Biomedical devices containing internal wetting agents

• US 7,691,916 B2
• Filed: 03/30/2007
• Issued: 04/06/2010
• Est. Priority Date: 09/10/2001
• Status: Active Grant

• Current Assignee: Johnson & Johnson Vision Care Incorporated (Johnson & Johnson)
• Original Assignee: Johnson & Johnson Vision Care Incorporated (Johnson & Johnson)
• Inventors: McCabe, Kevin P., Steffen, Robert B., Molock, Frank F., Vanderlaan, Douglas G., Alli, Azaam, Young, Kent A., Ford, James D.
• Primary Examiner(s): Zimmer; Marc S
• Application Number:
  US11/693,790
• Publication Number:
  US 20070229757A1
• Time in Patent Office: 1,103 Days
• Field of Search: None
• US Class Current: 522/99
• CPC Class Codes: A61L 27/18 obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
• CPC Class Codes: A61L 27/26 Mixtures of macromolecular compounds
• CPC Class Codes: A61L 27/52 Hydrogels or hydrocolloids
• CPC Class Codes: C08L 83/04 Polysiloxanes
• CPC Class Codes: G02B 1/043 Contact lenses

Abstract

This invention includes a wettable biomedical device containing a high molecular weight hydrophilic polymer and a hydroxyl-functionalized silicone-containing monomer.

Claims

1. A wettable silicone hydrogel comprising the reaction product of at least one siloxane containing macromer selected from the group consisting of methacrylate functionalized, silicone-fluoroether urethane macromers, methacrylate functionalized, silicone urethane macromers, styrene functionalized prepolymers of hydroxyl functional methacrylates and silicone methacrylates and vinyl carbamate functionalized polydimethylsiloxane;

at least one high molecular weight hydrophilic polymer; and

an effective amount of at least one compatibilizing component comprising mono-(3-methacryloxy-2-hydroxypropyloxy)propyl terminated, mono-butyl terminated polydimethylsiloxane.

2. The hydrogel of claim 1 wherein said siloxane containing macromer is present in an amount between about 5% to about 50%.

3. The hydrogel of claim 1 wherein the siloxane containing macromer is present in an amount between about 10% to about 50%.

4. The hydrogel of claim 1 wherein the siloxane containing macromer is present in an amount between about 15% to about 45%.

5. The hydrogel of claim 1 wherein said at least on siloxane containing macromer comprises at least one siloxane group, and at least one second group selected from the group consisting of urethane groups, alkylene groups, alkylene oxide groups, polyoxyalkalene groups, arylene groups, alkyl esters, amide groups, carbamate groups, perfluoroalkoxy groups, isocyanate groups, combinations thereof.

6. The hydrogel of claim 5 wherein said at least one siloxane containing macromers is formed via polymerizing said siloxane group with at least one acrylic or methacrylic compound.

7. The hydrogel of claim 1 comprising about 1% to about 15% high molecular weight hydrophilic polymer.

8. The hydrogel of claim 1 comprising about 3% to about 15% high molecular weight hydrophilic polymer.

9. The silicone hydrogel of claim 1 wherein said hydrophilic polymer is selected from the group consisting of polyamides, polylactones, polyimides, polylactams, functionalized polyamides, functionalized polylactones, functionalized polyimides, functionalized polylactams, and mixtures thereof.

10. The silicone hydrogel of claim 1 wherein said hydrophilic polymer is selected from the group consisting of poly-N-vinyl pyrrolidone, poly-N-vinyl-2-piperidone, poly-N-vinyl-2-caprolactam, poly-N-vinyl-3-methyl-2-caprolactam, poly-N-vinyl-3-methyl-2-piperidone, poly-N-vinyl-4-methyl-2-piperidone, poly-N-vinyl-4-methyl -2-caprolactam, poly-N-vinyl-3-ethyl-2-pyrrolidone, and poly-N-vinyl-4, 5-dimethyl-2-pyrrolidone, polyvinylimidazole, poly-N-N-dimethylacrylamide, polyvinyl alcohol, polyacrylic acid, polyethylene oxide, poly 2 ethyl oxazoline, heparin polysacoharides, polysacoharides, mixtures and copolymers thereof.

