Actinically curable silicone hydrogel copolymers and uses thereof

• US 20080143003A1
• Filed: 12/12/2007
• Published: 06/19/2008
• Est. Priority Date: 12/13/2006
• Status: Active Grant

• Current Assignee: Alcon Incorporated
• Original Assignee: Novartis Ag
• Inventors: Phelan, John Christopher
• Granted Patent: US 8,524,800 B2
• Time in Patent Office: Days
• US Class Current: 264/1.36
• CPC Class Codes: B29D 11/00038 Production of contact lenses
• CPC Class Codes: B29D 11/00317 Production of lenses with markings or patterns
• CPC Class Codes: B29D 11/00865 Applying coatings; tinting; colouring printing, marking or copying processes B41M; identification in general G09F3/00; producing decorative effects in general B44C; positioning or marking of lenses B24B13/0055
• CPC Class Codes: B29D 11/00923 on lens surfaces for colouring or tinting printing or marking in general B41M
• CPC Class Codes: C08F 220/14 Methyl esters , e.g. methyl (meth)acrylate
• CPC Class Codes: C08F 220/22 Esters containing halogen
• CPC Class Codes: C08F 220/26 Esters containing oxygen in addition to the carboxy oxygen
• CPC Class Codes: C08F 230/08 containing silicon
• CPC Class Codes: C09D 11/101 Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
• 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 present invention provides inks and methods for making colored silicone hydrogel contact lenses. The ink of the invention comprises an actinically-curable binder copolymer comprising fluorine-containing segments and is characterized by having capability to be cured actinically or thermally to form a colored film on a molding surface of a mold or a silicone hydrogel contact lens and by having an increased durability in a solvated state in a silicone-hydrogel lens formulation in relation to a control colored film obtained from a control ink including an actinically-curable fluorine-free binder copolymer. The invention also provides methods for making colored silicone hydrogel contact lenses based on print-on-mold processes for producing colored contact lenses.

Claims

1. An actinically-curable fluorine-containing copolymer comprising:

multiple ethylenically unsaturated groups;

hydrophilic segments derived from one or more hydrophilic vinylic monomers;

fluorine-containing segments derived from one or more fluorine-containing vinylic monomers; and

silicone-containing segments derived from at least one first silicone-containing vinylic monomer or macromer,

wherein the fluorine-containing copolymer is obtained by ethylenically functionalizing a fluorine-containing starting copolymer having pendant functional groups selected from the group consisting of hydroxyl groups (—

OH), primary amino groups (—

NH₂), secondary amino groups (—

NHR), carboxylic 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,

wherein the fluorine-containing starting copolymer with pendant functional groups is a copolymerization product of polymerizable composition (A) or (B),

wherein the composition (A) comprises (a) at least one fluorine-containing vinylic monomer, (b) at least one hydrophilic vinylic monomer, (c) at least one functionalizing vinylic monomer containing at least one functional group, and (d) at least one silicone-containing vinylic monomer or macromer, and

wherein the composition (B) comprises (a) at least one fluorine-containing vinylic monomer, (b) at least one hydrophilic vinylic monomer, (c) at least one chain transfer agent comprising a chain transfer group and a functional group to obtain a copolymerization product with functional groups.

2. The copolymer of claim 1, wherein the fluorine-containing monomer contains at least 3 fluorine atoms per monomer molecule and from about 4 to about 20 carbon atoms.

3. The copolymer of claim 2, wherein the fluorine-containing monomer is selected from the group consisting of 2-(N-ethyl-perfluorooctanesulfonamido)-ethylacrylate (FX-13), 2-(N-ethyl-perfluoro-octanesulfonamido)ethyl methacrylate (FX-14), 2,2,2-trifluoroethyl methacrylate (TEM), 1,1-dihydroperfluoroethylacrylate, 1H,1H,7H-dodecafluoroheptyl acrylate (DFHA), hexafluoroisopropyl acrylate, 1H,1H,2H,2H-heptadecafluorodecyl acrylate, pentafluorostyrene (PFS), trifluoromethylstyrene, pentafluoroethyl acrylate, pentafluoroethyl methacrylate, hexafluoroisopropyl acryrate, hexafluoroisopropyl methacrylate (HFIPMA), methacrylate-functionalized fluorinated polyethylene oxides, and a mixture thereof.

