Ink composition for cosmetic contact lenses

Abstract

To provide cosmetic contact lenses such as cosmetic silicone hydrogel contact lenses, without causing ink to significantly smear or rub off due to friction.SOLUTION: There are provided an ink composition for manufacturing cosmetic contact lenses, cosmetic contact lenses, and a method for preparing and using the ink composition and the cosmetic contact lenses. The ink composition contains (a) a coloring agent and (b) a non-reactive hydrophilic polymer.SELECTED DRAWING: None

Description

Technical Field

[0001] (Cross - Reference to Related Applications) This application claims priority to U.S. Patent Application No. 16 / 987,673, filed on August 7, 2020, and U.S. Provisional Patent Application No. 62 / 899,311, filed on September 12, 2019, the entireties of which are incorporated herein by reference.

[0002] (Field of the Invention) The present invention relates to cosmetic contact lenses, and more particularly to an ink composition that can be used to produce cosmetic contact lenses such as cosmetic silicone hydrogel lenses.

Background Art

[0003] For cosmetic purposes, it is known to use colored hydrogel contact lenses to change the natural color of the eyes. Ink compositions used to manufacture colored hydrogel contact lenses typically consist of a binder polymer and a colorant. Known ink compositions for cosmetic lenses are generally designed for conventional (non - silicone) lenses.

[0004] In recent years, contact lenses formed from silicone hydrogel have become popular. These contact lenses have higher oxygen permeability than conventional hydrogels. The improved oxygen permeability has reduced the symptoms of hypoxia in contact lens users wearing them. Unfortunately, the processes used to manufacture conventional hydrogel lenses do not function well enough to consistently manufacture silicone hydrogel contact lenses. An example of such a process is the manufacture of cosmetic silicone hydrogel contact lenses.

[0005] Providing cosmetic contact lenses such as cosmetic silicone hydrogel contact lenses without significant bleeding or rubbing off of the ink, and an ink composition compatible with the base lens material is an advancement in the art.

Summary of the Invention

Means for Solving the Problems

[0006] The present invention provides an ink composition containing a colorant, a non-reactive hydrophilic polymer, and optionally a binder polymer. When used, for example, in a silicone hydrogel contact lens, the ink composition provides a contact lens that is round (not distorted), and when applied to the lens, the ink does not smear and is not easily rubbed off. Thus, the ink composition is well-suited for the manufacture of cosmetic contact lenses.

[0007] Accordingly, in one aspect, the present invention provides an ink composition for making a cosmetic contact lens. The ink composition includes (a) a colorant, (b) a non-reactive hydrophilic polymer, and optionally (c) a binder polymer. The binder polymer may include a polymer formed from at least one hydrophilic monomer containing a functional group selected from the group consisting of hydroxyalkyl, aminoalkyl, and mixtures thereof, at least one silicone-containing macromer, and optionally a silicone-containing monomer.

[0008] In another aspect, the present invention provides a cosmetic contact lens. The cosmetic contact lens includes a contact lens having the ink composition described herein applied thereon. As is apparent, the cosmetic contact lens may optionally include a multi-layer ink composition (e.g., 2, 3, or 4 layers) having a multi-layer clear coat, and the composition of the multi-layer ink composition containing the pigments used may be the same or different. The cosmetic contact lens may further include an additional layer thereon that includes a layer containing a pigment but not containing a non-reactive hydrophilic polymer.

[0009] In a further aspect, the present invention provides a method for manufacturing a cosmetic contact lens. The method comprises: (i) applying a clear coat to the lens-forming surface of a first lens-forming mold; (ii) applying the ink composition described herein to the clear coat; (iii) optionally repeating step (i), step (ii), or both step (i) and step (ii); (iv) dispensing a lens material onto the first lens-forming mold; (v) applying a second lens-forming mold; and (vi) curing the lens material to form a cosmetic contact lens. comprises.

Embodiments for Carrying Out the Invention

[0010] It should be understood that the present invention is not limited to the details of the structures or process steps described in the following description. The present invention is capable of other embodiments and can be carried out or implemented in various ways using the teachings described herein.

[0011] As described above, in one aspect, the present invention provides an ink composition. The inventors have found that a cosmetic contact lens, such as a cosmetic silicone hydrogel contact lens having advantageous properties, can be manufactured using the ink composition described herein. For example, such lenses exhibit little or no haze, indicating good compatibility between the materials of the ink composition and the base lens. In addition, the ink exhibits little or no smearing or rubbing off of the ink. Furthermore, the ink composition does not adversely affect the shape of the lens. Thus, the lens generally retains its round shape.

[0012] Regarding the terms used in this disclosure, the following definitions are provided.

