Method for making improved UV-absorbing ophthalmic lenses

• US 10,338,408 B2
• Filed: 12/16/2013
• Issued: 07/02/2019
• Est. Priority Date: 12/17/2012
• Status: Active Grant

• Current Assignee: Alcon Incorporated
• Original Assignee: Novartis Ag
• Inventors: Bothe, Harald, Hagmann, Peter
• Primary Examiner(s): Wieczorek, Michael P
• Assistant Examiner(s): Miller, Michael G
• Application Number:
  US14/106,888
• Publication Number:
  US 20140178595A1
• Time in Patent Office: 2,024 Days
• Field of Search: 427162-169
• 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 7/049 Contact lenses having special fitting or structural features achieved by special materials or material structures

Abstract

Described herein is a cost-effective and time-efficient method for making UV-absorbing contact lenses. In contrast to the conventional method for making UV-absorbing contact lenses which involves copolymerizing a lens forming composition including a UV-absorbing vinylic monomer, a method of the invention involves dipping a contact lens in a solution of UV-absorbing polymer comprising carboxyl-containing monomeric units, UV-absorbing monomeric units and covalently bound radical-initiating moieties to form a UV-absorbing coating on the contact lens.

Claims

1. A method for producing UV-absorbing contact lenses, comprising the steps of:

(1) obtaining an ophthalmic lens;

(2) dipping the ophthalmic lens in a coating solution comprising an organic solvent and a UV-absorbing polymer for a period of time sufficient to form a UV-absorbing coating on the ophthalmic lens, wherein the coating solution comprises at least about 60% by weight of the organic solvent, wherein the UV-absorbing polymer comprises

a) UV-absorbing monomeric units,

b) covalently bound radical-initiating moieties,

c) and at least 50% by mole of carboxyl-containing monomeric units of at least one carboxyl-containing vinylic monomer selected from the group consisting of acrylic acid, C₁-C₁₂ alkylacrylic acid, N,N-2-acrylamidoglycolic acid, beta-methyl-acrylic acid (crotonic 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, tricarboxy ethylene, and combinations thereof;

(3) rinsing the ophthalmic lens having the UV-absorbing coating thereon with water or with a mixture of water and at most about 50% by weight of an organic solvent; and

(4) irradiating, with a light source, the ophthalmic lens obtained in step (3) in the presence of a hydrophilic vinylic monomer or crosslinker to graft the UV-absorbing coating onto the ophthalmic lens.

2. The method of claim 1, wherein each UV-absorbing monomeric unit comprises a benzotriazole or benzophenone moiety or combination thereof.

3. The method of claim 2, wherein the UV-absorbing polymer is obtained from an intermediary UV-absorbing polymer obtained by copolymerizing a polymerizable mixture comprising the carboxyl-containing vinylic monomer and at least one UV-absorbing vinylic monomer in the presence or absence of a vinylic monomer, provided that the carboxyl-containing vinylic monomer is present in an amount of at least 60% by mole in the polymerizable composition.

4. The method of claim 3, wherein the UV-absorbing vinylic monomer is selected from the group consisting of 2-(2-hydroxy-5-vinylphenyl)-2H-benzotriazole, 2-(2-hydroxy-5-acrylyloxyphenyl)-2H-benzotriazole, 2-(2-hydroxy-3-methacrylamido methyl-5-tert octylphenyl) benzotriazole, 2-(2′

-hydroxy-5′

-methacrylamidophenyl)-5-chlorobenzotriazole, 2-(2′

-hydroxy-5′

-methacrylamidophenyl)-5-methoxybenzotriazole, 2-(2′

-hydroxy-5′

-methacryloxypropyl-3′

-t-butyl-phenyl)-5-chlorobenzotriazole, 2-(2′

-hydroxy-5′

-methacryloxyethylphenyl) benzotriazole, 2-(2′

-hydroxy-5′

-methacryloxypropylphenyl) benzotriazole, 2-hydroxy-4-acryloxy alkoxy benzophenone, 2-hydroxy-4-methacryloxy alkoxy benzophenone, allyl-2-hydroxybenzophenone, and 2-hydroxy-4-methacryloxy benzophenone, and combinations thereof;

wherein the carboxyl-containing vinylic monomer is selected from the group consisting of acrylic acid, C₁-C₁₂ alkylacrylic acid, N,N-2-acrylamidoglycolic acid, beta-methyl-acrylic acid (crotonic 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, tricarboxy ethylene, and combinations thereof.

