MXPA06011295A - Colored ink for pad transfer printing of silicone hydrogel lenses - Google Patents

Abstract

The present invention provides a method for making colored silicone hydrogel contact lenses. The method of the invention comprises 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, wherein the ink comprises at least one colorant, a binder polymer, an adhesion promoter, and optionally a diluent, wherein the binder polymer is a copolymerization product of a polymerizable mixture including (I) at least one hydrophilic vinylic monomer;(II) at least one functionalizing vinylic monomer containing at least one functional group selected from the group consisting of hydroxyl group -OH, amino group -NHR (wherein R is hydrogen or C1, to C8 alkyl), carboxylic group -COON, epoxy group, amide group -CONHR, and combinations thereof;(III) at least one silicone-containing vinylic monomer or macromer, and (IV) optionally one or more components selected from the group consisting of a polymerization initiator, a chain transfer agent, and a solvent, wherein the mold has a lens-forming cavity between the molding surfaces, 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 ink printed on the mold;(c) dispensing a silicone hydrogel lens-forming material into the lens-forming cavity of the mold;(d) curing the lens-forming material within the lens-forming cavity to form the contact lens, whereby the colored coat detaches from the molding surface and becomes integral with the body of the contact lens.

Description

COLOR INK FOR IMPRESSION BY TRANSFER TAMPON FOR HIDROGEL LENSES OF SIUCONE.

