Wettable silicone resin optical devices and curable compositions therefor

• US 4,487,905 A
• Filed: 03/14/1983
• Issued: 12/11/1984
• Est. Priority Date: 03/14/1983
• Status: Expired due to Term

• Current Assignee: The Dow Chemical Company (Dow, Inc.)
• Original Assignee: Dow Corning Corporation (Dow, Inc.)
• Inventors: Mitchell, Darrell D.
• Primary Examiner(s): Marquis, Melvyn I.
• Application Number:
  US06/475,270
• Time in Patent Office: 638 Days
• Field of Search: 351/160 R, 351/160 H, 526/279, 528/15, 528/31, 528/32, 525/478
• US Class Current: 528/15
• CPC Class Codes: C08K 5/54 Silicon-containing compounds C08K5/0091 takes precedence
• CPC Class Codes: C08L 83/00 Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
• CPC Class Codes: C08L 83/06 containing silicon bound to oxygen-containing groups C08L83/12 takes precedence
• CPC Class Codes: G02B 1/04 made of organic materials, e.g. plastics G02B1/08 takes precedence

Abstract

This invention provides novel compositions curable to resins and particularly provides oxygen permeable, inherently wettable optical devices useful as eye contact or intraocular lenses. The lenses are composed of a cured polysiloxane resin having an advancing water-in-air contact angle of no greater than 80°. The polysiloxane resin is prepared from a catalyzed mixture of an acrylate-functional polysiloxane composition and an organosilicon cross-linking agent containing silicon hydride radicals. The acrylate-functional polysiloxane composition contains a sufficient amount of aliphatically unsaturated hydrocarbon radicals (e.g., vinyl radicals) other than acrylate-functional radicals to enable that composition to react on a mole to mole basis with the cross-linking agent to produce a cured polysiloxane resin. To provide the desired level of surface wettability, the acrylate-functional polysiloxane composition also contains an effective amount, typically from 7 to 30 mole percent of the total moles of siloxane units present in the cured polysiloxane resin, of H₂ C═CRCOOR'"'"'SiO₁.5 units to provide the aforementioned advancing water-in-air contact angles. The catalyzed mixture only contains a sufficient amount of cross-linking agent to react with the aliphatically unsaturated hydrocarbon radicals other than the acrylate-functional radicals and thus enables the unreacted acrylate-functional siloxane units to provide the desired wettability characteristics to the cured polysiloxane resin.

Claims

1. A curable polysiloxane composition consisting essentially of

(A) 100 parts by weight of an acrylate-functional polysiloxane composition containing acrylate-functional siloxane units of the unit formula H₂ C═

CROOR'"'"'SiO₁.5 where R is a methyl radical or hydrogen and R'"'"' is a divalent alkylene radical of from 1 to 4 inclusive carbon atoms and containing siloxane units possessing aliphatically unsaturated hydrocarbon radicals selected from the group consisting of vinyl, allyl and butenylene radicals, the remaining silicon-bonded substituents in addition to divalent oxygen radicals present in said polysiloxane essentially being selected from the group consisting of alkyl radicals of from 1 to 3 inclusive carbon atoms and phenyl radicals,

(B) an amount of an organosilicon cross-linking agent containing an average of at least two silicon-bonded hydrogen radicals per molecule, said amount being no greater than that required to provide a 1;

1 mole ratio of silicon-bonded hydrogen radicals to total moles of said aliphatically unsaturated hydrocarbon radicals present in (A), essentially any remaining substituents in addition to divalent oxygen radicals present in said agent being selected from the group consisting of alkyl radicals of from 1 to 3 inclusive carbon atoms and phenyl radicals, and

(C) a catalytic amount of a Group 8 Transition Metal catalyst which preferentially catalyzes the addition of said silicon-bonded hydrogen radicals to said aliphatically unsaturated hydrocarbon radicals instead of the >

C═

C<

portion of the acrylate-functional siloxane units, there being at least a sufficient amount of said aliphatically unsaturated hydrocarbon radicals in (A) such that when the mixture of (A), (B) and (C) is cured to form a resin, said resin possesses a flexural strength value of at least 3,500 p.s.i. at 21°

±

2°

C. in the unhydrated state, there further being an effective amount of said acrylate-functional siloxane units present in (A) such that the cured resin possesses an advancing water-in-air contact angle of no greater than 80°

at 21°

±

2°

C. in the hydrated state and wherein less than 30 mole percent of the total moles of silicon atoms present in (A) and (B) are derived from said acrylate-functional siloxane units.

2. The composition as claimed in claim 1 wherein the catalyst is a platinum catalyst and wherein at least 7 mole percent of the total moles of silicon atoms present in the mixture of (A) and (B) are derived from said acrylate-functional siloxane units, said cured resin having an oxygen gas permeability coefficient of at least 2×

10^-10 (cm³.cm)/(cm².sec.cm Hg) which results in a calculated open eye Equivalent Oxygen Performance value of at least 3 percent at 0.1 mm thickness at 21°

±

2°

C.

