Hydrogel copolymers for biomedical devices

• US 20060142525A1
• Filed: 12/02/2005
• Published: 06/29/2006
• Est. Priority Date: 12/29/2004
• Status: Abandoned Application

• Current Assignee: Bausch & Lomb Incorporated (Bausch Health Cos., Inc.)
• Original Assignee: Bausch & Lomb Incorporated (Bausch Health Cos., Inc.)
• Inventors: Lai, Yu-Chin, Quinn, Edmond T., Lang, Weihong, Ruscio, Dominic V.
• Application Number:
  US11/292,877
• Publication Number:
  US 20060142525A1
• Time in Patent Office: Days
• US Class Current: 528/25
• CPC Class Codes: A61L 27/165 Rubbers
• CPC Class Codes: A61L 27/18 obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
• CPC Class Codes: A61L 27/52 Hydrogels or hydrocolloids
• CPC Class Codes: C08F 290/06 Polymers provided for in subclass C08G
• CPC Class Codes: C08F 290/14 Polymers provided for in subclass C08G
• CPC Class Codes: C08G 18/10 Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
• CPC Class Codes: C08G 18/3206 aliphatic
• CPC Class Codes: C08G 18/61 Polysiloxanes
• CPC Class Codes: C08G 18/672 Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
• CPC Class Codes: C08G 18/8016 Masked aliphatic or cycloaliphatic polyisocyanates
• CPC Class Codes: C08G 2210/00 Compositions for preparing hydrogels
• CPC Class Codes: C08L 2666/02 Organic macromolecular compounds, natural resins, waxes or and bituminous materials
• CPC Class Codes: C08L 33/02 Homopolymers or copolymers of acids; Metal or ammonium salts thereof
• CPC Class Codes: C08L 33/26 Homopolymers or copolymers of acrylamide or methacrylamide
• CPC Class Codes: C08L 39/04 Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
• CPC Class Codes: C08L 39/06 Homopolymers or copolymers of N-vinyl-pyrrolidones
• CPC Class Codes: C08L 51/08 grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
• CPC Class Codes: C08L 51/085 on to polysiloxanes
• CPC Class Codes: C08L 53/00 Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
• CPC Class Codes: C08L 83/04 Polysiloxanes
• CPC Class Codes: G02B 1/043 : Contact lenses

Abstract

Hydrogel copolymers are useful for forming biomedical devices, particularly ophthalmic devices including contact lenses, intraocular lenses and ophthalmic implants. The copolymers have a desirable combination of oxygen permeability, tensile modulus, and water content, especially for soft contact lenses.

Claims

1. A hydrogel copolymer that is the hydrated polymerization product of a monomeric mixture comprising a polysiloxane prepolymer and a hydrophilic comonomer, the hydrogel copolymer having either:

a water content in the range of at least 20 to no greater than 40 weight percent, and an oxygen permeability greater than (320-6x) barrers, where x has a value equal to weight percent water content;

or

a water content in the range of 40 to 50 weight percent, and an oxygen permeability greater than 70 barrers.

2. The hydrogel copolymer of claim 1, having either:

a water content in the range of at least 20 to no greater than 40 weight percent, and an oxygen permeability greater than (350-6x) barrers, where x has a value equal to weight percent water content;

or

a water content in the range of 40 to no greater than 45 weight percent, and an oxygen permeability greater than 80 barrers;

or

a water content in the range of 45 to 50 weight percent, and an oxygen permeability greater than 70 barrers.

3. The hydrogel copolymer of claim 1, having either:

a water content in the range of at least 20 to no greater than 40 weight percent, and an oxygen permeability greater than (330-6x) barrers, where x has a value equal to weight percent water content;

or

a water content in the range of 40 to no greater than 45 weight percent, and an oxygen permeability greater than 80 barrers;

or

a water content in the range of 45 to 50 weight percent, and an oxygen permeability greater than 70 barrers.

4. The hydrogel copolymer of claim 1, having a water content in the range of at least 20 to no greater than 40 weight percent, and an oxygen permeability greater than (380-6x) barrers.

5. The hydrogel copolymer of claim 1, having a water content in the range of at least 20 to no greater than 40 weight percent, and an oxygen permeability greater than (410-6x) barrers.

6. The hydrogel copolymer of claim 1, having a water content in the range of at least 20 to no greater than 40 weight percent, and an oxygen permeability greater than (440-6x) barrers.

7. The hydrogel copolymer of claim 1, having a water content in the range of at least 40 to 50 weight percent, and an oxygen permeability greater than 100 barrers.

8. The hydrogel copolymer of claim 1, having a modulus no greater than 100 g/mm².

9. The hydrogel copolymer of claim 8, having a modulus between about 40 and 80 g/mm².

10. The hydrogel copolymer of claim 1, wherein the silicon atom content of the prepolymer is at least 30 weight % of the prepolymer.

11. The hydrogel copolymer of claim 1, wherein the silicon atom content of the prepolymer is at least 32 weight % of the prepolymer.

12. The hydrogel copolymer of claim 1, wherein the silicon atom content of the prepolymer is at least 33 weight % of the prepolymer.

13. The hydrogel copolymer of claim 1, wherein the prepolymer has a molecular weight (Mn) of at least 10,000.

14. The hydrogel copolymer of claim 1, wherein the prepolymer has a molecular weight (Mn) of at least 15,000.

15. The hydrogel copolymer of claim 1, wherein the prepolymer has a molecular weight (Mn) of at least 20,000.

16. The hydrogel copolymer of claim 1, wherein the monomeric mixture comprises at least one hydrophilic monomer selected form the group consisting of:

unsaturated carboxylic acids;

(meth)acrylic substituted alcohols;

vinyl lactams; and

(meth)acrylamides.