The present invention relates to a method for manufacturing colored contact lenses, and in particular colored silicone hydrogel contact lenses. The present invention also relates to inks for making colored silicone hydrogel contact lenses. BACKGROUND OF THE INVENTION Various methods have been disclosed for making printing inks suitable for printing either hydrophilic (hydrogel) contact lenses or the molds that are used to make the hydrogel contact lenses. For example, U.S. Patent No. 4,668,240 to Loshaek discloses colored inks comprising at least one pigment, a binder polymer having the same functional groups (such as -COOH, -OH, or -N HR , wherein R is hydrogen or alkyl of 1 to 8 carbon atoms), and an additional compound having at least two groups per molecule selected from at least one of -NCO and epoxy. Loshaek discloses that its inks are suitable for hydrophilic contact lenses produced with a lens polymer containing one or more of the functional groups -COOH, -OH, or -NHR, wherein R is hydrogen or alkyl of 1 to 8 carbon atoms. The lenses and binder polymers are then linked together by reaction of the -COOH, -OH, or -NH-R groups of the lens or binder polymer, and the binder polymers with the -NCO or epoxy groups of the binder polymer. or the lens. Narducy et al. Disclose, in U.S. Patent No. 4,857,072, that Loshaek inks are also suitable for hydrophilic contact lenses made of a lens polymer that is substantially devoid of the -COOH functional groups, - OH, or -NH-R, wherein R is hydrogen or alkyl of 1 to 8 carbon atoms. The Patent of the United States of America Number ,272,010 to Quinn discloses an ink comprising at least one pigment, binder polymer having the same functional groups (such as -COOH, -OH, or -NH-R, wherein R is hydrogen or alkyl of 1 to 8 atoms carbon), and an adhesion promoter having at least two functional groups per molecule of the formula -CH2-OR-), wherein Ri is hydrogen or alkyl of 1 to 16 carbon atoms, and the CH2-OR groups ? they bind to a carbon atom that is part of an aromatic ring, or they bind to a nitrogen or oxygen atom. Quinn ink is suitable for hydrophilic contact lenses similar to those of U.S. Patent Nos. 4,668,240 and 4,857,072. U.S. Patent Application Publication Number 2003/0054109 to Quinn et al. Discloses an ink comprising at least one dye, and a binder polymer having latent crosslinkable pendant groups (e.g., epoxy) , hydroxyl, alkenyl, isocyanate, peroxy, perester, anhydride, silane and combinations of the same). These inks are substantially free of a kind of separate adhesion promoter such as hexamethylene di-isocyanate or hexam ethoxy-methyl-melamine, and are for hydrophilic contact lenses. However, the inks described in the prior art are for hydrogel lenses that are not silicone, and their use with silicone hydrogens would be undesirable. In recent years, silicone hydrogel contact lenses, as for example, Focus N IG HT & GIVES? R (CI BA VISION), have become increasingly popular due to the health benefits of the cornea provided by its high oxygen permeability and its comfort. The inks described in the prior art may not be compatible with silicone hydrogel lenses, because they are designed for conventional hydrogels (not silicone) and not for silicone hydrogel lenses. They can have adverse effects for the properties (for example, oxygen permeability, ion permeability, etc.) of silicone hydrogel lenses, and can even affect lens parameters such as the base curve and diameter, because they are not compatible with the polymer of the lenses. glasses. Therefore, a method for making colored silicone hydrogel contact lenses, and suitable inks for printing a high quality color image on a silicone hydrogel contact lens is necessary. BRIEF DESCRIPTION OF THE INVENTION In one aspect, the present invention comprises a method for manufacturing colored silicone hydrogel contact lenses, which comprises the steps of: (a) applying a color coating to at least a portion of at least a molding surface of a lens mold with a strip, wherein the ink comprises at least one dye, a binder polymer containing silicone, an adhesion promoter, and optionally a diluent, wherein the binder polymer containing silicone is a product of the copolymerization of a polymerizable mixture that includes: (i) at least one hydrophilic vinyl monomer; (I) at least one vinyl functionalizing monomer containing at least one functional group selected from the group consisting of hydroxyl group -OH, amino group -NHR (wherein R is hydrogen or alkyl of 1 to 8 carbon atoms ), carboxylic group -COOH, epoxy group, amide group -CONHR, and combinations thereof, (iii) at least one vinyl monomer or macromer containing silicone, and (iv) optionally one or more components selected from the group consisting of consists of a polymerization initiator, a chain transfer agent, and a solvent, wherein the mold has a cavity forming the lens between the molding surfaces, wherein the colored coating contains a first surface exposed to the interior of the cavity which forms the lens, and a second surface in contact with the molding surface; (b) cure the printed ink. on the mold; (c) dosing a silicone hydrogel-forming material into the mold-forming cavity of the mold; (d) curing the material forming the lens within the cavity forming the lens to form the contact lens, whereby the colored coating of the molding surface is detached and integrated into the body of the contact lens In another aspect, the present invention provides a method for manufacturing colored silicone hydrogel contact lenses, which comprises the steps of (a) providing a contact lens constructed of silicone hydrogel, (b) applying a color coating to at least a portion of a lens surface with an ink, wherein the ink comprises at least one dye, a binder polymer containing silicone, an adhesion promoter, one or more vinyl monomers, and optionally a diluent, wherein the silicone-containing binder polymer is a product of the copolymerization of a polymerizable mixture including: (i) at least one hydrophilic vinyl monomer; (ii) at least one vinyl functionalizing monomer containing at least one functional group selected from the group consisting of a hydroxyl group -OH, amino group -NHR (wherein R is hydrogen or alkyl of 1 to 8 carbon atoms) , carboxylic group -COOH, epoxy group, amide group -CONHR, and combinations thereof, (iii) at least one vinyl or silicone-containing monomer or macromer, and (iv) optionally one or more components selected from the group consisting of in a polymerization initiator, a chain transfer agent, and a solvent; and (c) curing the ink, thereby causing the colored coating to adhere to the lens. In a further aspect, the present invention provides an ink for printing by transfer buffer of a silicone hydrogel. In yet another aspect, the present invention provides a method for manufacturing colored silicone hydrogel contact lenses, the method comprising the steps of: (a) applying a color coating to at least a portion of at least one of the surfaces molding a lens mold with an ink, wherein the ink comprises at least one dye, a binder polymer containing silicone, and optionally a diluent, wherein the binder polymer containing silicone is a product of the copolymerization of a mixture polymerizable which includes: (i) at least one hydrophilic vinyl monomer; (I) at least one silicone-containing monomer or vinyl macromer, and (iii) optionally one or more components selected from the group consisting of a polymerization initiator, a chain transfer agent, and a solvent, wherein the The mold has a cavity forming the lens between the molding surfaces, wherein the colored coating contains a first surface exposed to the interior of the cavity forming the lens, and a second surface in contact with the molding surface.; (b) curing the printed ink on the mold; (c) dosing a silicone hydrogel lens forming material in the mold lens cavity of the mold; (d) curing the material forming the lens within the lens forming cavity to form the contact lens, whereby the colored coating is detached from the molding surface and integrated into the body of the contact lens. In addition, one or more of the mold surfaces can be treated (e.g. by corona discharge) to improve their ability to accept the ink. In still a further aspect, the present invention provides a method for manufacturing a colored silicone hydrogel contact lens, the method comprising the steps of: (a) applying a color coating to at least a portion of at least one surface of molding a lens mold with an ink, wherein the ink comprises at least one dye, a silicone-containing binder polymer, and optionally a diluent, wherein the silicone-containing binder polymer is a product of the copolymerization of a polymerizable mixture which includes: (i) at least one hydrophilic vinyl monomer; . (ii) at least one vinyl functionalizing monomer containing at least one functional group selected from the group consisting of a hydroxyl group -OH, amino group -NHR (wherein R is hydrogen or alkyl of 1 to 8 carbon atoms) , carboxylic group -COOH, epoxy group, amide group -CONHR, and combinations thereof; (iii) at least one monomer or vinyl macromer containing silicone, and (iv) optionally one or more components selected from the group consisting of a polymerization initiator, a chain transfer agent, and a solvent, in d The molding has a cavity that forms the lens between the molding surfaces, where the colored coating contains a first surface exposed to the interior of the cavity that forms the lens, and a second surface in contact with the lens. with the surface of mold eo; (b) curing the printed ink on the mold; (c) d ossifying a material for forming the silicone hydrogel lens in the mold cavity forming the lens; (d) curing the material forming the lens within the cavity that forms the lens to form the contact lens, whereby the colored coating is detached from the molding surface and integrated into the body of the contact lens. DETAILED DESCRIPTION OF THE MODALITIES OF THE I NVENTION Reference will now be made in detail to the embodiments of the invention. It will be apparent to those skilled in the art that various modifications and variations may be made in the present invention without departing from the scope or spirit of the invention. For example, the features illustrated or described as a part of one embodiment may be used in another embodiment to still produce an additional modality. Thus, it is intended that the present invention cover these modifications and variations as long as they are within the scope of the appended claims and their equivalents. Other objects, features and aspects of the present invention are described in the following detailed description or are obvious from it. A person skilled in the art will understand that the present discussion is a description solely of exemplary embodiments and is not intended to limit the broader aspects of the present invention. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by a person skilled in the art to which this invention pertains. In general, the nomenclature and laboratory procedures used herein are well known and commonly used in the art. Conventional methods are used for these procedures, such as those provided in the art and in various general references. When a singular term is provided, the inventors also contemplate the plural of that term. The nomenclature used herein and the laboratory procedures described below are well known and commonly used in this field. The invention in general relates to a method for manufacturing colored silicone hydrogel contact lenses. "Contact Lens" refers to a structure that can be placed over or inside a user's eye. A contact lens can correct, improve or alter the view of a user, but this is not necessarily the case. A contact lens may be of any suitable material known in the art or further developed, and may be a soft lens, a hard lens or a hybrid lens. A contact lens can be in the dry state or in the wet state. "Dry state" refers to a soft lens in a state prior to hydration or the state of a hard lens in storage or in conditions of use. "Wet State" refers to a soft lens in a hydrated state. The "front or front surface" of a contact lens, as used herein, refers to the surface of the lens that faces away from the eye during use. The anterior surface, which is typically substantially convex, can also be called the front curve of the lens. The "back or rear surface" of a contact lens, as used herein, refers to the surface of the lens facing towards the eye during use. The back surface, which is typically substantially concave, can also be known as the base curve of the lens. A "colored contact lens" refers to a contact lens (hard or soft) having a color image printed thereon. A color image can be a cosmetic pattern, for example, iris-like patterns, Wild Eye ™ patterns, on-demand patterns (MTO), and the like; an investment mark that allows the user to easily handle and insert a contact lens; a rotation mark; toroid marks (cylindrical shaft, counterweight axis); or units for holding contact lenses (SKUs) in storage, for example, in the form of numbers or as bar codes. A color image can be a single color image or multiple color image. A color image is preferably a digital image, but it can also be an analog image. A "hydrogel" refers to a polymeric material that can absorb at least 10 percent by weight of water when fully hydrated. Usually, a hydrogel material is obtained by the polymerization or copolymerization of at least one hydrophilic monomer in the presence or absence of additional monomers and / or macromers. A "silicone hydrogel" refers to a hydrogel obtained by the copolymerization of a polymerizable composition comprising at least one vinyl monomer containing silicone or at least one macromer containing silicone. "Hydrophilic", as used herein, describes a material or portion thereof that will be more readily associated with water than with lipids. A "monomer" means a low molecular weight compound that can be polymerized. The low molecular weight typically means average molecular weights less than 700 Daltons. A "vinyl monomer", as used herein, refers to a low molecular weight compound that has an ethylenically unsaturated group and that can be polymerized actinically or thermally. Low molecular weight typically means average molecular weights less than 700 Daltons. The term "olefinically unsaturated group" is used herein in the broad sense and is intended to encompass any group containing at least one group >; C = C < . Exemplary ethylenically unsaturated groups include, without limitation, acryloyl, methacryloyl, allyl, vinyl, styrenyl or other groups containing C = C. As used herein "actinically" with reference to the curing or polymerization of a polymerizable composition or material means that curing (e.g., crosslinking and / or polymerization) is performed by actinic irradiation, such as, . for example, ultraviolet irradiation, ionized radiation (e.g., gamma ray or X-ray irradiation), microwave irradiation, and the like. Thermal curing or actinic cure methods are well known to a person skilled in the art. A "hydrophilic vinyl monomer", as used herein, refers to a vinyl monomer, which, as a homopolymer, typically produces a polymer that is soluble in water or can absorb at least 10 percent by weight of water . A "hydrophobic vinyl monomer", as used herein, refers to a vinyl monomer, which, as a homopolymer, typically produces a polymer that is insoluble in water and can absorb less than 10 percent by weight of water. A "macromer" refers to a medium and high molecular weight compound or polymer that contains functional groups capable of undergoing further polymerization / crosslinking reactions. The average and high molecular weight typically means average molecular weights greater than 700 Daltons. Preferably a macromer contains ethylenically unsaturated groups and can be polymerized actinically or thermally. A "polymer" means a material formed by the polymerization / crosslinking of one or more monomers. In one aspect, the present invention comprises a method for manufacturing a colored silicone hydrogel contact lens, the method comprising the steps of: (a) applying a color coating to at least a portion of at least one of the surfaces of molding a lens mold with an ink, wherein the ink comprises at least one dye, a silicone-containing binder polymer, an adhesion promoter, one or more vinyl monomers or macromers, and optionally a diluent, wherein the binder polymer containing silicone is a product of the copolymerization of a polymerizable mixture that includes: (i) at least one hydrophilic vinyl monomer; (ii) at least one vinyl functionalizing monomer containing at least one functional group selected from the group consisting of a hydroxyl group -OH, amino group -NHR (wherein R is hydrogen or alkyl of 1 to 8 carbon atoms) , carboxylic group -COOH, epoxy group, amide group -CONHR, and combinations thereof; (iii) at least one silicone-containing monomer or vinyl macromer, and (iv) optionally one or more components selected from the group consisting of a polymerization initiator, a chain transfer agent, and a solvent, wherein the template it has a cavity forming the lens between the molding surfaces, wherein the colored coating contains a first surface exposed to the interior of the cavity forming the lens, and a second surface in contact with the molding surface; (b) curing the printed ink on the mold; (c) dosing a silicone hydrogel lens forming material into the mold cavity forming the lens; (d) curing the material forming the lens within the cavity forming the lens to form the contact lens, whereby the colored coating is detached from the molding surface and integrated into the body of the contact lens. "A colored coating" refers to a coating on an object and having a color image printed thereon. A color image is what is described above. Methods for making mold sections for casting a contact lens by casting are generally well known to those skilled in the art. The process of the present invention is not limited to any particular method for forming a mold. In fact, any method can be used to form a mold in the present invention. However, for illustrative purposes, the following discussion has been provided as a method for forming a mold in which a colored coating can be applied, in accordance with the present invention. In general, a mold comprises at least two sections (or portions) of mold or mold halves, that is, the first and second mold halves. The first mold half defines a first molding (or optical) surface and the second mold half defines a second molding (or optical) surface. The first and second mold halves are configured to receive each other, so that a lens forming cavity is formed between the first molding surface and the second molding surface. The molding surface of a mold half is the surface which forms the mold cavity and which is in direct contact with the material forming the lens. The first and second halves of the mold can be formed by various techniques, such as injection molding. These sections of halves can then be joined together in such a way that a cavity is formed between them. Subsequently, a contact lens can be formed within the cavity of the sections of the mold using different processing techniques, such as actinic or thermal curing. Examples of suitable processes for the formation of mold halves are described in United States of America Patents Nos. 4,444,711 for Schad; 4,460,534 to Boehm et al .; 5,843,346 for Morrill; and 5,894,002 for Boneberger et al. Virtually all materials known in the art for making molds can be used to make molds for making contact lenses. For example, polymeric materials, such as polyethylene, polypropylene, and PMMA, can be used. Other materials that allow the transmission of ultraviolet light, such as quartz glass, could be used. "Colorant" means either a dye or a pigment or a mixture thereof which is used to print a color image on an article. "Dye" means a substance that is soluble in a solvent and used to impart color. The dyes are typically translucent and absorb but do not scatter light. The dyes can cover both the optical regions of contact lenses and the non-optical regions of contact lenses. Almost any dye can be used in the present invention, as long as it can be used in an apparatus as described below. These dyes include fluorescent dyes, phosphorescent dyes and conventional dyes. "Fluorescence" means the luminescence caused by the absorption of visible light or ultraviolet radiation at a wavelength followed by the almost immediate emission of a longer wavelength. The fluorescent emission ceases almost immediately when light or incident ultraviolet radiation is stopped. "Phosphorescence" is the luminescence caused by the absorption of radiation at a wavelength followed by the delayed emission at a different wavelength. The phosphorescent emission continues for a long time after the incident radiation stops. A "pigment" means a powdered substance that is suspended in a liquid in which it is insoluble. Pigments are used to impart color. The pigments, in general, are more opaque than the dyes. The term "a non-pearlescent or conventional pigment", as used herein, is intended to describe any absorption pigment that imparts color based on the diffuse scattering optical principle, and its color is independent of its geometry. Although any suitable non-pearlescent pigment can be used, it is currently preferred that the non-pearlescent pigment be heat resistant, non-toxic and soluble in aqueous solutions. Examples of the preferred non-pearlescent pigments include any dye allowed in medical devices and approved by the FDA, such as Blue D &C Number 6, Green D &C Number 6, Violet D &C Number 2, carbazole violet, certain complexes of copper, certain chromium oxides, various iron oxides, phthalocyanine green (PCN), phthalocyanine blue (PCN), titanium dioxides, and so on. See the Marmion DM Handbook of U.S Colorants manual for a list of colorants that can be used with the present invention. A more preferred embodiment of a non-pearlescent pigment includes (CI is the color index number), without limitation, for a blue color, phthalocyanine blue (blue pigment 15: 3, Cl 74160), cobalt blue (blue pigment) 36, Cl 77343), greenish blue for toner BG (Clariant), blue Permajet B2G (Clariant); for a green color, phthalocyanine green (Pigment green 7, C.l. 74260) and chromium sesquioxide; for the colors yellow, red, brown and black, different iron oxides; PR122, PY154, for violet, carbazole violet; for black, the black Monolithic C-K (CIBA Specialty Chemicals). "Perlescence" means that it has a pearly luster, similar to a pearl in physical appearance; or that has an intermediate gray color slightly blue, almost neutral. A "pearlescent pigment" refers to a class of interference pigments (effects) that are thin transparent lamellae of a material with a low refractive index (e.g., transparent mica flakes) covered with an optically thin coating of a material of high refractive index (for example, metal oxide, such as, for example, titanium oxide or iron oxide), and which imparts color primarily based on the optical principle of thin film interference. The optically thin coating of the metal oxide may consist of a single or several thin layers of metal oxide. The optically thin coatings applied to the lamellae contribute to the interference effects, which allow the appearance to vary depending on the lighting and the observation conditions. The color is determined by the thickness of the coating, the refractive index and the illumination angle. Optically thin coatings are also responsible for the rich effect of deep gloss due to partial reflection from, and partial transmission through, the mica lamellae. This kind of pigment can provide pearlescent luster and iridescent effects. Pearlescent pigments which are mica lamellae with an oxide coating are commercially available from Englehard Corp of Iselin, NJ, under the line "Mearlin Pigments", such as "Hi-Lite Interference Colors", "Dynacolor Pearlescent Pigments", " MagnaPearl "," Flamenco "and" Celini Colors'S Other manufacturers of pearlescent dyes are: Kemira, Inc. in Savannah, Georgia, the pigments that have the trade name of "Flonac Luster Colors"; and EM Industries, Inc. of Hawthorne, N.Y., pigments that have the trade name of "Affair Luster Pigments". In the case of pearlescent pigments, it is important during processing to minimize the rupture of the lamellae and maintain a sufficient level of dispersion. Pearlescent pigments require delicate handling during mixing and can not be sprayed or subjected to prolonged mixing, grinding or high shear, as these operations can damage the pigments. The distribution of particle sizes, shape and orientation greatly influence the final appearance. Grinding, high shear mixing, or prolonged processing of pearlescent pigments, should be avoided, because these operations can lead to delamination of the metal oxide coated layer, fragmentation of the lamellae, agglomeration of the lamellae, and the compaction of the lamellae. Delamination of metal oxide, compaction, fragmentation, and agglomeration will reduce pearlescent effects. A "colorant" can be a dye or preferably a pigment. In general, the dyes may not provide the highly opaque printing that the pigment can provide. Preferably, a colorant in an ink of the invention comprises at least one pigment. A colorant can also be a mixture of two or more pigments, which in combination provide a desired color, since any color can be obtained merely by mixing two or more primary colors with each other. As defined herein, "primary colors" mean: bluish green, yellow, magenta, black and white. A colorant can also be a mixture of at least one pigment and at least one dye. A person with experience in the technique will know how to select colorants. The pigment (s) preferably have a size of 5 microns or less. Larger particles of a pigment can be milled to obtain smaller particles. Any number of methods known in the art can be used to grind the pigments. Preferred example methods for reducing the size of the pigment particles include high speed mixers, Kady mills (stator rotor dispersion device), colloid mills, homogenizers, microfluidizers, sonalators, ultrasonic mills, roll mills, balls, roller mills, vibratory ball mills, grinders, sand mills, varicinetic dispensers, three-roll mills, Banbury mixers, or other methods well known to those skilled in the art. A "binder polymer" refers to a crosslinkable polymer comprising crosslinkable groups and can be crosslinked by means of a crosslinker or after initiation by a chemical or physical means (e.g., humidity, heat, ultraviolet irradiation or the like) to trap or sticking dyes on or in a contact lens such as that term is known in the art. The term "crosslinkable groups" is used herein in a broad sense and is intended to encompass, for example, functional groups and photo-crosslinkable or thermally crosslinkable groups, which are well known to a person skilled in the art. It is well known in the art that a pair of paired crosslinkable groups can form a covalent bond or ligation under the known reaction conditions, such as, oxidation-reduction conditions, dehydration-condensation conditions, addition conditions, substitution conditions ( or displacement), free radical polymerization conditions, 2 + 2 cycle-addition conditions, Diels-Alder reaction conditions, ROMP (Ring Opening Method of Polymerization) conditions, vulcanization conditions, cationic crosslinking conditions, and conditions of epoxy hardening. For example, an amino group can be covalently linked with aldehyde (the Schiff base that is formed with the aldehyde group and the amino group can be further reduced); a hydroxyl group and an amino group can be covalently linked to a carboxyl group; a carboxyl group and a sulfo group can be covalently linked to a hydroxyl group; a mercapto group can be covalently linked to an amino group; or a carbon-carbon double bond can be covalently linked to another carbon-carbon double bond. Crosslinking can occur by other means. For example, an amino group and a hydroxyl group can be covalently linked together using a coupling agent (e.g., a carbodiimide) to form an amide linkage. Examples of the carbodiimides are 1-ethyl-3- (3-dimethyl-amino-propyl) -carbodi-imide (EDC), N, N'-d-cyclohexyl-carbodiimide (DCC), -cyclone exyl-3- (2-morpholino-ethyl) -carbod ii mide, di-isopropyl-carbodiimide, or mixtures thereof. In the carbodi-mediated coupling reaction (e.g., EDC), N-hydroxy-succinimide (NHS) or N-hydroxy-sulfo-succinimide may be desirably included to improve coupling efficiency (conjugation). The EDC couples the NHS to carboxyls, resulting in an NHS activated site on a molecule. The NHS ester formed can react with amines to form amides. Exemplary covalent bonds or linkages that are formed between pairs of crosslinkable groups, include without limitation alkene (carbon-carbon single bond), alkene (carbon-carbon double bond), ester, ether, acetal, ketal, vinyl ether, carbamate, urea, amine, amide, enamine, imine, oxime, amidine, mino-ester, carbonate, ortho-ester, phosphonate, phosphinate, sulfonate, sulfinate, sulfide, sulfate, disulfide, sulfinamide, sulfonamide, thioester, aryl, silane, siloxane , heterocycles, thiocarbonate, thiocarbamate and phospho amide. Exemplary crosslinkable groups include, without limitation, hydroxyl group, amine group, amide group, sulfhydryl group, -COOR (R and R 'are hydrogen or alkyl of 1 to 8 carbon atoms), halide (chloride, bromide, iodide) , acyl chloride, isothiocyanate, isocyanate, monochloro-triazine, dichloro-triazine, pyridine substituted by mono- or di-halogen, diazine substituted by mono- or di-halogen, phosphoramidite, maleimide, azirinide, sulfonyl halide, hydroxy ester -succinimide, hydroxy-sulfo-succinimide ester, imido-ester, hydrazine, axidonitrophenyl group, azide, 3- (2-pyridyl-dithio) -propionamide, glyoxal, aldehyde, epoxy, olefinically unsaturated radicals. The crosslinkable groups may also be convenient groups containing reactive hydrogen. The crosslinking could also be carried out by a kind of free radical generated during the ultraviolet or thermal cure of the ink. The resulting free radicals could abstract a suitable group (such as a reactive hydrogen) onto, for example, the binder polymer to form a radical which in turn reacts with another species, such as another binder polymer to form a crosslinked structure. According to the invention, a binder polymer is a binder polymer containing silicone with crosslinkable groups. A binder containing silicone is intended to describe a binder polymer prepared from a composition containing at least one silicone-containing monomer. It is found that a binder polymer containing silicone is more compatible with a silicone hydrogel lens-forming material and / or a silicone hydrogel material thus produced, than a binder polymer that does not contain silicone. An ink comprising a binder polymer containing silicone to make a colored silicone hydrogel lens, can cause less internal stress in the colored silicone hydrogel lens. In one embodiment, a silicone-containing binder polymer of the invention is a product of the copolymerization of a polymerizable mixture that includes: (i) at least one hydrophilic vinyl monomer; (I) at least one functionalizing vinyl monomer containing at least one functional group selected from the group consisting of hydroxyl group -OH, amino group -NHR (wherein R is hydrogen or alkyl of 1 to 8 carbon atoms) , carboxylic group -COOH, epoxy group, amide group -CONHR, and combinations thereof; and (iii) at least one silicone-containing monomer or vinyl macromer, one or more components selected from the group consisting of a polymerization initiator (i.e., a photoinitiator or a thermal initiator), a chain transfer agent, and a solvent. The polymerizable mixture can also include a polymerization initiator (i.e., a photoinitiator or a thermal initiator), a solvent that is preferably the solvent used in an ink, and a chain transfer agent. The optionally polymerizable mixture may include a hydrophobic vinyl monomer, for example, such as 2-ethoxy-ethyl methacrylate (EOEMA). A "photoinitiator" refers to a chemical that initiates the crosslinking / radical polymerization reaction by the use of light. Suitable photoinitiators include, without limitation, benzoin methylether, diethoxy acetophenone, benzoyl phosphine oxide, 1-hydroxy-cyclohexyl phenyl ketone, Darocur® types, and Irgacure® types, preferably Darocur® 1173, and Irgacure® 2959. A "thermal initiator" refers to a chemical that initiates the radical crosslinking / polymerization reaction by the use of heat energy. Examples of suitable thermal initiators include, but are not limited to, 2,2'-azobis- (2,4-dimethyl-pentane-nitrile), 2,2'-azobis- (2-methylene) propane-nitrile), 2,2'-azobis- (2-methyl-butane-nitride), peroxides such as benzoyl peroxide, and the like. Preferably, the thermal initiator is azobis-isobutyronitrile (AlBN), 4,4-azobis-4-cyanovaleric acid (VAZO 68), or 2,2'-azobis-isobutronitrile (VAZO 64). More preferably, the thermal initiator is azobis-isobutyronitrile (AlBN) or 2,2'-azobis-isobutyronitrile (VAZO 64). Examples of the siloxane-containing monomers include, without limitation, methacryloxy-alkyl siloxanes, 3-methacryloxy-propyl-pentamethyl-disiloxane, bis ~ (methacryloxy-propyl) -tetramethyl-disiloxane, monomethacrylated polydimethyl-siloxane, polydimethylsiloxane. terminated in mercapto, N -. [tris- (trimethyl-siloxy) -silylyl-propyl] -acrylamide, N- [tris- (tr.methyl-siloxy) -silyl-propyl] -methacrylamide, tris - (pentamethyl-disloxianyl) -3-methacrylate-propyl-silane (T2), and tris-trimethyl-silyloxy-silyl-propyl methacrylate (TRIS). A preferred siloxane-containing monomer is TRIS, which is known as 3-methacryloxy-propyl-tris- (tr ymethyl-siloxy) -salon, and is represented by CAS No. 17096-07-0. The term "TRIS" also includes dimers of 3-methacryloxy-propyl-tris- (trimethylsiloxy) -silane. Any suitable known siloxane containing macromer can be used to prepare soft contact lenses. A particularly preferred siloxane-containing macromer is selected from the group consisting of Macromer A, Macromer B, Macromer C, and Macromer D, described in U.S. Patent No. US 5,760,100. Almost any hydrophilic vinyl monomer can be used in the fluid composition of the invention. The suitable hydrophilic monomers are, without this list being exhaustive, acrylates and methacrylates of lower alkyl (of 1 to 8 carbon atoms) substituted by hydroxyl, acrylamide, methacrylamide, (lower allyl) -acrylamides and -methacrylamides, acrylates and ethoxylated methacrylates , (lower alkyl) -acrylamides and hydroxy-substituted methacrylamides, lower alkyl-vinyl-substituted hydroxyl ethers, sodium vinyl sulfonate, sodium styrene-sulfonate, 2-acrylamido-2-methyl-propan-sulfonic acid, N -vinyl-pyrrole, N-vinyl-2-pyrrolidone, 2-vinyl-oxazoline, 2-vinyl-4,4'-d¡alkyl-oxazolyl-5-one, 2- and 4-vinyl-pyridine, acids vinyl unsaturated carboxylic acids with a total of 3 to 5 carbon atoms, acrylates and methacrylates of amino- (lower alkyl) (wherein the term "amino" also includes quaternary ammonium), of mono- (lower alkyl-amino) - (lower alkyl), and di- (lower alkyl-amino) - (lower alkyl); allyl alcohol, and the like. Among the preferred hydrophilic vinyl monomers are N, N-dimethylacrylamide (DMA), 2-hydroxyethyl methacrylate (HEMA), hydroxyethyl acrylate (HEA), hydroxypropyl acrylate, hydroxypropyl methacrylate (HPMA) ), trimethyl-ammonium 2-hydroxy-propyl-methacrylate hydrochloride, dimethyl-amino-ethyl methacrylate (DMAEMA), glycerol methacrylate (GMA), N-vinyl-2-pyrrolidone (NVP), dimethyl-amino-ethyl -methacrylamide, acrylamide, methacrylamide, allyl alcohol, vinyl pyridine, N- (1,1-dimethyl-3-oxobutyl) -acrylamide, acrylic acid, and methacrylic acid. Any known suitable vinyl monomer containing at least one functional group selected from the group consisting of hydroxyl group -OH, amino group -NHR (wherein R is hydrogen or alkyl of 1 to 8 carbon atoms), carboxylic group can be used. -COOH, epoxide group, amide group -CONHR, and combinations thereof, such as the functionalizing vinyl monomer in the present invention. Preferred examples of these vinyl monomers include methacrylic acid (MAA), acrylic acid, glycidyl methacrylate, glycidyl acrylate, HEMA, HEA, and N-hydroxy-methyl-acrylamide (NHMA). It should be understood that a vinyl monomer can be used either co or hydrophilic vinyl monomer and functionalization vinyl monomer in the polymerizable composition to prepare the silicone-containing polymer with pendant functional groups. Preferably the hydrophilic vinyl monomer is devoid of functional groups (e.g., DMA, NVP). Any suitable chain transfer agent known in the present invention can be used. Examples of the preferred chain transfer agent include mercapto-ethane, mercapto-ethanol, ethane-dithiol, propane-dithiol, and mercapto-terminated polydimethylsiloxane. A solvent may be water, an organic or inorganic solvent, a mixture of various organic solvents, or a mixture of water and one or more water-soluble or water-miscible organic solvents. Any known suitable solvent can be used, as long as it can dissolve the binder of the ink of the invention and aid in the stability of the dye. Exemplary solvents include, without limitation, water, acetone, alcohols (eg, methanol, ethanol, propanol, isopropanol, etc.), glycols, ketones, esters, cyclopentanone, cyclohexanone, tetrahydrofuran, acetone, methyl-2-pyrrolidone, dimethyl formamide, acetophenone, methylene dichloride, dimethyl sulfoxide, gamma-butyrolactone, ethylene dichloride, isophorone, o-dichloro-benzene, tetrahydrofuran, diacetone alcohol, methyl ethyl ketone, acetone, 2-nitro-propane, ethylene glycol monoethyl ether, propylene carbonate, cyclohexanol, chloroform, trichloro-ethylene, 1,4-dioxane, ethyl acetate, ethylene glycol monobutyl ether, chloro-benzene, nitro-ethane, ethylene glycol monomethyl ether, butyl acetate , 1-butanol, methyl isobutyl ketone, nitro-methane, toluene, ethanol, diethylene glycol, benzene, diethyl ether, ethanolamine, carbon tetrachloride, propylene glycol, hexane, ethylene glycol, and formamide. According to the invention, the copolymerization reaction for preparing an agglutinate polymer containing silicone can be initiated by heat or actinic radiation (eg, ultraviolet), in a polymerizable mixture that includes a solvent (eg, ethanol or cyclopentanone), a thermal initiator (e.g., AlBN) or a photoinitiator, a chain transfer agent (e.g., ethyl mercaptan (EISH)), a hydrophilic vinyl monomer devoid of functional groups (e.g., DMA), u? functionalizing vinyl monomer having at least one functional group (e.g., HEMA, MAA, or glycidyl methacrylate), an alkoxy silane monomer (e.g., TRIS), and a monomethacrylated polydimethyl siloxane. Preferably, the polymerization reaction is not complete, whereby a binder polymer containing silicone dissolved in a solvent is produced, which preferably contains some unreacted residual vinyl monomers. A person skilled in the art will know very well how to control the level of polymerization.

