Wettable silicone hydrogel compositions and methods for their manufacture

• US 5,451,617 A
• Filed: 11/02/1993
• Issued: 09/19/1995
• Est. Priority Date: 09/12/1991
• Status: Expired due to Term

• Current Assignee: Bausch & Lomb Incorporated (Bausch Health Cos., Inc.)
• Original Assignee: Bausch & Lomb Incorporated (Bausch Health Cos., Inc.)
• Inventors: Lai, Yu-Chan, Valint, Paul J. Jr.
• Primary Examiner(s): Kulkosky, Peter F.
• Application Number:
  US08/145,847
• Time in Patent Office: 686 Days
• Field of Search: 523/103, 526/279
• US Class Current: 523/107
• CPC Class Codes: C08F 230/08 containing silicon
• CPC Class Codes: C08F 283/124 on to polysiloxanes having carbon-to-carbon double bonds
• CPC Class Codes: C08F 290/068 Polysiloxanes

Abstract

Improved silicone-containing hydrogels with enhanced wettability comprising at least one silicone-containing prepolymer, and an equimolar amphoteric mixture of acid-containing comonomers and amine-containing comonomers are herein disclosed.

Claims

1. In a method of making a silicone-containing hydrogel composition by:

a) providing at least one hydrophilic monomer and at least one silicone-containing monomer to a monomer mix; and

b) curing the monomer mix resulting from step a) to form a silicone-containing hydrogel composition the improvement of which comprises

improving the wettability of the silicone-containing hydrogel composition, which is characterized by the composition having a contact angle of less than about 25 degrees, by providing from about 0.5 to about 10 weight percent of an amphoteric equimolar mixture of acid-containing and amine-containing comonomers different from the hydrophilic monomers of step a) to the monomer mix of step a).

2. The method of claim 1 wherein said silicone-containing monomer is a urethane-containing prepolymer.

3. The method of claim 1 wherein said silicone-containing monomer is an ethylenically terminated polysiloxane-containing prepolymer.

4. The method of claim 1 wherein said acid-containing comonomer is selected from the group consisting of methacrylic acid, 3-methacryl-β

-alanine, 3-acryl-β

-alanine, α

-methacrylamidoalkanoic acid, 2-acrylamido-2-methylpropane sulfonic acid, acrylic acid, itaconic acid, maleic acid, and 2-acrylamido-2-methylpropane sulfonic acid.

5. The method of claim 1 wherein said amine-containing comonomer is selected from the group consisting of 3-(N,N-dimethylamino)propyl methacrylamide, and 2-(N,N-dimethylamino)ethyl methacrylate.

6. The method of claim 1 wherein said silicone-containing monomer is a poly(organosiloxane) prepolymer represented by the formula:

##STR6## wherein;

A is an activated unsaturated group, such as an ester or amide of an acrylic or a methacrylic acid;

each R³ -R⁶ is independently selected from the group consisting of a monovalent hydrocarbon radical or a halogen substituted monovalent hydrocarbon radical having 1 to 18 carbon atoms which may have ether linkages between carbon atoms;

R⁷ is a divalent hydrocarbon radical having from 1 to 22 carbon atoms;

and

n is 0 or an integer greater than or equal to 1.

7. The method of claim 1 wherein the monomer mix additionally comprises a bulky polysiloxanylalkyl (meth)acrylic monomer having the 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.

8. The method of claim 7 wherein said bulky polysiloxanyalkyl methacrylic monomer is selected from the group consisting of methacryloxypropyl tris(trimethylsiloxy)silane, pentamethyldisiloxanylmethylmethacrylate, tris(trimethylsiloxy)methacryloxy propylsilane, phenyltetramethyldisiloxanylethyl acrylate, and methyldi(trimethylsiloxy)methacryloxymethyl silane.

9. The method of claim 1 wherein said silicone-containing monomer 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";

wherein

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^'"'"' 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 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.

10. The method of claim 9 wherein said urethane-containing prepolymer is represented by formula:

##STR10## wherein;

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

11. The method of claim 1 wherein said monomer mix contains N,N-dimethylacrylamide.

12. The method of claim 1 wherein said amphoteric mixture is present in an amount of from about 2 weight percent to about 5 weight percent.

