Ophthalmic devices fabricated from urethane acrylates of polysiloxane alcohols

• US 4,543,398 A
• Filed: 09/19/1984
• Issued: 09/24/1985
• Est. Priority Date: 04/28/1983
• Status: Expired due to Term

• Current Assignee: 3M Company
• Original Assignee: 3M Company
• Inventors: Williams, Todd R., Bany, Stephen W., Koshar, Robert J.
• Primary Examiner(s): Marquis, Melvyn I.
• Application Number:
  US06/652,417
• Time in Patent Office: 370 Days
• Field of Search: 351/160 R, 351/160 H, 204/159.13, 204/159.22, 204/159.23, 526/279, 528/32, 556/419, 525/474
• US Class Current: 525/474
• CPC Class Codes: C08F 30/08 containing silicon
• CPC Class Codes: C08G 18/61 Polysiloxanes
• CPC Class Codes: C08G 18/8116 esters of acrylic or alkylacrylic acid having only one isocyanate or isothiocyanate group
• CPC Class Codes: C08L 51/085 on to polysiloxanes
• CPC Class Codes: C08L 83/08 containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
• CPC Class Codes: G02B 1/041 Lenses

Abstract

Shaped articles, particularly ophthalmic devices, can be fabricated from oxygen transmissive, hydrolytically stable, polysiloxane copolymers of readily prepared poly(organosiloxane) monomers having monourethane acrylate groups and copolymerizable ethylenically-unsaturated monomers. The ophthalmic devices comprise copolymers of compositions containing 15 to 100 percent of said organopolysiloxane urethane acrylate and 85 to 0 percent of copolymerizable ethylenically-unsaturated monomers.

Ophthalmic devices which are fabricated from monourethane acrylates of polysiloxane alcohols have high oxygen permeability. A novel process is disclosed for the preparation of these polysiloxanes which have at least one urethane acrylate substituent.

Claims

1. An ophthalmic device comprising an addition polymer which is the reaction product of a composition comprising:

(a) 15 to 100 percent by weight of at least one organopolysiloxane urethane acrylate having the formula ##STR10## wherein each R is independently an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having from 3 to 6 carbon atoms, a phenyl group, a hydroxyalkyl group having 1 to 12 carbon atoms, a (polyalkoxyl)alkyl group having 1 to 3 alkoxy groups in which each alkyl group has 1 to 3 carbon atoms, or R¹ ;

wherein R¹ is an acryl- or methacryloyloxyalkyl carbamoyloxyalkyl group having the formula, ##STR11## in which R² is hydrogen or a methyl group, c is an integer of 2 to 6, and d is an integer of 1 to 12;

a is zero, one, or two;

b is a number having an average value from 2 to 100 such that when considered with the value of "a" provides a molecular weight to the organosiloxane urethane acrylate of between 500 and 20,000;

provided that at least 75 percent of all R groups are methyl and at least one of the R groups is an R¹ group, and no more than 25 percent of the R groups are R¹ groups; and

(b) 85 to 0 percent by weight of one or more ethylenically-unsaturated comonomers copolymerizable with the organopolysiloxane urethane acrylate.

2. The device according to claim 1 wherein said organopolysiloxane urethane acrylate has the formula ##STR12## in which R², c, and d are as defined for Formula I, and n is a number having an average value from 15 to 50.

3. The device of claim 1 wherein said polymer is the reaction product of 25 to 90 percent by weight of the organopolysiloxane urethane acrylate of Formula I and 75 to 10 percent by weight of one or more of the ethylenically-unsaturated comonomers.

4. The device according to claim 1 wherein said polymer is the reaction product of 30 to 80 weight percent of said organosiloxane urethane acrylate and said ethylenically-unsaturated comonomers which comprise

(a) 0 to 60 weight percent of a first ethylenically-unsaturated copolymerizable monomer having a hydrophilic group, and

(b) 0 to 70 weight percent of ethylenically-unsaturated non-hydrophilic group-containing copolymerizable monomers selected from

(1) a second polymerizable monomer having one ethylenically-unsaturated group, and

(2) a third polymerizable monomer having more than one ethylenically-unsaturated group.

5. The device according to claim 4 wherein said polymer is derived from said first ethylenically-unsaturated copolymerizable monomer which is present in the range of 2 to 20 weight percent.

6. The device according to claim 4 wherein said polymer is derived from said first ethylenically-unsaturated copolymerizable monomer which is selected from 2-hydroxyethyl acrylate and methacrylate, 2,3-dihydroxypropyl acrylate and methacrylate, and N-vinyl-2-pyrrolidone, and mixture thereof.

