Silicone hydrogels comprising desirable water content and oxygen permeability

• US 9,244,197 B2
• Filed: 12/09/2014
• Issued: 01/26/2016
• Est. Priority Date: 12/23/2011
• Status: Active Grant

• Current Assignee: Johnson & Johnson Vision Care Incorporated (Johnson & Johnson)
• Original Assignee: Johnson & Johnson Vision Care Incorporated (Johnson & Johnson)
• Inventors: Alli, Azaam, Ford, James D., Joslin, Scott L.
• Primary Examiner(s): Salamon, Peter A
• Application Number:
  US14/564,667
• Publication Number:
  US 20150094395A1
• Time in Patent Office: 413 Days
• Field of Search: None
• US Class Current: 1/1
• CPC Class Codes: C08F 220/20 of polyhydric alcohols or phenols , e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
• CPC Class Codes: C08F 220/56 Acrylamide; Methacrylamide
• 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: C08F 283/12 on to polysiloxanes
• CPC Class Codes: C08F 283/124 on to polysiloxanes having carbon-to-carbon double bonds
• CPC Class Codes: C08F 290/06 Polymers provided for in subclass C08G
• CPC Class Codes: C08F 290/068 Polysiloxanes
• CPC Class Codes: C08G 77/442 containing vinyl polymer sequences
• CPC Class Codes: G02B 1/043 Contact lenses

Abstract

The present invention relates to a process comprising the steps of reacting a reactive mixture comprising at least one silicone-containing component, at least one hydrophilic component, and at least one diluent to form an ophthalmic device having an advancing contact angle of less than about 80°; and contacting the ophthalmic device with an aqueous extraction solution at an elevated extraction temperature, wherein said at least one diluent has a boiling point at least about 10° higher than said extraction temperature.

Claims

1. A silicone hydrogel comprising a water content of at least about 50% and an oxygen permeability of at least about 80 barrers wherein said silicone hydrogel is formed from a reaction mixture comprising about 37 to about 75 wt % of at least one slow-reacting hydrophilic monomer having a slow-reacting hydrophilic monomer kinetic half life;

at least one silicone-containing component having a silicone-containing component kinetic half life, which may be optionally substituted with at least one hydroxyl containing group;

at least one hydroxyl-containing component selected from said silicone-containing components substituted with at least one hydroxyl group, at least one hydroxyalkyl monomer, and mixtures thereof,

wherein ratio of said slow-reacting hydrophilic component half life to said silicone-containing component half life is at least 2, said reaction mixture comprising between 9 and 14 wt % silicon from all components and less than 15 wt % TRIS and wherein all reactive components other than said slow-reacting hydrophilic monomer and said silicone containing components in the reaction mixture are ancillary components and the hydroxyl containing components are present in an amount sufficient to provide a molar ratio of hydroxyl groups in the reaction mixture to silicon atom content between about 0.16 and about 0.4.

2. The silicone hydrogel of claim 1 wherein said silicone containing components comprise less than 10 wt % TRIS.

3. The silicone hydrogel of claim 1 wherein said silicone containing components are free of TRIS.

4. The silicone hydrogel of claim 1 wherein said ancillary components in said reaction mixture in a concentration of less than 12 wt % based upon reactive components.

5. The silicone hydrogel of claim 1 wherein said water content is at least about 55%.

6. The silicone hydrogel of claim 1 wherein said water content is at least about 60%.

7. The silicone hydrogel of claim 1, 5 or 6 wherein said oxygen permeability is at least about 90 barrers.

8. The silicone hydrogel of claim 1, 5 or 6 wherein said oxygen permeability is at least about 100 barrers.

9. The silicone hydrogel of claim 1 wherein said ancillary components in amounts between about 38 and about 76 mmol/g reactive components.

10. The silicone hydrogel of claim 1, 5 or 6 wherein said oxygen permeability is between about 85 and about 150 barrers.

11. The silicone hydrogel of claim 1, 5 or 6 wherein said oxygen permeability is between about 85 and about 130 barrers.

12. The silicone hydrogel of claim 1, 5 or 6 further comprising a modulus of less than about 150 psi.

13. The silicone hydrogel of claim 1, 5 or 6 further comprising a contact angle of less than about 80°

.

14. The silicone hydrogel of claim 1, 5 or 6 further comprising an advancing contact angle of less than about 70°

.

