Water plasticized high refractive index polymer for ophthalmic applications

• US 6,281,319 B1
• Filed: 07/22/1999
• Issued: 08/28/2001
• Est. Priority Date: 04/12/1999
• Status: Expired due to Term

• Current Assignee: Advanced Vision Science, Inc. (Santen Pharmaceutical Company Limited)
• Original Assignee: Surgidev Corporation (Santen Pharmaceutical Company Limited)
• Inventors: Mentak, Khalid
• Primary Examiner(s): Wu, David W.
• Assistant Examiner(s): ZALUKAEVA, TATYANA
• Application Number:
  US09/358,757
• Time in Patent Office: 768 Days
• Field of Search: 526/264, 526/303.1, 526/328.5, 526/347, 526/320, 526/322, 526/323.2, 526/327, 526/346, 623/6, 623/318, 623/319
• US Class Current: 526/319
• CPC Class Codes: A61F 2/14 Eye parts, e.g. lenses, corneal implants; Implanting instruments specially adapted therefor; Artificial eyes
• CPC Class Codes: A61F 2/16 Intraocular lenses
• CPC Class Codes: A61L 2430/16 for reconstruction of eye parts, e.g. intraocular lens, cornea
• CPC Class Codes: A61L 27/16 obtained by reactions only involving carbon-to-carbon unsaturated bonds
• CPC Class Codes: C08L 33/06 of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
• CPC Class Codes: C08L 33/14 of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
• CPC Class Codes: G02B 1/041 Lenses
• CPC Class Codes: G02B 1/043 Contact lenses

Abstract

A high refractive index, foldable polymer suitable for use in ophthalmic devices, such as intraocular lenses, is provided. The polymer may be produced from a polymerization reaction of first, second and third monomeric components and a crosslinking agent. The first monomeric component includes an aryl acrylate or an aryl methacrylate. The second monomeric component, which is not an acrylate, includes a monomer having an aromatic ring with a substituent having at least one site of ethylenic unsaturation. The third monomeric component includes a high water content hydrogel-forming monomer. The resulting high refractive index copolymer is durable enough to be cut and polished when dry, and becomes soft and foldable when hydrated.

Claims

1. A hydratable copolymer comprising:

a) at least 20 weight percent of a first monomeric component, which comprises an aryl acrylate or an aryl methacrylate;

b) at least about 10 weight percent of a second monomeric component, which comprises a monomer having an aromatic ring with a substituent having at least one site of ethylenic unsaturation, wherein the second monomeric component is other than acrylate; and

c) at least 10 weight percent of a third monomeric component, which comprises a high water content hydrogel-forming monomer;

wherein the copolymer has a refractive index greater than about 1.50, is rigid at about room temperature when dry, is foldable at about room temperature when hydrated, and is machinable at about room temperature when dry.

2. The copolymer of claim 1 wherein the copolymer becomes foldable when hydrated, and wherein the hydrated copolymer expands less than about 10 volume percent compared to the unhydrated copolymer.

3. The copolymer of claim 1 wherein the copolymer becomes foldable when hydrated, and wherein the hydrated copolymer has an equilibrium water concentration less than about 5 weight percent.

4. The copolymer of claim 1 wherein the copolymer is for use in an ophthalmic device.

5. The copolymer of claim 4 wherein the ophthalmic device is an intraocular lens.

6. The copolymer of claim 1 wherein the copolymer further comprises a crosslinking agent.

7. The copolymer of claim 1 wherein the copolymer has a glass transition temperature greater than about room temperature.

8. The copolymer of claim 2 wherein the copolymer is machinable at normal room temperature and has a refractive index greater than about 1.50.

9. The copolymer of claim 1 wherein the first monomeric component corresponds to the formula:

wherein;

Z is —

H or —

CH₃, and

Q is a substituent containing at least one aromatic ring.

10. The copolymer of claim 9 wherein Q is selected from the group consisting of:

ethylene glycol phenyl ether, poly(ethylene glycol phenyl ether acrylate), phenyl, 2-ethylphenoxy, 2-ethylphenoxy, hexylphenoxy, hexylphenoxy, benzyl, 2-phenylethyl, 4-methylphenyl, 4-methylbenzyl, 2-2-methyphenylethyl, 2-3-methylphenylethyl methacrylate, 2-4-methylphenylethyl, 2-(4-propylphenyl)ethyl, 2-(4-(1-methylethyl)pheny)ethyl, 2-(4-methoxyphenyl)ethyl, 2-(4-cyclohexylpheny)ethyl, 2-(2-chlorophenyl)ethyl, 2-(3-chlorophenyl)ethyl, 2-(4-chlorophenyl)ethyl, 2-(4-bromophenyl)ethyl, 2-(3-phenylphenyl)ethyl, 2-(4-phenylphenyl)ethyl), and 2-(4-benzylphenyl)ethyl.