[0013] Unless otherwise defined, all scientific and technical terms used in this specification have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The definition of a polymer conforms to the definition disclosed in Compendium of Polymer Terminology and Nomenclature, IUPAC Recommendations 2008, edited by: Richard G. Jones, Jaroslav Kahovec, Robert Stepto, Edward S. Wilks, Michael Hess, Tatsuki Kitayama, and W. Val Metanomski. All publications, patent applications, patents, and other references mentioned in this specification are hereby incorporated by reference into this specification.

[0014] As used herein, the term “(meth)” means an optional methyl substitution. Thus, terms such as “(meth)acrylate” mean both methacrylate and acrylate.

[0015] Unless otherwise stated, ratios, percentages, parts, etc. are by weight.

[0016] Unless otherwise stated, a numerical range such as “2 - 10” includes the numbers defining the range (e.g., 2 and 10).

[0017] The term “contact lens” refers to an ophthalmic device that can be placed on the cornea of an individual's eye. A contact lens can provide corrective, cosmetic, or therapeutic benefits, including wound healing, delivery of drugs or nutritional supplements, diagnostic evaluation or monitoring, ultraviolet absorption, reduction of visible light or glare, or any combination thereof. A contact lens can be made of any suitable material known in the art and can be a soft lens, a hard lens, or a hybrid lens containing at least two distinct parts having different physical, mechanical, or optical properties such as modulus of elasticity, water content, light transmission, or combinations thereof.

[0018] The lens of the present invention may be composed of a silicone hydrogel or a conventional hydrogel. A silicone hydrogel typically contains at least one hydrophilic monomer and at least one silicone-containing component that are covalently bonded to each other within the cured device.

[0019] The ink composition according to the present invention comprises (a) a colorant, (b) a non-reactive hydrophilic polymer, and optionally (c) a binder polymer.

[0020] The colorant for use in the ink composition of the present invention may be any organic or inorganic pigment or dye suitable for use in contact lenses, or a combination of such pigments and / or dyes. Opacity can be controlled by varying the concentration of the colorant in the composition, with opacity increasing as the amount increases. Exemplary colorants include, but are not limited to, phthalocyanine blue, phthalocyanine green, carbazole violet, vat orange #1, iron oxide black, iron oxide brown, iron oxide yellow, iron oxide red, titanium dioxide, dichlorotriazine, vinyl sulfone-based dyes, and mixtures of two or more of these. Useful dyes and pigments are commercially available.

[0021] The ink composition of the present invention comprises at least one non-reactive hydrophilic polymer. "Non-reactive" means that when the hydrophilic polymer is used in the formulation, it does not contain free-radical polymerizable groups that can copolymerize with other components in the formulation under the free-radical polymerization conditions described herein. Without being bound by theory, the non-reactive hydrophilic polymer is thought to help stabilize the colorant within the ink composition.

[0022] The non-reactive hydrophilic polymer can be a polyamide. As used herein, the term "polyamide" refers to polymers and copolymers containing repeating units that contain amide groups. Polyamides can include cyclic amide groups, acyclic amide groups, and combinations thereof. Acyclic polyamides contain pendant acyclic amide groups. Cyclic polyamides contain cyclic amide groups.

[0023] Examples of suitable acyclic polyamides include polymers and copolymers containing repeating units of formulas G1 and G2,

[0024]

Chemical formula

[0025] R 40 and R 41 are independently selected from H, substituted or unsubstituted C 1 ~C 2 alkyl groups. X may be a direct bond, R 40 and R 41 are independently selected from H, substituted or unsubstituted C 1 ~C 2 alkyl groups. R 42 and R 43 are independently selected from H, substituted or unsubstituted C 1 ~C 2 alkyl groups, methyl, ethoxy, hydroxyethyl, and hydroxymethyl.

[0026] The acyclic polyamide may contain a majority of the repeating units of formula G1 or formula G2, or the acyclic polyamide may contain at least about 70 mol% and at least 80 mol% of at least 50 mol% of the repeating units of formula G1 or formula G2. Specific examples of the repeating units of formula G1 and formula G2 include N-vinyl-N-methylacetamide, N-vinylacetamide, N-vinyl-N-methylpropionamide, N-vinyl-N-methyl-2-methylpropionamide, N-vinyl-2-methyl-propionamide, N-vinyl-N,N'-dimethylurea, N,N-dimethylacrylamide, methacrylamide, and repeating units derived from the acyclic amides of formula G3 and G4.