According to a preferred embodiment of the invention, the binder polymer is not purified from the resulting solution after partial polymerization of the polymerizable mixture. The resulting solution containing binder polymer containing silicone and the residual vinyl monomers are used directly for the preparation of an ink of the invention. In another embodiment of the invention, a binder polymer containing silicone is a polyurethane and / or polyurea polymer having at least two functional groups which may be hydroxyl, amino (primary or secondary), and isocyanate groups. A polyurethane / polyurea binder polymer can be prepared by reacting (polymerizing) a mixture containing: (a) at least one amino-alkyl polyalkylene glycol (a poly- (oxyalkylene) -diamine) or a polyakylene glycol (poly- ( alkylene oxide)), or a polysiloxane capped with α, β-dihydroxy alkyl; (b) optionally at least one compound having at least two hydroxyl or amino groups (primary or secondary), (c) at least one di-isocyanate, and (d) optionally a polyisocyanate. The hydroxyl-capped polysiloxanes can be synthesized according to any known process, for example, by reacting a disiloxane or dimethoxy-dimethylsilane or diethoxy-dimethylsilane with cyclopolydimethylsiloxane under acidic conditions. Examples of amino-alkyl polyalkylene glycol are the so-called Jeffamines® compounds. The poly (alkylene glycol) is, for example, include, but is not limited to, a poly (ethylene glycol), a poly (propylene glycol), a block polymer of poly (ethylene glycol) / (polypropylene glycol), a block polymer of poly (ethylene glycol) / poly (propylene glycol) / poly (butylene glycol), a polytetrahydrofuran, a poloxamer, and mixtures thereof An "adhesion promoter" refers to a compound (or crosslinker) which comprises two or more functional groups A crosslinking molecule can be used to crosslink two or more monomers or polymer molecules Many different crosslinking reactions can be employed to cause chemical bonds between different molecules of binding polymers to entrap the pigmented particles. Most crosslinking agents are identified by bi- or multi-functional reactive groups, for example diphenolic, diepoxide, dimelamine, di-isocyanate, or dialdehyde resins. multi-functional have structures as follows: (HOH2CPh) n-R9, where Ph is a phenol group. The multi-functional epoxides have structures as follows: (CH2OCH) n-Rg. The multi-functional aldehydes have the following structure: (HCO) n-R9 or (CH3CO) n-R9. The multi-functional isocyanates have the following structure: (OCN) n-R9. Melamine resins have the following structure: (HOH2C-Mel) n -R9, where Mei is: For the above examples, R9 may be an aliphatic, alicyclic, aliphatic-alicyclic, aromatic, aliphatic-aromatic, vinyl alcohol, vinyl-butyral, or vinyl acetate hydrocarbon, and n is a greater number than 1. Mixed functional groups (i.e., an epoxide with an isocyanate) could be used. Exemplary isocyanate compounds include hexamethylene diisocyanate (HMDI), 2,4-toluene di-isocyanate, and bis- (isocyanato-phenyl) -methane. Groups containing exemplary epoxide include bisphenol, diepoxide, and epichlorohydrin. The ink of the invention preferably comprises one or more vinyl monomers or macromers, more preferably at least one monomer? Functionalization vinyl containing at least one functional group selected from the group consisting of hydroxyl group -OH, amino group -NHR (wherein R is hydrogen or alkyl of 1 to 8 carbon atoms), carboxylic group -COOH, epoxy group , amide group -CON HR, and combinations thereof, even more preferably a mixture of a functionalizing vinyl monomer, a monomer. hydrophilic vinyl, and optionally a silicone-containing monomer or vinyl macromer (for example, H EMA, DMA, and TRIS (or monometacryloxy-propyl-terminated polydimethylsiloxane)) in order to improve its compatibility with silicone hydrogels. In particular, the vinyl monomers for making a silicone hydrogel contact lens to be printed are added to the ink of the invention.