4. The copolymer of claim 1, wherein the hydrophilic vinylic monomer is selected from the group consisting of N,N-dimethylacrylamide (DMA), 2-hydroxyethylmethacrylate (HEMA), 2-hydroxyethyl acrylate (HEA), hydroxypropyl acrylate, hydroxypropyl methacrylate (HPMA), trimethylammonium 2-hydroxy propylmethacrylate hydrochloride, dimethylaminoethyl methacrylate (DMAEMA), glycerol methacrylate (GMA), N-vinyl-2-pyrrolidone (NVP), dimethylaminoethylmethacrylamide, acrylamide, methacrylamide, allyl alcohol, vinylpyridine, N-(1,1-dimethyl-3-oxobutyl)acrylamide, acrylic acid, methacrylic acid, and a mixture thereof, wherein the silicone-containing vinylic monomer is selected from the group consisting of methacryloxyalkylsiloxanes, 3-methacryloxy propylpentamethyldisiloxane, bis(methacryloxypropyl)tetramethyl-disiloxane, monomethacrylated polydimethylsiloxane, monoacrylated polydimethylsiloxane, mercapto-terminated polydimethylsiloxane, N-[tris(trimethylsiloxy)silylpropyl]acrylamide, N-[tris(trimethylsiloxy)silylpropyl]methacrylamide, and tristrimethylsilyloxysilylpropyl methacrylate, N-[tris(trimethylsiloxy)silylpropyl]methacrylamide, N-[tris(trimethylsiloxy)silylpropyl]acrylamide, 3-methacryloxy-2-hydroxypropyloxy)propylbis(trimethylsiloxy)methylsilane, (3-methacryloxy-2-hydroxypropyloxy)propyltris(trimethylsiloxy)silane, bis-3-methacryloxy-2-hydroxypropyloxypropyl polydimethylsiloxane, 3-methacryloxy-2-(2-hydroxyethoxy)propyloxy)propylbis(trimethylsiloxy)methyl-silane, N,N,N′

,N′

-tetrakis(3-methacryloxy-2-hydroxypropyl)-alpha,omega-bis-3-aminopropyl-polydimethylsiloxane, a monomethacrylated polydimethylsiloxane, a monoacrylated polydimethylsiloxane, 1,3-bis[4-vinyloxycarbonyloxy)but-1-yl]tetramethyl-disiloxane;

3-(trimethylsilyl), propyl vinyl carbonate, 3-(vinyloxycarbonylthio)propyl-[tris(trimethylsiloxy)silane], 3-[tris(trimethylsiloxy)silyl]propylvinyl carbamate, 3-[tris(trimethylsiloxy)silyl]propyl allyl carbamate, 3-[tris(trimethylsiloxy)silyl]propyl vinyl carbonate, t-butyldimethylsiloxyethyl vinyl carbonate;

trimethylsilylethyl vinyl carbonate, trimethylsilylmethyl vinyl carbonate, and combinations thereof.

5. The copolymer of claim 1, wherein the chain transfer agent is a cycloaliphatic or aliphatic thiol having from 2 to about 24 carbon atoms and having a further functional group which is amino, hydroxy or carboxy group.

6. The copolymer of claim 5, wherein the chain transfer agent is thioglycolic acid, 2-mercaptoethanol, ethanedithiol, propanedithiol, or 2-aminoethane thiol (cysteamine).

7. The copolymer of claim 1, which is obtained by reacting the fluorine-containing starting copolymer having pendant functional groups with an ethylenically functionalizing agent which comprises an iethylenically unsaturated group and a group capable of reacting with one of the functional groups of the fluorine-containing starting copolymer to form covalent linkages.