[0027]

Chemical formula

[0028] Examples of suitable cyclic amides that can be used to form cyclic polyamides include α-lactam, β-lactam, γ-lactam, δ-lactam, and ε-lactam. Examples of suitable cyclic polyamides include polymers and copolymers containing repeating units of formula G5,

[0029]

Chemical formula

[0030] The cyclic polyamide can contain 50 mol% or more of the repeating units of formula G5, or the cyclic polyamide can contain at least 50 mol% of the repeating units of formula G5, including at least 70 mol% and at least 80 mol%.

[0031] The polyamide may also be a copolymer containing repeating units of both cyclic amides and acyclic amides. The polyamide may be selected from the group consisting of polyvinylpyrrolidone (PVP), polyvinylmethylacetamide (PVMA), polydimethylacrylamide (PDMA), polyvinylacetamide (PNVA), poly(hydroxyethyl (meth)acrylamide), polyacrylamide, and copolymers and mixtures thereof. The polyamide may be a mixture of PVP (e.g., PVP K90) and PVMA (e.g., having an M of about 570KDa). w having).

[0032] A preferred non-reactive hydrophilic polymer is PVP. PVP polymers suitable for use in the present invention are commercially available or can be readily prepared by those skilled in the art. A preferred commercially available PVP is PVP K30 having a weight average molecular weight of about 55,000 daltons. Another preferred commercially available PVP is PVP K60 having a weight average molecular weight of about 400,000 daltons. Even more preferred is a mixture of PVP K30 and PVP K60. PVP K30 and PVP K90 can be used in various weight ratios, for example, in the range of PVP K30:PVP K90 weight ratios of 5:1 to 1:5, or 4:1 to 1:1, or 3:1 to 1:1, or 2:1 to 1:1. For example, the PVP K30:PVP K90 weight ratio can be 3:1, or 2:1, or 1.7:1, or 1:1.

[0033] Exemplary non-reactive hydrophilic polymers that can be used in the ink composition of the present invention include, but are not limited to, dextran, poly(ethylene oxide), polyvinyl alcohol (PVA), poly(N-isopropylacrylamide), poly(oligoethylene oxide), polyethylene glycol (PEG), poly(N,N-dimethylaminoethyl acrylate), poly(imine), poly(acrylic acid), or a mixture of two or more of these.

[0034] Preferably, the non-reactive hydrophilic polymer has a weight average molecular weight of about 30,000 to about 500,000, or about 40,000 to about 80,000, or about 50,000 to about 60,000. Suitable molecular weight ranges may include, for example, 40,000 to 500,000, or 40,000 to 80,000, or 200,000 to 500,000.

[0035] The ink composition may contain a total amount of at least 1 wt%, or at least 2 wt%, or at least 3 wt% of all non-reactive hydrophilic polymers based on the total weight of the ink composition (including the solvent). The ink composition may contain a total amount of all non-reactive hydrophilic polymers of 50% or less, or 40% or less, or 35% or less, or 25% or less, or 20% or less, or 15% or less, or 10% or less based on the total weight of the ink composition (including the solvent). For example, the total amount of all non-reactive hydrophilic polymers may range from 1% to 40%, or from 3% to 35%.

[0036] The ink composition of the present invention may contain a binder polymer. The binder polymer may include a copolymer formed from at least one hydrophilic monomer containing a functional group selected from the group consisting of hydroxyalkyl, aminoalkyl, and mixtures thereof, at least one silicone-containing macromer, and optionally a silicone-containing monomer.

[0037] The binder polymer is C 2 ~C 8Linear or branched hydroxyalkyl (meth)acrylate, C 2 ~C 8 Linear or branched dihydroxyalkyl (meth)acrylate, C 2 ~C 8 Linear or branched trihydroxyalkyl (meth)acrylate, N-C 2 ~C 6 Linear or branched hydroxyalkyl (meth)acrylamide, N,N-bisC 2 ~C 6 Linear or branched hydroxyalkyl (meth)acrylamide, N-C 2 ~C 8 Linear or branched dihydroxyalkyl (meth)acrylamide, N,N-bisC 2 ~C 8 Linear or branched dihydroxyalkyl (meth)acrylamide, N-C 2 ~C 8 Linear or branched trihydroxyalkyl (meth)acrylamide, N,N-bisC 2 ~C 8 It can be formed from at least one hydrophilic monomer containing linear or branched trihydroxyalkyl (meth)acrylamide, or a mixture thereof.

[0038] The binder polymer can be formed from at least one hydrophilic monomer including 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2,3-dihydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, N-(2-hydroxyethyl)(meth)acrylamide, N,N-bis(2-hydroxyethyl)(meth)acrylamide, N-(2-hydroxypropyl)(meth)acrylamide, N,N-bis(2-hydroxypropyl)(meth)acrylamide, N-(3-hydroxypropyl)(meth)acrylamide, N-(2-hydroxybutyl)(meth)acrylamide, N-(3-hydroxybutyl)(meth)acrylamide, N-(4-hydroxybutyl)(meth)acrylamide, or a mixture thereof.

