutes.

17. The method of claim 7, wherein the water-soluble thermally crosslinkable hydrophilic polymeric material is a poly(2-oxazoline-co-ethyleneimine)-epichlorohydrin, a chemically-modified poly(2-oxazoline-co-ethyleneimine)-epichlorohydrin, a chemically-modified polyamidoamine-epichlorohydrin, or combinations thereof, wherein the chemically-modified poly(2-oxazoline-co-ethyleneimine)-epichlorohydrin or the chemically-modified polyamidoamine-epichlorohydrin comprises (i) from about 20% to about 95% by weight of first polymer chains derived from a polyamidoamine-epichlorohydrin or a poly(2-oxazoline-co-ethyleneimine)-epichlorohydrin, (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 azetitdinium group of the polyamidoamine-epichlorohydrin or the poly(2-oxazoline-co-ethyleneimine)-epichlorohydrin 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.

18. The method of claim 17, wherein the water-soluble thermally crosslinkable hydrophilic polymeric material is a chemically-modified poly(2-oxazoline-co-ethyleneimine)-epichlorohydrin or a chemically-modified polyamidoamine-epichlorohydrin, wherein the chemically-modified poly(2-oxazoline-co-ethyleneimine)-epichlorohydrin and the chemically-modified polyamidoamine-epichlorohydrin independently of each other comprise:

(i) from about 20% to about 95% by weight of first polymer chains derived from a polyamidoamine-epichlorohydrin or a poly(2-oxazoline-co-ethyleneimine)-epichlorohydrin;

(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; and

(iii) positively-charged azetidinium groups which are parts of the first polymer chains or pendant or terminal groups covalently attached to the first polymer chains, 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 azetitdinium group of the polyamidoamine-epichlorohydrin or the poly(2-oxazoline-co-ethyleneimine)-epichlorohydrin and one amino, carboxyl or thiol group of the hydrophilicity-enhancing agent.

19. The method of claim 18, 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 diamino-, dicarboxyl-, monoamino- or monocarboxyl-terminated homo- or co-polymer of a non-reactive hydrophilic vinylic monomer;

or combinations thereof, wherein PEG is a polyethylene glycol segment, wherein the non-reactive vinylic monomer is selected from the group consisting of acrylamide, methacrylamide, N,N-dimethylacrylamide, N,N-dimethylmethacrylamide, N-vinylpyrrolidone, N,N-dimethylaminoethylmethacrylate, N,N-dimethylaminoethylacrylate, N,N-dimethylaminopropylmethacrylamide, N,N-dimethylaminopropylacrylamide, 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, a phosphorylcholine-containing vinylic monomer, C₁-C₄-alkoxy polyethylene glycol (meth)acrylate having a number 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, and combinations thereof.

20. The method of claim 18, wherein the hydrophilicity-enhancing agent is a copolymer which is a polymerization product of a composition comprising (1) about 60% by weight or less by weight of at least one reactive vinylic monomer and (2) at least one non-reactive hydrophilic vinylic monomer, wherein the reactive vinylic monomer is selected from the group consisting of amino-C₁-C₆ alkyl (meth)acrylate, C₁-C₆ alkylaminoC₁-C₆ alkyl (meth)acrylate, allylamine, vinylamine, aminoC₁-C₆ alkyl (meth)acrylamide, C₁-C₆ alkylamino-C₁-C₆ alkyl (meth)acrylamide, acrylic acid, 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-carboxy-4-phenyl butadiene-1,3, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, aconitic acid, maleic acid, fumaric acid, tricarboxy ethylene, and combinations thereof;

wherein the non-reactive vinylic monomer is selected from the group consisting of acrylamide, methacrylamide, N,N-dimethylacrylamide, N,N-dimethylmethacrylamide, N-vinylpyrrolidone, N,N-dimethylaminoethylmethacrylate, N,N-dimethylaminoethylacrylate, N,N-dimethylaminopropylmethacrylamide, N,N-dimethylaminopropylacrylamide, glycerol methacrylate, 3-acryloylamino-1-propanol, N-hydroxyethyl acrylamide, N-hydroxyethyl methacrylamide, N-hydroxypropyl acrylamide, N-hydroxypropyl methacrylamide, 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, a phosphorylcholine-containing vinylic monomer, C₁-C₄-alkoxy polyethylene glycol (meth)acrylate having a number 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, and combinations thereof.

21. The method of claim 18, wherein the hydrophilicity-enhancing agent is an amino- or carboxyl-containing polysaccharide, hyaluronic acid, chondroitin sulfate, and combinations thereof.

22. The method of claim 18, wherein the hydrophilicity-enhancing agent is:

amino-, carboxyl- or thiol-containing monosaccharides;

amino-, carboxyl- or thiol-containing disaccharides; and

amino-, carboxyl- or thiol-containing oligosaccharides.