11. The hydrogel of claim 1, wherein the high molecular weight hydrophilic polymer is poly-N-vinylpyrrolidone.

12. The hydrogel of claim 1, wherein the high molecular weight hydrophilic polymer is poly-N-vinylpyrrolidone.

13. The hydrogel of claim 1 wherein said compatibilizing component is present in an amount between about 5 and about 90 weight %.

14. The hydrogel of claim 1 comprising at least one oxygen permeable component in addition to said siloxane containing macromer or prepolymer.

15. The hydrogel of claim 14 wherein said oxygen permeable component is selected from the group consisting of amide analogs of 3-methacryloxypropyltris(trimethylsiloxy)silane;

siloxane vinyl carbamate analogs, siloxane vinyl carbonate analogs, and siloxane containing monomers, combinations and oligomers thereof.

16. The hydrogel of claim 14 wherein said oxygen permeable component is selected from the group consisting of 3-methacryloxypropyltris(trimethylsiloxy)silane, monomethacryloxypropyl terminated polydimethylsiloxanes, polydimethylsiloxanes, 3-methacryloxypropylbis(trimethylsiloxy)methylsilane, methacryloxypropylpentamethyl disiloxane and combinations thereof.

17. The hydrogel of claim 14 wherein said oxygen permeable component is present in an amount of about 5 to about 60%.

18. The hydrogel of claim 14 wherein said oxygen permeable component is present in an amount of about 10 to about 40%.

19. The hydrogel of claim 1 further comprising at least one hydrophilic monomer.

20. The hydrogel claim 19 wherein said at least one hydrophilic monomer comprises at least one acrylic group, vinyl group or a combination thereof.

21. The hydrogel of claim 20 wherein said acrylic group has the formula CH₂═

CRCOX, where R is hydrogen or C_1-6alkyl and X is O or N.

22. The hydrogel of claim 19 wherein said at least one hydrophilic monomer is selected from the group consisting of N,N-dimethylacrylamide, 2-hyd roxyethyl methacrylate, glycerol methacrylate, 2-hydroxyethyl methacrylamide, polyethyleneglycol monomethacrylate, methacrylic acid, acrylic acid, N-vinyl pyrrolidone, N-vinyl-N-methyl acetamide, N-vinyl-N-ethyl acetamide, N-vinyl-N-ethyl formamide, N-vinyl formamide, hydrophilic vinyl carbonate monomers, vinyl carbamate monomers, hydrophilic oxazolone monomers, polydextran and copolymers and combinations thereof.

23. The hydrogel of claim 19 wherein said at least one hydrophilic monomer is selected from the group consisting of N,N-dimethylacrylamide, 2-hydroxyethyl methacrylate, glycerol methacrylate, 2-hydroxyethyl methacrylamide, N-vinylpyrrolidone, polyethyleneglycol monomethacrylate, methacrylic acid, acrylic acid and combinations thereof.

24. The hydrogel of claim 19 wherein said at least one hydrophilic monomer comprises N,N-dimethylacrylamide.

25. The hydrogel of claim 19 wherein said at least one hydrophilic monomer is present in amounts of about 5 to about 60 weight %.

26. The hydrogel of claim 19 wherein said at least one hydrophilic monomer is present in amounts of about 10 to 50 weight %.

27. The hydrogel of claim 1 comprising about 1 about 15 weight % high molecular weight hydrophilic polymer and about 5 to about 90 weight % hydroxyl-functionalized silicone-containing monomer.

28. The hydrogel of claim 1 comprising about 3% to about 15% high molecular weight hydrophilic polymer;

about 10 to about 80 weight % compatibilizing component;

about 10 to about 50 weight % said siloxane containing macromer, 5 to about 60 weight % siloxane containing momoner and 5 to about 60 weight % hydrophilic monomer.

29. A silicone hydrogel contact lens comprising the hydrogel of claim 1 and wherein said contact lens is not surface modified.

30. The lens of of claim 29, wherein the contact lens is a soft contact lens.

31. The lens of claim 29 wherein said lens has an advancing dynamic contact angle of less than about 70°

.

32. The lens of claim 29 wherein said lens has an advancing dynamic contact angle of less than about 60°

.

33. The lens of claim 29 wherein said lens further comprises a modulus of less than about 90 psi.

34. The lens of claims 29 wherein said lens further comprises a water content between about 10 and about 60%.

88. The hydrogel claim 14 wherein said oxygen permeable component comprises at least one monomethacryloxypropyl terminated polydimethylsiloxane.