The ink of the invention may also include a thermal initiator or a photoinitiator. Any suitable photo can be used in the ink formulations. Examples of photoinitiators include, but are not limited to, Irgacure 2959, Irgacure 907, Irgacure 500, Irgacure 651, Irgacure 369, Darocur 1173, and Darocur 4265. In addition, combinations of initiators can be used. According to the invention, a diluent can be a solvent or a solution of one or more vinyl monomers. The ink of the invention may further comprise one or more components selected from the group consisting of surfactant, humectant, antimicrobial agents, antioxidant agents, anticoagulant agents, and other additives known in the art. The invention ink can be used to produce an opaque, translucent or transparent color image. According to the invention, a colored coating (with a color image) can be applied on the molding surface of one or both mold portions using any known printing technique, such as, for example, tampon transfer printing (or tampon printing) or inkjet printing. A colored coating can be applied on the molding surface defining the posterior (concave) surface of a contact lens, or on the molding surface defining the anterior surface of a contact lens, or on both portions of the mold. Preferably, a colored coating (with a color image) is applied on the molding surface defining the anterior surface of a contact lens.

Buffer transfer printing is well known in the art (see, for example, U.S. Patent Nos. 3,536,386 for Spivack, 4,582,402 and 4,704,017 for Knapp, 5,034,166 for Rawlings et al.). A typical example of this impression is as follows: An image is recorded in metal to form a cliché. The cliché is placed in a printer. As soon as it is in the printer, the cliché is inked either by an open partial electro-deposition system or by a closed ink cup that slides along the image. Then, a silicone tampon collects the inked image of the cliche and transfers the image to the contact lens. The silicone buffers are made of a material comprising silicone that can vary in elasticity. The properties of the silicone material allow the inks to adhere to the tampon temporarily and to completely peel off the tampon when contacted with a contact lens or a mold. Suitable transfer buffer printing structures include, but are not limited to, Tampo type printing structures (Tampo vario 90/130), rubber seals, thimbles, deposition sheet, direct printing or transfer printing as are known in the art.