8. The copolymer of claim 7, wherein the ethylenically functionalizing agent is glycidylmethacrylate, glycidylacrylate, 2-isocyanatoethylmethacrylate (IEM), N-hydroxymethylacrylamide (NHMA), acryloylchloride, methacrylolylchloride, methacrylic acid, acrylic acid, 2-bromoethylmethacrylate, or methacrylic anhydride.

9. A method for making a colored silicone hydrogel contact lens, comprising the steps of:

(a) applying a color coat to at least a portion of at least one of molding surfaces of a lens mold with an ink comprising at least one colorant, a solvent, and a fluorine-containing binder copolymer, wherein the fluorine-containing binder copolymer comprises multiple ethylenically unsaturated groups, hydrophilic segments derived from one or more hydrophilic vinylic monomers, fluorine-containing segments derived from one or more fluorine-containing vinylic monomers, and silicone-containing segments derived from at least one first silicone-containing vinylic monomer or macromer, wherein the colored coat contains a first surface exposed to the interior of the lens-forming cavity and a second surface in contact with the molding surface;

(b) curing the color coat to form a color film which comprises a colorant-entrapping polymer network and the colorant entrapped therein, wherein the amount of the ethylenically unsaturated groups in the fluorine-containing binder polymer is high enough to ensure that the fluorine-containing binder copolymer can be crosslinked actinically or thermally to form the colorant-entrapping polymer network capable of entrapping the colorant in the ink;

(c) dispensing a lens-forming material into the lens-forming cavity of the mold, wherein the lens-forming material comprises at least one second silicone-containing vinylic monomer or macromer or a silicone-containing prepolymer; and

(d) curing the lens-forming material within the lens-forming cavity to form the silicone hydrogel contact lens, whereby the colored coat detaches from the molding surface and becomes integral with the body of the silicone hydrogel contact lens.

10. The method of claim 9, wherein the fluorine-containing binder copolymer is obtained by ethylenically functionalizing a fluorine-containing starting copolymer having pendant functional groups selected from the group consisting of hydroxyl groups (—

OH), primary amino groups (—

NH₂), secondary amino groups (—

NHR), carboxylic 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.

11. The method of claim 10, wherein the fluorine-containing starting copolymer with pendant functional groups is a copolymerization product of polymerizable composition (A) or (B), wherein the composition (A) comprises (a) at least one fluorine-containing vinylic monomer, (b) at least one hydrophilic vinylic monomer, (c) at least one functionalizing vinylic monomer containing at least one functional group, and (d) at least one silicone-containing vinylic monomer or macromer, and

wherein the composition (B) comprises (a) at least one fluorine-containing vinylic monomer, (b) at least one hydrophilic vinylic monomer, (c) at least one chain transfer agent comprising a chain transfer group and a functional group to obtain a copolymerization product with functional groups.

12. The method of claim 10, wherein before applying the color coat, a clear solution which comprises polymerizable components and is free of colorant is applied to a molding surface of a mold to form a transferable clear coating onto which the color coat can be applied.

13. The method of claim 12, wherein the clear solution includes the actinically-curable fluorine-containing copolymer.

14. The method of claim 9, wherein the lens-forming material is a solution, solvent-free liquid, or melt of one or more silicone-containing prepolymers with ethylenically unsaturated groups optionally in presence of other components, wherein the mold is a reusable mold, wherein the lens-forming material is cured actinically under a spatial limitation of actinic radiation to form a contact lens.

