Granted Patent B2

US 8,980,956 · App. 13/601,067 · Granted Mar 17, 2015

Abstract

Claims (63)

1. A method comprising dissolving an ethylenically unsaturated zwitterionic monomer in a co-monomer system comprising a functionalised ethylenically unsaturated monomer in which the zwitterionic monomer is soluble, a siloxane group-containing monomer, and a crosslinking agent, to produce a homogeneous polymerisable solution,

wherein the siloxane group-containing monomer is a material of formula (A) or (B):

(T 1 -Y 1 ) k -G 1 (Y 2 —Z) l   (A)

[(T 1 ) k -Y 3 (Z) u ] v -G 1 -R 24   (B)

wherein

T 1 is a polymerisable group;

Y 1 and Y 2 are each independently a linker group selected from the group consisting of a bond, C 1-12 alkylene, C 2-12 alkenylene, C 2-12 alkenylene, C 3-12 cycloalkylene, C 3-12 cycloalkenylene, C 2-12 heteroalkenylene, C 2-12 heteroalkynylene, arylene, heteroarylene, —C(O)—C 1-12 alkylene, —C(S)—C 1-12 alkylene, —C(O)O—C 1-12 alkylene, —C(O)S—C 1-12 alkylene, —C(O)N(R M )—C 1-12 alkylene, —C(S)—C 1-12 alkylene, —C(S)O—C 1-12 alkylene, —C(S)S—C 1-12 alkylene, —C(S)N(R M )—C 1-12 alkylene, —(CH 2 ) qq (OCH 2 CH 2 ) rr — and —(CH 2 CH 2 O) rr (CH 2 ) qq —, wherein R M is hydrogen or C 1-4 alkyl, qq is an integer from 1 to 10, rr is an integer from 1 to 10, wherein one or more carbon atoms in the C 1-12 alkylene group may be optionally replaced with a heteroatom selected from the group consisting of S and O and the alkylene, alkenylene, alkynylene, cycloalkylene, cycloalkenylene, heteroalkenylene, heteroalkynylene, arylene and heteroarylene groups may be optionally substituted with one or more R N , wherein each R N is independently selected from the group consisting of —H, —OH, —CN, —NO 2 , —CF 3 , —OCF 3 , —CO 2 H, —NH 2 , C 1 -C 10 alkyl, C 2 -C 10 alkenyl, C 2 -C 10 alkynyl, —O(C 1 -C 10 alkyl), —O(C 2 -C 10 alkenyl), —O(C 2 -C 10 alkynyl), halogen, —C(O)H, —C(O)—(C 1 -C 10 alkyl), —C(O)—O(C 1 -C 10 alkyl), —NH(C 1 -C 10 alkyl), —N(C 1 -C 10 alkyl) 2 , —C(O)—NH(C 1 -C 10 alkyl), —C(O)—N(C 1 -C 10 alkyl) 2 , —NH—C(O)—(C 1 -C 10 alkyl), —NH(C 1 -C 10 alkyl)-C(O)—(C 1 -C 10 alkyl), —NH—S(O) 2 —(C 1 -C 10 alkyl), —NH—(C 1 -C 10 alkyl)-S(O) 2 —(C 1 -C 10 alkyl), —(C 0 -C 10 )—SH, —S(O)—(C 1 -C 10 alkyl), —S(O) 2 —(C 1 -C 10 alkyl), —S(O) 2 —NH 2 , —S(O) 2 —NH—(C 1 -C 10 alkyl), —S(O) 2 —N(C 1 -C 10 alkyl) 2 and ═O;

Y 3 is a linker group;

R 24 is a C 1-12 alkyl group which may be optionally substituted with one or more R N ;

G 1 is a siloxane group-containing component;

Z is a zwitterionic group;

k is an integer from 1 to 10;

l is an integer from 1 to 3;

u is an integer from 1 to 3; and

v is an integer from 1 to 3.