Any known suitable silicone buffer or buffer made of any other suitable material can be used in the present invention. Silicone buffers are commercially available. However, different tampons could give different printing qualities. A person with experience in the art will know how to select a tampon for a given ink. The clichés can be made of ceramic or metals (for example, steel). When a cliche is made of steel, it would be desirable to neutralize the pH of a water-based ink (for example, adjusting the pH from 6.8 to about 7.8) by adding a regulator (such as, for example, phosphate salts). The images can be recorded in a cliché according to any method known to a person experienced in this field, for example, by chemical etching or laser abrasion, or the like. It is also desirable to clean the clichés after use employing conventional cleaning techniques known to a person skilled in the art, such as, for example., immersion in a solvent, sonication, or mechanical abrasion. The printing of contact lenses or molds for manufacturing contact lenses using an inkjet printing process are described in the published United States Patent Applications Numbers: 2001/0050753, 2001/0085934, 2003/0119943 , and 2003/0184710. After printing an ink of the invention on a molding surface of a mold, the printed ink can be cured by a chemical or physical means (e.g., moisture, heat, actinic irradiation or the like) according to the invention. It is desirable that the printed ink be cured to a degree that minimizes the loss of the pattern definition of the colored coating resulting from the subsequent filling of a lens-forming material. It should be understood that an ink of the invention should have good ability to transfer the colored layer from a mold to a contact lens and good adhesion to the molded lens. A "good possibility of transfer from a mold to a contact lens", with reference to an ink or a colored coating, means that a color image printed on a mold surface of a mold with the ink, can be transferred completely over a contact lens cured in that mold. A "good adhesion to a contact lens or a silicone hydrogel contact lens", with reference to a colored coating or an ink, means that the colored coating (with a color image) generated on the lens with the ink, You can pass at least one rubbing test with your finger, and you can preferably pass the rubbing test with your finger and a survival test in alcohol sonication. The finger rubbing test is carried out by removing the hydrated contact lens from a packing solution, for example serum, and by digitally rubbing the lens across any two fingers, or between a finger and a palm for up to about 10 seconds. The visible and microscopic observation (approximately 10X) of dye output, stain, or delamination, indicates the failure of the rub test. The sonication test in alcohol is carried out as follows. A colored contact lens is immersed in 5 milliliters of alcohol, sonicated for approximately 1 minute, and then placed in a bottle containing borate-regulated serum (BBS). After about 10 seconds, the serum is drained, and about 5 milliliters of serum is added with fresh borate. After equilibrating for approximately 5 minutes in the borate-regulated serum, the lens is inspected for signs of adhesion failure (eg, dye output, stain, or delamination). The good possibility of transfer and adhesion can be achieved by crosslinking the binder polymer to the lens polymer, and / or by forming an interpenetrating network, during the curing of the lens forming material in the mold. Interpenetrating networks are also formed when the binder polymer is crosslinked to the lens polymer. An "interpenetrating polymer network (IPN)", as used herein, refers broadly to an intimate network of two or more polymers, at least one of which is synthesized and / or crosslinked in the presence of the others. The techniques for preparing the interpenetrating polymer network are known to one skilled in the art. For a general procedure, see the Patents of the United States of North America Numbers 4,536,554; 4,983,702; 5,087,392, and 5,656,210. The polymerization is generally carried out at temperatures in the range from about room temperature to about 145 ° C. Preferably, the curing of the printed ink on the mold does not consume all the ethylenically unsaturated groups of the ink. The ethylenically unsaturated groups or other unreacted crosslinkable groups of the ink may be copolymerized with the vinyl monomers and / or macromers of the lens-forming material when the lens-forming material is cured in the mold. Without limiting this invention to any particular mechanism or theory, it is believed that the ink binders of the invention can form interpenetrating networks (IPN) with the lens material of a silicone hydrogel lens. Adhesion of an ink of the invention to the lens by forming interpenetrating networks does not require the presence of reactive functional groups in the lens polymer. First, a color image can be printed with an ink of the invention on a mold for making a contact lens, and the printed ink is cured. A lens-forming material is then dosed into the mold. The lens forming material is allowed to penetrate the cured ink, and then cured to form a colored contact lens onto which a color image is transferred from the mold. The lens material (polymer or polymers) of the colored contact lens is crosslinked in the presence of a polymer (ie, binder polymer crosslinked in the ink). In one embodiment, a transferable transparent coating can be applied to a molding surface of a mold prior to applying the ink by transfer buffer printing. A transparent transfer coating is intended to describe a coating that can be peeled from a molding surface of a mold, and can become integral with the body of a contact lens molded into the mold. A transferable transparent coating can be applied to a mold molding surface by any suitable technique, such as, for example, spraying, printing, swabbing, or dipping. A transferable transparent coating can be prepared from a solution comprising polymerizable components and free of any colorants. For example, a transferable transparent coating with a substantially uniform thickness (less than 200 microns) can be prepared by spraying a molding surface. with a solution having the composition (without colorant) of an ink to be used, or of a prepolymer solution, or of a lens-forming material to be used. This transferable coating can optionally be dried or cured to form a transferable transparent film (without pigment, but optionally with dyes, including reactive dyes). Then one or more colored patterns can be printed on this transferable transparent film or coating. By applying a transferable transparent coating prior to printing, a colored lens can be made where colored patterns printed directly below a film derived from the transferable transparent coating are embedded. This lens may be more convenient to use and may have much less susceptibility to leaching the dye away from the colored lens. Alternatively, a color image can be printed directly with an ink of the invention on a preformed silicone hydrogel contact lens, to produce a colored contact lens. The printed ink is allowed to penetrate at least partially into the material of the contact lens, and then to cure (crosslink). Healing can be activated by ultraviolet radiation or heat. The binder polymer of the ink is crosslinked in the presence of the lens material of the silicone hydrogel to form interpenetrating polymer networks. A "lens-forming material" refers to a curable composition that can be cured (i.e., polymerize and / or crosslink) thermally or actinically, to obtain a crosslinked polymer. The lens forming materials are well known to a person skilled in the art. According to the invention, a lens-forming material comprises at least one monomer or vinyl macromer containing silicone. A colored silicone hydrogel contact lens can also be produced by printing a high quality color image directly onto a contact lens, using an ink of the invention. A contact lens can be transparent before printing. Alternatively, a contact lens can be dyed before printing. That is, a colorant may have been added to that lens employing methods that are well known in the art, before printing the lens, with the use of a printing method of the invention. In another aspect, the present invention provides a method for making a colored silicone hydrogel contact lens, which comprises the steps of: (a) providing a contact lens constructed of a silicone hydrogel; (b) applying a color coating to at least a portion of a lens surface with an ink, wherein the ink comprises at least one dye, a silicone-containing binder polymer, an adhesion promoter, one or more vinyl monomers, and optionally a diluent, wherein the silicone-containing binder polymer is a product of the copolymerization of a polymerizable mixture that includes: (i) at least one hydrophilic vinyl monomer; (ii) at least one vinyl functionalizing monomer containing at least one functional group selected from the group consisting of hydroxyl group -OH, amino group -NHR (wherein R is hydrogen, or alkyl of 1 to 8 carbon atoms ), carboxylic group -COOH, epoxy group, amide group -CONHR, and combinations thereof; (iii) at least one monomer or vinyl macromer containing silicone; and (iv) optionally one or more components selected from the group consisting of a polymerization initiator, a chain transfer agent, and a solvent; and (c) curing the ink, thereby making the color coating adhere to the lens. Factors that could influence the quality of the printing and the adhesion of the ink to the lenses include, but are not limited to, the molecular weight, the molecular weight distribution, the composition of the binder polymer, the composition of the lens, the type and content of solvent in both the lens and the ink. It is expected that the solvents that swell the lens material will improve the penetration of the binder polymer into the lens. In addition, the particle size and particle size characteristics of the pigment inks can also affect print quality and adhesion. In a preferred embodiment, a method of the invention further comprises a step of applying a transparent coating that covers at least the colored portion of the lens surface. A clear coating can be formed on the colored central area or on the entire surface of the lens, by applying a layer of a transparent polymerizable solution free of any dye, on the surface of the lens, with color prints, and then polymerizing the transparent polymerizable solution layer. A clear coating can minimize the leaching of a colorant, and can improve user comfort. In a further aspect, the present invention provides an ink for printing by transfer buffer of a silicone hydrogel. The ink of the present invention also has good adhesion to a contact lens, preferably to a silicone hydrogel contact lens. The ink of the invention comprises at least one dye, a silicone-containing binder polymer, an adhesion promoter, and optionally a diluent, wherein the silicone-containing binder polymer is a product of the copolymerization of a polymerizable mixture that includes: (i) at least one hydrophilic vinyl monomer; (I) at least one functionalizing vinyl monomer containing at least one functional group selected from the group consisting of hydroxyl group -OH, amino group -NHR (wherein R is hydrogen or alkyl of 1 to 8 carbon atoms ), carboxylic group -COOH, epoxy group, amide group -CONHR, and combinations thereof; (iii) at least one silicone-containing monomer or vinyl macromer, and (v) optionally one or more components selected from the group consisting of a polymerization initiator, a chain transfer agent, and a solvent. In a preferred embodiment of the invention, an ink of the invention comprises: a solvent in an amount of about 25 percent to 99 percent by weight, preferably about 40 to 75 percent by weight, more preferably from about 50 percent to 60 percent by weight; a photocurable or thermosetting binder polymer, in an amount of about 1 percent to about 50 percent by weight, preferably from about 10 percent to about 40 percent by weight, more preferably about 20 percent at about 35 weight percent; a colorant in an amount of from about 0 percent to about 40 percent by weight, preferably from about 2 percent to about 25 percent by weight, more preferably from about 4 percent to 15 percent by weight weight; and a polymerization initiator in an amount of from about 0 percent to about 15 percent by weight, preferably from about 0.5 percent to about 10 percent by weight, and most preferably about 2 percent by weight 7 percent by weight. This invention has utility for the production of colored silicone hydrogel contact lenses. These lenses can be long-term contact lenses, daily contact lenses, and / or eye prosthetic devices. The above disclosure will make it possible for an ordinary expert in this field to practice the invention. In order to make it possible for the reader to better understand the specific modalities and their advantages, the reference to the following Examples is suggested. The percentages of the formulations are based on percentages by weight, unless otherwise specified. Example 1: Synthesis of the Macromer containing Silicone 51.5 grams (50 millimoles) of the perfluoro-polyether Fomblin® ZDOL (from Ausimont S. p.A., Milan), which has an average molecular weight of 1.030 grams / mol, and which contains 1.96 milliequivalents / gram of hydroxyl groups, according to the titration of end groups, are introduced in a three-necked flask, together with 50 milligrams of dibutyl tin dilaurate. The contents of the flask are evacuated to about 20 mbar with stirring, and subsequently decompressed with argon. This operation is repeated twice. Subsequently, 22.2 grams (0.1 moles) of freshly distilled isophorone diisocyanate kept under argon is added in a counter current of argon. The temperature of the flask is kept below 30 ° C by cooling with a water bath. After stirring overnight at room temperature, the reaction is complete. The isocyanate titration gives an NCO content of 1.40 milliequivalents / gram (theory: 1.35 milliequivalents / gram). 202 grams of the Shin-Etsu α, α-hydroxypropyl poly-dimethyl-siloxane-terminated poly-dimethylsiloxane having an average molecular weight of 2,000 grams / mol (1.00 milliequivalents / gram of hydroxyl groups) are introduced into a flask. agreement with the degree). The contents of the flask are evacuated to approximately 0. 1 mbar, and decompressed with argon. This operation is repeated twice. The degassed siloxane is dissolved in 202 milliliters of freshly distilled toluene maintained under argon, and 100 milligrams of dibutyltin dllaurate (DBTDL) are added. After complete homogenization of the solution, all the perfluoro-polyether that reacted with isophorone di-isocyanate (IPDI) under argon is added. After stirring overnight at room temperature, the reaction is complete. The solvent is removed under a high vacuum at room temperature. The microtiter shows 0.36 milliequivalents / gram of hydroxyl groups (theory: 0.37 milliequivalents / gram). 13.78 grams (88.9 mmol) of 2- isocyanate-ethyl methacrylate (IEM) under argon are added to 247 grams of the α, β-hydroxypropyl-terminated polysiloxane-perfluoro-polyether-polysiloxane copolymer copolymer (a copolymer) of three blocks in stoichiometric average, but other block lengths are also present). The mixture is stirred at room temperature for 3 days. Then, the microtiter no longer shows isocyanate groups (limit of detection: 0.01 milliequivalents / gram). 0.34 millequivalents / gram of methacryl groups are found (theory: 0.34 m / 1 equivalents / gram). The macromer prepared in this way is completely colorless and transparent. It can be stored in air at room temperature for several months in the absence of light, without changes in molecular weight.

Example 2: Synthesis of a Binding Polymer Containing Silicone A binder polymer is prepared in a single batch as follows. A mixture of the components listed in Table 1 is reacted at 40 ° C under a nitrogen flow.

Table 1 TRIS = Tris-trimethyl-silyloxy-silyl-propyl methacrylate; V68 = 4,4-azobls-4-clanovaleric acid; EtSH = Ethyl mercaptan. Preparation of the Ink Inks are prepared by mixing a binder polymer solution obtained above, without separation or purification of the binder polymer synthesized with other components according to the formulation shown in Table 2. Table 2 Blue ground PCN; # lens-forming material prepared in this example. In the ink formulations in which HDI is used, it is added at a level of approximately 4 percent. The binder and the diluent are added in a ratio (binder: diluent) in the range of 1.6: 2 to 3.4: 1, the value being adjusted to give the viscosity and color intensity necessary for a good transfer of the printing pattern to the lens. Micro-Bronze and Micro-Russet pigments are obtained from Engelhard Corporation of Iselin, New Jersey. Blue PCN and TiO2 are supplied by Sun Chemical, and the TRIS by Shin-Etsu. Lens Formation Material The siloxane-containing macromer prepared in Example 1 is used in the preparation of a lens-forming material, which comprises 25.92 percent of the siloxane-containing macromer prepared in Example 3, 1 9.25 percent of TRIS, 28.88 percent of DMA, 24.95 percent of ethanol denatured, and 1.0 percent of 2-hydroxy-2-methyl-1-phenyl-o-ene (Darocur 1 173). Preparation of Colored Silicone Glass Lenses The portions of the base curve (male mold halves) of the polypropylene lens molds are printed with tampon, with an ink listed in Table 2. In most cases, the male mold halves are treated with a crown. In some experiments, the ink printed on the male mold half is subjected to a thermal cure treatment (i.e., about 45 minutes at 85 ° C in air). The female portions of the molds are filled with approximately 1000 microllters of the prepared lens-forming material. The mold halves are combined and closed. The molds are then placed under an ultraviolet lamp for 45 minutes, and irradiated at 3.0 mW / cm2. After curing, the lenses are demoulded and hydrated in borate-regulated serum (BBS). The results are shown in Table 3. Table 3 lens formulation.

