Silicone hydrogels having a structure formed via controlled reaction kinetics

• US 9,994,665 B2
• Filed: 01/05/2017
• Issued: 06/12/2018
• 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.
• Primary Examiner(s): Whiteley, Jessica
• Application Number:
  US15/398,830
• Publication Number:
  US 20170114174A1
• Time in Patent Office: 523 Days
• Field of Search: 522167, 522 1, 520 1
• CPC Class Codes: A61F 2/142 Cornea, e.g. artificial corneae, keratoprostheses or corneal implants for repair of defective corneal tissue
• CPC Class Codes: A61F 2/16 Intraocular lenses
• CPC Class Codes: A61F 2002/16965 Lens includes ultraviolet absorber
• CPC Class Codes: B29C 59/16 by wave energy or particle radiation , e.g. infrared heating B29C59/007 takes precedence
• CPC Class Codes: C08F 2/46 Polymerisation initiated by wave energy or particle radiation
• CPC Class Codes: C08F 2/50 with sensitising agents
• CPC Class Codes: C08F 20/36 containing oxygen in addition to the carboxy oxygen , e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate
• CPC Class Codes: C08F 220/20 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 283/124 on to polysiloxanes having carbon-to-carbon double bonds
• CPC Class Codes: C08F 290/068 Polysiloxanes
• CPC Class Codes: C08G 2210/00 Compositions for preparing hydrogels
• CPC Class Codes: C08G 77/26 nitrogen-containing groups
• CPC Class Codes: C08G 77/442 containing vinyl polymer sequences
• CPC Class Codes: C08K 3/20 Oxides; Hydroxides graphene oxides C08K3/042
• CPC Class Codes: C08K 5/3475 condensed with carbocyclic rings
• CPC Class Codes: C08L 2201/54 Aqueous solutions or dispersions
• CPC Class Codes: C08L 2203/02 for biomedical use
• CPC Class Codes: C08L 51/085 : on to polysiloxanes
• CPC Class Codes: C08L 77/02 : Polyamides derived from omega-amino carboxylic acids or from lactams thereof C08L77/10 takes precedence
• CPC Class Codes: C08L 83/04 : Polysiloxanes
• CPC Class Codes: C08L 83/08 : containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
• CPC Class Codes: C09D 4/00 : Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
• CPC Class Codes: G02B 1/043 : Contact lenses
• CPC Class Codes: G02B 2207/109 : Sols, gels, sol-gel materials
• CPC Class Codes: G02C 7/02 : Lenses; Lens systems ; Methods of designing lenses
• CPC Class Codes: G02C 7/04 : Contact lenses for the eyes disinfection or sterilisation of contact lenses A61L12/00
• CPC Class Codes: G02C 7/049 : Contact lenses having special fitting or structural features achieved by special materials or material structures

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 process for forming a silicone hydrogel comprising photocuring a reaction mixture comprising about 39 to about 75 wt % of at least one slow-reacting hydrophilic monomer;

at least one silicone-containing component;

at least one photoinitiator; and

optional additional hydrophilic components;

wherein said photocuring is completed in about 30 minutes or less and at least one of said silicone-containing component, optional additional hydrophilic components or both comprises at least one hydroxyl group.

2. The process of claim 1 wherein said reaction mixture further comprises at least one UV absorbing compound.

3. The process of claim 2 wherein said at least one UV absorbing compound is selected from benzotriazoles.

4. The process of claim 2 wherein said at least one UV absorbing compound is selected from the group consisting of reactive 2-(2′

-hydroxyphenyl)benzotriazoles, 2-hydroxybenzophenones, 2-hydroxyphenyltriazines, oxanilides, cyanoacrylates, salicylates and 4-hydroxybenzoates.

5. The process of claim 2 wherein said at least one UV absorbing compound is selected from the group consisting of 2-(2′

-hydroxy-5-methacrylyloxyethylphenyl)-2H-benzotriazole, 5-vinyl and 5-isopropenyl derivatives of 2-(2,4-dihydroxyphenyl)-2H-benzotriazole and 4-acrylates or 4-methacrylates of 2-(2,4-dihydroxyphenyl)-2H-benzotriazole or 2-(2,4-dihydroxyphenyl)-1,3-2H-dibenzotriazole, and mixtures thereof.

6. The process of claim 2 comprising between about 0.5 and about 4 wt. %, of at least one UV absorber.

7. The process of claim 2 comprising between about 1 wt % and about 2 wt % UV absorber.

8. The process of claim 1 wherein said reaction mixture is free of diluent.

9. The process of claim 1 wherein said reaction mixture is free of TRIS.

10. The process of claim 1 wherein said reaction mixture is substantially free of silicone containing macromers or prepolymers.

11. The process 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 and said silicone-containing component comprises a reactive group selected from the group consisting of (meth)acrylates, styryls, amides and mixtures thereof.

12. The process 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 silicone-containing component comprises a reactive group selected from the group consisting of (meth)acrylates, styryls, amides and mixtures thereof.

13. The process of claim 1 wherein said slow-reacting hydrophilic monomer is present in an amount between about 39 and about 70 wt %.

14. The process of claim 1 wherein said slow-reacting hydrophilic monomer is present in an amount between about 39 and about 60 wt %.

