Wettable silicone hydrogel compositions and methods for their manufacture

• US 5,352,714 A
• Filed: 07/30/1992
• Issued: 10/04/1994
• Est. Priority Date: 11/05/1991
• Status: Expired due to Term

• Current Assignee: Bausch & Lomb Incorporated (Bausch Health Cos., Inc.)
• Original Assignee: Bausch & Lomb Incorporated (Bausch Health Cos., Inc.)
• Inventors: Friends, Gary D., Lai, Yu-Chin, Valint, Paul L. Jr.
• Primary Examiner(s): Michl, Paul R.
• Assistant Examiner(s): DEWITT, LAVONDA R
• Application Number:
  US07/922,594
• Time in Patent Office: 796 Days
• Field of Search: 523/107, 526/279, 526/260, 524/95-97
• US Class Current: 523/107
• CPC Class Codes: A61L 27/18 obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
• CPC Class Codes: C08F 290/068 Polysiloxanes
• CPC Class Codes: C08L 43/04 Homopolymers or copolymers of monomers containing silicon
• 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

Improved silicone-containing hydrogels are disclosed with enhanced wettability comprising a silicone-containing monomer, hydrophilic monomers, and a relatively non-polar ring-containing monomer able to be converted to a highly polar amino acid upon hydration.

Claims

1. A method for making a silicone-containing hydrogel composition comprising the steps of a) combining a ring-containing oxazolone monomer in the amount of from about 0.5 to about 10 weight percent able to be converted to a highly polar hydrophilic amino acid upon hydration with an α

, ω

-bis(methacryloxyalkyl)polysiloxane monomer and at least one additional hydrophilic monomer into a monomer mix and b) curing the monomer mix resulting from step a) to form a silicone-containing hydrogel composition.

7. The method of claims 1, 2 or 4 wherein said ring-containing oxazolone monomer is selected from the group consisting of 2-vinyl-4,4-dimethyl-2-oxazolin-5-one, 2-isopropenyl-4,4-dimethyl-2-oxazolin-5-one, cyclohexane-spiro-4'"'"'-(2'"'"'-isopropenyl-2'"'"'-oxazol-5'"'"'-one), cyclohexane-spiro-4'"'"'-(2'"'"'-vinyl-2'"'"'-oxazol-5'"'"'-one) and 2-(1-propenyl)-4,4-dimethyl-oxazol-5-one.

8. The method of claim 1, 2 or 4 wherein said ring-containing oxazolone monomer is 2-vinyl-4,4-dimethyl-2-oxazolin-5-one.

9. The method of claims 1, 2, or 4 wherein said additional hydrophilic monomer is selected from the group consisting of N,N-dimethylacrylamide and N-vinyl pyrrolidone.

2. A method for making a silicone-containing hydrogel composition comprising the steps of a) combining a ring-containing oxazolone monomer in the amount of from about 0.5 to about 10 weight percent able to be converted to a highly polar hydrophilic amino acid upon hydration with a bulky polysiloxanylalkyl (meth)acrylic monomer having the following formula:

##STR7## wherein;

X is O or NR;

each R is independently hydrogen or methyl; and

each R₁ is independently a lower alkyl or phenyl group; and

f is 1 or 3 to 10;

and at least one additional hydrophilic monomer into a monomer mix and b) curing the monomer mix resulting from step a) to form a silicone-containing hydrogel composition.

3. The method of claim 2 wherein said bulky polysiloxanylalkyl (meth)acrylic monomer is selected from the group consisting of methacryloxypropyl tris(trimethylsiloxy)silane, pentamethyldisiloxanylmethylmethacrylate, tris(trimethylsiloxy)methacryloxy propylsilane, phenyltetramethyldisiloxanylethyl acetate, and methyldi(trimethylsiloxy)methacryloxymethyl silane.

4. A method for making a silicone-containing hydrogel composition comprising the steps of a) combining a ring-containing oxazolone monomer in the amount of from about 0.5 to about 10 weight percent able to be converted to a highly polar hydrophilic amino acid upon hydration with a urethane-containing prepolymer and at least one additional hydrophilic monomer into a monomer mix and b) curing the monomer mix resulting from step a) to form a silicone-containing hydrogel composition.