Yes Yes Good print quality, good transfer of printing to the lens.

Yes The impression remains on the mold half of the base curve.

Yes Yes The impression remains on the mold half of the base curve.

The impression remains on the half of the mold of the base curve.

Yes Yes The impression remains on the mold half of the base curve.

Yes Yes The impression remains on the mold half of the base curve.

Yes No The impression remains on the mold half of the base curve.

Yes Bad quality of printing. Good transfer of printing to the lens.

Yes No Poor printing quality. Good transfer of printing to the lens.

Yes Yes Dispersion of ink on contact with the lens formulation. 10 Yes Yes Dispersion of ink on contact with the * Molds are pre-treated with a crown. # Ink imprinted on a mold is thermally cured. Example 3: Synthesis of a Binder Polymer Containing S ilicone A binder polymer is prepared in a single batch as follows. A mixture of 20.38 percent of H EMA, 14.87 percent of TRIS, 22.1 percent of DMA, 0.1 percent of Vazo 64, 0.33 percent of EtS H, 42.1 percent of clclopentanone, is reacted to 40 ° C under a flow of nitrogen. Preparation of the Ink Activation formulations are prepared by mixing the components listed in Table 4. The inks are prepared by mixing: (1) a binder polymer solution obtained above, without separation or purification of the synthesized binder polymer, from the other non-reactive components; and (2) other components (Mearlln Microrusset 9450M pigment from Engelhard, cyclopentanone, activation formulation listed in Table 4) according to the form shown in Table 5. Table 4 Table 5 Lens Formation Material The siloxane-containing macromer prepared in Example 1 is used in the preparation of a lens-forming material, which comprises 25.92 percent of the siloxane-containing macromolecule prepared in Example 3. , 9.25 percent of TR IS, 28.88 percent of D MA, 24.95 percent of denatured ethanol, and 1.0 percent of 2-hydroxy-2-methyl-1-phenyl-o-ene Darocur 1 1 73). Preparation of Colored Silicone Hypotheses (A) Thermal Curing of the Ink. The portions of the base curve (male mold halves) of the polypropylene lens molds are printed with tampon, with ink # 17. A FreshLook color pattern is printed on the male mold halves. The ink printed on the male mold halves is subjected to a thermal cure treatment (i.e. about 45 minutes at 85 ° C in air). The female portions of the molds are filled with approximately 1000 microliters of the prepared lens-forming material. The mold halves are combined and closed. The printed pattern is completely retained, even after leaving the molds filled for 1 hour before curing. The molds are then placed under a UVA lamp for 40 minutes, and irradiation 3.0 mW / cm2 from above and below. After curing, the molds are opened, and the mold halves with lenses thereon are placed in 100 percent isopropanol for 3 hours.

After this time, the lenses are detached from the mold halves, and rinsed in deionized water twice (30 minutes each rinse cycle). All ink is transferred from the mold to the lens, and the definition of the printed pattern is completely retained. The colored lenses look cosmetically acceptable. The lenses are then placed in phosphate-regulated serum, and autoclaved at 120 ° C for 20 minutes. After autoclaving, some lenses undergo adhesion testing (both the finger rub test and the alcohol sonic survival test) as described above. All tested lenses pass the adhesion tests. (B) Ultraviolet Curing of the Ink. The portions of the base curve (male mold halves) of the polypropylene lens molds, they are printed with buffer, with an ink (ink 18 or 19 listed in Table 5). A FreshLook color pattern is pressed over the male mold halves. The printed male mold halves are placed in an ultraviolet tunnel (UVA lamps at the bottom and top) at maximum intensity (approximately 3.0 mW / cm2). Two mold halves of the ultraviolet tunnel are removed at different times, and the level of cure is verified by filling with the lens forming material in the mold (ie, the female mold halves are filled with approximately 100 microliters of the forming material of lenses prepared, and then the mold halves are combined and closed). The loss of the definition of the pattern is a sign of the uncured ink. The printed inks (with any of the inks 18 or 19) are washed out immediately after adding the lens-forming material. The base curve portions (male mold halves) of the polypropylene lens molds are printed with tampon, with an ink (ink 18 or 19 listed in Table 5). A FreshLook color pattern is printed on the male mold halves. The printed ink on the male mold half is subjected to a curing treatment with UVB (Hamamatsu lamp with 298 nanometer filter, distance of 30 millimeters from the light guide to the diffuser, 11 millimeters from the diffuser to the top of the half of the mold). Two different intensities are obtained by changing the size of an obturator aperture (100 percent aperture, estimated at approximately 60 mW / cm2; and 12 percent opening, measured at approximately 10 mW / cm2). Different exposure times are used (see Table 6), and the results of the ink curing are shown in Table 6. Table 6 Only the mold halves with ink cured therein (see Table 6) are used to make colored lenses. The hemmed portions of the glasses are filled with approximately 1, 000 microliters of prepared lens preparation material. The mold shapes of males and males are combined and closed. Then the molds are placed under a UVA lamp for 40 minutes and irradiated at 3.0 mW / cm2 from above and below. After curing, the molds are opened, and the mold halves with lenses thereon are placed in 100 percent isopropanol for 3 hours. After this time, the lenses are detached from the mold halves, and rinsed in deionized water twice. (30 minutes each rinse cycle). For both inks (inks 1 8 and 1 9), printing is not transferred completely from the mold to the lens. Most of the printed ink remains on the mold, especially in the center of the pattern, near the optical zone, while the edges are transferred better. After the steps of swelling with isopropanol and rinsing with water, the lenses show a very poor impression, and a very poor adhesion. It is believed that the difference in the possibility of transfer between the thermal and ultraviolet curing may be due to the differential consumption of ethylenically unsaturated groups of the binder polymer and the vinyl monomers, and / or due to the presence or absence of a crosslinking agent ( H DI). In the case of thermal curing, the adhesion promoter (e.g., HM DI). it reacts with the functional groups of the binder polymer and the vinyl monomers, while consuming the minimally ethylenically unsaturated groups, which may react with a lens-forming material during the curing step of the forming material. Lenses to form a lens, producing a good adhesion of the colored coating to the lens, as well as a good possibility of transferring the colored coating from the lens to the lens. Example 4: Synthesis of a Binding Polymer Containing Silicone A binder polymer is prepared in a single batch as follows. A mixture of 20.82 percent of H EMA, 15.46 percent of TRIS, 23.20 percent of DMA, 0.20 percent of azobisisobutyronitrile (Al BN), 0.22 percent EtSH, 40.1 percent of ethanol, is reacted to 55 ° C for 7 hours under nitrogen flow, then removed from heat, and stabilized with 120 parts per million TEMPO (free radical of 4-hydroxy-2,2,6,6-tetramethyl-1-pperidinyloxy) (CAS # 2226-96-2). Preparation of the Ink Paste. A pigment dispersion is prepared by grinding the pigments (3.1 1 weight percent phthalocyanine blue, 1. 8.24 weight percent titanium dioxide) with a solvent (78.65 weight percent ethanol (in a ball mill during 1 day The polymeric binder solution (61. 15 weight percent) obtained above, without separation or purification of the binder polymer synthesized from the other non-reactive components, is added to the dispersion (38.85 weight percent). to form non-reactive pastes Ink Preparation and Printing Ink paste is "activated", or made reactive, by introducing an activation solution (28.84 percent HEMA, 21.71 percent TRIS, 32.32 percent of DMA, 17.12 percent of HDI, and 0.1 percent of Vazo 64), the activation solution comprising 21 percent of the resulting ink.The activation solution is added to the paste, and mixed immediately before printing (ink A). A second ink (ink B) is prepared by: a non-reactive paste is first prepared by grinding, in a ball mill, a mixture of 24.4 percent ethyl lactate, 64.15 percent of a HEMA-based binder, 0.07 percent of PCN blue, 0.73 percent of Ti02, 1.85 percent of red iron oxide (D605), 8.77 percent of yellow iron oxide (D641); and then adding an activation solution (75.7 percent of HEMA, 8.45 percent of EOEMA, 15.42 percent of HDI, 0.43 percent of VAZO 64). The finished control ink contains 21.1 percent activation solution. The HEMA-based binder is prepared by polymerizing a composition comprising 38.33 percent HEMA, 4.20 percent EOEMA (2-ethoxyethyl methacrylate), 0.32 percent ME (2-mercaptoethanol), 0.21 percent AlBN (azobis- (isobutyronitrile)), and 56.93 percent cyclopentanone, according to a procedure similar to that described in U.S. Patent Number 4,668,240 (the polymerization reaction can be stopped by the addition of monoethyl-hydroquinone). The HEMA-based polymeric binder solution obtained above without separation or purification of the binder polymer synthesized from the other non-reactive components, is added to the ink paste, and mixed immediately before printing. Lens Formation Material. The siloxane-containing macromer prepared in Example 1 is used in the preparation of a lens-forming material, which comprises 25.92 percent of the siloxane-containing macromer prepared in Example 3, 19.25 percent of TRIS, 28.88 percent DMA, 24.95 percent denatured ethanol, and 1.0 percent 2-hydroxy-2-methyl-1-phenol-ene (Darocur 1173). Printing and Thermal Curing of the Ink. The portions of the base curve (male mold halves) of the polypropylene lens molds are printed with tampon, with an ink. The ink printed on the male mold halves is subjected to a thermal cure treatment (i.e. about 45 minutes at 85 ° C in an oven). The female portions of the molds are filled with the prepared lens-forming material. The halves of the molds are combined, closed, allowed to settle for 30 minutes to allow the lens-forming material to permeate the impression, and then cured with ultraviolet light. After curing, the molds are opened, and the mold halves with lenses thereon are placed in 100 percent isopropanol for 3 hours for extraction. After this time, the lenses are detached from the mold halves, and rinsed in deionized water twice (30 minutes each rinse cycle). The colored lenses thus produced are further subjected to plasma treatment, hydration, and sterilization. All ink is transferred from the mold to the lens, and the definition of the printed pattern is completely retained. The ink B mlgles slightly towards the bulk material of a colored lens, while the ink A remains substantially on the side of the base curve of a colored lens. The colored lenses look cosmetically acceptable. All tested lenses pass the adhesion tests (lens is swelled in isopropyl alcohol instead of methanol) and toxicity tests. All colored lenses have mechanical properties, Dk, and ionic permeability, equivalent to control lenses without impressions and made from the same lens-forming material. The parameters of the lenses (diameter, radius of base curve, central thickness) of the colored lenses printed with the ink A, have the closest match to those of the control lenses, while the parameters of the colored lenses printed with the B ink are more than one standard deviation above those of the colored lenses. The stress induced by the printing is examined as follows. A thin strip of a colored lens with impressions, or a lens without impressions, is cut in cross section, and left to equilibrate in a saline solution. Then, the shape of a thin strip of a colored lens is compared to the shape of a thin strip of an uncolored lens (control lens). It is found that cross sections of colored lenses printed with ink A or with ink B, show distortions in the form, comparing with the control lenses, indicating that there are some internal stresses induced by the impressions. However, the internal stress observed in the colored lenses printed with the ink B is more severe than that observed in the colored lenses printed with the ink A, indicating that a binder polymer containing silicone may be more compatible with a film forming material. silicone rubber lenses, and / or a silicone hydrogel material thus produced, than a binder polymer that does not contain silicone. This difference in the internal stress induced by the impression can explain the difference in the change of parameters of the lenses induced by the impressions. Example 5: Synthesis of a Binder Polymer Containing Silicone A binder polymer is prepared in a single batch as follows. A mixture of 21.21 percent HEMA, 15.75 percent TRIS, 23.63 percent DMA, 0.12 percent azobisisobutyronitrile (AlBN), 0.22 percent EtSH, 38.95 percent ethanol, is reacted at 53 ° C during 44 hours under nitrogen flow, then removed from heat, and stabilized with 1 2 parts per million TEMPO (free radical of 4-hydroxy-2,2,6,6-tetramethyl-1-piperidinyloxy) ) (CAS # 2226-96-2). Preparation of the Hazelnut Ink Plate. 5 A pigment dispersion is prepared by mixing in a ball mill a mixture of 0.07 percent PCN blue, 0.73 percent Ti02, and 1.85 percent iron oxide red ( D605), 8.77 percent iron oxide yellow (D641), 24.4 percent ethanol, and 64.15 percent of the binder polymer that contains silicone prepared above (without separation or purification of the binder polymer synthesized from the other non-reactive components). Preparation of Green Ink Paste. A pigment dispersion is prepared by grinding in a ball mill a mixture of 0.03 percent PCN blue, 8.08 percent Cr2O3 (E240), 28.5 percent ethanol, and 63.36 percent silicone-containing binder polymer. prepared above (without separation or purification of the synthesized binder polymer from the other non-reactive components). 0 Activation Solution. An activation solution is prepared to contain 29.64 percent of H EMA, 22.31 percent of TRIS, 33.21 percent of DMA, 14.83 percent of H DI, and 0.1 percent of Vazo 64. Training Material Of lenses. The siloxane-containing macromer prepared in Example 1 is used in the preparation of a lens-forming material, which comprises 25.92 percent of the siloxane-containing macromer prepared in Example 3, 19.25 percent of Tris, 28.88 percent DMA, 24.95 percent denatured ethanol, and 1.0 percent 2-hydroxy-2-methyl-1-phenyl-o-ene (Darocur 1173). Preparation of Colored Silicone Hydrogel Lenses. The ink paste is "activated", or made reactive by introducing the activation solution prepared above, the activation solution comprising 21 percent of the resulting ink. The activation solution is added to the paste, and mixed immediately before printing. The portions of the base curve (male mold halves) of the polypropylene lens molds are printed with buffer, with one of the inks prepared above. The ink printed on the male mold halves is subjected to a thermal cure treatment (i.e. about 45 minutes at 90 ° C in an oven).