13. In an improved silicone-containing hydrogel composition formed by at least one hydrophilic monomer and at least one silicone-containing monomer incorporated into a monomer mix which is cured into a silicone-containing hydrogel composition, the improvement of which comprises:

improving the weltability of the silicone-containing hydrogel composition by having a contact angle of less than about 25 degrees by providing an amphoteric equimolar mixture of acid-containing and amine-containing comonomers different from the hydrophilic monomer in an amount of from about 0.5 to about 10 weight percent into the monomer mix.

14. The hydrogel of claim 13 wherein said silicone-containing monomer is a urethane-containing prepolymer.

15. The hydrogel of claim 13 wherein said silicone-containing prepolymer is an ethylenically terminated polysiloxane-containing prepolymer.

16. The hydrogel of claim 13 wherein acid-containing comonomer is selected from the group consisting of methacrylic acid, 3-methacryl-β

-alanine, -acryl-β

-alanine, α

-methacrylamidoalkanoic acid, 2-acrylamido-2-methylpropane sulfonic acid, acrylic acid, itaconic acid, maleic acid, and 2-acrylamido-2-methylpropane sulfonic acid.

17. The hydrogel of claim 13 wherein said amine-containing comonomer is selected from the group consisting of 3-(N,N-dimethylamino)propyl methacrylamide, and 2-(N,N-dimethylamino)ethyl methacrylate.

18. The hydrogel of claim 13 wherein said silicone-containing monomer is a poly(organosiloxane) prepolymer represented by the formula:

##STR11## wherein;

A is an activated unsaturated group, such as an ester or amide of an acrylic or a methacrylic acid;

each R³ -R⁶ is independently selected from the group consisting of a monovalent hydrocarbon radical or a halogen substituted monovalent hydrocarbon radical having 1 to 18 carbon atoms which may have ether linkages between carbon atoms;

R⁷ is a divalent hydrocarbon radical having from 1 to 22 carbon atoms; and

n is 0 or an integer greater than or equal to 1.

19. The method of claim 13 wherein the monomer mix additionally comprises a bulky polysiloxanylalkyl (meth)acrylic monomer having the formula:

##STR12## 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.

20. The hydrogel of claim 19 wherein said bulky polysiloxanyalkyl (meth)acrylate monomer is selected from the group consisting of methacryloxypropyl tris(trimethylsiloxy)silane, pentamethyldisiloxanylmethylmethacrylate, tris(trimethylsiloxy)methacryloxy propylsilane, phenyltetramethyldisiloxanylethyl acetate, and methyldi(trimethylsiloxy)methacryloxymethyl silane.

21. The hydrogel of claim 13 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'"'"';

wherein

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;

##STR13## 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 formula;

##STR14## 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.

22. The hydrogel of claim 13 wherein said urethane-containing prepolymer is represented by formula:

##STR15## wherein;

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

23. The hydrogel of claim 13 wherein said silicone-containing monomer is α

, ω

bis(methacryloxybutyl) polysiloxane.

24. The hydrogel of claim 13 wherein said silicone-containing monomer is α

, ω

bis(methacryloxybutyl) polysiloxane, said acid-containing monomer is methacrylic acid, and said amine-containing monomer is 3-(N,N-dimethylamino)propylmethacrylamide.

25. The hydrogel of claim 13 wherein said silicone-containing monomer is α

, ω

bis(methacryloxybutyl) polysiloxane, said acid-containing monomer is 2-acrylamido-2-methylpropanesulfonic acid, and said amine-containing monomer is 3-(N,N-dimethylamino)propylmethacrylamide.

26. The hydrogel of claim 13 wherein said silicone-containing monomer is α

, ω

bis(methacryloxybutyl) polysiloxane, said acid-containing monomer is acrylic acid, and said amine-containing monomer is 3-(N,N-dimethyl amino)propylmethacryl amide.

27. The hydrogel of claim 13 wherein said silicone-containing monomer is a urethane-containing prepolymer, said acid-containing monomer is 2-acrylamido-2-methylpropanesulfonic acid and said amine-containing monomer is 3-(N,N-dimethylamino)propyl methacrylamide.

28. The hydrogel of claim 13 wherein said silicone-containing monomer is a urethane-containing prepolymer, said acid-containing monomer is acrylic acid, and said amine-containing monomer is 3-(N,N-dimethylamino)propyl methacrylamide.

29. A biomedical device made from the hydrogel composition of claim 13.

30. A contact lens made from the hydrogel composition of claim 13.