3. The composition as claimed in claim 2 wherein the silicon-bonded substituents present in said (A) and (B) are essentially selected from the group consisting of H₂ C═

CRCOOR'"'"'--, vinyl radicals, divalent oxygen radicals, methyl radicals and phenyl radicals, and the silicon-bonded substitutents present in said (B) are essentially selected from the group consisting of hydrogen radicals, divalent oxygen radicals, methyl radicals and phenyl radicals, there being no more than one vinyl radical per silicon atom in said (A), the mole percentage of silicon atoms containing vinyl radicals is from 15 to 30 mole percent of the total moles of silicon atoms present in (A) and (B) and the mole percentage of H₂ C═

CRCOOR'"'"'SiO₁.5 units is less than 30 mole percent of the total moles of silicon atoms present in (A) and (B), the phenyl radical to silicon atom ratio of the total polysiloxane in (A) and (B) is in the range of 0.2 to 0.7 and the methyl radical to silicon atom ratio of the total polysiloxane in (A) and (B) is at least 0.6.

4. The composition as claimed in claim 2 wherein the mole percentage of said acrylate-functional siloxane units based upon the total moles of silicon atoms in both (A) and (B) is in the range of from 10 to 20 mole percent, R is a methyl radical and R'"'"' is a --CH₂ CH₂ CH₂ -- radical.

5. The composition as claimed in claim 4 wherein the silicon-bonded substituents present in said (A) are essentially selected from the group consisting of H₂ C═

C(CH₃)COOCH₂ CH₂ CH₂ --, vinyl radicals, divalent oxygen radicals, methyl radicals and phenyl radicals, and the silicon-bonded substituents present in said (B) are essentially selected from the group consisting of hydrogen radicals, divalent oxygen radicals, methyl radicals and phenyl radicals, there being no more than one vinyl radical per silicon atom and the mole percentage of silicon atoms containing vinyl radicals is from 15 to 30 mole percent of the total moles of silicon atoms present in both (A) and (B) and the phenyl radical to silicon atom ratio of the total polysiloxane in (A) and (B) is in the range of 0.2 to 0.7, the methyl radical to silicon atom ratio of the total polysiloxane in (A) and (B) is at least 0.6, said (B) is selected from the group consisting of HMe₂ SiO(Ph₂ SiO)SiMe₂ H, (HMe₂ SiO)₃ SiPh, (HMe₂ SiO)₄ Si and a polysiloxane containing an average of 10 mole percent Me₃ SiO₀.5 units, 55 mole percent MeHSiO units and 35 mole percent Ph₂ SiO units wherein Me is a methyl radical and Ph is a phenyl radical.

6. A polysiloxane resin article which comprises the product formed upon curing the composition of claim 1.

7. A polysiloxane resin article which comprises the product formed upon curing the composition of claim 2.

8. A polysiloxane resin article which comprises the product formed upon curing the composition of claim 3.

9. A polysiloxane resin article which comprises the product formed upon curing the composition of claim 4.

10. A polysiloxane resin article which comprises the product formed upon curing the composition of claim 5.

11. As an optical device, a lens to be worn against or inside of the eye, said lens consisting essentially of an optically clear, biocompatible, cured polysiloxane resin having a flexural strength value of at least 3,500 p.s.i. at 21°

±

2°

C. in the unhydrated state, an advancing water-in-air contact angle of no greater than 80°

at 21°

±

2°

C. in the hydrated state and an oxygen gas permeability coefficient of at least 2×

10^-10 (cm³.cm)/(cm².sec.cm Hg) which results in a calculated open eye Equivalent Oxygen Performance value of at least 3 percent at 0.1 mm thickness at 21°

±

2°

C., said resin having been prepared by curing a composition consisting essentially of

(A) 100 parts by weight of an acrylate-functional polysiloxane composition containing acrylate-functional siloxane units of the unit formula H₂ C═

CROOR'"'"'SiO₁.5 where R is a methyl radical or hydrogen and R'"'"' is a divalent alkylene radical of from 1 to 4 inclusive carbon atoms and containing siloxane units possessing aliphatically unsaturated hydrocarbon radicals selected from the group consisting of vinyl, allyl and butenylene radicals, the remaining silicon-bonded substituents in addition to divalent oxygen radicals present in said polysiloxane essentially being selected from the group consisting of alkyl radicals of from 1 to 3 inclusive carbon atoms and phenyl radicals,

(B) an amount of an organosilicon cross-linking agent containing an average of at least two silicon-bonded hydrogen radicals per molecule, said amount being no greater than that required to provide a 1;