15. The silicone hydrogel of claim 1 wherein said at least one slow reacting monomer selected from the group consisting of N-vinylamide monomer of Formula I, vinyl pyrrolidone of Formula II-IV, N-vinyl piperidone of Formula V:

16. The silicone hydrogel of claim 1 wherein said at least one slow reacting hydrophilic monomer is selected from the group consisting of N-vinylamide monomer of Formula I, vinyl pyrrolidone of Formula II or IV:

17. The silicone hydrogel of claim 15 or 16 wherein each R₃ is independently selected from ethyl and methyl groups.

18. The silicone hydrogel of claim 15 or 16 wherein all R₃ are methyl.

19. The silicone hydrogel of claim 15 or 16 wherein R₁₃ is selected from the group consisting of C₁-C₆ alkylene group which may be substituted with ether, hydroxyl and combinations thereof.

20. The silicone hydrogel of claim 15 or 16 wherein R₁₃ is selected from the group consisting of C₁ or C₃-C₆ alkylene groups which may be substituted with ether, hydroxyl and combinations thereof.

21. The silicone hydrogel of claim 15 or 16 wherein R₁₆ is H or methyl.

22. The silicone hydrogel of claim 15 or 16 wherein R₁₂ and each R₁₄ are methyl.

23. The silicone hydrogel of claim 15 or 16 wherein at least one R₁₄ is 3,3,3-trifluoropropyl.

24. The silicone hydrogel of claim 15 or 16 wherein R₄ is methyl or 2-hydroxyethyl.

25. The silicone hydrogel of claim 15 wherein a is 5 to 15.

26. The silicone hydrogel of claim 15 or 16 wherein the slow-reacting hydrophilic monomer is selected from the vinyl pyrrolidone of Formula II or IV or the N-vinyl amide monomer of Formula I, having a total number of carbon atoms in R₁ and R₂ of 4 or less.

27. The silicone hydrogel of claim 15 or 16 wherein the slow-reacting hydrophilic monomer is selected from a vinyl pyrrolidone of Formula III or IV and R₆ is methyl, R₇ is hydrogen, R₉ is CH═

CH₂, R₁₀ and R₁₁ are H.

28. The silicone hydrogel of claim 15 or 16 wherein the slow-reacting hydrophilic monomer is selected from ethylene glycol vinyl ether (EGVE), di(ethylene glycol) vinyl ether (DEGVE), N-vinyl pyrrolidone (NVP), 1-methyl-3-methylene-2-pyrrolidone, 1-methyl-5-methylene-2-pyrrolidone, 5-methyl-3-methylene-2-pyrrolidone;

1-ethyl-5-methylene-2-pyrrolidone, N-methyl-3-methylene-2-pyrrolidone, 5-ethyl-3-methylene-2-pyrrolidone, 1-n-propyl-3-methylene-2-pyrrolidone, 1-n-propyl-5-methylene-2-pyrrolidone, 1-isopropyl-3-methylene-2-pyrrolidone, 1-isopropyl-5-methylene-2-pyrrolidone, N-vinyl-N-methyl acetamide (VMA), N-vinyl-N-ethyl acetamide, N-vinyl-N-ethyl formamide, N-vinyl formamide, N-vinyl acetamide, N-vinyl isopropylamide, allyl alcohol, N-vinyl caprolactam, N-2-hydroxyethyl vinyl carbamate, N-carboxy-β

-alanine N-vinyl ester;

N-carboxyvinyl-β

-alanine (VINAL), N-carboxyvinyl-α

-alanine and mixtures thereof.

29. The silicone hydrogel of claim 15 or 16 wherein the slow-reacting hydrophilic monomer is selected from the group consisting of N-vinylpyrrolidone, N-vinylacetamide, 1-methyl-3-methylene-2-pyrrolidone, 1-methyl-5-methylene-2-pyrrolidone, 5-methyl-3-methylene-2-pyrrolidone, and mixtures thereof.

30. The silicone hydrogel of claim 15 or 16 wherein the slow-reacting hydrophilic monomer is selected from the group consisting of NVP, VMA and 1-methyl -5-methylene-2-pyrrolidone.

31. The silicone hydrogel of claim 15 or 16 wherein the slow-reacting hydrophilic monomer comprises NVP.

32. The silicone hydrogel of claim 15 or 16 wherein R₁ is H or methyl, X is oxygen and R is selected from C₂-C₄ mono or dihydroxy substituted alkyl, and poly(ethylene glycol) having 1-10 repeating units.

33. The silicone hydrogel of claim 15 or 16 wherein R₁ methyl, X is oxygen and R is selected from C₂-C₄ mono or dihydroxy substituted alkyl, and poly(ethylene glycol) having 2-20 repeating units.

34. The silicone hydrogel of claim 15 or 16 wherein at least one R₁₄ is 3,3,3-trifluoropropyl.

35. The silicone hydrogel of claim 15 or 16 wherein R₁₃ is selected from C₁-C₆ alkylene groups which may be substituted with ether, hydroxyl and combinations thereof.

36. The silicone hydrogel of claim 15 or 16 wherein R₁₃ is selected from C₁ or _C3-6 alkylene groups which may be substituted with ether, hydroxyl and combinations thereof.