The female portions of the molds are filled with the lens-forming material prepared above, and closed with the corresponding male mold halves, with the impressions cured thereon. After closing the molds, the lens forming material in each mold is cured to form a colored lens. The colored lenses thus produced are further subjected to extraction, plasma treatment, hydration, and sterilization. Different curing geometries are used, locating the male or female mold half in the lower part of the mold for curing up (above the mold), or from below (under the mold), in the experiments. There is no significant difference between all curing configurations. Parallel experiments are carried out to examine the effect of the cooling of the printed mold before filling with the lens-forming material, one with the mold halves and the impressions thereon which are cooled for 2 hours after the thermal curing of the molds. inks, and the other with the mold halves with the impressions on them without cooling after the thermal curing of the inks. There is no noticeable difference between the two experiments. In a series of experiments, the male mold halves are subjected to corona treatment before being printed with the inks. Like all other experiments with male mold halves without corona treatment, all inks are transferred from the mold to the lens, and the definition of the printed pattern is retained substantially or completely. However, with the corona treatment of the molds, the printed inks tend to remain substantially in or substantially close to the surface of the base curve of a colored lens thus produced. Without pre-treatment with the mold's crown, the printed inks may migrate slightly toward the bulk material of a colored lens thus produced. It is understood that a significant migration of the printed inks can adversely affect the cosmetic appearance of a colored lens, especially its consistency in production. Pretreatment of the molds prior to printing can reduce this migration. All colored lenses look cosmetically acceptable. All tested lenses pass the adhesion tests (lenses swollen in isopropyl alcohol instead of methanol). The internal stress induced by the printing is examined according to the procedure described in Example 4. All the colored lenses show some internal stress induced by the printing. There is some improvement in the reduction of the internal stress induced by printing with the modification of the ink formulation, compared to Example 4. Although different embodiments of the invention have been described using specific terms, devices, and methods, this description is only for illustrative purposes. The words used are description words instead of limitation. It should be understood that those skilled in the art can make changes and variations without departing from the spirit or scope of the present invention, which is stipulated in the following claims. In addition, it must be understood that aspects of the different modalities can be exchanged, either in whole or in part. Accordingly, the spirit and scope of the appended claims should not be limited to the description of the preferred versions contained therein.

Claims (30)

1. CLAIMS 1 . A method for making a colored seat chair hydrogel contact lens, which comprises the steps of: (a) applying a color coating to at least a portion of at least one of the molding surfaces of a lens mold with an ink, wherein the ink comprises at least one dye, a silicone-containing binder polymer, an adhesion promoter, and optionally a diluent, wherein the silicone-containing binder polymer is a copolymerization product of a polymerizable blend that Includes: (i) at least one hydrophilic vinyl monomer; (i) at least one vinyl functionalizing monomer, which contains at least one functional group selected from the group consisting of hydroxyl group -OH, amino group -NHR (wherein R is hydrogen or alkyl of 1 to 8 carbon atoms), carboxylic group -COOH, epoxy group, amide group -COM NRH, and combinations thereof; (Ii) at least one vinyl monomer or macromer 20 containing silicone, and (iv) optionally one or more. components selected from the group consisting of a polymerization initiator, a chain transfer agent, and a solvent, wherein the lens mold includes a first half of