11. The copolymer of claim 1 wherein the first monomeric component is selected from the group consisting of ethylene glycol phenyl ether acrylate, poly(ethylene glycol phenyl ether acrylate), phenyl methacrylate, 2-ethylphenoxy methacrylate, 2-ethylphenoxy acrylate, hexylphenoxy methacrylate, hexylphenoxy acrylate, benzyl methacrylate, 2-phenylethyl methacrylate, 4-methylphenyl methacrylate, 4-methylbenzyl methacrylate, 2-2-methyphenylethyl methacrylate, 2-3-methylphenylethyl methacrylate, 2-4-methylphenylethyl methacrylate, 2-(4-propylphenyl)ethyl methacrylate, 2-(4-(1-methylethyl)pheny)ethyl methacrylate, 2-(4-methoxyphenyl)ethylmethacrylate, 2-(4-cyclohexylpheny)ethyl methacrylate, 2-(2-chlorophenyl)ethyl methacrylate, 2-(3-chlorophenyl)ethyl methacrylate, 2-(4-chlorophenyl)ethyl methacrylate, 2-(4-bromophenyl)ethyl methacrylate, 2-(3-phenylphenyl)ethyl methacrylate, 2-(4-phenylphenyl)ethyl methacrylate), 2-(4-benzylphenyl)ethyl methacrylate, and mixtures thereof.

12. The copolymer of claim 1 wherein the first monomeric component is selected from the group consisting of ethylene glycol phenyl ether acrylate and poly ethylene glycol phenyl ether acrylate.

13. The copolymer of claim 1 wherein the second monomeric component includes substituted styrene or unsubstituted styrene.

14. The copolymer of claim 1 wherein the second monomeric component is selected from the group consisting of styrene and styrene substituted with at least one halogen, lower alkyl or lower alkoxy substituent.

15. The copolymer of claim 1 wherein the second monomeric component is selected from the group consisting of styrene and chloro styrene.

16. The copolymer of claim 1 wherein the third monomeric component includes a methacrylate without an aromatic substituent.

17. The copolymer of claim 1 wherein the third monomeric component is selected from the group consisting of:

hydroxyethyl methacrylate, hydroxyethoxyethyl methacrylate, hydroxydiethoxyethyl methacrylate, methoxyethyl methacrylate, methoxyethoxyethyl methacrylate, methoxydiethoxyethyl methacrylate, ethylene glycol dimethacrylate, n-vinyl-2-pyrrolidone, methacrylic acid, vinyl acetate, and mixtures thereof.

18. The copolymer of claim 1 wherein the third monomeric component is selected from the group consisting of hydroxyethyl methacrylate, hydroxy ethoxyethyl methacrylate, and methacrylic acid.

19. The copolymer of claim 6 wherein the crosslinking agent comprises a diacrylate or a dimethacrylate.

20. A hydratable copolymer comprising:

a) at least about 20 weight percent of a first monomeric component selected from the group consisting of ethylene glycol phenyl ether acrylate, and polyethylene glycol phenyl ether acrylate;

b) at least about 10 weight percent of a second monomeric component selected from the group consisting of substituted styrene and unsubstituted styrene;

c) at least about 10 weight percent of a third monomeric component selected from the group consisting of hydroxy ethyl methacrylate, hydroxyethoxy ethyl methacrylate, and methacrylic acid; and

d) less than about 10 weight percent of a crosslinking agent selected from the group consisting of a diacrylate and a dimethacrylate,

wherein the copolymer has a refractive index greater than about 1.50, is rigid at about room temperature when dry, and is foldable at about room temperature when hydrated, and is machinable at about room temperature when dry.

21. The copolymer of claim 20 wherein the crosslinking agent comprises ethylene glycol dimethacrylate.

22. The copolymer of claim 20 wherein the first monomeric component comprises polyethylene glycol phenyl ether acrylate, the second monomeric component comprises styrene, the third monomeric component comprises hydroxy ethyl methacrylate, and the crosslinking agent comprises an ethylene glycol dimethacrylate.

23. The copolymer of claim 20 wherein the copolymer comprises:

a) less than about 50 weight percent of the first monomeric component;

b) less than about 40 weight percent of the second monomeric component;

c) less than about 60 weight percent of the third monomeric component; and

d) at least about 1 weight percent of the crosslinking agent.

24. The copolymer of claim 20 wherein the copolymer comprises:

a) from about 30 to about 45 weight percent ethylene glycol phenyl ether acrylate, polyethylene glycol phenyl ether acrylate, or mixtures thereof;

b) from about 20 to about 30 weight percent styrene;

c) from about 25 to about 40 weight percent hydroxy ethyl methacrylate, hydroxy ethyl methacrylate, or mixtures thereof; and

d) from about 1 to about 5 weight percent of the crosslinking agent.