[0039] The binder polymer can be formed from a reactive monomer mixture comprising at least one hydrophilic monomer independently selected from the group consisting of acrylamide, N,N-dimethylacrylamide (DMA), N-vinylpyrrolidone (NVP), N-vinylacetamide (NVA), N-vinyl-N-methylacetamide (VMA), N-isopropylacrylamide, polyethylene glycol monoacrylate, polyethylene glycol monomethacrylate, acrylic acid (AA), methacrylic acid (MAA), N-[(ethenyloxy)carbonyl]-β-alanine, 3-acrylamidopropanoic acid (ACA1), 5-acrylamidopropanoic acid (ACA2), 2-(methacryloyloxy)ethyltrimethylammonium chloride (METAC or Q salt), 2-acrylamido-2-methylpropanesulfonic acid (AMPS), 1-propanaminium, N-(2-carboxyethyl)-N,N-dimethyl-3-[(1-oxo-2-propen-1-yl)amino]-, inner salt (CBT); 1-propanaminium, N,N-dimethyl-N-[3-[(1-oxo-2-propen-1-yl)amino]propyl]-3-sulfo-, inner salt (SBT); 3,5-dioxa-8-aza-4-phosphaundec-10-en-1-aminium, 4-hydroxy-N,N,N-trimethyl-9-oxo-, inner salt, 4-oxide (9CI) (PBT), and mixtures thereof.

[0040] The binder polymer can preferably be formed from a silicone-containing macromer in addition to hydrophilic monomers such as one or more of the above-described hydrophilic monomers. The silicone-containing macromer can contain one polymerizable functional group selected from the group consisting of (meth)acrylate, (meth)acrylamide, styryl, vinyl, N-vinyl lactam, N-vinylamide, O-vinyl ether, O-vinyl carbonate, and O-vinyl carbamate, and can have from about 1 to about 200 divalent disubstituted siloxane repeating units, C 1 ~C 8It may be terminated with a linear, branched, or cyclic alkyl group.

[0041] The silicone-containing macromer may include a chemical structure represented by Formula I,

[0042] [Chemical formula] wherein Z is selected from O, N, S, or NCH 2 CH 2 O; when Z = O or S, R 2 is unnecessary, R 1 is a hydrogen atom or methyl, n is an integer from 1 to 200, or 1 to 100, or 1 to 50, or 1 to 20, and R 3 is an alkylene segment (CH 2 ) y where y is an integer from 1 to 6, 1 to 4, or 2 to 4, and each methylene group may optionally and independently be substituted with a group selected from the group consisting of ether, amine, ester, ketone, carbonyl, carboxylate, and carbamate, or when y is 2 or more, the non-terminal methylene group may optionally be substituted with a carbamate group, or R 3 is an oxyalkylene segment O(CH 2 ) z where z is an integer from 1 to 3, or R 3 is a mixture of an alkylene segment and an oxyalkylene segment, the sum of y and z is from 1 to 9, and R 2 and R 4 are independently a hydrogen atom, a linear, branched, or cyclic alkyl group containing 1 to 6 carbon atoms, a linear, branched, or cyclic alkoxy group containing 1 to 6 carbon atoms, a linear or branched polyethyleneoxyalkyl group, an alkyl-siloxanyl-alkyl group, a phenyl group, a benzyl group, a substituted or unsubstituted aryl group, a fluoroalkyl group, a partially fluorinated alkyl group, a perfluoroalkyl group, a fluorine atom, a mono-, di-, or tri-hydroxyalkyl group containing 1 to 6 carbon atoms, or a combination thereof, and R5 is a substituted or unsubstituted linear, branched, or cyclic alkyl group having 1 to 8 carbon atoms, or an aryl group, any of which may be further substituted with one or more fluorine atoms or trimethylsiloxy groups.