15. An ink for making colored contact lenses, comprising:

at least one colorant,

a solvent, and

a fluorine-containing binder copolymer,

wherein the fluorine-containing binder copolymer comprises multiple ethylenically unsaturated groups, hydrophilic segments derived from one or more hydrophilic vinylic monomers, fluorine-containing segments derived from one or more fluorine-containing vinylic monomers, and silicone-containing segments derived from at least one silicone-containing vinylic monomer or macromer,

wherein the amount of the ethylenically unsaturated groups in the fluorine-containing binder polymer is high enough to ensure that the fluorine-containing binder copolymer can be crosslinked actinically or thermally to form a colorant-entrapping polymer network capable of entrapping the colorant in the ink, wherein the ink is characterized by having capability to be cured actinically or thermally to form a colored film on a molding surface of a mold, wherein the colored film comprises the colorant-entrapping polymer network and the colorant entrapped therein, wherein the colored film is characterized by having an increased durability in a solvated state in a silicone-hydrogel lens formulation in relation to a control colored film obtained from a control ink including an actinically-curable fluorine-free binder copolymer, wherein the colored film has good adhesion to the contact lens without being covalently attached to the lens material of the contact lens.

16. The ink of claim 15, wherein the fluorine-containing binder copolymer is obtained by ethylenically functionalizing a fluorine-containing starting copolymer having pendant functional groups selected from the group consisting of hydroxyl groups (—

OH), primary amino groups (—

NH₂), secondary amino groups (—

NHR), carboxylic 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.

17. The ink of claim 16, wherein the fluorine-containing starting copolymer with pendant functional groups is a copolymerization product of polymerizable composition (A) or (B),

wherein the composition (A) comprises (a) at least one fluorine-containing vinylic monomer, (b) at least one hydrophilic vinylic monomer, (c) at least one functionalizing vinylic monomer containing at least one functional group, and (d) at least one silicone-containing vinylic monomer or macromer, and

wherein the composition (B) comprises (a) at least one fluorine-containing vinylic monomer, (b) at least one hydrophilic vinylic monomer, (c) at least one chain transfer agent comprising a chain transfer group and a functional group to obtain a copolymerization product with functional groups.

18. The ink of claim 17, wherein the fluorine-containing monomer contains at least 3 fluorine atoms per monomer molecule and from about 4 to about 20 carbon atoms.

19. The ink of claim 17, wherein the fluorine-containing monomer is selected from the group consisting of 2-(N-ethyl-perfluorooctanesulfonamido)-ethylacrylate (FX-13), 2-(N-ethyl-perfluoro-octanesulfonamido)ethyl methacrylate (FX-14), 2,2,2-trifluoroethyl methacrylate (TEM), 1,1-dihydroperfluoroethylacrylate, 1H,1H,7H-dodecafluoroheptyl acrylate (DFHA), hexafluoroisopropyl acrylate, 1H,1H,2H,2H-heptadecafluorodecyl acrylate, pentafluorostyrene (PFS), trifluoromethylstyrene, pentafluoroethyl acrylate, pentafluoroethyl methacrylate, hexafluoroisopropyl acrylate, hexafluoroisopropyl methacrylate (HFIPMA), methacrylate-functionalized fluorinated polyethylene oxides, and a mixture thereof, wherein the hydrophilic vinylic monomer is selected from the group consisting of N,N-dimethylacrylamide (DMA), 2-hydroxyethylmethacrylate (HEMA), 2-hydroxyethyl acrylate (HEA), hydroxypropyl acrylate, hydroxypropyl methacrylate (HPMA), trimethylammonium 2-hydroxy propylmethacrylate hydrochloride, dimethylaminoethyl methacrylate (DMAEMA), glycerol methacrylate (GMA), N-vinyl-2-pyrrolidone (NVP), dimethylaminoethylmethacrylamide, acrylamide, methacrylamide, allyl alcohol, vinylpyridine, N-(1,1dimethyl-3-oxobutyl)acrylamide, acrylic acid, methacrylic acid, and a mixture thereof, wherein the silicone-containing vinylic monomer is selected from the group consisting of methacryloxyalkylsiloxanes, 3-methacryloxy propylpentamethyldisiloxane, bis(methacryloxypropyl)tetramethyl-disiloxane, monomethacrylated polydimethylsiloxane, monoacrylated polydimethylsiloxane, mercapto-terminated polydimethylsiloxane, N-[tris(trimethylsiloxy)silylpropyl]acrylamide, N-[tris(trimethylsiloxy)silylpropyl]methacrylamide, and tristrimethylsilyloxysilylpropyl methacrylate, N-[tris(trimethylsiloxy)silylpropyl]methacrylamide, N-[tris(trimethylsiloxy)silylpropyl]acrylamide, 3-methacryloxy-2-hydroxypropyloxy)propylbis(trimethylsiloxy)methylsilane, (3-methacryloxy-2-hydroxypropyloxy)propyltris(trimethylsiloxy)silane, bis-3-methacryloxy-2-hydroxypropyloxypropyl polydimethylsiloxane, 3-methacryloxy-2-(2-hydroxyethoxy)propyloxy)propylbis(trimethylsiloxy)methyl-silane, N,N,N′

