PREPOLYMERS SUITABLE FOR MAKING ULTRA-VIOLET ABSORBING CONTACT LENSES

• US 20110063567A1
• Filed: 09/13/2010
• Published: 03/17/2011
• Est. Priority Date: 09/15/2009
• Status: Active Grant

• Current Assignee: Alcon Incorporated
• Original Assignee: Novartis Ag
• Inventors: Turek, Richard Charles, Holland, Troy Vernon, Domschke, Angelika Maria
• Granted Patent: US 8,431,624 B2
• Time in Patent Office: Days
• US Class Current: 351/160.H
• CPC Class Codes: C08F 220/20 of polyhydric alcohols or phenols , e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
• CPC Class Codes: C08F 220/36 containing oxygen in addition to the carboxy oxygen , e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate
• CPC Class Codes: C08F 220/54 Amides , e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
• CPC Class Codes: C08F 220/56 Acrylamide; Methacrylamide
• CPC Class Codes: C08F 220/58 containing oxygen in addition to the carbonamido oxygen , e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine
• CPC Class Codes: C08F 230/08 containing silicon
• CPC Class Codes: C08F 290/067 Polyurethanes; Polyureas
• CPC Class Codes: C08F 290/068 Polysiloxanes
• CPC Class Codes: C08G 77/16 to hydroxyl groups
• CPC Class Codes: C08G 77/26 nitrogen-containing groups
• CPC Class Codes: C08G 77/388 containing nitrogen
• CPC Class Codes: C08K 5/57 Organo-tin compounds
• CPC Class Codes: C08L 101/14 the macromolecular compounds being water soluble or water swellable, e.g. aqueous gels
• CPC Class Codes: C08L 83/04 Polysiloxanes
• CPC Class Codes: G02B 1/043 Contact lenses
• CPC Class Codes: G02C 7/04 Contact lenses for the eyes disinfection or sterilisation of contact lenses A61L12/00

Abstract

The invention provides a class of actinically-crosslinkable silicone-containing prepolymers which comprise (1) ethylenically-unsaturated groups and (2) UV-absorbing polymeric units, latent UV-absorbing polymeric units, and/or dual photo-functional polymeric units. The prepolymer of the invention can be used to prepare silicone hydrogel contact lenses capable of absorbing UV/visible radiation. The present invention is also related to silicone hydrogel contact lenses made from a prepolymer of the invention and methods for making the contact lenses in a cost-effective way and with high consistency and high fidelity to the original lens design.

Claims

1. An actinically crosslinkable prepolymer, comprising:

in the branched copolymer chains of the prepolymer, (1) crosslinking polysiloxane polymeric units derived from at least one polysiloxane-containing crosslinker;

(2) hydrophilic polymeric units derived from one or more hydrophilic vinylic monomers;

(3) UV-absorbing polymeric units, latent UV-absorbing polymeric units, or dual photo-functional polymeric units, wherein the UV-absorbing polymeric units are derived from a polymerizable UV-absorbing agent, wherein the latent UV-absorbing polymeric units are derived from a polymerizable latent UV-absorbing agent, wherein the dual photo-functional polymeric units are derived from a polymerizable compound having a photoinitiating moiety and a UV-absorbing or latent UV-absorbing moiety;

(4) optionally dangling polysiloxane polymeric units derived from one or more monoethylenically functionalized polysiloxane-containing vinylic monomers or macromers, wherein the dangling polysiloxane units is free of ethylenically unsaturated group; and

(5) optionally siloxane polymeric units derived from at least one siloxane-containing vinylic monomer, wherein the prepolymer comprises three or more ethylenically unsaturated groups and is soluble in a solvent to form a solution and capable of being actinically crosslinked, in the absence of one or more vinylic monomers or a crosslinking agent, to form a UV absorbing or blocking silicone hydrogel contact lens.

2. The prepolymer of claim 1, wherein the prepolymer is obtained from an intermediary copolymer with one or more first functional groups by reacting the intermediary copolymer with a vinylic monomer having a second function group to covalently attach an ethylenically unsaturated group to the intermediary copolymer through one of the first functional groups, wherein the first and second functional groups are different from each other and selected from the group consisting of hydroxy groups, amino groups (—

NH₂), carboxyl groups (—

COOH), epoxy groups, aldehyde groups (—

CHO), amide groups (—

CONH₂), acid halide groups (—

COX, X═

Cl, Br, or I), isothiocyanate groups, isocyanate groups, halide groups (—

X, X═

Cl, Br, or I), acid anhydride groups, and combinations thereof, provided that each second functional group is coreactive with one of the first function groups to form a covalent linkage,

wherein the intermediary copolymer is obtained by copolymerization of a reactive mixture A or B,

wherein the reactive mixture A comprises (1) at least one polysiloxane-containing crosslinker;

(2) one or more hydrophilic vinylic monomers;

(3) a polymerizable UV-absorbing agent or a polymerizable latent UV-absorbing agent;

(4) a free radical initiator;