2. The method of claim 1 , wherein the ethylenically unsaturated zwitterionic monomer is a monomer of formula (I):

wherein:

J is selected from the group consisting of

a valence bond;

—W—X—Y—, wherein W is (CR 1 2 ) n ; X is O, S or NR 2 and Y is a linker group; and

—K—X—Y—, wherein K is (CR 1 2 ) n C(O) and X and Y are as defined above;

Z is a zwitterionic group;

each R 1 is independently selected from H, halogen or C 1-4 alkyl;

R 2 is H or C 1-4 alkyl;

n is an integer from 0 to 6; and

m is an integer from 0 to 6.

3. The method of claim 2 , wherein the ethylenically unsaturated zwitterionic monomer is a monomer of formula (ID):

4. The method of claim 3 , wherein R 1 is methyl, X is O and m is 2.

5. The method of claim 2 , wherein Z is a group of formula (IVB):

wherein each R 4 and R 4A is independently selected from hydrogen and C 1-4 alkyl and b is an integer from 1 to 4.

6. The method of claim 1 , wherein the ethylenically unsaturated zwitterionic monomer is a monomer of formula (III):

wherein J is selected from the group consisting of

a valence bond;

—W—X—Y—, wherein W is (CR 1 2 ) n ; X is O, S or NR and Y is a linker group; and

—K—X—Y—, wherein K is (CR 1 2 ) n C(O) and X and Y are as defined above;

Z is a zwitterionic group;

each R 1 is independently selected from H, halogen or C 1-4 alkyl;

R 2 is H or C 1-4 alkyl;

n is an integer from 0 to 6; and

mm is an integer from 1 to 20.

7. The method of claim 1 , wherein the ethylenically unsaturated zwitterionic monomer is 2-methacryloyloxyethyl-2′-(trimethylammoniumethyl)phosphate inner salt (MPC).

8. The method of claim 1 , wherein the functionalised ethylenically unsaturated monomer in which the zwitterionic monomer is soluble is HEMA or GMA.

9. The method of claim 8 , wherein the functionalised ethylenically unsaturated monomer in which the zwitterionic monomer is soluble is HEMA.

10. The method of claim 1 , wherein the co-monomer system further comprises one or more components selected from the group consisting of hydrophilic monomers, macromers, UV absorbers, tinting agents, antibacterial agents, therapeutic agents, pigments, diluents and combinations thereof.

11. The method of claim 10 , wherein the co-monomer system further comprises a hydrophilic monomer.

12. The method of claim 11 , wherein the hydrophilic monomer is selected from the group consisting of dimethylacrylamide, 2-hydroxyethylmethacrylate and N-vinylpyrollidone.

13. The method of claim 1 , wherein the ethylenically unsaturated zwitterionic monomer is included in an amount such that the ratio of ethylenically unsaturated zwitterionic monomer to siloxane group-containing monomer or macromer in the polymerisable solution is about 0.1 to about 5.

14. The method of claim 1 , wherein the ethylenically unsaturated zwitterionic monomer is pre-dissolved in the functionalised ethylenically unsaturated monomer in which it is soluble prior to mixing with the siloxane group-containing monomer or macromer and the crosslinking agent.

15. The method of claim 1 , wherein the method comprises a further step of polymerising the homogeneous polymerisable solution.

16. The method of claim 15 comprising a further step of hydrating the polymer obtained after polymerisation.

17. A polymer obtainable by the method of claim 15 .

18. A xerogel comprising the polymer of claim 17 , which is free from water.

19. A silicone hydrogel comprising the polymer of claim 17 , and water in an amount of 30 to 80% by weight of hydrogel.

20. The polymer of claim 17 , which has an equilibrium water content in the range from 30 to 50%.

21. The polymer of claim 17 , which has a modulus in the range from 0.5 to 1.0 MPa.

22. An article comprising the polymer of claim 17 .

23. The article of claim 22 , which is a contact lens.

24. The contact lens of claim 23 , which has an oxygen permeability of about 30 barriers or more.

25. The contact lens of claim 23 , which has an equilibrium water content in the range from 30 to 50%.

26. The method of claim 1 , wherein the co-monomer system further comprises a non-reactive diluent.

27. The method of claim 26 , wherein the non-reactive diluent is water or an alcohol.

28. The method of claim 26 , wherein the method comprises a further step of removing the non-reactive diluent after the homogeneous polymerisable solution has been polymerised.

29. A homogeneous polymerisable solution produced by the method of claim 1 .

Assignments (19)