7. The device according to claim 4 wherein said polymer is derived from said second ethylenically-unsaturated copolymerizable monomer which is selected from methyl and ethyl acrylate, methyl and ethyl methacrylate, cyclohexyl methacrylate, methyl 2-chloroacrylate, 2-ethoxyethyl methacrylate, 2,2,2-trifluoroethyl acrylate and methacrylate, 2-cyanoethyl methacrylate, 2-(N-methylcarbamoyloxy)ethyl acrylate and methacrylate, acrylic acid, methacrylic acid, vinylidene chloride, styrene, methylstyrene, t-butylstyrene, vinylidene fluoride, methacryloyloxypropyl-tris(trimethylsiloxy) silane, and methacryloyloxymethylpentamethyldisiloxane, and mixture thereof.

8. The device according to claim 7 wherein said second ethylenically-unsaturated copolymerizable monomer is selected from methyl methacrylate, ethyl methacrylate, cyclohexyl methacrylate, and t-butylstyrene.

9. The device of claim 4 wherein said first copolymerizable monomer is 2-hydroxyethyl methacrylate.

10. The device of claim 4 wherein said first copolymerizable monomer is N-vinyl-2-pyrrolidone.

11. The device of claim 4 wherein said polymer is derived from said third copolymerizable comonomer which is selected from ethyleneglycol diacrylate, ethyleneglycol dimethacrylate, diethyleneglycol dimethacrylate, tetraethyleneglycol dimethacrylate, allyl methacrylate, trimethylolpropane trimethacrylate, divinyl benzene, diallyl phthalate, tris(2-acryloyloxyethyl)isocyanurate, and 1,3,5-tri(2-methacryloxyethyl)-s-triazine.

12. The device of claim 4 wherein said second ethylenically-unsatuated comonomer is methyl methacrylate.

13. The device of claim 4 wherein said second ethylenically-unsaturated comonomer is t-butylstyrene.

14. The device of claim 1 wherein said polymer is the reaction product of (1) 35 to 60 percent by weight of the organopolysiloxane of Formula I, (2) 5 to 20 percent by weight of the ethylenically-unsaturated, hydrophilic group-containing, comonomer 2-hydroxyethyl methacrylate, and (3) 35 to 60 percent by weight of the ethylenically-unsaturated, non-hydrophilic, group-containing comonomer methyl methacrylate.

15. The device of claim 1 wherein said polymer is the reaction product of (1) 35 to 60 percent by weight of the organopolysiloxane of Formula I, (2) 5 to 20 percent by weight of the ethylenically-unsaturated, hydrophilic group-containing comonomer 2-hydroxyethyl methacrylate, and (3) 35 to 60 percent by weight of the ethylenically-unsaturated, non-hydrophilic, group-containing comomer t-butylstyrene.

16. A contact lens according to claim 1.

20. The device according to claim 2 wherein R² is methyl, c is 2, and d is 3.

21. The ophthalmic device according to claim 1 wherein two of the R groups of said organopolysiloxane urethane acrylate are terminal R¹ groups.

27. A process for preparing a contact lens comprising the steps of:

(a) preparing a polysiloxane according to claim 1,

(b) forming a contact lens from said polysiloxane, and

(c) subjecting the surface of said contact lens to a glow discharge treatment.

28. The process according to claim 27 further comprising the step of:

subjecting said contact lens to a water vapor treatment.

29. The ophthalmic device according to claim 1 which is a corneal implant.

30. The ophthalmic device according to claim 1 which is a corneal transplant.

31. The ophthalmic device according to claim 1 which is an intraocular lens.

17. A process for preparing polysiloxanes which have at least one urethane acrylate group and have the formula:

##STR13## wherein each R is independently an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having from 3 to 6 carbon atoms, a phenyl group, a hydroxyalkyl group having 1 to 12 carbon atoms, a (polyalkoxyl)alkyl group having 1 to 3 alkoxy groups in which each alkyl group has 1 to 3 carbon atoms, or R¹ ;

wherein R¹ is an acryl- or methacryloyloxyalkyl carbamoyloxyalkyl group having the formula, ##STR14## in which R² is hydrogen or a methyl group, c is an integer of 2 to 6, and d is an integer of 1 to 12;

a is zero, one, or two;

b is a number having an average value from 2 to 100 such that when considered with the value of "a" provides a molecular weight to the organosiloxane urethane acrylate of between 500 and 20,000;

provided that at least 75 percent of all R groups are methyl and at least one of the R groups is an R¹ group, and no more than 25 percent of the R groups are R¹ groups;

