Biomedical devices containing amphiphilic block copolymers

• US 7,247,692 B2
• Filed: 09/30/2004
• Issued: 07/24/2007
• Est. Priority Date: 09/30/2004
• Status: Active Grant

• Current Assignee: Johnson & Johnson Vision Care Incorporated (Johnson & Johnson)
• Original Assignee: Johnson & Johnson Vision Care Incorporated (Johnson & Johnson)
• Inventors: Laredo, Walter R.
• Primary Examiner(s): Moore; Margaret G.
• Application Number:
  US10/954,560
• Publication Number:
  US 20060074208A1
• Time in Patent Office: 1,027 Days
• Field of Search: 526/279, 524/714, 524/731, 524/865, 523/107, 351/160.R, 351/160.H
• US Class Current: 526/279
• CPC Class Codes: A61L 2430/16 for reconstruction of eye parts, e.g. intraocular lens, cornea
• CPC Class Codes: A61L 27/18 obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
• CPC Class Codes: C08L 83/04 Polysiloxanes
• CPC Class Codes: C08L 83/10 Block- or graft-copolymers containing polysiloxane sequences obtained by polymerising a compound having a carbon-to-carbon double bond on to a polysiloxane C08L51/08, C08L53/00
• CPC Class Codes: G02B 1/043 Contact lenses

Abstract

This invention relates to wettable biomedical devices comprising amphiphilic block copolymers. The amphiphilic block copolymers are useful as internal wetting agents for biomedical applications, such as implantable devices, ophthalmic devices and in one embodiment, contact lenses.

Claims

1. A silicone hydrogel comprising the reaction product of a reaction mixture comprising at least one silicone containing component;

at least one substantially non-polymerizable amphiphilic block copolymer; and

at least one hydrophilic component.

2. The hydrogel of claim 1 comprising about 1 percent to about 15 percent amphiphilic block copolymer.

3. The hydrogel of claim 1 comprising about 3 percent to about 15 percent amphiphilic block copolymer.

4. The hydrogel of claim 1 comprising about 5 percent to about 12 percent amphiphilic block copolymer.

5. The hydrogel of claim 1 wherein said amphiphilic block copolymer has weight average molecular weight of at least about 100,000.

6. The hydrogel of claim 1 wherein said amphiphilic block copolymer has weight average molecular weight of between about 100,000 and about 2,000,000.

7. The hydrogel of claim 1 wherein said amphiphilic block copolymer has weight average molecular weight of between about 140,000 and about 1,000,000.

8. The hydrogel of claim 1 wherein said amphiphilic copolymer comprises about 1 to about 20 weight % hydrophobic segments and about 80 to about 99 weight % hydrophilic segments.

9. The hydrogel of claim 1 wherein said amphiphilic copolymer comprises about 2 to about 15 weight % hydrophobic segments and about 85 to about 98 weight % hydrophilic segments.

10. The hydrogel of claim 8 wherein said hydrophilic segments are derived from hydrophilic polymers selected from the group consisting of polyamides, polylactones, polyimides, polylactams and functionalized polyamides, polylactones, polyimides, polylactams, ionic polymers, hydrophilic polyacrylates, hydrophilic polymethacrylates and combinations and copolymers thereof.

11. The hydrogel of claim 8 wherein said hydrophilic segments are derived from hydrophilic polymers selected from the group consisting of poly-N-vinyl-2-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, poly-N-vinly-N-methylacetamide, polyvinyl alcohol, polyacrylic acid, polymethacrylic acid, poly(hydroxyethyl methacrylate), mixtures and copolymers thereof.

12. The hydrogel of claim 8 wherein said hydrophilic segments are derived from hydrophilic polymers selected from the group consisting of poly-N-vinylpyrrolidone, poly-N,N-methacrylamide, poly-N-vinyl-N-methylacetamide and combinations and copolymers thereof.

13. The hydrogel of claim 8 wherein said hydrophobic segments are derived from hydrophobic polymers selected from the group consisting of linear polydimethylsiloxanes with terminal reactive groups.

14. The hydrogel of claim 8 wherein said hydrophobic segments are derived from hydrophobic polymers formed from monomers selected from the group consisting of octamethylcyclotetrasiloxane;

1,3-bis-aminopropyltetramethyldisiloxane;

1,3-bis-hydroxypropyltetramethyldisiloxane;

dichlorodimethylsilane, 1,1,3,3-tetramethyldisiloxane;

4,4′

-azobis(4-cyanovaleric acid);

toluenediisocyanate, isophoronediisocyanate;

1,3-bis-vinyltetramethyldisiloxane;

3-methacryloxypropyltris(trimethylsiloxy)silane;

pentamethyldisiloxanyl methylmethacrylate; and

methyldi(trimethylsiloxy)methacryloxymethyl silane;

monomethacryloxypropyl terminated mono-n-butyl terminated polydimethylsiloxane;

3-[tris(trimethylsiloxy)silyl] propyl allyl carbamate;

3-[tris(trimethylsiloxy)wily1] propyl vinyl carbamate;

trimethylsilylethyl vinyl carbonate;

trimethylsilylmethyl vinyl carbonate; and

2-propenoic acid, 2-methyl-2-hydroxy-3-[3-[1,3,3,3-tetramethyl-1-[trimethylsilyl)oxy]disiloxanyl]propoxy] propyl ester and combinations thereof.

15. The hydrogel of claim 1, wherein the amphiphilic block copolymer is derived from poly-N-vinylpyrrolidone and poly(dimethylsiloxane) segments.

16. The hydrogel of claim 1 wherein said silicone containing component is present in an amount between about 5 percent to about 75 percent, based upon all reactive components.