   25. mold having a first molding surface defining the anterior surface of a contact lens, and a second mold half having a second molding surface defining the posterior surface of the contact lens, wherein the first and second halves of The mold is shaped to receive one another, such that a contact lens formation cavity is formed between the first and second molding surfaces, wherein the colored coating contains a first surface exposed towards the interior of the mold cavity. formation of the lens, and a second surface in contact with the molding surface; (b) partially or completely cure the printed ink on the mold, to convert the colored coating into a colored film; (c) dosing a silicone hydrogel lens forming material in the mold lens cavity of the mold; and (d) curing the lens forming material within the lens forming cavity to form the contact lens, whereby the colored film is detached from the molding surface, and becomes integral with the body of the lens. contact lens.
2. 2. The method of claim 1, wherein the hydrophilic vinyl monomer has no functional groups, wherein the functionalizing vinyl monomer is selected from the group consisting of methacrylic acid, acrylic acid, glycidyl methacrylate, glycidyl acrylate, methacrylate 2-hydroxy-ethyl, hydroxy-ethyl acrylate, hydroxy-propyl acrylate, hydroxyl-propyl methacrylate, N-hydroxy-methyl-acrylamide, and mixtures thereof.
3. 3. The method of claim 2, wherein the hydrophilic vinyl monomer is DMA or NVP.
4. 4. The method of claim 3, wherein the functional vinyl monomer is HEMA or HEA.
5. The method of claim 2, wherein the siloxane-containing monomer or macromer is methacryloxy-alkyl-siloxane, 3-methacryloxy-propyl-pentamethyl-disiloxane, bis- (methacryloxy-propyl) -tetra-methyl-disiloxane, poly mono-methacrylated dimethyl siloxane, mercapto-terminated polydimethylsiloxane, N- [tris- (trimethylsiloxy) -silylyl-propylj-acryl amide, N- [tris- (trimethylsiloxy) -syl- propyl] -methacrylamide, tris- (pentamethylldysiloxanyl) -3-methacrylate propyl silane (T2), tristrimethylsilyloxy silylpropylmethacrylate, or a combination thereof.
6. The method of claim 2, wherein the polymerizable mixture comprises a solvent, a thermal initiator, or a photoinitiator, and a chain transfer agent.
7. The method of claim 1, wherein the adhesion promoter is a diphenolic compound, a diepoxide compound, a dimethylamine compound, a di-isocyanate compound, or a dialdehyde compound, (H0H2CPh) n -R9, (CH2OCH) n -R9, (HCO) n -R9 or (CH3CO) n- R9, (OCN) n -R9, or (HOH2C-Mel) n -R9, wherein Ph is a phenol group, wherein R9 is an aliphatic radical of 1 to 35 carbon atoms, alicyclic, aliphatic-alicyclic, aromatic, or aliphatic-aromatic, a vinyl alcohol radical, a vinyl-butyral radical, or a vinyl acetate radical, wherein n is a number greater than 1, and wherein Mei is:
8. 8. The method of claim 7, wherein the adhesion promoter is hexamethylene di-isocyanate, 2,4-toluene di-isocyanate, bis- (isocyanato-phenyl) -methane, bisphenol, diepoxide, eplchlorohydrin, or combinations thereof. same.
9. The method of claim 1, wherein the ink includes one or more vinyl monomers or macromers, a photoinitiator, or a thermal initiator.
10. The method of claim 9, wherein the ink includes a mixture of vinyl monomer having a functionalizing vinyl monomer, and a hydrophilic vinyl monomer, and optionally a silicone-containing monomer or vinyl macromer, wherein the vinyl monomer of functionalization contains at least one functional group selected from the group consisting of hydroxyl group -OH, amino group -NHR (wherein R is hydrogen or alkyl of 1 to 8 carbon atoms), carboxyl group -COOH, epoxide group, group amide -CONHR, and combinations thereof.
11. The method of claim 1, wherein the color coating is applied to at least a portion of the molding surface of the first mold half.
12. The method of claim 1, wherein a colored coating is applied on at least a portion of the molding surface of each of the first and second mold halves.
13. The method of claim 12, wherein a transferable transparent coating is applied on the molding surface of the mold before step (a).
14. The method of claim 1, wherein a transferable transparent coating is applied on the molding surface of the mold before step (a).
15. 15. A method for making a colored silicone hydrogel contact lens, which comprises the steps of: (a) providing a contact lens constructed of a silicone hydrogel; (b) applying a color coating to at least a portion of a lens surface with an ink, wherein the ink comprises at least one dye, a silicone-containing binder polymer, an adhesion promoter, one or more vinyl monomers, and optionally a diluent, wherein the silicone-containing binder polymer is a copolymerization product of a polymerizable mixture that includes: (i) at least one hydrophilic vinyl monomer; (ii) at least one functionalizing vinyl monomer containing at least one functional group selected from the group consisting of hydroxyl group -OH, amino group -NHR (wherein R is hydrogen or alkyl of 1 to 8 carbon atoms) , carboxylic group -COOH, epoxy group, amide group -CONHR, and combinations thereof; (Ii) at least one monomer or vinyl macromer containing silicone; and (iv) optionally one or more components selected from the group consisting of a polymerization initiator, a chain transfer agent, and a solvent; and (c) curing the ink, thereby making the color coating adhere to the lens.
16. The method of claim 15, wherein the hydrophilic vinyl monomer has no functional groups, wherein the functional vinyl monomer is selected from the group consisting of methacrylic acid, acrylic acid, glycidyl methacrylate, glycidyl acrylate, 2-hydroxy-ethyl methacrylate, hydroxy-ethyl acrylate, hydroxy-propyl acrylate, hydroxy-propyl methacrylate, N-hydroxy-methyl-acrylamide, and mixtures thereof.
17. 17. The method of claim 16, wherein the hydrophilic vinyl monomer is DMA or NVP.
18. 18. The method of claim 17, wherein the functionalizing vinyl monomer is HEMA or HEA.
19. 19. The method of claim 16, wherein the siloxane-containing monomer or macromer is methacryloxy-alkyl-siloxane, 3-methacryloxy-propyl-pentamethyl-d-siloxane, bis- (methacryloxy-propyl) -tetramethyl- disiloxane, poly-dimethyl-siloxane mono-methacrylate, poly-dimethyl-siloxane finished in mercapto, N- [tris- (trimethylsiloxy) -silylyl-propyl-acrylamide, N- [tris- (tnmethyl-siloxy) -syl) I-pro-pil-methacrylamide, tris- (pentamethyl-d) Siloxyanil) -3-methacrylate-propyl-silane (T2), tris-trimethyl-silyloxy-silyl-propyl methacrylate, or a combination thereof.
20. The method of claim 16, wherein the polymerizable mixture comprises a solvent, a thermal initiator, or a photoinitiator, and a chain transfer agent.
21. The method of claim 15, wherein the adhesion promoter is a diphenolic compound, a diepoxide compound, a dimethylamine compound, a di-isocyanate compound, or a dialdehyde compound, (HOH2CPh) n-R9, (CH2OCH) n -R9, (HCO) n -R9 or (CH3CO) n -R9, (OCN) n -R9, or (HOH2C-Mel) n -R9, where Ph is a phenol group, wherein R9 is an aliphatic radical of 1 to 35 carbon atoms, alicyclic, aliphatic-alicyclic, aromatic, or aliphatic-aromatic, a vinyl alcohol radical, a vinyl-butyral radical, or a vinyl acetate radical, wherein n is a number greater than 1, and where Mei is:
22. 22. The method of claim 21, wherein the adhesion promoter is hexamethylene di-isoclanate, 2,4-toluene di-isocyanate, bis- (isocyanato-phenyl) -methane, bisphenol, diepoxide, epichlorohydrin, or combinations thereof. same. The method of claim 15, wherein the ink includes one or more vinyl monomers or macromers, a photoinitiator, or a thermal initiator. The method of claim 23, wherein the ink includes a mixture of vinyl monomer having a functionalizing vinyl monomer, and a hydrophilic vinyl monomer, and optionally a silicone-containing vinyl monomer or macromer, wherein the vinyl monomer functionalization contains at least one functional group selected from the group consisting of hydroxyl group -OH, amino group -NHR (wherein R is hydrogen or alkyl of 1 to 8 carbon atoms), carboxylic group -COOH, epoxide group, amide group -CONHR, and combinations thereof. 25. The method of claim 15, wherein the color coating is applied to at least a portion of the front surface of the colored silicone hydrogel contact lens. 26. The method of claim 15, wherein the method further comprises forming a transparent coating that covers at least the colored coating after step (b). 27. An ink for making colored contact lenses, which comprises at least one dye, a silicone-containing binder polymer, an adhesion promoter, a solvent, optionally a mixture of vinyl monomer, and optionally a photoinitiator or thermal initiator, wherein the silicone-containing binder polymer is: (A) a polyurethane and / or polyurea polymer containing sllicone, having at least two functional groups selected from the group consisting of hydroxyl, amino (primary or secondary), isocyanate groups , and combinations thereof, or (B) a copolymerization product of a polymerizable mixture, which includes: (i) at least one hydrophilic vinyl monomer; (1) at least one functionalizing vinyl monomer containing at least one functional group selected from the group consisting of hydroxyl group -OH, amino group -NHR (wherein R is hydrogen or alkyl of 1 to 8 carbon atoms ), carboxylic group -COOH, epoxy group, amide group -CONHR, and combinations thereof; (iii) at least one silicone-containing monomer or vinyl macromer, and (iv) optionally one or more components selected from the group consisting of a polymerization initiator, a chain transfer agent, and a solvent, wherein the polyurethane and / or polyurea polymer containing slllcone is a polymerization product of a mixture containing: (a) at least one aminoalkyl-polyalkylene glycol (a poly (oxyalkylene) -diaamine), or a polyalkylene glycol (polyol) (alkylene oxide)), or a p.olsiloxane capped at the end with a, β-dihydroxy-alkyl, (b) optionally at least one compound having at least two hydroxyl or amino groups (primary or secondary), (c) ) at least one di-isocyanate, and (d) a polyisocyanate, wherein the ink is characterized as having the ability to actinically or thermally cure, to form a colored coating on a contact lens, wherein the colored coating has a bu in adhesion to the contact lens without covalently bonding to the contact lens material. 28. An ink for making contact lenses colored, which comprises at least one dye, a binder polymer containing silicone, an adhesion promoter, a solvent, optionally a mixture of vinyl monomer, and optionally a photoinitiator or thermal initiator, in wherein the silicone-containing binder polymer is: (A) a polyurethane and / or polyurea polymer containing silicone, which has at least two functional groups selected from the group consisting of hydroxyl, amino (primary or secondary), isocyanate groups , and combinations thereof, or (B) a copolymerization product of a polymerizable mixture, which includes: (i) at least one hydrophilic vinyl monomer; (ii) at least one functionalizing vinyl monomer containing at least one functional group selected from the group consisting of hydroxyl group -OH, amino group -NHR (wherein R is hydrogen or alkyl of 1 to 8 carbon atoms) , carboxylic group -COOH, epoxy group, amide group -CONHR, and combinations thereof; (iii) at least one silicone-containing monomer or vinyl macromer, and (iv) optionally one or more compounds selected from the group consisting of a polymerization initiator, a chain transfer agent, and a solvent, wherein the polyurethane and / or poly urea polymer containing silicone is a polymerization product of a mixture containing: (a) at least one aminealkyl-polyalkylene glycol (a poly (oxyalkylene) - diam ina), or a polyalkylene glycol (poly- (alkylene oxide)), or a polysiloxane capped with α, β-dihydroxy-alkyl, (b) optionally at least one compound having at least two hydroxyl groups or amino (primary or secondary), (c) at least one dl-isocyanate, and (d) optionally a polyisocyanate, wherein the ink is characterized by having a good possibility of transfer from a mold to a hydrogel contact lens. silicone cured in the mold, and for having a good adhesion to the silicone hydrogel coniacfo lens. 29. A method for making a colored silicone hydrogel lens, which comprises the steps of: (a) applying a color coating to at least a portion of at least one of the mold surfaces of a lens mold. with a purpose, wherein the metal comprises at least one colorant, a polymer agglutinating which contains silicone, and optionally a diluent, wherein the polymer agglutinates that contains silicone is a copolymerization product of a polymerizable mixture which includes: (i) at least one hydrophilic vinyl monomer; (ii) at least one functionalizing vinyl monomer containing at least one functional group selected from the group consisting of hydroxyl group -OH, amino group -NHR (wherein R is hydrogen or alkyl of 1 to 8 carbon atoms) , carboxylic group -COOH, epoxy group, amide group -COMNHR, and combinations thereof; (iii) at least one silicone-containing vinyl monomer or macromer, and (iv) optionally one or more components selected from the group consisting of a polymerization initiator, a chain transfer agent, and a solven, wherein the Lens mold includes a first mold view that has a first molding surface that defines the lower surface of a contact lens, and a second mold half having a second molding surface that defines the back surface of the contact lens, wherein the first and second mold halves are configured to receive one another, such that a conical void forming cavity is formed between the first and second molding surfaces, wherein the colored coating contains a first surface exposed to the interior of the lens-forming cavity, and a second surface in contact with the molding surface; (b) partially or completely cure the printed matter on the mold, to convert the colored coating into a colored film; (c) dosing a silicone hydrogel lens forming material into the mold forming cavity of the mold; and (d) curing the forming material of the inner layer of the film forming cavity to form the lens of the film, whereby the colored film is detached from the molding surface, and becomes integral with the body. of the contact lens. 30. A method for making a colored seat chair hydrogel contact lens, which comprises the steps of: (a) applying a color coating to at least a portion of at least one of the mold surfaces of a mold lens with a dye, wherein the feint comprises at least one dye, a polymer agglutinates that contains silicone, and optionally a diluent, wherein the binder polymer which 15 contains silicone is a product of the copolymerization of a polymerizable mixture which includes: (i) at least one hydrophilic vinyl monomer; (ii) at least one silicone-containing monomer or vinyl macromer, and (iii) optionally one or more components selected from the group consisting of a polymerization initiator, a chain transfer agent, and a solvent, where the mold of lentils includes a first mold mifad which has a first molding surface which defines the 25 the anterior surface of a conical lens, and a second mold view having a second molding surface that defines the back surface of the contact lens, wherein the first and second mold miiades are configured to be received one at a time, in such a way that a contact lens formation cavity is formed between the first and second molding surfaces, wherein the colored coating contains a first surface exposed towards the interior of the lens forming cavity, and a second surface in a counting with the molding surface; (b) partial or complete cure printed on the mold, to convert the colored coating into a colored film; (c) dosing a silicone gel lens forming material in the mold lens cavity of the mold; and (d) curing the lens-forming material within the lens-forming cavity to form the counting lens, whereby the colored film is detached from the molding surface, and becomes integral with the body of the lens. contact lens. SUMMARY The present invention provides a method for manufacturing colored sllicone hldrogel con tamium heads. The method of the invention comprises the steps of: (a) applying a color coating to at least a portion of at least one of the molding surfaces of a lens mold with an ink, wherein the dye comprises at least one colorant, an aglyfinanter polymer, an adhesion promoter, and optionally a diluent, wherein the polymer is a product of the copolymerization of a polymerizable mixture which includes: (I) at least one hydrophilic vinyl monomer; (II) at least one functionalizing vinyl monomer containing at least one functional group selected from the group consisting of a hydroxyl group -OH, amino group -NHR (wherein R is hydrogen or alkyl of 1 to 8 carbon atoms) , carboxylic group -COON, epoxy group, amide group -CONH R, and combinations thereof; (III) at least one vinyl monomer or silicone-containing macromer, and (IV) optionally one or more selected components include the group consisting of a polymerization initiator, a chain transfer agent, and a solvent, wherein the The mold has a cavity forming the lens between the molding surfaces, wherein the colored coating contains a first surface exposed to the interior of the cavity forming the lens and a second surface in contact with the molding surface; (b) cure the printed matter on the mold; (c) dosing a silicone hydrogel lens forming material into the mold cavity forming the lens; (d) curing the lens-forming material in the cavity formed by the lens to form the conical lens, whereby the colored coating is detached from the molding surface and integrated into the body of the lens. * * * * *