5. The method of claim 2, wherein the UV-absorbing polymer is obtained by:

reacting a precursor polymer having at least 60% by mole of carboxyl-containing monomeric units, in a coupling reaction, simultaneously or sequentially with a UV-absorbing compound and a radical-initiating compound,

wherein the UV-absorbing compound is represented by formula I, II, III, or IV

6. The method of claim 5, wherein the precursor polymer is:

(1) a homopolymer of acrylic acid or C₁-C₁₂ alkylacrylic acid;

(2) a copolymer of acrylic acid and C₁-C₁₂ alkylacrylic acid;

(3) a copolymer of a carboxyl-containing vinylic monomer which is acrylic acid or C₁-C₁₂ alkylacrylic or combination thereof and an amino-containing vinylic monomer selected from the group consisting of amino-C₂-C₆ alkyl (meth)acrylate, C₁-C₆ alkylamino-C₂-C₆ alkyl (meth)acrylate, allylamine, vinylamine, amino-C₂-C₆ alkyl (meth)acrylamide, C₁-C₆ alkylamino-C₂-C₆ alkyl (meth)acrylamide), and combination thereof;

(4) a copolymer of a carboxyl-containing vinylic monomer which is acrylic acid or C₁-C₁₂ alkylacrylic or combination thereof and one or more hydrophilic vinylic monomers being free of carboxyl or amino group and selected from the group consisting of acrylamide, methacrylamide N,N-dimethylacrylamide, N,N-dimethyl methacrylamide, N-vinylpyrrolidone, N, N,-dimethylaminoethylmethacrylate, N,N-dimethylaminoethylacrylate, N,N-dimethylaminopropyl methacrylamide, 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, 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, and combinations thereof.

7. The method of claim 5, wherein the precursor polymer is polyacrylic acid, polymethacrylic acid, poly(C₂-C₁₂ alkylacrylic acid), poly(acrylic acid-co-methacrylic acid), poly[C₂-C₁₂ alkylacrylic acid-co-(meth)acrylic acid], poly(N,N-2-acrylamidoglycolic acid), poly[(meth)acrylic acid-co-acrylamide], poly[(meth)acrylic acid-co-vinylpyrrolidone], poly[C₂-C₁₂ alkylacrylic acid-co-acrylamide], poly[C₂-C₁₂ alkylacrylic acid-co-vinylpyrrolidone], hydrolyzed poly[(meth)acrylic acid-co-vinylacetate], hydrolyzed poly[C₂-C₁₂ alkylacrylic acid-co-vinylacetate], or combinations thereof.

8. The method of claim 3, wherein the organic solvent is present in an amount of at least 70% by weight in the coating solution, wherein the ophthalmic lens having the UV-absorbing coating thereon is rinsed with a mixture of water and at most 50% by weight of an organic solvent.

9. The method of claim 4, wherein the organic solvent is present in an amount of at least 70% by weight in the coating solution, wherein the ophthalmic lens having the UV-absorbing coating thereon is rinsed with a mixture of water and at most 50% by weight of an organic solvent.

10. The method of claim 5, wherein the organic solvent is present in an amount of at least 70% by weight in the coating solution, wherein the ophthalmic lens having the UV-absorbing coating thereon is rinsed with a mixture of water and at most 50% by weight of an organic solvent.

11. The method of claim 6, wherein the organic solvent is present in an amount of at least 70% by weight in the coating solution, wherein the ophthalmic lens having the UV-absorbing coating thereon is rinsed with a mixture of water and at most 50% by weight of an organic solvent.

12. The method of claim 7, wherein the organic solvent is present in an amount of at least 70% by weight in the coating solution, wherein the ophthalmic lens having the UV-absorbing coating thereon is rinsed with a mixture of water and at most 50% by weight of an organic solvent.

13. The method of claim 2, wherein the organic solvent is present in an amount of at least 70% by weight in the coating solution, wherein the ophthalmic lens having the UV-absorbing coating thereon is rinsed with a mixture of water and at most 50% by weight of an organic solvent.

14. The method of claim 13, wherein the covalently bound radical-initiating moieties are derived from a functionalized radical-initiating compound which comprises a group which is co-reactive to carboxy group.

15. The method of claim 14, wherein the radical-initiating part belongs to the thioxanthone type or to the benzoin type.

16. The method of claim 15, wherein the covalently bound radical-initiating moieties are derived from an Irgacure type photoinitiator.

17. The method of claim 16, wherein the covalently bound radical-initiating moieties are present in the UV-absorbing polymer from about 3 to about 15 mole percent.

18. The method of claim 1 wherein the UV-absorbing monomeric units are present in the UV-absorbing polymer from about 4 to about 15 mole percent.

19. The method of claim 1 wherein the irradiation after the dipping step is conducted in the presence of a hydrophilic vinylic crosslinker which is a poly(ethyleneglycol) diacrylate or an acrylamide-modified polyvinylalcohol.

20. The method of claim 1, wherein the UV-absorbing coating further comprises a blue light-absorbing polymer.