,N′

-tetrakis(3-methacryloxy-2-hydroxypropyl)-alpha,omega-bis-3-aminopropyl-polydimethylsiloxane, a monomethacrylated polydimethylsiloxane, a monoacrylated polydimethylsiloxane, 1,3-bis[4-vinyloxycarbonyloxy)but-1-yl]tetramethyl-disiloxane;

3-(trimethylsilyl), propyl vinyl carbonate, 3-(vinyloxycarbonylthio)propyl-[tris(trimethylsiloxy)silane], 3-[tris(trimethylsiloxy)silyl]propylvinyl carbamate, 3-[tris(trimethylsiloxy)silyl]propyl allyl carbamate, 3-[tris(trimethylsiloxy)silyl]propyl vinyl carbonate, t-butyldimethylsiloxyethyl vinyl carbonate;

trimethylsilylethyl vinyl carbonate, trimethylsilylmethyl vinyl carbonate, and combinations thereof.

20. A silicone hydrogel contact lens comprising a silicone hydrogel material which is a copolymerization product of a polymerizable composition comprises:

an actinically-curable fluorine-containing copolymer, wherein the actinically-curable fluorine-containing copolymer is obtained by ethylenically functionalizing a fluorine-containing starting copolymer having pendant functional groups selected from the group consisting of hydroxyl groups (—

OH), primary amino groups (—

NH₂), secondary amino groups (—

NHR), carboxylic 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, wherein the fluorine-containing starting copolymer with pendant functional groups is a copolymerization product of polymerizable composition (A) or (B),

wherein the composition (A) comprises (a) at least one fluorine-containing vinylic monomer, (b) at least one hydrophilic vinylic monomer, (c) at least one functionalizing vinylic monomer containing at least one functional group, and (d) at least one silicone-containing vinylic monomer or macromer, and wherein the composition (B) comprises (a) at least one fluorine-containing vinylic monomer, (b) at least one hydrophilic vinylic monomer, (c) at least one chain transfer agent comprising a chain transfer group and a functional group to obtain a copolymerization product with functional groups.

21. The contact lens of claim 20, wherein the fluorine-containing monomer contains at least 3 fluorine atoms per monomer molecule and from about 4 to about 20 carbon atoms.

22. The contact lens of claim 21, wherein the fluorine-containing monomer is selected from the group consisting of 2-(N-ethyl-perfluorooctanesulfonamido)-ethylacrylate (FX-13), 2-(N-ethyl-perfluoro-octanesulfonamido)ethyl methacrylate (FX-14), 2,2,2-trifluoroethyl methacrylate (TEM), 1,1-dihydroperfluoroethylacrylate, 1H,1H,7H-dodecafluoroheptyl acrylate (DFHA), hexafluoroisopropyl acrylate, 1H,1H,2H,2H-heptadecafluorodecyl acrylate, pentafluorostyrene (PFS), trifluoromethylstyrene, pentafluoroethyl acrylate, pentafluoroethyl methacrylate, hexafluoroisopropyl acrylate, hexafluoroisopropyl methacrylate (HFIPMA), methacrylate-functionalized fluorinated polyethylene oxides, and a mixture thereof.

