Actinically-crosslinkable siloxane-containing copolymers

• US 9,066,981 B2
• Filed: 12/11/2013
• Issued: 06/30/2015
• Est. Priority Date: 05/22/2009
• Status: Active Grant

• Current Assignee: Alcon Incorporated
• Original Assignee: Novartis Ag
• Inventors: Chang, Frank, Huang, Jinyu, Scott, Robert, Wang, Guigui
• Primary Examiner(s): MOORE, MARGARET G
• Application Number:
  US14/102,741
• Publication Number:
  US 20140100291A1
• Time in Patent Office: 566 Days
• US Class Current: 1/1
• CPC Class Codes: A61K 47/32 Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. carbomers , poly(meth)acrylates, or polyvinyl pyrrolidone
• CPC Class Codes: A61P 27/02 Ophthalmic agents
• CPC Class Codes: B29D 11/00038 Production of contact lenses
• CPC Class Codes: C08F 220/06 Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
• 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 220/56 Acrylamide; Methacrylamide
• CPC Class Codes: C08F 226/10 N-Vinyl-pyrrolidone
• CPC Class Codes: C08F 2438/01 Atom Transfer Radical Polymerization [ATRP] or reverse ATRP
• CPC Class Codes: C08F 2810/30 leading to the formation or introduction of aliphatic or alicyclic unsaturated groups
• CPC Class Codes: C08F 2810/40 taking place solely at one end or both ends of the polymer backbone, i.e. not in the side or lateral chains
• CPC Class Codes: C08F 283/12 on to polysiloxanes
• CPC Class Codes: C08F 290/068 Polysiloxanes
• CPC Class Codes: C08F 291/04 on to halogen-containing macromolecules
• CPC Class Codes: C08F 293/005 using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
• CPC Class Codes: C08F 299/08 from polysiloxanes
• CPC Class Codes: C08F 8/14 Esterification
• CPC Class Codes: C08F 8/26 Removing halogen atoms or halogen-containing groups from the molecule
• CPC Class Codes: C08G 77/14 containing silicon bound to oxygen-containing groups C08G77/045 takes precedence
• CPC Class Codes: C08G 77/26 nitrogen-containing groups
• CPC Class Codes: C08G 77/38 Polysiloxanes modified by chemical after-treatment C08G77/045 takes precedence
• CPC Class Codes: C08G 77/385 : containing halogens
• CPC Class Codes: C08G 77/392 : containing sulfur
• CPC Class Codes: C08J 2300/14 : Water soluble or water swellable polymers, e.g. aqueous gels
• CPC Class Codes: C08J 2383/06 : containing silicon bound to oxygen-containing groups C08J2383/12 takes precedence
• CPC Class Codes: C08J 2383/07 : containing silicon bound to unsaturated aliphatic groups
• CPC Class Codes: C08J 2383/08 : containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
• CPC Class Codes: C08J 3/075 : Macromolecular gels
• CPC Class Codes: C08J 3/28 : Treatment by wave energy or particle radiation
• CPC Class Codes: C08L 101/14 : the macromolecular compounds being water soluble or water swellable, e.g. aqueous gels
• CPC Class Codes: C08L 53/00 : Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
• 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 provide a class of actinically-crosslinkable silicone-containing prepolymers obtained by functionalizing an intermediary copolymer to have two or more thiol or ethylenically-unsaturated groups covalently attached thereto, wherein the intermediary copolymer is an atom-transfer radical polymerization (ATRP) product of a reactive mixture comprising a polysiloxane ATRP macroinitiator and at least one hydrophilic vinylic monomer. 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. A soft contact lens, comprising a silicone hydrogel material which is a polymerization product of a lens-forming material, wherein the lens-forming material comprises an actinically crosslinkable prepolymer of formula (1) or (2)

2. The contact lens of claim 1, 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 Ionoflux 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 65%.

3. The contact lens of claim 1, wherein the lens-forming material comprises one or more components selected from the group consisting of a photoinitiator or thermal initiator, a visibility tinting agent, a polymerizable UV-absorbing agent, a polymerizable latent UV-absorbing agent, an antimicrobial agent, a bioactive agent, and a leachable lubricant.

4. The contact lens of claim 1, wherein the lens-forming material comprises one or more components selected from the group consisting of a hydrophilic vinylic monomer, a silicone-containing vinylic monomer, a hydrophobic vinylic monomer free of silicone atom, a crosslinking agent.