35. A method comprising the steps of (a) mixing reactive components comprising at least one high molecular weight hydrophilic polymer, at least one siloxane containing macromer selected from the group consisting of methacrylate functionalized, silicone urethane macromers, styrene functionalized prepolymers of hydroxyl functional methacrylates and silicone methacrylates and vinyl carbamate functionalized polydimethylsiloxane;

and an effective amount of at least one compatibilizing component comprising mono-(3-methacryloxy-2-hydrooxypropyloxy)propyl-terminated, and mono butyl terminated polydimethylsiloxane having a number average molecular weight of about 1100 and (b) curing the product of step (a) to form a biomedical device.

36. The method of claim 35 wherein said biomedical device comprises an ophthalmic device.

37. The method of claim 35 wherein said ophthalmic device is a silicone hydrogel contact lens.

38. The method of claim 35 wherein said reactive components are mixed in the presence of a diluent to form a reaction mixture.

39. The method of claim 38 wherein said diluent is selected from the group consisting of ethers, esters, alkanes, alkyl halides, silanes, amides, alcohols and mixtures thereof.

40. The method of claim 38 wherein said diluent selected from the group consisting amides, alcohols and mixtures thereof.

41. The method of claim 38 wherein said diluent selecting the group consisting of tetrahydrofuran, ethyl acetate, methyl lactate, i-propyl lactate, ethylene chloride, octamethylcyclotetrasiloxane, dimethyl formamide, dimethyl acetamide, dimethyl propionamide, N methyl pyrrolidinone mixtures thereof and mixtures of any of the foregoing with at least one alcohol.

42. The method of claim 38 wherein said diluent comprises at least one alcohol having at least 4 carbon atoms.

43. The method of claim 38 wherein said diluent comprises at least one alcohol having at least 5 carbons atoms.

44. The method of claim 38 wherein said diluents are inert and easily displaceable with water.

45. The method of claim 38 wherein said diluent comprises at least one alcohol selected from the group consisting of tert-butanol, tert-amyl alcohol, 2-butanol, 2-methyl-2-pentanol, 2,3-dimethyl-2-butanol, 3-methyl-3-pentanol, 3-ethyl-3-pentanol, 3,7-dimethyl-3-octanol and mixtures thereof.

46. The method of claim 38 wherein said diluent is selected from the group consisting of hexanol, heptanol, octanol, nonanol, decanol, tert-butyl alcohol, 3-methyl-3-pentanol, isopropanol, t amyl alcohol, ethyl lactate, methyl lactate, -propyl lactate, 3,7-dimethyl-3-octanol, dimethyl formamide, dimethyl acetamide, dimethyl propionamide, N methyl pyrrolidinone and mixtures thereof.

47. The method of claim 38 wherein said diluent is selected from the group consisting of 1-ethoxy-2-propanol, 1-methyl-2-propanol, t-amyl alcohol, tripropylene glycol methyl ether, isopropanol, 1-methyl-2-pyrrolidone, N,N-dimethylpropionamide, ethyl lactate, dipropylene glycol methyl ether and mixtures thereof.

48. The method of claim 38 wherein said diluent is present in an amount less than about 40 weight % based upon the reaction mixture.

49. The method of claim 38 wherein said diluent is present in an amount between about 10 and about 30 weight % based upon the reaction mixture.

50. The method of claim 38 wherein said diluent is water soluble at processing conditions and said process further comprises (c) removing said device from a mold in which said device was cured and (d) hydrating said device, wherein both steps (c) and (d) are performed in aqueous solutions which comprise water as a substantial component.

51. The method of claim 38 wherein said curing is conducted via heat, exposure to radiation or a combination thereof and said reaction mixture further comprises at least one initiator.

52. The method of claim 51 wherein said curing is conducted via irradiation comprises ionizing and/or actinic radiation and said initiator comprises at least one photoinitiator.

53. The method of claim 52 wherein said radiation comprises light having a wavelength of about 150 to about 800nm and said initiator is selected from the group consisting of aromatic alpha-hydroxy ketones, alkoxydoxybenzoins, acetophenones, acyl phosphine oxides, mixtures of tertiary amines and diketones, and mixtures thereof.

