Curable colored inks for making colored silicone

Abstract

The present invention provides an actinically or thermally curable ink for making colored silicone hydrogel contact lenses. The ink of the invention comprises at least one colorant, a solvent and a binder polymer including ethylenically unsaturated groups and segments derived from at least one silicone-containing vinylic monomer or macromer. The ink of the invention is characterized by having capability to be cured actinically or thermally to form a colored coat on a silicone hydrogel contact lens, wherein the colored coat has good adhesion to the silicone hydrogel contact lens without being covalently attached to the lens material of the contact lens. The invention also provides methods for making colored silicone hydrogel contact lenses.

1 - 35 . (canceled) 
     
     
         36 . An ink for making colored contact lenses, comprising at least one colorant, a solvent and a photo-curable or thermo-curable binder polymer including ethylenically unsaturated groups and segments derived from at least one silicone-containing vinylic monomer or macromer, wherein the ink is characterized by having capability to be cured actinically or thermally to form a colored coat on a contact lens, wherein the colored coat has good adhesion to the contact lens without being covalently attached to the lens material of the contact lens. 
     
     
         37 . The ink of  claim 36 , wherein the contact lens is a silicone hydrogel contact lens. 
     
     
         38 . The ink of  claim 37 , wherein the ink has a good transferability from a mold to a contact lens. 
     
     
         39 . The ink of  claim 37 , wherein the amount of the solvent is from about 10% to 95% by weight, wherein the amount of the binder polymer is from about 1% to about 90% by weight, and wherein the amount of the colorant is about 25% by weight or less. 
     
     
         40 . The ink of  claim 37 , wherein the colorant comprises at least a pigment and/or at least a dye which is either sparingly soluble or insoluble in the solvent. 
     
     
         41 . The ink of  claim 40 , wherein the solvent is one or more organic solvents selected from the group consisting of acetone, alcohols, glycols, ketones, esters, cyclopentanone, cyclohexanone, tetrahydrofuran, acetone, methyl-2-pyrrolidone, dimethyl formamide, acetophenone, methylene dichloride, dimethyl sulfoxide, gamma-butyrolactone, ethylene dichloride, isophorone, o-dichlorobenzene, tetrahydrofuran, diacetone alcohol, methyl ethyl ketone, acetone, 2-nitropropane, ethylene glycol monoethyl ether, propylene carbonate, cyclohexanol, chloroform, trichloroethylene, 1,4-dioxane, ethyl acetate, ethylene glycol monobutyl ether, chlorobenzene, nitroethane, ethylene glycol monomethyl ether, butyl acetate, 1-butanol, methyl isobutyl ketone, nitromethane, toluene, ethanol, diethylene glycol, benzene, diethyl ether, ethanolamine, carbon tetrachloride, propylene glycol, hexane, ethylene glycol, and formamide. 
     
     
         42 . The ink of  claim 37 , wherein the binder polymer is an ethylenically functionalized derivative of a silicon-containing polymer having pendant functional groups selected from the group consisting of hydroxyl groups (—OH), primary amino groups (—NH 2 ), secondary amino groups (—NHR), carboxylic groups (—COOH), epoxy groups, aldehyde groups (—CHO), amide groups (—CONH 2 ), 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. 
     
     
         43 . The ink of  claim 42 , wherein the silicon-containing polymer is a copolymerization product of a polymerizable composition comprising: (a) at least one hydrophilic vinylic monomer; (b) at least one functionalizing vinylic monomer containing at least one functional group selected from the group consisting of hydroxyl group (—OH), primary amino group (—NH 2 ), secondary amino group (—NHR), carboxylic group (—COOH), epoxy group, aldehyde group (—CHO), amide group (—CONH 2 ), acid halide group (—COX, X═Cl, Br, or I), isothiocyanate group, isocyanate group, halide group (—X, X═Cl, Br, or I), acid anhydride group, and combinations thereof; (c) at least one silicone-containing vinylic monomer or macromer; and (d) optionally one or more components selected from the group consisting of a polymerization initiator, a chain transfer agent, and a solvent. 
     
     
         44 . The ink of  claim 43 , wherein the siloxane-containing vinylic monomers is methacryloxyalkylsiloxanes, 3-methacryloxy propylpentamethyldisiloxane, bis(methacryloxypropyl)tetramethyl-disiloxane, monomethacrylated polydimethylsiloxane, mercapto-terminated polydimethylsiloxane, N-[tris(trimethylsiloxy)silylpropyl]acrylamide, tristrimethylsilyloxysilylpropyl methacrylate (TRIS), or N-[tris(trimethylsiloxy)silylpropyl]methacrylamide. 
     
     
         45 . The ink of  claim 43 , wherein the hydrophilic vinylic monomer is hydroxyl-substituted lower alkyl(C 1  to C 8 )acrylates, hydroxyl-substituted lower alkyl(C 1  to C 8 )methacrylates, acrylamide, methacrylamide, (lower alkyl)acrylamides and (lower alkyl)methacrylamides, ethoxylated acrylates, ethoxylated methacrylates, hydroxyl-substituted (lower alkyl)acrylamides, hydroxyl-substituted (lower alkyl)methacrylamides, hydroxyl-substituted lower alkyl vinyl ethers, sodium vinylsulfonate, sodium styrenesulfonate, 2-acrylamido-2-methylpropanesulfonic acid, N-vinylpyrrole, N-vinyl-2-pyrrolidone, 2-vinyloxazoline, 2-vinyl-4,4′-dialkyloxazolin-5-one, 2- and 4-vinylpyridine, vinylically unsaturated carboxylic acids having a total of 3 to 5 carbon atoms, amino(lower alkyl)acrylates (where the term “amino” also includes quaternary ammonium), mono(lower alkylamino)(lower alkyl)acrylates, di(lower alkylamino)(lower alkyl)acrylates, amino(lower alkyl)-methacrylates (where the term “amino” also includes quaternary ammonium), mono(lower alkylamino)(lower alkyl)methacrylates, di(lower alkylamino)(lower alkyl)methacrylates, or allyl alcohol. 
     
     
         46 . The ink of  claim 43 , wherein the functionalizing vinylic monomer is methacrylic acid (MAA), acrylic acid, glycidylmethacrylate, glycidylacrylate, HEMA, HEA, methacrylic anhydride, N-hydroxymethylacrylamide (NHMA), 2-bromoethylmethacrylate, or vinylbenzylchloride. 
     
     
         47 . The ink of  claim 43 , wherein the hydrophilic vinylic monomer is devoid of functional groups. 
     
     
         48 . The ink of  claim 43 , wherein the polymerizable composition comprises a chain transfer agent selected from the group consisting mercaptoethane, mercaptoethanol, ethanedithiol, propanedithiol, and mercapto-terminated polydimethylsiloxane. 
     
     
         49 . The ink of  claim 43 , wherein the binder polymer is a reaction product of the silicon-containing polymer with an ethylenically functionalizing agent which comprises an ethylenically unsaturated group and a group capable of reacting with the functional groups of the silicone-containing polymer to form covalent linkages. 
     
     
         50 . The ink of claim of  49 , 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. 
     
     
         51 . The ink of  claim 41 , wherein the alcohol is one or more alcohols selected from the group consisting of methanol, ethanol, propanol, 2-ethoxyethanol, isopropanol, and 2-ethyoxy-ethanol.