said process comprising the steps of

a. reacting an organopolysiloxane polyol having the formula ##STR15## wherein each R³ is independently an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having from 3 to 6 carbon atoms, a phenyl group, a (polyalkoxyl)alkyl group having 1 to 3 alkoxy groups in which each alkyl group has 1 to 3 carbon atoms, or R⁴ ;

wherein R⁴ is

space="preserve" listing-type="equation">HO--CH.sub.2 --.sub.d

a is zero, one, or two;

b is a number having an average value from 2 to 100 such that when considered with the value of "a" provides a molecular weight to the organopolysiloxane polyol of between 500 and 20,000; and

d is an integer of 1 to 12;

provided that at least 75 percent of all R³ groups are methyl and at least one of the R³ groups is an R⁴ group, preferably two of the R³ groups are terminal R⁴ groups, and no more than 25 percent of the R³ groups are R⁴ groups;

with an amount of acryl- or methacryloyloxyalkyl isocyanate compound sufficient to completely esterify at least one hydroxyl group present, said compound having the formula ##STR16## wherein R² is hydrogen or a methyl group and c is an integer of 2 to 6;

b. cooling the resulting organopolysiloxane urethane acryate for a time and at a temperature sufficient to precipitate insoluble material, and

c. recovering the organopolysiloxane urethane acrylate free of precipitated material.

18. A polysiloxane urethane acrylate prepared according to the process of claim 17.

19. The polysiloxane urethane acrylate according to claim 18 which is an ophthalmic device.

22. The process according to claim 17 wherein two of the R³ groups of said organopolysiloxane polyol are terminal R⁴ groups.

26. The process according to claim 17 wherein said polysiloxane is in the form of a contact lens, the surface of which has been subjected to a glow discharge treatment.

23. An ophthalmic device comprising an addition polymer which is the reaction product of a composition comprising:

(a) 15 to 100 percent by weight of at least one organopolysiloxane urethane acrylate having the formula ##STR17## wherein each R is independently an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having from 3 to 6 carbon atoms, a phenyl group, a hydroxyalkyl group having 1 to 12 carbon atoms, a (polyalkoxyl)alkyl group having 1 to 3 alkoxy groups in which each alkyl group has 1 to 3 carbon atoms, or R¹ ;

wherein R¹ is an acryl- or methacryloyloxyalkyl carbamoyloxyalkyl group having the formula, ##STR18## in which R² is hydrogen or a methyl group, c is an integer of 2 to 6, and d is an integer of 1 to 12;

a is zero, one, or two;

b is a number having an average value from 2 to 100 such that when considered with the value of "a" provides a molecular weight to the organosiloxane urethane acrylate of between 500 and 20,000;

provided that at least 75 percent of all R groups are methyl and at least one of the R groups is an R¹ group, and no more than 25 percent of the R groups are R¹ groups; and

(b) 85 to 0 percent by weight of one or more ethylenically-unsaturated comonomers copolymerizable with the organopolysiloxane urethane acrylate;

with the additional feature that the surface of said ophthalmic device has been exposed to a glow discharge treatment.

24. A contact lens, the surface of which is hydrolytically stable and resists deposition of tear components comprising an addition polymer which is the reaction product of a composition comprising:

(a) 15 to 100 percent by weight of at least one organopolysiloxane urethane acrylate having the formula ##STR19## wherein each R is independently an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having from 3 to 6 carbon atoms, a phenyl group, a hydroxyalkyl group having 1 to 12 carbon atoms, a (polyalkoxyl)alkyl group having 1 to 3 alkoxy groups in which each alkyl group has 1 to 3 carbon atoms, or R¹ ;

wherein R¹ is an acryl- or methacryloyloxyalkyl carbamoyloxyalkyl group having the formula, ##STR20## in which R² is hydrogen or a methyl group, c is an integer of 2 to 6, and d is an integer of 1 to 12;

a is zero, one, or two;

b is a number having an average value from 2 to 100 such that when considered with the value of "a" provides a molecular weight to the organosiloxane urethane acrylate of between 500 and 20,000;

provided that at least 75 percent of all R groups are methyl and at least one of the R groups is an R¹ group, and no more than 25 percent of the R groups are R¹ groups; and

(b) 85 to 0 percent by weight of one or more ethylenically-unsaturated comonomers copolymerizable with the organopolysiloxane urethane acrylate.

25. The contact lens according to claim 24 in which said surface resistance to deposition of tear components is achieved by glow discharge treatment and an optional water vapor treatment.