17. The hydrogel copolymer of claim 16, wherein the monomeric mixture comprises at least one hydrophilic monomer selected form the group consisting of:

methacrylic acid;

acrylic acid;

2-hydroxyethylmethacrylate;

N-vinyl pyrrolidone;

methacrylamide; and

N,N-dimethylacrylamide.

18. The hydrogel copolymer of claim 1, wherein the monomeric mixture comprises at least one (meth)acrylic substituted alcohol.

19. The hydrogel copolymer of claim 18, wherein the monomeric mixture includes at least one of 2-hydroxyethylmethacrylate and glyceryl methacrylate.

20. The hydrogel copolymer of claim 19, wherein the monomeric mixture further includes at least one vinyl lactam.

21. The hydrogel copolymer of claim 20, wherein the monomeric mixture comprises 2-hydroxyethylmethacrylate and N-vinyl pyrrolidone.

22. The hydrogel copolymer of claim 1, wherein the monomeric mixture further comprises a monofunctional silicone-containing monomer.

23. The hydrogel copolymer of claim 22, wherein the monomeric mixture further comprises methacryloxypropyl tris(trimethylsiloxy)silane.

24. The hydrogel copolymer of claim 1, wherein the prepolymer is terminated at each end with a polymerizable ethylenic unsaturated radical.

25. The hydrogel copolymer of claim 24, wherein the ethylenic unsaturated radical has the formula:

26. The hydrogel copolymer of claim 1, wherein the prepolymer comprises soft segments that are a diradical residue of the formula (PS′

);

27. The hydrogel copolymer of claim 26, wherein each R is alkylene, and each R′

is independently alkyl or fluoroalkyl optionally including ether linkages.

28. The hydrogel copolymer of claim 26, wherein the prepolymer further comprises at least one member selected from the group consisting of:

strong hard segments represented by *Dii*Diol*Dii*; and

weak hard segments represented by *Dii*;

wherein each Dii is independently a diradical residue of a diisocyanate, each Diol is independently a diradical residue of a diol having 1 to 10 carbon atoms, and each * is independently —

NH—

CO—

NH—

, —

NH—

COO—

or —

OCONH—

.

29. The hydrogel copolymer of claim 28, wherein the prepolymer comprises said soft segments and said strong hard segments, represented by *Dii*Diol*Dii*PS*Dii* wherein PS is the diradical residue of formula (PS′

).

30. The hydrogel copolymer of claim 29, wherein the weight ratio of said soft segments to said strong hard segments is at least 5:

1 and no greater than 13;

1.

31. The hydrogel copolymer of claim 30, wherein the weight ratio of said soft segments to said strong hard segments is at least 7:

1 and no greater than 11;

1.

32. The hydrogel copolymer of claim 1, wherein the prepolymer is selected from one of the following formulae:

M(*Dii*Diol*Dii*PS)_x(*Dii*PS)_y*Dii*M
M(*Dii*Diol*Dii*PS)_x(*Dii*PS)_y*Dii*Diol*Dii*M
M(*Dii*PS*Dii*Diol)_x*Dii*PS*Dii*M
M(*Dii*Diol*Dii*PS)_x*Dii*Diol*Dii*M
M(*Dii*PS)_x*Dii*M

wherein;

each M is independently a polymerizable ethylenically unsaturated radical;

each Dii is independently a diradical residue of a diisocyanate;

each Diol is independently a diradical residue of a diol having 1 to 10 carbon atoms;

each PS is independently a diradical residue of a polysiloxane-diol;

each * is independently —

NH—

CO—

NH—

or —

NH—

COO—

x is at least 2, and

y is at least 1.

33. A contact lens made of the hydrogel copolymer of claim 1.

34. A contact lens made of the hydrogel copolymer of claim 2.

35. A contact lens made of the hydrogel copolymer of claim 3.

36. A contact lens made of the hydrogel copolymer of claim 4.

37. A contact lens made of the hydrogel copolymer of claim 5.

38. A contact lens made of the hydrogel copolymer of claim 6.

39. A contact lens made of the hydrogel copolymer of claim 7.

40. The hydrogel copolymer of claim 1, having either:

a water content in the range of at least 20 to no greater than 30 weight percent, and an oxygen permeability of at least 200 barrers;

or

a water content in the range of at least 30 to no greater than 40 weight percent, and an oxygen permeability greater than 150 barrers;

or

a water content in the range of 40 to 50 weight percent, and an oxygen permeability greater than 100 barrers.

41. A contact lens made of the hydrogel copolymer of claim 39.

42. A hydrogel copolymer that is the hydrated polymerization product of a monomeric mixture comprising a polysiloxane prepolymer and a hydrophilic comonomer, the hydrogel copolymer having a water content of at least 40 weight percent, and an oxygen permeability greater than 70 barrers.

43. A silicone hydrogel copolymer that is the hydrated polymerization product of a monomeric mixture comprising a polysiloxane prepolymer, a vinyl lactam, and a (meth)acrylated alcohol.

44. The silicone hydrogel copolymer of claim 43, wherein the monomeric mixture includes at least one of 2-hydroxyethylmethacrylate and glyceryl methacrylate.

45. The hydrogel copolymer of claim 43, wherein the monomeric mixture comprises 2-hydroxyethylmethacrylate and N-vinyl pyrrolidone.

46. A contact lens made of the hydrogel copolymer of claim 43.

47. A contact lens made of the hydrogel copolymer of claim 45.

48. A silicone hydrogel copolymer that is the hydrated polymerization product of a monomeric mixture comprising a silicone-containing monomer, a vinyl lactam, and a (meth)acrylated alcohol.