37. The silicone hydrogel of claim 15 or 16 wherein a is 7 to 30.

38. The silicone hydrogel of claim 15 or 16 whereinR₁₆ is H or methyl.

39. The silicone hydrogel of claim 1 wherein said silicone-containing component comprises at least one monomethacryloxyalkylpolydimethylsiloxane methacrylate is selected from the group consisting of monomethacryloxypropyl terminated mono-n-butyl terminated polydimethylsiloxane, monomethacryloxypropyl terminated mono-n-methyl terminated polydimethylsiloxane, monomethacryloxypropyl terminated mono-n-butyl terminated polydiethylsiloxane, monomethacryloxypropyl terminated mono-n-methyl terminated polydiethylsiloxane, N-(2,3-dihydroxypropane)-N′

-(propyl tetra(dimethylsiloxy) dimethylbutylsilane)acrylamide;

α

-(2-hydroxy-1-methacryloxypropyloxypropyl)-ω

-butyl-octamethylpentasiloxane and mixtures thereof.

40. The silicone hydrogel of claim 1 wherein said silicone-containing component comprises at least one monomethacryloxyalkylpolydimethylsiloxane methacrylate is selected from the group consisting of monomethacryloxypropyl terminated mono-n-butyl terminated polydimethylsiloxane, monomethacryloxypropyl terminated mono-n-methyl terminated polydimethylsiloxane, N-(2,3-dihydroxypropane)-N′

-(propyl tetra(dimethylsiloxy) dimethylbutylsilane)acrylamide.

41. The silicone hydrogel of claim 15 or 16 wherein R₁ is H or methyl, X is oxygen and R is selected from C₂-C₄ mono or dihydroxy substituted alkyl, and poly(ethylene glycol) having 1-10 repeating units.

42. The silicone hydrogel of claim 15 or 16 wherein R₁ methyl, X is oxygen and R is selected from C₂-C₄ mono or dihydroxy substituted alkyl, and poly(ethylene glycol) having 2-20 repeating units.

43. The silicone hydrogel of claim 15 or 16 wherein R is 2-hydroxyethyl, 2,3-dihydroxypropyl, 2-hydroxypropyl.

44. The silicone hydrogel of claim 1 wherein said hydroxyalkyl monomer is selected from the group consisting of 2-hydroxyethyl (meth)acrylate, 3 -hydroxypropyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 1-hydroxypropyl-2-(meth)acrylate, 2-hydroxy-2-methyl-propyl (meth)acrylate, 3-hydroxy-2,2-dimethyl-propyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, glycerol (meth)acrylate, 2-hydroxyethyl (meth)acrylamide, polyethyleneglycol monomethacrylate, bis-(2-hydroxyethyl) (meth)acrylamide, 2,3-dihydroxypropyl (meth)acrylamide, and mixtures thereof.

45. The silicone hydrogel of claim 1 wherein said hydroxyalkyl monomer is selected from the group consisting of 2-hydroxyethyl methacrylate, glycerol methacrylate, 2-hydroxypropyl methacrylate, hydroxybutyl methacrylate, 3-hydroxy-2,2-dimethyl-propyl methacrylate, and mixtures thereof.

46. The silicone hydrogel of claim 1 wherein said hydroxyalkyl monomer comprises 2-hydroxyethyl methacrylate, 3-hydroxy-2,2-dimethyl-propyl methacrylate, glycerol methacrylate and mixtures comprising them.

47. The silicone hydrogel of claim 1 further comprising a contact angle of less than about 80°

.

48. The silicone hydrogel of claim 1 further comprising a % haze of less than about 50%.

49. The silicone hydrogel of claim 1 further comprising a % haze of less than about 10%.

50. The silicone hydrogel of claim 1 wherein said reaction mixture further comprises at least one slow reacting crosslinker and at least one fast reacting crosslinker.

51. The silicone hydrogel of claim 50 wherein said at least one slow reacting crosslinker and at least one fast reacting crosslinker are each present in said reaction mixture in amounts between about 0.05 to about 0.3 wt %.

52. The silicone hydrogel of claim 50 wherein said at least one slow reacting crosslinker and at least one fast reacting crosslinker are each present in said reaction mixture in amounts between about 0.1 to about 0.2 wt %.

53. The silicone hydrogel of claim 1 wherein said at least one silicone-containing component and said at least one hydroxyl-containing component have the same reactive functionality.

54. The silicone hydrogel of claim 1 wherein the at least one hydroxyalkyl monomer does not contain any silicone and is present in the reactive mixture in an amount sufficient such that the molar ratio of hydroxyl groups in non-silicone containing hydroxyalkyl monomer to silicon atom is between about 0.13 and about 0.35.