6. The contact lens of claim 1, wherein LC is a divalent radical of a linear polymer chain of one or more hydrophilic vinylic monomers selected from the group consisting of N,N-dimethylacrylamide, N,N-dimethylmethacrylamide, 2-acrylamidoglycolic acid, 3-acryloylamino-1-propanol, N-hydroxyethyl acrylamide, N-[tris(hydroxymethyl)methyl]-acrylamide, N-methyl-3-methylene-2-pyrrolidone, 1-ethyl-3-methylene-2-pyrrolidone, 1-methyl-5-methylene-2-pyrrolidone, 1-ethyl-5-methylene-2-pyrrolidone, 5-methyl-3-methylene-2-pyrrolidone, 5-ethyl-3-methylene-2-pyrrolidone, 1-n-propyl-3-methylene-2-pyrrolidone, 1-n-propyl-5-methylene-2-pyrrolidone, 1-isopropyl-3-methylene-2-pyrrolidone, 1-isopropyl-5-methylene-2-pyrrolidone, 1-n-butyl-3-methylene-2-pyrrolidone, 1-tert-butyl-3-methylene-2-pyrrolidone, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, trimethylammonium 2-hydroxy propylmethacrylate hydrochloride, aminopropyl methacrylate hydrochloride, dimethylaminoethyl methacrylate, glycerol methacrylate, N-vinyl-2-pyrrolidone, allyl alcohol, vinylpyridine, acrylic acid, a C₁-C₄-alkoxy polyethylene glycol(meth)acrylate having a weight average molecular weight of up 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 contact lens of claim 6, wherein LC is a divalent radical of a linear polymer chain composed of monomeric units of N,N-dimethylacrylamide or N,N-dimethylacrylamide and one or more hydrophilic vinylic monomer other than N,N-dimethylacrylamide.

8. The contact lens of claim 6, wherein LC is a divalent radical of a linear polymer chain composed of monomeric units of N-Vinylpyrrolidone or N-Vinylpyrrolidone and one or more hydrophilic vinylic monomer other than N-Vinylpyrrolidone.

9. The contact lens of claim 6, wherein LC is a divalent radical of a linear polymer chain composed of monomeric units of 3-acryloylamino-1-propanol, N-hydroxyethyl acrylamide, N-[tris(hydroxymethyl)methyl]-acrylamide, 2-hydroxyethylmethacrylate (HEMA), 2-hydroxyethyl acrylate (HEA), hydroxypropyl acrylate, hydroxypropyl methacrylate (HPMA), glycerol methacrylate (GMA), allyl alcohol, a C₁-C₄-alkoxy polyethylene glycol(meth)acrylate having a weight average molecular weight of up to 1500, or a combination thereof.

10. The contact lens of claim 6, wherein the prepolymer is represented by formula (1) in which r₂ is zero, and G₂ is a linear or branched C₁-C₁₀ alkyl radical or a monovalent radical of alk′

-O_qalk- in which q and alk″

are defined as above and alk″

is C₁-C₆ alkyl.

11. The contact lens of claim 6, wherein the prepolymer is represented by formula (1) in which r₂ is an integer of 1.

12. The contact lens of claim 2, wherein LC is a divalent radical of a linear polymer chain of one or more hydrophilic vinylic monomers selected from the group consisting of N,N-dimethylacrylamide, N,N-dimethylmethacrylamide, 2-acrylamidoglycolic acid, 3-acryloylamino-1-propanol, N-hydroxyethyl acrylamide, N-[tris(hydroxymethyl)methyl]-acrylamide, N-methyl-3-methylene-2-pyrrolidone, 1-ethyl-3-methylene-2-pyrrolidone, 1-methyl-5-methylene-2-pyrrolidone, 1-ethyl-5-methylene-2-pyrrolidone, 5-methyl-3-methylene-2-pyrrolidone, 5-ethyl-3-methylene-2-pyrrolidone, 1-n-propyl-3-methylene-2-pyrrolidone, 1-n-propyl-5-methylene-2-pyrrolidone, 1-isopropyl-3-methylene-2-pyrrolidone, 1-isopropyl-5-methylene-2-pyrrolidone, 1-n-butyl-3-methylene-2-pyrrolidone, 1-tert-butyl-3-methylene-2-pyrrolidone, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, trimethylammonium 2-hydroxy propylmethacrylate hydrochloride, aminopropyl methacrylate hydrochloride, dimethylaminoethyl methacrylate, glycerol methacrylate, N-vinyl-2-pyrrolidone, allyl alcohol, vinylpyridine, acrylic acid, a C₁-C₄-alkoxy polyethylene glycol(meth)acrylate having a weight average molecular weight of up 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.

