SILICONE HYDROGELS FORMED FROM ZERO DILUENT REACTIVE MIXTURES

• US 20170129983A1
• Filed: 01/25/2017
• Published: 05/11/2017
• 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, Vanderlaan, Douglas G., Ford, James D., Joslin, Scott L.
• Granted Patent: US 10,017,596 B2
• Time in Patent Office: Days
• 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 220/36 containing oxygen in addition to the carboxy oxygen , e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate
• CPC Class Codes: C08F 220/54 Amides , e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
• 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 226/06 by a heterocyclic ring containing nitrogen
• CPC Class Codes: C08F 226/10 N-Vinyl-pyrrolidone
• CPC Class Codes: C08F 283/124 on to polysiloxanes having carbon-to-carbon double bonds
• 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 silicone hydrogels having a desirable balance of properties which can be formed without diluents. The silicone hydrogels are formed from reactive mixtures comprising at least one hydroxyl substituted, monofunctional polydialkylsiloxane monomer having between 2 and 120 dialkylsiloxane repeating units, at least one slow reacting hydrophilic monomer and at least one hydroxyl containing hydrophilic monomer.

Claims

1. A silicone hydrogel comprising about 8 to about 17 wt % silicon, an advancing dynamic contact angle of less than about 80°

without surface modification formed from a reactive mixture comprising

at least one monofunctional polydialkylsiloxane monomer having between 7 and 120 dialkylsiloxane repeating units and which may be optionally substituted with at least one hydroxyl group;

optionally one or more monofunctional, hydroxyl-containing siloxane monomer having less than 7 dialkylsiloxane repeating units, trialkyl siloxane groups or a combination thereof;

with the proviso that if said monofunctional polydialkylsiloxane does not comprise at least one hydroxyl at least one monofunctional, hydroxyl-containing siloxane monomer is included;

about 40-about 60 wt % of at least one slow reacting hydrophilic monomer;

at least one hydroxyl containing hydrophilic monomer, wherein the molar ratio of hydroxyl containing components to the slow reacting hydrophilic monomer is between about 0.15 to about 0.4, wherein the reactive mixture is free of diluent.

3. The silicone hydrogel of claim 1 comprising between about 8 to about 15 wt % silicon.

4. The silicone hydrogel of claim 1 wherein said monofunctional siloxane monomer comprises 7 to 60 dialkylsiloxane repeating units.

5. The silicone hydrogel of claim 1 wherein said monofunctional siloxane monomer comprises 7 to 30 dialkylsiloxane repeating units.

6. The silicone hydrogel of claim 1 wherein said monofunctional siloxane monomer comprises one or two hydroxyl groups.

7. The silicone hydrogel of claim 6 wherein said hydroxyl are located near either a monofunctional reactive end or a terminal end.

8. The silicone hydrogel of claim 1 wherein said silicone hydrogel comprises about 45 to about 60 wt % hydroxyalkyl (meth)acrylate or (meth)acrylamide.

9. The silicone hydrogel of claim 1 further comprising a Dk of at least about 60.

10. The silicone hydrogel of claim 1 further comprising a Dk of at least about 80.

11. The silicone hydrogel of claim 1 further comprising a water content of at least about 55%.

12. The silicone hydrogel of claim 1 further comprising a water content of at least about 60%.

13. The silicone hydrogel of claim 1 further comprising an advancing contact angle of less than about 80°

.

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

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

16. The silicone hydrogel of claim 1 further comprising a modulus of less than about 120 psi.

17. The silicone hydrogel of claim 1 further comprising a modulus of about 100 psi or less.

18. The silicone hydrogel of claim 1 wherein said slow-reacting hydrophilic monomer comprises a reactive group selected from the group consisting of (meth)acrylamides, vinyls, allyls and combinations thereof.

19. The silicone hydrogel of claim 1 wherein said slow-reacting hydrophilic monomer comprises a reactive group selected from the group consisting of vinyls, allyls and combinations thereof and said monofunctional polydialkylsiloxane monomer and said monofunctional, hydroxyl-containing siloxane monomer comprise a reactive group selected from the group consisting of (meth)acrylates, styryls, amides and mixtures thereof.

20. The silicone hydrogel of claim 1 wherein said slow-reacting hydrophilic monomer comprises a reactive group selected from the group consisting of N-vinyl amides, O-vinyl carbamates, O-vinyl carbonates, N-vinyl carbamates, O-vinyl ethers, O-2-propenyl, wherein the vinyl or allyl groups may be further substituted with a methyl group.

21. The silicone hydrogel of claim 1 wherein said slow reacting hydrophilic monomer comprises at least one hydrophilic group selected from the group consisting of hydroxyls, amines, ethers, amides, ammonium groups, carboxylic acid, carbamates and combinations thereof.

