Silicone acrylamide copolymer

Patent metadata

Field	Value
Publication number	US-9745460-B2
Application number	US-201514670981-A
Country	US
Kind code	B2
Filing date	Mar 27, 2015
Priority date	Mar 31, 2014
Publication date	Aug 29, 2017
Grant date	Aug 29, 2017

Abstract

The present invention relates to a silicone acrylamide copolymer of high acrylamide monomer content which has transparency and low modulus, employing the following configuration. The copolymer is suitably used for various kinds of medical devices, particularly ophthalmic lenses such as a contact lens, an intraocular lens, an artificial cornea, and is especially suitable for a contact lens. A copolymer comprising (A) a multi-functional (meth)acrylamide monomer having at least one siloxane bond and at least two (meth)acrylamide groups within a molecule and (B) a mono-functional linear silicone (meth)acrylamide monomer.

First claim

The invention claimed is:

1. A copolymer formed from a reactive mixture comprising radically polymerizable components comprising:
(A) a multi-functional (meth)acrylamide monomer of Formula (a1):

wherein R 1 is independently selected from hydrogen and methyl;
R 2 is independently selected from hydrogen, or an alkyl which may be substituted and has 1 to 20 carbon atoms, or an aryl which may be substituted and has 6 to 20 carbon atoms;
R 3 to R 6 are each an alkyl which may be substituted and has 1 to 20 carbon atoms, or an aryl which may be substituted and has 6 to 20 carbon atoms;
X 1 is independently selected from substituted or unsubstituted divalent organic groups having 1 to 20 carbon atoms; and
a represents an integer of 1 to 15; and

(B) a mono-functional linear silicone (meth)acrylamide monomer of formula (a2) a2)

wherein R 7 is selected from hydrogen and methyl; R 8 is hydrogen, an alkyl which may be substituted with a hydroxy group and has 1 to 20 carbon atoms, or an aryl which may be substituted with a hydroxy group and has 6 to 20 carbon atoms; R 9 to R 14 are each an alkyl which may be substituted and has 1 to 20 carbon atoms, or an aryl which may be substituted and has 6 to 20 carbon atoms; X 2 represents a C 1 -C 20 alkylene group which may be substituted with a hydroxy group or may contain oxygen; n is 1 to 1000; R 15 is an alkyl which may be substituted and has 1 to 20 carbon atoms, or an aryl which may be substituted and has 6 to 20 carbon atoms; with the proviso that at least one of R 8 and X 2 has at least one hydroxy group; and

(C) a non-silicone hydrophilic monomer.

2. The copolymer according to claim 1 , wherein the mass average molecular weight of the multi-functional (meth)acrylamide monomer is 1500 or less.

3. The copolymer according to any of claim 1 or 2 , wherein the mono-functional linear silicone (meth)acrylamide monomer has at least one hydroxy group.

4. The copolymer according to claim 1 , wherein R 7 in general formula (a2) is hydrogen.

5. The copolymer according to claim 1 , wherein R 8 in general formula (a2) is hydrogen or an alkyl which is substituted with a hydroxy group and has 1 to 20 carbon atoms.

6. The copolymer according to claim 1 , wherein the X 2 in general formula (a2) is a propylene or a structure represented by the following formula (b):
—CH 2 CH(OH)CH 2 OCH 2 CH 2 CH 2 —.  (b)

7. The copolymer according to claim 5 , wherein R 8 is a 2,3-dihydroxypropyl.

8. The copolymer according to claim 1 , wherein at least one of R 9 to R 14 is methyl.

9. The copolymer according to claim 1 , wherein R 15 is methyl or n-butyl.

10. The copolymer according to claim 1 , wherein n is an integer of 1 to 6 and has no distribution.

11. The copolymer according to claim 1 , wherein the non-silicone hydrophilic monomer is selected from the group consisting of N,N-dimethyl acrylamide (DMA), N-vinylpyrrolidone (NVP), 2-hydroxyethyl acrylate, glycerol methacrylate, 2-hydroxyethyl methacrylamide, polyethylene glycol monomethacrylate, methacrylic acid, acrylic acid, N-vinyl-N-methylacetamide, N-vinyl-N-ethylacetamide, N-vinyl-N-ethylformamide, N-vinylformamide, N-2-hydroxyethylvinyl carbamate, N-carboxy-β-alanine N-vinyl ester, a reactive polyethylene polyol, a hydrophilic vinyl carbonate, a vinyl carbamate monomer, a hydrophilic oxazolone monomer, a hydrophilic oxazoline monomer and a combination thereof.