23. The contact lens of claim 20, wherein the hydrophilic vinylic monomer is selected from the group consisting of N,N-dimethylacrylamide (DMA), 2-hydroxyethylmethacrylate (HEMA), 2-hydroxyethyl acrylate (HEA), hydroxypropyl acrylate, hydroxypropyl methacrylate (HPMA), trimethylammonium 2-hydroxy propylmethacrylate hydrochloride, dimethylaminoethyl methacrylate (DMAEMA), glycerol methacrylate (GMA), N-vinyl-2-pyrrolidone (NVP), dimethylaminoethylmethacrylamide, acrylamide, methacrylamide, allyl alcohol, vinylpyridine, N-(1,1dimethyl-3-oxobutyl)acrylamide, acrylic acid, methacrylic acid, and a mixture thereof, wherein the chain transfer agent is a cycloaliphatic or aliphatic thiol having from 2 to about 24 carbon atoms and having a further functional group which is amino, hydroxy or carboxy group, wherein the silicone-containing vinylic monomer is selected from the group consisting of methacryloxyalkylsiloxanes, 3-methacryloxy propylpentamethyldisiloxane, bis(methacryloxypropyl)tetramethyl-disiloxane, monomethacrylated polydimethylsiloxane, monoacrylated polydimethylsiloxane, mercapto-terminated polydimethylsiloxane, N-[tris(trimethylsiloxy)silylpropyl]acrylamide, N-[tris(trimethylsiloxy)silylpropyl]methacrylamide, and tristrimethylsilyloxysilylpropyl methacrylate, N-[tris(trimethylsiloxy)silylpropyl]methacrylamide, N-[tris(trimethylsiloxy)silylpropyl]acrylamide, 3-methacryloxy-2-hydroxypropyloxy)propylbis(trimethylsiloxy)methylsilane, (3-methacryloxy-2-hydroxypropyloxy)propyltris(trimethylsiloxy)silane, bis-3-methacryloxy-2-hydroxypropyloxypropyl polydimethylsiloxane, 3-methacryloxy-2-(2-hydroxyethoxy)propyloxy)propylbis(trimethylsiloxy)methyl-silane, N,N,N′

,N′

-tetrakis(3-methacryloxy-2-hydroxypropyl)-alpha,omega-bis-3-aminopropyl-polydimethylsiloxane, a monomethacrylated polydimethylsiloxane, a monoacrylated polydimethylsiloxane, 1,3-bis[4-vinyloxycarbonyloxy)but-1-yl]tetramethyl-disiloxane;

3-(trimethylsilyl), propyl vinyl carbonate, 3-(vinyloxycarbonylthio)propyl-[tris(trimethylsiloxy)silane], 3-[tris(trimethylsiloxy)silyl]propylvinyl carbamate, 3-[tris(trimethylsiloxy)silyl]propyl allyl carbamate, 3-[tris(trimethylsiloxy)silyl]propyl vinyl carbonate, t-butyldimethylsiloxyethyl vinyl carbonate;

trimethylsilylethyl vinyl carbonate, trimethylsilylmethyl vinyl carbonate, and combinations thereof.

24. The contact lens of claim 20, which is obtained by reacting the fluorine-containing starting copolymer having pendant functional groups with an ethylenically functionalizing agent which comprises an ethylencially unsaturated group and a group capable of reacting with one of the functional groups of the fluorine-containing starting copolymer to form covalent linkages.

25. The contact lens of claim 34, wherein the ethylenically functionalizing agent is glycidylmethacrylate, glycidylacrylate, 2-isocyanatoethylmethacrylate (IEM), N-hydroxymethylacrylamide (NHMA), acryloylchloride, methacrylolylchloride, methacrylic acid, acrylic acid, 2-bromoethylmethacrylate, or methacrylic anhydride.