15. The process 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.

16. The process 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.

17. The process 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.

18. The process 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:

19. The process of claim 18 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.

20. The process of claim 18 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.

21. The process of claim 1 wherein the slow-reacting hydrophilic monomer is selected from 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.

22. The process of claim 1 wherein the slow-reacting hydrophilic monomer is selected from NVP, VMA and 1-methyl-5-methylene-2-pyrrolidone.

23. The process of claim 1 wherein the slow-reacting hydrophilic monomer comprises NVP.

24. The process of claim 1 wherein said silicone-containing component comprises at least one hydroxyl group.

25. The process of claim 1 further comprising at least one hydroxyalkyl monomer.

26. The process of claim 25 wherein said hydroxyalkyl monomer is selected from hydroxyalkyl (meth)acrylate or (meth)acrylamide monomer of Formula VII or a styryl compound of Formula VIII

27. The process of claim 26 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.

28. The process of claim 26 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.

29. The process of claim 26 wherein said hydroxyalkyl monomer is selected from 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.

30. The process of claim 26 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.

31. The process of claim 26 wherein said hydroxyalkyl monomer comprises 2-hydroxyethyl methacrylate, 3-hydroxy-2,2-dimethyl-propyl methacrylate, glycerol methacrylate and mixtures comprising them.

32. The process of claim 1 wherein the at least one silicone-containing monomer is monofunctional and comprises (a) a reactive group selected from (meth)acrylates, styryls, amides and mixtures thereof and (b) a polydialkyl siloxane chain and may optionally contain fluorine.

33. The process of claim 1 wherein said silicone-containing component is selected from mono (meth)acryloxyalkyl polydialkylsiloxane monomer of Formula IX or the styryl polydialkylsiloxane monomer of Formula X:

34. The process of claim 33 wherein each R₁₄ is independently selected from ethyl and methyl groups.

35. The process of claim 33 wherein all R₁₄ are methyl.

36. The process of claim 33 wherein R₁₂ and each R₁₄ are methyl.

37. The process of claim 33 wherein at least one R₁₄ is 3,3,3-trifluoropropyl.

38. The process of claim 33 wherein R₁₃ is selected from C1-C6 alkylene groups which may be substituted with ether, hydroxyl and combinations thereof.

39. The process of claim 33 wherein R₁₃ is selected from C1 or C3-C6 alkylene groups which may be substituted with ether, hydroxyl and combinations thereof.

40. The process of claim 33 wherein a is 5 to 15.

41. The process of claim 33 wherein R₁₆ is H or methyl.

42. The process of claim 33 wherein said 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)-w-butyl-octamethylpentasiloxane, and mixtures thereof.

43. The process of claim 33 wherein said 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, and mixtures thereof.

44. The process of claim 25 wherein said slow reacting hydrophilic monomer and said hydroxyl monomer form a molar ratio of hydroxyl groups to the slow-reacting hydrophilic monomer of between about 0.15 and about 0.4.

45. The process of claim 1 further comprising at least one crosslinking monomer.

46. The process of claim 1 wherein said slow-reacting hydrophilic monomer is selected from 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.

47. The process of claim 1 wherein said photoinitiator is a visible light initiator.

49. The process of claim 1 further comprising from about 5 to about 20 wt % of at least one polar diluent, based upon all components in the reaction mixture.

50. The process of claim 49 wherein said diluent further comprises at least polyhydric codiluent.

51. The process of claim 50 wherein said polyhydric codiluent is present in an amount between about 0.5 and 5 wt %, based upon all components in the reaction mixture.

52. The process of claim 49 wherein said polar diluent is selected from the group consisting of carboxylic acids, secondary and tertiary alcohols.

53. The process of claim 50 wherein said polyhydric codiluent is selected from the group consisting of glycerin, boric acid, boric acid glycerol esters, polyalkylene glycols and mixtures thereof.

54. The process of claim 49 wherein said polar diluent further comprises up to about 3 wt % of at least one lactam polymer or copolymer.

55. The process of claim 1 wherein said reaction mixture further comprises at least one slow reacting crosslinker and at least one fast reacting crosslinker.

56. The process of claim 55 wherein said slow reacting crosslinkers have only vinyl reactive functionality and said fast reacting crosslinkers have (meth)acrylate reactive functionality only.

57. The process of claim 55 wherein said slow reacting crosslinker comprises TAC and said fast reacting crosslinker is selected from the group consisting of EGDMA, TEGDMA and mixtures thereof.

58. The process of claim 1 wherein said reaction mixture is free from additional hydrophilic components.

59. The process of claim 49 wherein said reaction mixture comprises less than about 5% of intermediate reacting hydrophilic components.

60. The process of claim 56 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 %.

61. The process of claim 56 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 %.

62. The process of claim 56 wherein all crosslinkers are present in an amount less than about 0.5 wt %.

63. The process of claim 2 wherein said at least one UV absorbing compound is reactive.

48. A process for forming a silicone hydrogel comprising photocuring via ebeam irradiation, a reaction mixture comprising about 39 to about 75 wt % of at least one slow-reacting hydrophilic monomer;

at least one silicone-containing component; and

at least one photoinitiator;

wherein at least one of said silicone-containing component, optional additional hydrophilic components or both comprises at least one hydroxyl group.