5. The method of claim 4 wherein said silicone-containing prepolymer is a urethane-containing prepolymer having the following schematic representations:

space="preserve" listing-type="equation">E(*D*A'"'"'*D*G).sub.a *D*A"*D*E'"'"';

or

space="preserve" listing-type="equation">E(*D*G*D*A").sub.a *D*G*D*E'"'"';

where

D denotes an alkyl diradical, an alkyl cycloalkyl diradical, a cycloalkyl diradical, an aryl diradical or an alkylaryl diradical having 6 to 30 carbon atoms;

G denotes an alkyl diradical, a cycloalkyl diradical, an alkyl cycloalkyl diradical, an aryl diradical or an alkylaryl diradical having 1 to 40 carbon atoms and which may contain ether, thio or amine linkages in the main chain;

*denotes a urethane or ureido linkage;

a is at least 1;

A" denotes a divalent polymeric radical of formula;

##STR8## wherein;

R^s and R^s'"'"' independently denote an alkyl or fluoro-substituted alkyl group having 1 to 10 carbon atoms which may contain ether linkages between carbon atoms;

m is at least 1; and

p provides a moiety weight of 400 to 10,000;

E and E'"'"' independently denote a polymerizable unsaturated organic radical represented by the formula;

##STR9## wherein;

R¹⁴ denotes a divalent alkylene radical having 1 to 10 carbon atoms;

R¹² denotes H or CH₃ ;

R¹³ denotes H, a (C₁ -C₆) alkyl radical or a --CO--Y--R¹⁵ group wherein Y is --O--, --S-- or --NH-- and R¹⁵ is a alkyl radical having 1 to 12 carbon atoms;

X is --CO-- or --OCO--;

Z is --O-- or --NH--;

Ar denotes an aromatic radical having 6 to 30 carbon atoms;

w is 0 to 6;

x is 0 or 1;

y is 0 or 1; and

z is 0 or 1.

6. The method of claim 5 wherein said urethane-containing prepolymer is represented by the formula:

##STR10## wherein;

R¹⁶ is a diradical of a diisocyanate after removal of the isocyanate group, and is most preferably the diradical of isophorone diisocyanate, and m, p and a are the same as previously defined.

10. A silicone-containing hydrogel composition prepared by polymerizing a monomer mix comprising 0.5 to 10 weight percent of a ring-containing oxazolone monomer able to be converted to a highly polar hydrophilic amino acid upon hydration, with an α

, ω

-bis(methacryloxyalkyl)polysiloxane monomer, and at least one additional hydrophilic monomer.

16. The composition of claims 10, 11 or 13 wherein said ring-containing oxazolone monomer is selected from the group consisting of 2-vinyl-4,4-dimethyl-2-oxazolin-5-one, 2-isopropenyl-4,4-dimethyl-2-oxazolin-5-one, cyclohexane-spiro-4'"'"'-(2'"'"'-isopropenyl-2'"'"'-oxazol-5'"'"'-one), cyclohexane-spiro-4'"'"'-(2'"'"'-vinyl-2'"'"'-oxazol-5'"'"'-one) and 2-(1-propenyl)-4,4-dimethyl-oxazol-5-one.

17. The composition of claims 10, 11 or 13 wherein said ring-containing oxazolone monomer is 2-vinyl-4,4-dimethyl-2-oxazolin-5-one.

18. The composition of claims 10, 11 or 13 wherein said additional hydrophilic monomer is selected from the group consisting of N,N-dimethylacrylamide and N-vinyl pyrrolidone.

23. A contact lens made from the composition of claims 10, 11 or 13.

11. A silicone-containing hydrogel composition prepared by polymerizing a monomer mix comprising from about 0.5 to about 10 weight percent of a ring-containing oxazolone monomer able to be converted to a highly polar hydrophilic amino acid upon hydration with a bulky polysiloxanylalkyl (meth)acrylic monomer having the following formula:

##STR11## wherein;

X is O or NR;

each R is independently hydrogen or methyl; and

each R₁ is independently a lower alkyl or phenyl group; and

f is 1 or 3 to 10; and

at least one additional hydrophilic monomer into a monomer mix and b) curing the monomer mix resulting from step a) to form a silicone-containing hydrogel composition.