[0043] Non-limiting examples of these silicone-containing macromers include mono-n-alkyl-terminated mono-methacryloxypropyl-terminated polydimethylsiloxane shown in Formula II (wherein n is 3 to 50, 3 to 25, and 3 to 15, and R 5 is a linear, branched, or cyclic alkyl group containing 1 to 8 carbon atoms), mono-n-butyl-terminated mono-methacryloxypropyl-terminated polydimethylsiloxane (mPDMS) shown in Formula III (wherein n is 3 to 50, 3 to 25, or 3 to 15), and macromers having chemical structures shown in Formulas IV to XI (wherein R 1 is a hydrogen atom or a methyl group, each R 2 and R 4 are independently a hydrogen atom, a linear, branched, or cyclic alkyl group containing 1 to 6 carbon atoms, a linear, branched, or cyclic alkoxy group containing 1 to 6 carbon atoms, a linear or branched polyethyleneoxyalkyl group, a phenyl group, a benzyl group, a substituted or unsubstituted aryl group, a fluoroalkyl group, a partially fluorinated alkyl group, a perfluoroalkyl group, a fluorine atom, or a combination thereof, and R 5 is a linear, branched, or cyclic alkyl group containing 1 to 8 carbon atoms, and n is 3 to 50, 3 to 25, or 3 to 15).

[0044]

Chemical Structure

[0045]

Chemical Structure

[0046] Examples of suitable mono-alkyl terminated mono(meth)acryloxyalkyl terminated polydialkylsiloxanes include mono-n-butyl terminated mono(meth)acryloxypropyl terminated polydimethylsiloxane, mono-n-methyl terminated mono(meth)acryloxypropyl terminated polydimethylsiloxane, mono-n-butyl terminated mono(meth)acryloxypropyl terminated polydiethylsiloxane, mono-n-methyl terminated mono(meth)acryloxypropyl terminated polydiethylsiloxane, mono-alkyl terminated mono(meth)acrylamidealkyl terminated polydialkylsiloxane, mono-alkyl terminated mono(meth)acryloxyalkyl terminated polydiarylsiloxane, and mixtures thereof.

[0047] The silicone-containing macromer may include a monofunctional hydroxyl-substituted poly(dialkylsiloxane) having a chemical structure represented by Formula XII,

[0048]

Chemical formula

[0049] Examples of hydroxyl-containing macromers include mono-(2-hydroxy-3-methacryloxypropyl)propyl ether-terminated mono-n-butyl-terminated polydimethylsiloxane (OH-mPDMS) as shown in Formula XIII (wherein n is 4 to 30, 4 to 8, or 10 to 20), and macromers having chemical structures as shown in Formulas XIV and XV (wherein R 1 is a hydrogen atom or a methyl group, n is 4 to 30, 4 to 8, or 10 to 20, and R 4 is independently a hydrogen atom, a linear, branched, or cyclic alkyl group containing 1 to 6 carbon atoms, a linear, branched, or cyclic alkoxy group containing 1 to 6 carbon atoms, a linear or branched polyethyleneoxyalkyl group, a phenyl group, a benzyl group, a substituted or unsubstituted aryl group, a fluoroalkyl group, a partially fluorinated alkyl group, a perfluoroalkyl group, a fluorine atom, or a combination thereof, and R 5 is a substituted or unsubstituted linear, branched, or cyclic alkyl group having 1 to 8 carbon atoms, or an aryl group, any of which may be further substituted with one or more fluorine atoms or trimethylsiloxy groups).

[0050]

Chemical formula

[0051] The silicone-containing macromer may include the chemical structure shown in Formula XVI.

[0052]

Chemical formula

[0053] The silicone-containing macromer may be a mixture of macromers having the chemical structures shown in Formulas I to XVI.

[0054] Preferably, the silicone-containing macromer is selected from the group consisting of monoalkyl-terminated, mono(meth)acrylate-terminated poly(dialkylsiloxane), monoalkyl-terminated, monoalkyl-terminated, mono(meth)acrylate-terminated poly(diarylsiloxane), monoalkyl-terminated, mono(meth)acrylate-terminated poly(alkylarylsiloxane), and mixtures thereof.

[0055] Most preferably, the silicone-containing macromer is selected from the group consisting of mono-n-butyl-terminated monomethacryloxypropyl-terminated polydimethylsiloxane (Formula III), mono-n-butyl-terminated mono-(2-hydroxy-3-methacryloxypropyl)-propyl ether-terminated polydimethylsiloxane (Formula XIII), and mixtures thereof.

[0056] The silicone-containing macromer can have a number average molecular weight of about 500 Daltons to about 10,000 Daltons, or about 500 Daltons to about 5,000 Daltons, or about 500 Daltons to about 2,000 Daltons.

[0057] Preferably, the binder polymer is a copolymer of a silicone-containing macromer and a hydrophilic monomer, and is composed of repeating units of about 30 to about 80 wt%, or about 30 to about 70 wt%, or about 40 to about 60 wt%, or about 45 to about 55 wt%, or about 50 wt% of the silicone-containing macromer of the copolymer.