1 mole ratio of silicon-bonded hydrogen radicals to total moles of said aliphatically unsaturated hydrocarbon radicals present in (A), essentially any remaining substituents in addition to divalent oxygen radicals present in said agent being selected from the group consisting of alkyl radicals of from 1 to 3 inclusive carbon atoms and phenyl radicals, and

(C) a catalytic amount of a Group 8 Transition Metal catalyst which preferentially catalyzes the addition of said silicon-bonded hydrogen radicals to said aliphatically unsaturated hydrocarbon radicals instead of the >

C═

C<

portion of the acrylate-functional siloxane units, there being at least a sufficient amount of said aliphatically unsaturated hydrocarbon radicals in (A) such that when the mixture of (A), (B) and (C) is cured to form a resin, said resin possesses the aforementioned flexural strength value, there further being an effective amount of said acrylate-functional siloxane units present in (A) such that the cured resin possesses the aforementioned water-in-air contact angle and is inherently wettable by the tear fluid of a wearer of such a lens and wherein less than 30 mole percent of the total moles of silicon atoms present in (A) and (B) are derived from said acrylate-functional siloxane units.

12. The device as claimed in claim 11 wherein the catalyst is a platinum catalyst and wherein at least 7 mole percent of the total moles of silicon atoms present in the mixture of (A) and (B) are derived from said acrylate-functional siloxane units.

13. The device as claimed in claim 12 wherein the silicon-bonded substituents present in said (A) and (B) are essentially selected from the group consisting of H₂ C═

CRCOOR'"'"'--, vinyl radicals, divalent oxygen radicals, methyl radicals and phenyl radicals, and the silicon-bonded substituents present in said (B) are essentially selected from the group consisting of hydrogen radicals, divalent oxygen radicals, methyl radicals and phenyl radicals, there being no more than one vinyl radical per silicon atom in said (A), the mole percentage of silicon atoms containing vinyl radicals is from 15 to 30 mole percent of the total moles of silicon atoms present in (A) and (B) and the mole percentage of H₂ C═

CRCOOR'"'"'SiO₁.5 units is less than 30 mole percent of the total moles of silicon atoms present in (A) and (B), the phenyl radical to silicon atom ratio of the total polysiloxane in (A) and (B) is in the range of 0.2 to 0.7 and the methyl radical to silicon atom ratio of the total polysiloxane in (A) and (B) is at least 0.6, said resin having an oxygen gas permeability coefficient of at least 8×

10^-10 (cm³.cm)/(cm².sec.cm Hg) which results in a calculated open eye Equivalent Oxygen Performance Value of at least 10 percent at 0.1 mm thickness at 21°

±

2°

C.

14. The device as claimed in claim 12 wherein the mole percentage of said acrylate-functional siloxane units based upon the total moles of silicon atoms in both (A) and (B) is in the range of from 10 to 20 mole percent, R is a methyl radical and R'"'"' is a --CH₂ CH₂ CH₂ -- radical.

15. The device as claimed in claim 14 wherein the silicon-bonded substituents present in said (A) are essentially selected from the group consisting of H₂ C═

C(CH₃)COOCH₂ CH₂ CH₂ --, vinyl radicals, divalent oxygen radicals, methyl radicals and phenyl radicals, and the silicon-bonded substituents present in said (B) are essentially selected from the group consisting of hydrogen radicals, divalent oxygen radicals, methyl radicals and phenyl radicals, there being no more than one vinyl radical per silicon atom and the mole percentage of silicon atoms containing vinyl radicals is from 15 to 30 mole percent of the total moles of silicon atoms present in both (A) and (B) and the phenyl radical to silicon atom ratio of the total polysiloxane in (A) and (B) is in the range of 0.2 to 0.7, the methyl radical to silicon atom ratio of the total polysiloxane in (A) and (B) is at least 0.6, said (B) is selected from the group consisting of HMe₂ SiO(Ph₂ SiO)SiMe₂ H, (HMe₂ SiO)₃ SiPh, (HMe₂ SiO)₄ Si and a polysiloxane containing an average of 10 mole percent Me₃ SiO₀.5 units, 55 mole percent MeHSiO units and 35 mole percent Ph₂ SiO units wherein Me is a methyl radical and Ph is a phenyl radical, said resin having an oxygen gas permeability coefficient of at least 8×

10^- (cm³.cm)/(cm².sec.cm Hg) which results in a calculated open eye Equivalent Oxygen Performance value of at least 10 percent at 0.1 mm thickness at 21°

±

2°

C.

16. The device as claimed in claim 11 wherein the device is an eye contact lens.

17. The device as claimed in claim 12 wherein the device is an eye contact lens.

18. The device as claimed in claim 13 wherein the device is an eye contact lens.

19. The device as claimed in claim 14 wherein the device is an eye contact lens.

20. The device as claimed in claim 15 wherein the device is an eye contact lens.