54. The method of claim 52 wherein said initiator is selected from the group consisting of 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, bis(2,6-dimethoxybenzoyl)-2,4-4-trimethylpentyl phosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphineoxide, 2,4,6-trimethylbenzyldiphenyl phosphine oxide and 2,4,6-trimethylbenzyoyl diphenylphosphine oxide, benzoin methyl ester, combinations of camphorquinone and ethyl 4-(N,N-dimethylamino)benzoate and mixtures thereof.

55. The method of claim 52 wherein said initiator is present in the reaction mixture in amounts from about 0.1 to about 2 weight percent based upon said reactive components.

56. The method of claim 52 wherein said curing is conducted via visible light irradiation.

57. The method of claim 56 wherein said initiator comprises 1-hydroxycyclohexyl phenyl ketone, bis(2,6-dimethoxybenzoyl)-2,4-4-trimethylpentyl phosphine oxide and mixtures thereof.

58. The method of claim 56 wherein said initiator comprises bis(2,4,6-trimethylbenzoyl)-phenylphosphineoxide.

59. The method of claims 52 wherein said reactive components further comprises at least one UV absorbing compound.

60. The method of claim 56 wherein said curing step is conducted at a cure intensity between about 0.1 and about 6 mW/cm².

61. The method of claim 56 wherein said curing step is conducted at a cure intensity of between about 0.2 mW/cm² to about 3 mW/cm².

62. The method of claims 60 wherein said curing step further comprises a cure time of at least about 1 minute.

63. The method of claims 60 wherein said curing step further comprises a cure time of between about 1 and about 60 minutes.

64. The method of claim 60 wherein said curing step further comprises a cure time of between about 1 and about 30 minutes.

65. The method of claim 60 wherein said curing step is conducted at a temperature greater than about 25°

C.

66. The method of claim 60 wherein said curing step is conducted at a temperature between about 25°

C. and 70°

C.

67. The method of claim 60 wherein said curing step is conduct at a temperature between about 40°

C. and 70°

C.

68. The method of claim 38 wherein said reaction mixture is cured in a mold and said method further comprises the step deblocking said ophthalmic device from said mold.

69. The method of claim 68 wherein said reaction mixture further comprises at least one low molecular weight hydrophilic polymer.

70. The method of claim 68 wherein said low molecular weight hydrophilic polymer has a number average molecular weight of less than about 40,000 Daltons.

71. The method of claim 69 wherein said low molecular weight hydrophilic polymer has a number average molecular weight of less than about 20,000 Daltons.

72. The method of claim 69 wherein the low molecular weight polymer is selected from the group consisting of water soluble polyamides, lactams and polyethylene glycols, and mixtures thereof.

73. The method of claim 69 wherein the low molecular weight polymer is selected from the group consisting poly-vinylpyrrolidone, polyethylene glycols, poly 2 ethyl-2-oxazoline and mixtures thereof.

74. The method of claim 69 wherein the low molecular weight hydrophilic polymer is present in amounts up to about 20 weight % based upon the reaction mixture.

75. The method of claim 69 wherein the low molecular weight hydrophilic polymer is present in amounts between about 5 and about 20 weight % based upon the reaction mixture.

76. The method of claim 69 wherein said deblocking is conducted using an aqueous solution.

77. The method of claim 69 wherein said aqueous solution further comprises at least one surfactant.

78. The method of claim 77 wherein said surfactant comprises at least one non-ionic surfactant.

79. The method of claim 77 wherein said surfactant comprises polyoxyethylene (20) sorbitan monooleate, or PEG-120 methyl glucose dioleate.

80. The method of claim 77 wherein said surfactant is present in amounts up to about 10,000 ppm.

81. The method of claim 77 wherein said surfactant is present in amounts between about 100 and about 1200 ppm.

82. The method of claim 68 wherein said aqueous solution comprises at least one organic solvent.

83. The method of claim 68 wherein said deblocking is conducted at a temperature between about ambient and about 100°

C.

84. The method of claim 68 wherein said deblocking is conducted at a temperature between about 70°

C. and about 95°

C.

85. The method of claim 68 wherein said deblocking is conducted using agitation.

86. The method of claim 68 wherein said agitation comprises sonication.

87. The method of claim 35 wherein said compatibilizing component is not a hydroxyl functionalized macromer made by group transfer polymerization.