(5) optionally one or more monoethylenically functionalized polysiloxane-containing vinylic monomers or macromers; and

(6) optionally siloxane units derived from at least one siloxane-containing vinylic monomer, provided that at least one of components (1)-(3) and (5) further comprises at least one first functional group,

wherein the reactive mixture B comprises (1) at least one polysiloxane-containing crosslinker;

(2) one or more hydrophilic vinylic monomers;

(3) a polymerizable UV-absorbing agent or a polymerizable latent UV-absorbing agent;

(4) a free radical initiator;

(5) optionally one or more monoethylenically functionalized polysiloxane-containing vinylic monomers or macromers;

(6) optionally siloxane units derived from at least one siloxane-containing vinylic monomer; and

(7) at least one chain transfer agent having a first functional group.

3. The prepolymer of claim 2, wherein the intermediary copolymer is obtained by copolymerization of a reactive mixture B.

4. The prepolymer of claim 1, wherein the polysiloxane crosslinker is defined by formula (1)

Q-X₁-A₁-PDMS-A₂-X₂-Q 

 

(1)

in which

A₁ and A₂ independent of each other is a linear or branched C₁-C₁₀ alkyl diradical which optionally comprises one or more hydroxyl or amino groups, a divalent radical of

5. The prepolymer of claim 1, wherein the prepolymer comprises siloxane polymeric units derived from at least one siloxane-containing vinylic monomer of formula (6)

6. The prepolymer of claim 1, wherein the prepolymer comprises hydrophilic polymeric units derived from at least one hydrophilic vinylic monomer selected from the group consisting of N,N-dimethylacrylamide (DMA), N,N-dimethylmethacrylamide (DMMA), 2-acrylamidoglycolic acid monohydrate, 3-acryloylamino-1-propanol, N-hydroxyethyl acrylamide, N-[tris(hydroxymethyl)methyl]-acrylamide, N-methyl-3-methylene-2-pyrrolidone, 2-hydroxyethylmethacrylate (HEMA), 2-hydroxyethyl acrylate (HEA), hydroxypropyl acrylate, hydroxypropyl methacrylate (HPMA), trimethylammonium 2-hydroxy propylmethacrylate hydrochloride, aminopropyl methacrylate hydrochloride, dimethylaminoethyl methacrylate (DMAEMA), glycerol methacrylate (GMA), N-vinyl-2-pyrrolidone (NVP), allyl alcohol, vinylpyridine, acrylic acid, a C₁-C₄-alkoxy polyethylene glycol (meth)acrylate having a weight average molecular weight of from 200 to 1500, methacrylic acid, N-vinyl formamide, N-vinyl acetamide, N-vinyl isopropylamide, N-vinyl-N-methyl acetamide, allyl alcohol, N-vinyl caprolactam, and mixtures thereof.

7. The prepolymer of claim 1, wherein the prepolymer comprises UV-absorbing polymeric units derived from a polymerizable UV-absorbing agent which comprises a benzotriazole-moiety and/or a benzophenone-moiety.

8. The prepolymer of claim 7, wherein the polymerizable UV-absorbing agent is selected from the group consisting of 2-(2-hydroxy-5-vinylphenyl)-2H-benzotriazole, 2-(2-hydroxy-5-acrylyloxyphenyl)-2H-benzotriazole, 2-(2-hydroxy-3-methacrylamido methyl-5-tert octylphenyl)benzotriazole, 2-(2′

-hydroxy-5′

-methacrylamidophenyl)-5-chlorobenzotriazole, 2-(2′

-hydroxy-5′

-methacrylamidophenyl)-5-methoxybenzotriazole, 2-(2′

-hydroxy-5′

-methacryloxypropyl-3′

-t-butyl-phenyl)-5-chlorobenzotriazole, 2-(2′

-hydroxy-5′

-methacryloxyethylphenyl)benzotriazole, 2-(2′

-hydroxy-5′

-methacryloxypropylphenyl)-benzotriazole, 2-hydroxy-4-acryloxy alkoxy benzophenone, 2-hydroxy-4-methacryloxy alkoxy benzophenone, allyl-2-hydroxybenzophenone, 2-hydroxy-4-methacryloxy benzophenone, and mixtures thereof.

9. The prepolymer of claim 1, wherein the prepolymer comprises latent UV-absorbing polymeric units derived from a polymerizable latent UV-absorbing agent which comprises a benzotriazole-moiety and/or a benzophenone-moiety, wherein the hydroxyl radical of the phenol moiety of the benzotriazole moiety is replaced with a protective labile group to form a latent UV-absorbing moiety, wherein the at least one hydroxyl radical of the phenolic radical of the benzophenone moiety is replaced with a protective labile group to form a latent UV-absorbing moiety.

10. The prepolymer of claim 1, wherein the prepolymer comprises dual photo-functional polymeric units derived from a polymerizable compound having a photoinitiating moiety and a UV-absorbing or latent UV-absorbing moiety.