13. The contact lens of claim 12, wherein LC is a divalent radical of a linear polymer chain composed of monomeric units of N,N-dimethylacrylamide or N,N-dimethylacrylamide and one or more hydrophilic vinylic monomer other than N,N-dimethylacrylamide.

14. The contact lens of claim 12, wherein LC is a divalent radical of a linear polymer chain composed of monomeric units of N-Vinylpyrrolidone or N-Vinylpyrrolidone and one or more hydrophilic vinylic monomer other than N-Vinylpyrrolidone.

15. The contact lens of claim 12, wherein LC is a divalent radical of a linear polymer chain composed of monomeric units of 3-acryloylamino-1-propanol, N-hydroxyethyl acrylamide, N-[tris(hydroxymethyl)methyl]-acrylamide, 2-hydroxyethylmethacrylate (HEMA), 2-hydroxyethyl acrylate (HEA), hydroxypropyl acrylate, hydroxypropyl methacrylate (HPMA), glycerol methacrylate (GMA), allyl alcohol, a C₁-C₄-alkoxy polyethylene glycol(meth)acrylate having a weight average molecular weight of up to 1500, or a combination thereof.

16. The contact lens of claim 12, wherein the prepolymer is represented by formula (1) in which r₂ is zero, and G₂ is a linear or branched C₁-C₁₀ alkyl radical or a monovalent radical of alk′

-O_qalk″

in which q and alk′

are defined as above and alk″

is C₁-C₆ alkyl.

17. The contact lens of claim 12, wherein the prepolymer is represented by formula (1) in which r₂ is an integer of 1.

18. The contact lens of claim 3, wherein LC is a divalent radical of a linear polymer chain of one or more hydrophilic vinylic monomers selected from the group consisting of N,N-dimethylacrylamide, N,N-dimethylmethacrylamide, 2-acrylamidoglycolic acid, 3-acryloylamino-1-propanol, N-hydroxyethyl acrylamide, N-[tris(hydroxymethyl)methyl]-acrylamide, N-methyl-3-methylene-2-pyrrolidone, 1-ethyl-3-methylene-2-pyrrolidone, 1-methyl-5-methylene-2-pyrrolidone, 1-ethyl-5-methylene-2-pyrrolidone, 5-methyl-3-methylene-2-pyrrolidone, 5-ethyl-3-methylene-2-pyrrolidone, 1-n-propyl-3-methylene-2-pyrrolidone, 1-n-propyl-5-methylene-2-pyrrolidone, 1-isopropyl-3-methylene-2-pyrrolidone, 1-isopropyl-5-methylene-2-pyrrolidone, 1-n-butyl-3-methylene-2-pyrrolidone, 1-tert-butyl-3-methylene-2-pyrrolidone, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, trimethylammonium 2-hydroxy propylmethacrylate hydrochloride, aminopropyl methacrylate hydrochloride, dimethylaminoethyl methacrylate, glycerol methacrylate, N-vinyl-2-pyrrolidone, allyl alcohol, vinylpyridine, acrylic acid, a C₁-C₄-alkoxy polyethylene glycol(meth)acrylate having a weight average molecular weight of up 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.

19. The contact lens of claim 18, wherein the prepolymer is represented by formula (1) in which r₂ is zero, and G₂ is a linear or branched C₁-C₁₀ alkyl radical or a monovalent radical of alk′

-O_qalk″

in which q and alk′

are defined as above and alk″

is C₁-C₆ alkyl.

20. The contact lens of claim 18, wherein the prepolymer is represented by formula (1) in which r₂ is an integer of 1.

5. A method for producing soft contact lenses, comprising the steps of:

providing a mold for making a soft contact lens, wherein the mold has a first mold half with a first molding surface defining the anterior surface of a contact lens and a second mold half with a second molding surface defining the posterior surface of the contact lens, wherein said first and second mold halves are configured to receive each other such that a cavity is formed between said first and second molding surfaces;

introduce a lens-forming material into the cavity, wherein the lens-forming material comprises an actinically crosslinkable prepolymer of formula (1) or (2)