[0058] The binder polymer may include repeating units derived from mono-n-butyl-terminated monomethacryloxypropyl-terminated polydimethylsiloxane (mPDMS), mono-n-butyl-terminated mono-(2-hydroxy-3-methacryloxypropyl)-propyl ether-terminated polydimethylsiloxane (OH-mPDMS), and combinations thereof.

[0059] Most preferably, the binder polymer includes repeating units derived from mono-n-butyl-terminated monomethacryloxypropyl-terminated polydimethylsiloxane (mPDMS) and 2-hydroxyethyl methacrylate (HEMA). Preferably, mPDMS constitutes about 30 to about 80 wt%, or about 30 to about 70 wt%, or about 40 to about 60 wt%, or about 45 to about 55 wt%, or about 50 wt% of the copolymer.

[0060] The binder polymer can have a weight average molecular weight in the range of about 10 to about 100 kDa, or in the range of about 20 to about 80 kDa, or in the range of about 20 to about 60 kDa, or in the range of about 20 to about 50 kDa.

[0061] Preferably, the binder polymer is not a block copolymer or a terpolymer. Preferably, the binder polymer is a random polymer such as a random copolymer.

[0062] The binder polymers described herein can be made by methods known to those skilled in the art. For example, the binder polymer can be formed via any free radical polymerization reaction involving at least two monomers or macromers, regardless of the statistics of the copolymerization, to produce a random or statistical or statistical random or graft copolymer. A graft copolymer is formed from a macromer when the composition of the side chains of the macromer is different from the backbone of the copolymer. The copolymer can be blocky based on the statistics of the copolymerization. However, copolymers that can be properly classified as diblock copolymers or triblock copolymers (e.g., based on known methods for making such diblock and triblock copolymers) are excluded from the definition of the copolymers used in this application.

[0063] The ink composition preferably further comprises a solvent for facilitating the mixing of the components and the formation of the cosmetic lens. Suitable solvents include, but are not limited to, ethanol, 1-propanol, 2-propanol, 1-ethoxy-2-propanol (1E2P), t-butyl alcohol, t-amyl alcohol, and 3,7-dimethyl-1,7-octanediol (D3O), tripropylene glycol methyl ether (TPME), isopropyl lactate (IPL), 1-(2-hydroxyethyl)-2-pyrrolidone (HEP), glycerol, or a mixture of two or more thereof. Preferred solvents are 1E2P, IPL, D3O, HEP, 1-propanol, or a mixture thereof.

[0064] Preferred ink compositions according to the present invention comprise, based on the total weight of the ink composition, 0.1 to about 25% by weight, preferably about 5 to about 15% by weight, of a colorant, about 1 to about 50% by weight, preferably about 10 to about 40% by weight, of a hydrophilic polymer, about 1 to 60% by weight, preferably about 5 to about 40% by weight, of a triblock copolymer, and about 50 to about 95% by weight, preferably about 55 to about 80% by weight, of a solvent.

[0065] The ink composition may be applied or printed on one or more surfaces of the lens, or printed on one or more surfaces of the molding die, and the lens molding material may be deposited and cured on the molding die. In a preferred method for forming a cosmetic lens incorporating the ink composition of the present invention, a thermoplastic optical molding die made of any suitable material, including but not limited to cyclic polyolefins and polyolefins such as polypropylene or polystyrene resin, is used. The ink composition is deposited on a desired portion of the molding surface of the molding die. The "molding surface" means the surface of the molding die or half of the molding die used to form the surface of the lens. Preferably, this deposition is performed by pad printing as follows.

[0066] Preferably, a metal plate made of steel, more preferably stainless steel, is covered with a photoresist material capable of becoming water-insoluble after curing. Each element is selected or designed and then reduced to the desired size using any of a number of techniques such as photographic techniques, placed on the metal plate, and the photoresist material is cured. Thereafter, the plate is washed with an aqueous solution, and the resulting image is etched into the plate to a suitable depth, for example, up to about 20 micrometers. Then, the ink composition is deposited on the element and the recesses are filled.

[0067] Also, the metal plate may be laser-etched using appropriate software and a laser to extract the metal within the region having the preferred image, thereby creating a cavity that replicates the image with a depth of 15 μm to 30 μm. Further, laser etching of a preferred pattern may be performed on other substrates such as ceramics.

[0068] A silicon pad, which is a geometric shape suitable for use in printing on a surface and has various hardnesses, is pressed against an image on a plate to remove the ink composition. The pad is then pressed against the molding surface of an optical mold. The mold is degassed for up to 12 hours to remove excess solvent and oxygen, and then the mold is filled with lens material. Next, a complementary mold half is used to complete the mold assembly, and this mold assembly is exposed to conditions suitable for curing the lens material used. Such conditions are well known in the art and also depend on the selected lens material. After curing is complete and the lens is removed from the mold, the lens is equilibrated in buffered saline.