11. The prepolymer of claim 1, further comprising hydrophobic polymeric units derived from at least one hydrophobic vinylic monomer selected from the group consisting of methylacrylate, ethyl-acrylate, propylacrylate, isopropylacrylate, cyclohexylacrylate, 2-ethylhexylacrylate, methylmethacrylate, ethylmethacrylate, propyl methacrylate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl valerate, styrene, chloroprene, vinyl chloride, vinylidene chloride, acrylonitrile, 1-butene, butadiene, methacrylonitrile, vinyl toluene, vinyl ethyl ether, perfluorohexylethyl-thio-carbonyl-aminoethyl-methacrylate, isobornyl methacrylate, isobornyl acrylate, norbornyl methacrylate, norbornyl acrylate, trifluoroethyl methacrylate, hexafluoro-isopropyl methacrylate, hexafluorobutyl methacrylate.

12. A soft contact lens, having a UV-absorbing property characterized by being able to absorbing at least about 80 percent of a UV light in the range of from about 280 nm to about 370 nm that impinges on the lens;

and comprising a silicone hydrogel material that is obtained by curing a lens-forming material in a mold, wherein the lens-forming material comprises an actinically crosslinkable prepolymer which comprises, in the branched copolymer chains of the prepolymer, (1) crosslinking polysiloxane polymeric units derived from at least one polysiloxane-containing crosslinker;

(2) hydrophilic polymeric units derived from one or more hydrophilic vinylic monomers;

(3) UV-absorbing polymeric units, latent UV-absorbing polymeric units, or dual photo-functional polymeric units, wherein the UV-absorbing polymeric units are derived from a polymerizable UV-absorbing agent, wherein the latent UV-absorbing polymeric units are derived from a polymerizable latent UV-absorbing agent, wherein the dual photo-functional polymeric units are derived from a polymerizable compound having a photoinitiating moiety and a UV-absorbing or latent UV-absorbing moiety;

(4) optionally dangling polysiloxane polymeric units derived from one or more monoethylenically functionalized polysiloxane-containing vinylic monomers or macromers, wherein the dangling polysiloxane units is free of ethylenically unsaturated group; and

(5) optionally siloxane polymeric units derived from at least one siloxane-containing vinylic monomer.

13. The soft contact lens of claim 12, wherein the prepolymer is obtained from an intermediary copolymer with two or more first functional groups by reacting the intermediary copolymer with a vinylic monomer having a second function group to covalently attach an ethylenically unsaturated group to the intermediary copolymer through one of the first functional groups, wherein the first and second functional groups are different from each other and selected from the group consisting of hydroxy groups, amino groups (—

NH₂), carboxyl groups (—

COOH), epoxy groups, aldehyde groups (—

CHO), amide groups (—

CONH₂), acid halide groups (—

COX, X═

Cl, Br, or I), isothiocyanate groups, isocyanate groups, halide groups (—

X, X═

Cl, Br, or I), acid anhydride groups, and combinations thereof, provided that each second functional group is coreactive with one of the first function groups to form a covalent linkage,

wherein the intermediary copolymer is obtained by copolymerization of a reactive mixture A or B,

wherein the reactive mixture A comprises (1) at least one polysiloxane-containing crosslinker;

(2) one or more hydrophilic vinylic monomers;

(3) a polymerizable UV-absorbing agent or a polymerizable latent UV-absorbing agent;

(4) a free radical initiator;

(5) optionally one or more monoethylenically functionalized polysiloxane-containing vinylic monomers or macromers; and

(6) optionally siloxane units derived from at least one siloxane-containing vinylic monomer, provided that at least one of components (1)-(3) and (5) further comprises at least one first functional group,

wherein the reactive mixture B comprises (1) at least one polysiloxane-containing crosslinker;

(2) one or more hydrophilic vinylic monomers;

(3) a polymerizable UV-absorbing agent or a polymerizable latent UV-absorbing agent;

(4) a free radical initiator;

(5) optionally one or more monoethylenically functionalized polysiloxane-containing vinylic monomers or macromers;

(6) optionally siloxane units derived from at least one siloxane-containing vinylic monomer; and

(7) at least one chain transfer agent having a first functional group.

14. The soft contact lens of claim 12, wherein the polysiloxane crosslinker is defined by formula (1)

Q-X₁-A₁-PDMS-A₂-X₂-Q 

 

(1)

in which

A₁ and A₂ independent of each other is a linear or branched C₁-C₁₀ alkyl diradical which optionally comprises one or more hydroxyl or amino groups, a divalent radical of

15. The soft contact lens of claim 14, wherein the contact lens has at least one property selected from the group consisting of an oxygen permeability of at least about 40 barrers, an elastic modulus of about 2.0 MPa or less, an lonoflux Diffusion Coefficient, D, of at least about 1.5×

10<sup>−

6</sup> mm²/min, and a water content of from about 15% to about 70%.

16. The soft contact lens of claim 14, further comprising a visibility tinting agent, an antimicrobial agent, bioactive agent, a leachable lubricant, or a combination thereof.