12. The copolymer according to any of claim 1 or 2 , wherein the mass of the (meth)acrylamide monomer component is 90% by mass or greater based on the mass of all monomer components.

13. The copolymer according to any of claim 1 or 2 , wherein the mono-functional linear silicone (meth)acrylamide monomer is present in an amount of about 30 parts by mass to about 98 parts by mass.

14. A material for medical device comprised of the copolymer according to any of claim 1 or 2 .

15. The material for medical device according to claim 14 , wherein the material for medical device is any one selected from a contact lens, an endoscope, a catheter, a transfusion tube, a gas transport tube, a stent, a sheath, a cuff, a tube connector, an access port, a drainage bag, a blood circuit, a wound covering material and a medicine carrier.

16. An ophthalmic lens comprised of the copolymer according to any of claim 1 or 2 .

17. A contact lens comprised of the copolymer according to any of claim 1 or 2 .

18. The copolymer of claim 1 comprising a modulus of less than 100 psi.

19. The copolymer according to any of claim 1 , 2 or 18 comprising a water content of about 20 to about 75%.

20. The copolymer according to any of claim 1 , 2 or 18 wherein the reactive mixture further comprises at least one reactive or non-reactive wetting agent.

21. The copolymer of claim 20 wherein reactive mixture comprises about 1 to about 30% by weight wetting agent based upon total amount of reactive components.

22. The copolymer of claim 20 wherein the wetting agent is selected from the group consisting of poly-N-vinyl 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, poly-N-vinyl-4,5-dimethyl-2-pyrrolidone, polyvinyl imidazole, poly-N-vinyl formamide, poly-N-vinyl (methyl)acetamide, poly-N-methyl-N-vinyl (methyl)acetamide, poly-N-vinyl-N-(methyl)propionamide, poly-N-vinyl-N-methyl-2-(methyl)propionamide, poly-N-vinyl-2-(methyl)propionamide, poly-N-vinyl-N,N′-dimethylurea, poly-N,N-dimethyl acrylamide, poly-N,N-diethyl acrylamide, poly-N-isopropyl acrylamide, polyvinyl alcohol, polyacrylate, polyethylene oxide, poly-2-ethyl oxazoline, heparine, polysaccharide, poly-acryloyl morpholine, and mixtures and copolymers thereof.

23. The copolymer of claim 21 wherein the wetting agent is selected from the group consisting of polyvinylpyrrolidone, poly-N,N-dimethyl acrylamide, polyacrylic acid, polyvinyl alcohol, poly-N-methyl-N-vinyl (methyl)acetamide and copolymers and mixtures thereof.

24. The copolymer of claim 21 wherein the wetting agent is selected from the group consisting of polyvinylpyrrolidone and poly-N,N-dimethyl acrylamide.

25. The copolymer of claim 20 wherein reactive mixture comprises about 3 to about 20% by weight wetting agent based upon total amount of reactive components.

26. The copolymer of claim 1 wherein:
the multi-functional (meth)acrylamide monomer is a compound of formula (S1):

or a compounds of formula (S2):

wherein n in formula (S2) is a natural number and the average molecular weight of the compound is about 1000; and
wherein the mono-functional linear silicone (meth)acrylamide monomer is a compound of formula (X1)

Assignees

• Johnson & Johnson Vision Care

Inventors

• Tamiya Ryuta
• Fujisawa Kazuhiko
• Nakamura Masataka
• Maggio Thomas L
• Turnage Michelle Carman
• Clark Michael R

Classifications

• C08F222/38

  Amides · CPC title

• C08F230/08 Primary

  containing silicon · CPC title

• C08F222/385 Primary

  Monomers containing two or more (meth)acrylamide groups, e.g. N,N'-methylenebisacrylamide · CPC title

• C08L43/04

  Homopolymers or copolymers of monomers containing silicon · CPC title

• C08L39/06 Primary

  Homopolymers or copolymers of N-vinyl-pyrrolidones · CPC title