[0069] In a preferred embodiment, first, a clear coat is applied to the molding surface and dried, and then the ink composition is added. Preferably, such a clear coat forms the entire outermost surface of the lens. The clear coat may be the same as the ink composition described herein, except that it does not contain a colorant, for example. However, other materials may be used for the clear coat. In addition, multiple layers of the clear coat and / or the ink composition may be applied to the mold before adding the lens material to form a desired cosmetic pattern.

[0070] Using the ink composition of the present invention, such lenses can be provided that are made of any known lens-forming material or a material suitable for manufacturing colored hard or soft contact lenses. Preferably, the lens of the present invention is a soft contact lens, and the material selected for forming the lens is any material suitable for the manufacture of soft contact lenses. Preferred materials suitable for forming soft contact lenses using the method of the present invention include, but are not limited to, silicone elastomers, silicone-containing macromers, hydrogels, silicone-containing hydrogels, etc. disclosed in U.S. Patent Nos. 5,371,147, 5,314,960, and 5,057,578, the entire disclosures of which are incorporated herein by reference, as well as combinations thereof. More preferably, the lens includes, but is not limited to, silicone hydrogels or hydrogels formed from monomers containing siloxane functional groups, polydimethylsiloxane macromers, methacryloxypropyl polyalkylsiloxanes, and mixtures thereof, and containing hydroxy groups, carboxyl groups, or both, and combinations thereof.

[0071] Materials for manufacturing software contact lenses are well-known and commercially available. For example, silicone hydrogels can be made from at least one hydrophilic component and at least one silicone-containing component, which, when polymerized, form the base material of the lens. Examples of suitable families of hydrophilic components that may be present in the reactive mixture from which the lens is formed include (meth)acrylates, styrenes, vinyl ethers, (meth)acrylamides, N-vinyl lactams, N-vinyl amides, N-vinyl imides, N-vinyl ureas, O-vinyl carbamates, O-vinyl carbonates, other hydrophilic vinyl compounds, and mixtures thereof. Silicone-containing components are well-known and widely described in the patent literature. For example, the silicone-containing component may include at least one polymerizable group (e.g., (meth)acrylate, styryl, vinyl ether, (meth)acrylamide, N-vinyl lactam, N-vinyl amide, O-vinyl carbamate, O-vinyl carbonate, vinyl group, or mixtures thereof), at least one siloxane group, and one or more linking groups that link the polymerizable group and the siloxane group. The silicone-containing component may contain, for example, 1 to 220 siloxane repeating units. The silicone-containing component may also contain at least one fluorine atom.

[0072] As a further example, the lens material may be any of acquafilcon, asmofilcon, balafilcon, comfilcon, delefilcon, enfilcon, fanfilcon, formofilcon, galyfilcon, lotrafilcon, narafilcon, riofilcon, samfilcon, senofilcon, somofilcon, and stenfilcon (including all variations thereof), as well as U.S. Patent Nos. 4,659,782, 4,659,783, 5,244,981, 5,314,960, 5,331,067, 5,371,147, 5,998,498, 6,087,415, 5,760,100, 5,776,999, 5,789,461, 5,849,811, 5,965,631, 6,367,929, 6,822,016, 6,867,245, 6,943,203, 7,247,692, 7,249,848, 7,553,880, 7,666,921, 7,786,185, 7,956,131, 8,022,158, 8,273,802, 8,399,538, 8,470,906, 8,450,387, 8,487,058, 8,507,577, 8,637,621, 8,703,891, 8,937,110, 8,937,111, 8,940,812, 9,056,878, 9,057,821, 9,125,808, 9,140,825, 9156,934, 9,170,349, 9,244,196, 9,244,197, 9,260,544, 9,297,928, 9,297,It can be a silicone hydrogel as prepared in No. 929, as well as International Publication Nos. 03 / 22321, 2008 / 061992, US Patent Application Publication No. 2010 / 0048847, and US Patent Application No. 15 / 691,829. In another embodiment, the lens can be made from conventional hydrogel materials such as etafilcon, genfilcon, hilafilcon, lenefilcon, nesofilcon, ocufilcon, omafilcon, polymacon, and vifilcon (including all variations thereof).

