Oxygen permeable hard contact lens

• US 4,508,884 A
• Filed: 05/25/1983
• Issued: 04/02/1985
• Est. Priority Date: 05/25/1983
• Status: Expired due to Fees

• Current Assignee: Coopervision Technology, Inc.
• Original Assignee: CooperVision Incorporated (The Cooper Cos., Inc.)
• Inventors: Evans, John M., Wittmann, Joseph W.
• Primary Examiner(s): Marquis, Melvyn I.
• Application Number:
  US06/497,929
• Time in Patent Office: 678 Days
• Field of Search: 526/279, 351/160 R, 351/160 H, 528/32
• US Class Current: 526/279
• CPC Class Codes: C08F 220/1804 C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
• CPC Class Codes: C08F 220/1811 C10or C11-(Meth)acrylate, e.g. isodecyl (meth)acrylate, isobornyl (meth)acrylate or 2-naphthyl (meth)acrylate
• CPC Class Codes: C08F 222/102 of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
• CPC Class Codes: C08F 226/10 N-Vinyl-pyrrolidone
• CPC Class Codes: C08F 230/08 containing silicon
• CPC Class Codes: C08L 43/04 Homopolymers or copolymers of monomers containing silicon
• CPC Class Codes: G02B 1/043 Contact lenses

Abstract

Oxygen permeable hard contact lenses from the copolymerization of ethylenically unsaturated silicone ester; sterically hindered or bulky aliphatic ester of ethylenically unsaturated carboxylic acid, and hydrophilic monomer; and method for the polymerization thereof.

Claims

1. A hard oxygen permeable contact lens of concavo-convex shape with the concave surface substantially conforming to the cornea of the eye, fabricated from a material formed by the copolymerization of

(a) about 9 to 90% by weight of a polymerizable ethylenically unsaturated silicone ester having the following formula:

##STR20## wherein R is hydrogen or methyl;

each R^I individually is methyl or O--SiR₃^II ;

each R^II individually is methyl or phenyl;

R^III is methyl or phenyl, and R^IV is methyl or phenyl or R^III and R^IV together form a bond with a bridging --O-- between the Si atom and R^III to form a cyclic ring;

each a, b, to form a cyclic ring;

each a, b, and c individually is an integer of 0-3;

p is an integer of 2-4;

q is an integer of 0-10;

n is an integer of 1-3; and

r is an integer of 0-1;

(b) about 5 to about 90% by weight of a polymerizable ethylenically unsaturated ester selected from the group of isobornyl methacrylate, isobornyl acrylate, isobornyl crotonate, dicyclopentadienyl methacrylate, dicyclopentadienyl acrylate, dicyclopentadienyl crotonate, isopinocamphyl methacrylate, isopinocamphyl acrylate, isopinocamphyl crotonate, t-butylcyclohexyl methacrylate, 5-butylcyclohexyl crotonate, 3,3,5-trimethylcyclohexyl methacrylate, 3,3,5-trimethylcyclohexyl acrylate, 3,3,5-trimethylcyclohexyl crotonate, neopentyl methacrylate, neopentyl acrylate, neopentyl crotonate, or mixtures thereof;

(c) about 1 to 30% by weight of a hydrophilic monomer for wettability selected from the group of 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, acrylic acid, methacrylic acid, N-vinyl pyrrolidone, maleic anhydride, acrylamide, methacrylamide, N,N-dimethylacrylamide, glyceryl acrylate, glyceryl methacrylate, dimethylaminoethyl methacrylate, dimethylaminoethyl acrylate, polyethyleneglycol monoacrylates and polyethylene glycol monomethacrylates and their corresponding methyl ethers thereof, or mixtures thereof;

(d) about 0-20% by weight of a cross-linking agent selected from the group of acrylate and methacrylate diesters of a compound selected from the group of dihydric alcohols, polyhydric alcohols, and phenols;

methylene bisacrylamide;

methylene bismethacrylamide;

hexamethylene bisacrylamide;

hexamethylene bismethacrylamide;

divinyl esters;

diallyl esters;

or mixtures thereof;

(e) about 0 to 20% by weight of a C₂ -C₂₀ straight or branched aliphatic monoester or diester of an ethylenically unsaturated carboxylic acid.

2. The contact lens of claim 1 wherein the amount of said silicone ester is about 40 to 60% by weight;

the amount of said ester (b) is about 10 to 40% by weight;

the amount of said hydrophilic monomer is about 1 to 30% by weight;

the amount of said cross-linking agent is about 1 to 20% by weight; and

the amount of such ester (e) is about 1 to 20% by weight.