12. The composition of claim 11 wherein said bulky polysiloxanylalkyl (meth)acrylic monomer is selected from the group consisting of methacryloxypropyl tris(trimethylsiloxy)silane, pentamethyldisiloxanylmethylmethacrylate, tris(trimethylsiloxy)methacryloxy propylsilane, phenyltetramethyldisiloxanylethyl acetate, and methyldi(trimethylsiloxy)methacryloxymethyl silane.

13. A silicone-containing hydrogel composition prepared by polymerizing a monomer mix comprising from about 0.5 to about 10 weight percent of a ring-containing oxazolone monomer able to be converted to a highly polar hydrophilic amino acid upon hydration with a urethane-containing prepolymer and at least one additional hydrophilic monomer into a monomer mix and b) curing the monomer mix resulting from step a) to form a silicone-containing hydrogel composition.

14. The composition of claim 13 wherein said silicone-containing prepolymer is urethane-containing prepolymer having the following schematic representations:

space="preserve" listing-type="equation">E(*D*A"*D*G).sub.a *D*A"*D*E'"'"';

or

space="preserve" listing-type="equation">E (*D*G*D*A").sub.a *D*G*D*E'"'"';

where

D denotes an alkyl diradical, an alkyl cycloalkyl diradical, a cycloalkyl diradical, an aryl diradical or an alkylaryl diradical having 6 to 30 carbon atoms;

G denotes an alkyl diradical, a cycloalkyl diradical, an alkyl cycloalkyl diradical, an aryl diradical or an alkylaryl diradical having 1 to 40 carbon atoms and which may contain ether, thio or amine linkages in the main chain;

*denotes a urethane or ureido linkage;

a is at least 1;

A" denotes a divalent polymeric radical of formula;

##STR12## wherein;

R^s and R^s'"'"' independently denote an alkyl or fluoro-substituted alkyl group having 1 to 10 carbon atoms which may contain ether linkages between carbon atoms;

m is at least 1; and

p provides a moiety weight of 400 to 10,000;

E and E'"'"' independently denote a polymerizable unsaturated organic radical represented by the formula;

##STR13## wherein R¹⁴ denotes a divalent alkylene radical having 1 to 10 carbon atoms;

R¹² denotes H or CH₃ ;

R¹³ denotes H, a (C₁ -C₆) alkyl radical or a --CO--Y--R¹⁵ group wherein Y is --O--, --S-- or --NH-- and R¹⁵ is a alkyl radical having 1 to 12 carbon atoms;

X is --CO-- or --OCO--;

Z is --O-- or --NH--;

Ar denotes an aromatic radical having 6 to 30 carbon atoms;

w is 0 to 6;

x is 0 or 1;

y is 0 or 1; and

z is 0 or 1.

15. The composition of claim 14 wherein said urethane-containing prepolymer is represented by the formula:

##STR14## wherein;

R¹⁶ is a diradical of a diisocyanate after removal of the isocyanate group, and is most preferably the diradical of isophorone diisocyanate, and m, p and a are the same as previously defined.

19. A method for making a silicone-containing hydrogel composition comprising the steps of a) combining at least one hydrophilic (meth)acrylamido alkanoic acid monomer in the amount of from about 0.5 to about 10 weight percent with silicone-containing monomer and at least one hydrophilic monomer in addition to and different from said hydrophilic (meth)acrylamido alkanoic acid monomer into a monomer mix and b) curing the monomer mix resulting from step a) to form a silicone-containing hydrogel composition.

20. A silicone-containing hydrogel composition prepared by polymerizing a monomer mix comprising a hydrophilic (meth)acrylamido alkanoic acid, at least one silicone-containing monomer, and at least one hydrophilic monomer in addition to and different from said hydrophilic monomer.

22. A contact lens made from the composition of claim 20.

21. An improved silicone-containing hydrogel formulation prepared by polymerizing a monomer mix comprising a silicone-containing monomer, and at least one hydrophilic monomer the improvement of which comprises the addition to said monomer mix of a hydrophilic ring-containing monomer able to be converted to a highly polar amino acid upon hydration in the amount of from about 0.5 to about 10 weight percent.