17. The hydrogel of claim 1 wherein the silicone containing component is present in an amount between about 10 percent to about 50 percent, based upon all reactive components.

18. The hydrogel of claim 1 wherein said at least one silicone containing component is selected from the group consisting of silicone containing monomers, silicone containing macromers and mixtures thereof.

19. The hydrogel of claim 1 wherein said at least one silicone containing component is selected from the group consisting of polysiloxyalkyl(meth)acrylic monomers, poly(organosiloxane)prepolymers, silicone containing vinyl carbonate monomers, silicone containing vinyl carbamate monomers, and mixtures thereof.

20. The hydrogel of claim 1 wherein said at least one silicone containing component is selected from the group consisting of α

,ω

-bismethacryloxypropyl poly-dimethylsiloxane, monomethacryloxypropyl terminated mono-n-butyl terminated polydimethylsiloxane, methacryloxypropyl tris(trimethylsiloxy)silane and combinations thereof.

21. The hydrogel of claim 1 wherein said hydrophilic component is selected from the group consisting of acrylic containing monomers, hydrophilic vinyl-containing monomers, hydrophilic vinyl carbonate or vinyl carbamate monomers, polyoxyethylene polyols and combinations thereof.

22. The hydrogel of claim 1 wherein said hydrophilic component is selected from the group consisting of N,N-dimethylacrylamide (DMA), 2-hydroxyethyl acrylate, 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, N-2-hydroxyethyl vinyl carbamate, N-carboxy-β

-alanine N-vinyl ester, reactive polyethylene polyols, ydrophilic vinyl carbonates, vinyl carbamate monomers, hydrophilic oxazolone monomers, hydrophilic oxazoline monomers and combinations thereof.

23. The hydrogel of claim 1 wherein said hydrophilic component is selected from the group consisting of N,N-dimethyl acrylamide, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, glycerol methacrylate, 2-hydroxyethyl methacrylamide, N-vinylpyrrolidone, polyethyleneglycol monomethacrylate and combinations thereof.

24. The hydrogel of claim 1 wherein said hydrophilic component is selected from the group consisting of N,N-dimethylacrylamide, N-vinylpyrrolidone and mixtures thereof.

25. The hydrogel of claim 1 wherein said at least one hydrophilic component is present in amounts of about 0 to about 70 weight percent.

26. The hydrogel of claim 1 wherein said at least one hydrophilic component is present in amounts of about 5 to about 60 weight percent.

27. The hydrogel of claim 1 wherein said at least one hydrophilic component is present in amounts of about 10 to 50 weight percent.

28. The hydrogel of claim 1 wherein said reaction mixture optionally further comprises at least one compatibilizing component in an amount between about 0 and about 90 weight percent.

29. The hydrogel of claim 28 wherein said compatibilizing component comprises at least one hydroxyl containing monomer or macromer.

30. The hydrogel of claim 28 wherein said compatibilizing component comprises at least one hydroxyl containing monomer selected from the group consisting of 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylamide, 2-hydroxyethyl acrylamide, N-2-hydroxyethyl vinyl carbamate, 2-hydroxyethyl vinyl carbonate, 2-hydroxypropyl methacrylate, hydroxyhexyl methacrylate, hydroxyoctyl methacrylate, hydroxyl functional monomers including silicone or siloxane functionalities, and combinations thereof.

31. The hydrogel of claim 28 wherein said compatibilizing component comprises at least one hydroxyl containing monomer selected from the group consisting of 2-hydroxyethyl methacrylate, 2-propenoic acid, 2-methyl-2-hydroxy-3-[3-[1,3,3,3-tetramethyl-1-[trimethylsilyl)oxy]disiloxanyl]propoxy]propyl ester (which can also be named (3-methacryloxy-2-hydroxypropyloxy)propylbis(trimethylsiloxy)methylsilane), 3-methacryloxy-2-hydroxypropyloxy)propyltris(trimethylsiloxy)silane, bis-3-methacryloxy-2-hydroxypropyloxypropyl polydimethylsiloxane, 3-methacryloxy-2-(2-hydroxyethoxy)propyloxy) propylbis(trimethylsiloxy)methylsilane, N-2-methacryloxyethyl-O-(methyl-bis-trimethylsiloxy-3-propyl)silyl carbamate and N,N,N′

,N′

-tetrakis(3-methacryloxy-2-hydroxypropyl)-α

,ω

-bis-3-aminopropyl-polydimethylsiloxane and mixtures thereof.

32. The hydrogel of claim 28 wherein said compatibilizing component comprises at least one hydroxyl containing monomer selected from the group consisting of 2-hydroxyethyl methacrylate, 3-methacryloxy-2-hydroxypropyloxy)propylbis(trimethylsiloxy)methylsilane), 3-methacryloxy-2-hydroxypropyloxy)propyltris(trimethylsiloxy)silane and mixtures thereof.

33. A biomedical device comprising the hydrogel of claim 1.

34. An ophthalmic device comprising the hydrogel of claim 1.

35. A contact lens comprising the hydrogel of claim 1.

36. A method comprising the steps of (a) mixing a low molecular weight, substantially non-polymerizable amphiphilic polymer and reactive components comprising at least one silicone containing component and at least one hydrophilic component, (b) curing the product of step (a) in a mold to form a biomedical device and (c) deblocking said ophthalmic device from said mold.

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

38. The method of claim 36 wherein said ophthalmic device is a silicone hydrogel contact lens.

39. The method of claim 36 wherein said low molecular weight amphiphilic polymer has a number average molecular weight of less than about 40,000 Daltons.

40. The method of claim 36 wherein said low molecular weight amphiphilic polymer is present in amounts up to about 20 wt %, based upon total weight of the reactive components.