3. The contact lens of claim 2 wherein the amount of said crosslinking agent is about 2 to 15% by weight;

and the amount of said ester (e) is about 5 to 10%.

4. The contact lens of claim 1 wherein the amount of said silicone ester is about 40 to 50% by weight;

the amount of said ester (b) is about 15 to 35% by weight;

the amount of said hydrophilic monomer is about 2 to 15% by weight;

the amount of said crosslinking agent is about 5 to 15% by weight; and

the amount of said ester (e) is about 5 to 15% by weight

5. The contact lens of claim 1 wherein said silicone ester is tris(trimethylsiloxy)-α

-methacryloxypropylsilane.

6. The contact lens of claim 1 wherein said ester (b) is isobornyl methacrylate.

7. The contact lens of claim 1 wherein said hydrophilic monomer is N-vinylpyrrolidone.

8. A process for polymerizing a composition containing:

(a) about 9 to 90% by weight of a polymerizable ethylenically unsaturated silicone ester having the following formula;

##STR21## wherein R is hydrogen or methyl;

each R^I individually is methyl or O--SiR₃^II ;

each R^II individually is methyl or phenyl;

R^III is methyl or phenyl, and R^IV is methyl or phenyl or R^III and R^IV together form a bond with a bridging --O-- between the Si atom and R^III to form a cyclic ring;

each a, b, and c individually is an integer of 0-3;

p is an integer of 2-4;

q is an integer of 0-10;

n is an integer of 1-3; and

r is an integer of 0-1.

(b) about 5 to about 90% by weight of a polymerizable ethylenically unsaturated ester selected from the group of isobornyl methacrylate, isobornyl acrylate, isobornyl crotonate, dicyclopentadienyl methacrylate, dicyclopentadienyl acrylate, dicyclopentadienyl crotonate, isopinocamphyl methacrylate, isopinocamphyl acrylate, isopinocamphyl crotonate, t-butylcyclohexyl methacrylate, 5-butylcyclohexyl crotonate, 3,3,5-trimethylcyclohexyl methacrylate, 3,3,5-trimethylcyclohexyl acrylate, 3,3,5-trimethylcyclohexyl crotonate, neopentyl methacrylate, neopentyl acrylate, neopentyl crotonate, or mixtures thereof;

(c) about 1 to 30% by weight of a hydrophilic monomer for wettability selected from the group of 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, acrylic acid, methacrylic acid, N-vinyl pyrrolidone, maleic anhydride, acrylamide, methacrylamide, N,N-dimethylacrylamide, glyceryl acrylate, glyceryl methacrylate, dimethylaminoethyl methacrylate, dimethylaminoethyl acrylate, polyethylene glycol monoacrylates and polyethylene glycol monomethacrylates and their corresponding methyl ethers thereof, or mixtures thereof;

(d) about 0-20% by weight of a cross-linking agent selected from the group of acrylate and methacrylate diesters of a compound selected from the group of dihydric alcohols, polyhydric alcohols, and phenols;

methylene bisacrylamide;

methylene bismethacrylamide;

hexamethylene bisacrylamide;

hexamethylene bismethacrylamide;

divinyl esters;

diallyl esters;

or mixtures thereof;

(e) about 0 to 20% by weight of a C₂ -C₂₀ straight or branched aliphatic monoester or diester of an ethylenically unsaturated carboxylic acid.

9. The process of claim 8 wherein said ultraviolet light is in the range of about 200 to about 400 mm.

10. The process of claim 8 which further includes subjecting the composition after irradiation to elevated temperature of about 80°

to 140°

C.

11. The process of claim 10 wherein said temperature is about 80°

to about 120°

C.

12. The process of claim 8 wherein said composition is subjected to heating for about 1 to 7 hours.

13. The process of claim 8 wherein said composition is subjected to heating for about 1 to about 3 hours.

14. The process of claim 8 wherein said composition includes a photoinitiator or photosensitizer.

15. The process of claim 8 wherein said composition includes a benzoin ether in amount of about 0.01 to 2% by weight.

16. The process of claim 8 wherein said composition includes a benzoin methyl ether in amount of about 0.01 to 1% by weight.

17. The process of claim 8 wherein said composition includes a thermal-free radical initiator.

18. The process of claim 17 wherein said initiator is selected from the group of t-butyl peroctoate, dilauryl peroxide, azobisisobutyronitrile, or mixtures thereof.

19. The process of claim 17 wherein the amount of said initiator is about 0.01 to about 2% by weight.

20. The process of claim 17 wherein the amount of said initiator is about 0.01 to about 1% by weight.