22. The silicone hydrogel of claim 1 wherein said slow reacting hydrophilic monomer comprises at least one hydrophilic group selected from the group consisting of hydroxyls, ethers, amides, carboxylic acid combinations thereof.

23. The silicone hydrogel of claim 1 wherein said slow reacting hydrophilic monomer is selected from N-vinylamide monomer of Formula I, a vinyl pyrrolidone of Formula II-IV, n-vinyl piperidone of Formula V:

24. The silicone hydrogel of claim 23 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, and the total number of carbon atoms in R₁ and R₂ is 4 or less.

25. The silicone hydrogel of claim 23 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.

26. The silicone hydrogel of claim 1 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.

27. The silicone hydrogel of claim 1 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

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

29. The silicone hydrogel of claim 1 wherein the slow-reacting hydrophilic monomer comprises NVP.

30. The silicone hydrogel of claim 1 wherein said hydroxyalkyl monomer is selected from hydroxyalkyl (meth)acrylate or (meth)acrylamide monomer of Formula X or a styryl compound of Formula XI

31. The silicone hydrogel of claim 30 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.

32. The silicone hydrogel of claim 30 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.

33. The silicone hydrogel of claim 1 wherein said hydroxyalkyl monomer is selected from the group consisting of 2-hydroxyethyl methacrylate, 2-hydroxyethyl 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.

34. 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.

35. 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.

36. The silicone hydrogel of claim 1 wherein said monofunctional polydialkylsiloxane monomer is selected from mono (meth)acryloxyalkyl polydialkylsiloxane monomer of Formula VI or the styryl polydialkylsiloxane monomer of Formula VII:

37. The silicone hydrogel of claim 36 wherein each R₁₄ is independently selected from ethyl and methyl groups.

38. The silicone hydrogel of claim 36 wherein all R₁₄ are methyl.

39. The silicone hydrogel of claim 36 wherein R₁₂ and each R₁₄ are methyl.

40. The silicone hydrogel of claim 36 wherein at least one R₁₄ is 3,3,3-trifluoropropyl.

41. The silicone hydrogel of claim 36 wherein R₁₃ is selected from C1-C6 alkylene groups which may be substituted with ether, hydroxyl and combinations thereof.

42. The silicone hydrogel of claim 36 wherein R₁₃ is selected from C₁ or C_3-6 alkylene groups which may be substituted with ether, hydroxyl and combinations thereof.

43. The silicone hydrogel of claim 36 wherein a is 7 to 30.

44. The silicone hydrogel of claim 36 wherein R₁₆ is H or methyl.

45. The silicone hydrogel of claim 1 wherein said monofunctional polydialkylsiloxane monomer 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 polydiethyl siloxane, monomethacryloxypropyl terminated mono-n-methyl terminated polydiethyl siloxane, N-(2,3-dihydroxypropane)-N′

-(propyl tetra(dimethylsiloxy) dimethylbutylsilane)acrylamide, α

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

-butyl-octamethylpentasiloxane, and mixtures thereof.

46. The silicone hydrogel of claim 1 wherein said monofunctional polydialkylsiloxane monomer 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, and mixtures thereof.

47. The silicone hydrogel of claim 1 further comprising at least one crosslinking monomer.

48. The silicone hydrogel of claim 47 wherein said crosslinker is present in a molar concentration between about 0.6 to about 2.4 mmole/100 g reactive components.

49. The silicone hydrogel of claim 47 wherein said crosslinker is present in a molar concentration between about 0.6 to about 1.8 mmole/100 g reactive components.

50. The silicone hydrogel of claim 1 further comprising at least one photoinitiator.

51. The silicone hydrogel of claim 1 wherein said reaction mixture further comprises at least one UV absorbing compound.

52. The silicone hydrogel of claim 51 wherein said at least one UV absorbing compound is reactive.

53. The silicone hydrogel of claim 51 comprising between about 1 wt % and about 2 wt % UV absorber.

54. The silicone hydrogel of claim 47 wherein said reaction mixture further comprises at least one slow reacting crosslinker and at least one fast reacting crosslinker.

55. The silicone hydrogel of claim 54 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 %.

56. The silicone hydrogel of claim 54 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 %.

57. The silicone hydrogel of claim 1 wherein all components which comprise at least one hydroxyl group and a fast reacting reactive group are present in a concentration sufficient to provide a molar ratio of hydroxyl to silicon between about 0.16 and about 0.4.

58. The silicone hydrogel of claim 1 wherein said hydroxyalkyl (meth)acrylate or (meth)acrylamide monomers are present in a concentration sufficient to provide a HO:

Si ratio of 0.13 to 0.35.

2. (canceled)