Ionic silicone hydrogels

• US 10,259,900 B2
• Filed: 10/26/2016
• Issued: 04/16/2019
• 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., Vanderlaan, Douglas G., Joslin, Scott L.
• Primary Examiner(s): Pepitone, Michael F
• Application Number:
  US15/334,717
• Publication Number:
  US 20170044293A1
• Time in Patent Office: 902 Days
• CPC Class Codes: C08F 220/26 Esters containing oxygen in addition to the carboxy oxygen
• CPC Class Codes: C08F 222/10 Esters
• 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: C08L 101/14 the macromolecular compounds being water soluble or water swellable, e.g. aqueous gels
• CPC Class Codes: C08L 2201/54 Aqueous solutions or dispersions
• CPC Class Codes: C08L 2203/02 for biomedical use
• CPC Class Codes: C08L 33/14 of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
• CPC Class Codes: C08L 33/24 Homopolymers or copolymers of amides or imides
• CPC Class Codes: C08L 39/06 Homopolymers or copolymers of N-vinyl-pyrrolidones
• CPC Class Codes: C08L 51/085 on to polysiloxanes
• CPC Class Codes: C08L 83/04 Polysiloxanes
• 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 formed from a reaction mixture comprising about 37 to about 75 wt % of a mixture of slow-reacting hydrophilic monomers, each having a slow-reacting hydrophilic monomer kinetic half life;

said mixture of slow reacting hydrophilic monomers comprising at least one slow-reacting ionic monomer;

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; and

at least one hydroxyalkyl (meth)acrylate monomer,

wherein the ratio of each of said slow-reacting hydrophilic component half lives to said silicone-containing component half life is at least 2.

2. The silicone hydrogel of claim 1 wherein said slow-reacting ionic component is selected from the group consisting of anionic components, cationic components, zwitterionic components and mixtures thereof.

3. The silicone hydrogel of claim 1 wherein said slow-reacting ionic component comprise at least one anionic component selected from the group consisting of carboxylic acids, sulfonic acids, boronic acids, phosphonic acids and their salts and mixtures thereof.

4. The silicone hydrogel of claim 1 wherein said slow-reacting ionic component comprises reactive functionality selected from the group consisting of ionic vinyl ethers, ionic vinyl amines and ionic vinyl enamines.

5. The silicone hydrogel of claim 1 wherein said slow-reacting ionic component is selected from the group consisting of 4-acrylamidobutanoic acid (ACAII), (3-acrylamidophenyl)boronic acid (APBA), 3-acrylamidopropionic acid, 5-acrylamidopentanoic acid, 3-acrylamido-3-methylbutanoic acid (AMBA), N-vinyloxycarbonyl-α

-alanine, N-vinyloxycarbonyl-β

-alanine (VINAL), 2-vinyl-4,4-dimethyl-2-oxazolin-5-one (VDMO), vinyl sulphonate salt, 3-((3-acrylamidopropyl)dimethylammonio)propane-1-sulfonate (AMPDAPS), 3-((3-methacrylamidopropyl)dimethylammonio)propane-1-sulfonate (MAMPDAPS);

acetic acid, 2 carboxymethoxy-1-ethenylesters of Formula Q

6. The silicone hydrogel of claim 5 wherein said slow-reacting ionic component is selected from the group consisting of N-vinyloxycarbonyl-α

-alanine;

N-vinyloxycarbonyl-β

-alanine (VINAL);

2-vinyl-4,4-dimethyl-2-oxazolin-5-one (VDMO);

vinyl sulphonate sodium salt;

acetic acid, -2-carboxymethoxy-1-ethenylesters of Formula Q, and mixtures thereof.

7. The silicone hydrogel of claim 1 wherein said slow-reacting ionic component is present in the reactive mixture in an amount below about 20 mole %.

8. The silicone hydrogel of claim 1 wherein all of said slow-reacting components have the same reactive functionality.

9. The silicone hydrogel of claim 1 wherein all of said slow-reacting components have vinyl functionality.

10. 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.

11. The silicone hydrogel of claim 10 wherein said slow reacting crosslinkers have only vinyl reactive functionality and said fast reacting crosslinkers have (meth)acrylate reactive functionality only.

12. The silicone hydrogel of claim 10 wherein said slow reacting crosslinker comprises TAC and said fast reacting crosslinker is selected from the group consisting of EDGMA, TEGDMA and mixtures thereof.

13. The silicone hydrogel of claim 10 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 0.4 to about 2.0 mmoles per 100 g of reactive components.

14. The silicone hydrogel of claim 10 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 0.3 to about 2.0 mmol/100 g of polymerizable components.

15. The silicone hydrogel of claim 1 wherein said reactive mixture further comprises at least one reactive cationic component.

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

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

18. The silicone hydrogel of claim 1 wherein said reaction mixture is substantially free of diluent.

19. The silicone hydrogel of claim 1 wherein said reaction mixture is substantially free of TRIS.

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

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

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

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

24. 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.

25. 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.

26. 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.

27. 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:

28. The silicone hydrogel of claim 27 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.

29. The silicone hydrogel of claim 27 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.

30. The silicone hydrogel 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-ß

-alanine N-vinyl ester;

N-carboxyvinyl-β

-alanine (VINAL), N-carboxyvinyl-α

-alanine and mixtures thereof.

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

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

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

34. The silicone hydrogel of claim 1 wherein said hydroxyalkyl (meth)acrylate monomer is a monomer of Formula VII

35. The silicone hydrogel of claim 1 wherein said hydroxyalkyl (meth)acrylate 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, polyethyleneglycol monomethacrylate, and mixtures thereof.

36. The silicone hydrogel of claim 1 wherein said hydroxyalkyl (meth)acrylate 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.

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

38. The silicone hydrogel 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.

39. The silicone hydrogel 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:

40. The silicone hydrogel of claim 39 wherein each R₁₄ is independently selected from ethyl and methyl groups.

41. The silicone hydrogel of claim 39 wherein all R₁₄ are methyl.

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

43. The silicone hydrogel of claim 39 wherein at least one R₁₄ is 3,3,3-trifluoropropyl.

44. The silicone hydrogel of claim 39 wherein R₁₃ is selected from C1-C6 alkylene groups which may be substituted with ether, hydroxyl and combinations thereof.

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

46. The silicone hydrogel of claim 39 wherein a is 5 to 15.

47. The silicone hydrogel of claim 39 wherein R₁₆ is H or methyl.

48. The silicone hydrogel of claim 39 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)-ω

-butyl-octamethylpentasiloxane, and mixtures thereof.

49. The silicone hydrogel of claim 39 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.

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

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

52. The silicone hydrogel 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.

53. 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.

54. The silicone hydrogel of claim 1 further comprising at least one silicone-containing component substituted with at least one hydroxyl containing group.