Ophthalmic devices fabricated from urethane acrylates of polysiloxane alcohols

Claim 2

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 R 1 ; wherein R 1 is an acryl- or methacryloyloxyalkyl carbamoyloxyalkyl group having the formula, ##STR11## in which R 2 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 R 1 group, and no more than 25 percent of the R groups are R 1 groups; and (b) 85 to 0 percent by weight of one or more ethylenically-unsaturated comonomers copolymerizable with the organopolysiloxane urethane acrylate.

Claim 3

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

Claim 4

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.

Claim 5

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.

Claim 6

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.

Claim 7

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.

Claim 8

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.

Claim 9

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.

Claim 10

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

Claim 11

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

Claim 12

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.

Claim 13

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

Claim 14

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

Claim 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 comonomer methyl methacrylate.

Claim 16

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.

Claim 17

A contact lens according to claim 1.

Claim 18

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 R 1 ; wherein R 1 is an acryl- or methacryloyloxyalkyl carbamoyloxyalkyl group having the formula, ##STR14## in which R 2 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 R 1 group, and no more than 25 percent of the R groups are R 1 groups; said process comprising the steps of a. reacting an organopolysiloxane polyol having the formula ##STR15## wherein each R 3 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 R 4 ; wherein R 4 is 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 R 3 groups are methyl and at least one of the R 3 groups is an R 4 group, preferably two of the R 3 groups are terminal R 4 groups, and no more than 25 percent of the R 3 groups are R 4 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 R 2 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.

Claim 19

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 R 1 ; wherein R 1 is an acryl- or methacryloyloxyalkyl carbamoyloxyalkyl group having the formula, ##STR14## in which R 2 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 R 1 group, and no more than 25 percent of the R groups are R 1 groups; said process comprising the steps of a. reacting an organopolysiloxane polyol having the formula ##STR15## wherein each R 3 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 R 4 ; wherein R 4 is 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 R 3 groups are methyl and at least one of the R 3 groups is an R 4 group, preferably two of the R 3 groups are terminal R 4 groups, and no more than 25 percent of the R 3 groups are R 4 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 R 2 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.

Claim 20

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

Claim 21

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

Claim 22

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

Claim 23

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

Claim 24

The process according to claim 17 wherein two of the R 3 groups of said organopolysiloxane polyol are terminal R 4 groups.

Claim 25

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 R 1 ; wherein R 1 is an acryl- or methacryloyloxyalkyl carbamoyloxyalkyl group having the formula, ##STR18## in which R 2 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 R 1 group, and no more than 25 percent of the R groups are R 1 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.

Claim 26

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 R 1 ; wherein R 1 is an acryl- or methacryloyloxyalkyl carbamoyloxyalkyl group having the formula, ##STR18## in which R 2 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 R 1 group, and no more than 25 percent of the R groups are R 1 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.

Claim 27

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 R 1 ; wherein R 1 is an acryl- or methacryloyloxyalkyl carbamoyloxyalkyl group having the formula, ##STR20## in which R 2 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 R 1 group, and no more than 25 percent of the R groups are R 1 groups; and (b) 85 to 0 percent by weight of one or more ethylenically-unsaturated comonomers copolymerizable with the organopolysiloxane urethane acrylate.

Claim 28

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 R 1 ; wherein R 1 is an acryl- or methacryloyloxyalkyl carbamoyloxyalkyl group having the formula, ##STR20## in which R 2 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 R 1 group, and no more than 25 percent of the R groups are R 1 groups; and (b) 85 to 0 percent by weight of one or more ethylenically-unsaturated comonomers copolymerizable with the organopolysiloxane urethane acrylate.

Claim 29

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.

Claim 30

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.

Claim 31

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.

Claim 32

The process according to claim 27 further comprising the step of: subjecting said contact lens to a water vapor treatment.

Claim 33

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

Claim 34

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

Claim 35

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