[0073] Preferred compositions for the lens material include a hydrophilic component selected from N,N-dimethylacrylamide (“DMA”), 2-hydroxyethyl methacrylate (“HEMA”), and mixtures thereof, a silicone-containing component selected from 2-hydroxy-3-[3-methyl-3,3-bis(trimethylsiloxy)silylpropoxy]-propyl methacrylate (SiMAA), mono-methacryloxypropyl-terminated mono-n-butyl-terminated polydimethylsiloxane (mPDMS), mono-(2-hydroxy-3-methacryloxypropyl)-propyl ether-terminated mono-n-butyl-terminated polydimethylsiloxane (OH-mPDMS), and mixtures thereof, an internal wetting agent (preferably a polyamide such as poly(N-vinylpyrrolidone) (PVP), poly(N,N-dimethylacrylamide) (PDMA), or polyvinylmethylacetamide (PVMA)), and a free radical initiator. For the hydrophilic component, a mixture of DMA and HEMA is preferred. For the silicone-containing component, OH-mPDMS, or a mixture of SiMAA and mPDMS is preferred. The composition may contain other components known in the art for making soft contact lenses, including but not limited to diluents, cross-linking agents, light-absorbing compounds (e.g., UV or high-energy visible light blockers).

[0074] The present invention will be further described by the following non-limiting examples.

Example

[0075] Imaging was used to qualitatively evaluate the overall quality of the printed pattern by comparing it with the desired design ("smear" in the table). The level of smear was classified based on severity ("mild, moderate, severe, or none" in the table). Also, imaging was used to evaluate the roundness and distortion level of the lens ("round" or "out of round (OOR)" in the table). Unacceptable levels of haze or translucency were also described by imaging (haze or none). Images of silicone hydrogel printed contact lenses were captured using a Nikon SMZ18 stereomicroscope equipped with a P2-DBF Fiber diascopic illumination base (1x objective lens with a magnification of 0.75 - 1x). The printed silicone hydrogel contact lens was placed concave side up in a crystal cell completely filled with a boric acid buffered filling solution. The sample was placed within the field of view window, and the microscope was adjusted to focus the image.

[0076] The durability of the printed pattern was evaluated by rubbing the printed surface with a cotton swab. The test consisted of wiping the lens 50 times. Each time, wiping started from the center of the lens on the printed surface and then proceeded in one direction. Each lens was wiped in four orthogonal directions for systematic evaluation. If the pattern remained intact after being wiped 50 times in this way, the pattern was considered permanent ("no rubbing off" in the table). Alternatively, if any part of the printed pattern was removed, disrupted, or erased during the 50 wipes, the pattern was considered to have been rubbed off ("rubbing off" in the table).

[0077] The wettability of the lens was measured at room temperature using the drop technique with a KRUSS DSA-100 (trademark) instrument and using deionized water as the probe solution (「Droplet」 in the table). The lens to be tested was rinsed in deionized water to remove the filling solution. Each test lens was placed on lint-free blotting paper moistened with the filling solution. Both sides of the lens were brought into contact with this blotting paper to remove surface water without drying the lens. To ensure proper flattening, the lens was placed 「with the dish part down」 on the convex surface of the plastic mold of the contact lens. The plastic mold and the lens were placed in the droplet instrument holder to ensure proper central syringe alignment. A droplet of 3 - 4 microliters of deionized water was formed on the tip of the syringe using DSA 100 - Drop Shape Analysis software such that the droplet would surely fall away from the lens. The droplet was smoothly released onto the surface of the lens by moving the needle downward. The needle was immediately retrieved after dispensing the droplet. The droplet was kept in equilibrium on the lens for 5 - 10 seconds, and the contact angle was measured between the droplet image and the lens surface. Typically, 3 - 5 lenses were evaluated and the average contact angle was reported. The standard deviation was determined and reported in parentheses () in the table.

[0078] The following abbreviations are used throughout the examples and have the following meanings. L: liter mL: milliliter equiv. or eq.: equivalent kg: kilogram g: gram mg: milligram mol: mole mmol: millimole min: minute cm: centimeter nm: nanometer rpm: revolutions per minute Da: Dalton or gram / mole kDa: kilodalton, or atomic mass unit equal to 1,000 daltons wt%: weight % TL03 light: Phillips TLK 40W / 03 bulb BC: Base curve plastic molding die FC: Front curve plastic molding die PP: A homopolymer of propylene, polypropylene used as a plastic molding die resin or component TT: Hydrogenated styrene-butadiene block copolymer, Tuftec (Asahi Kasei Chemicals) used as a plastic molding die resin or component Z: Polyscycloolefin thermoplastic polymer, Zeonor (Nippon Zeon Co Ltd) used as a plastic molding die resin or component RMM: Reactive monomer mixture DMA: N,N-dimethylacrylamide (Jarchem) NVP: N-vinylpyrrolidone HEMA: 2-hydroxyethyl methacrylate (Bimax) PVP, PVP K30, PVP K60, PVP K90: Poly(N-vinylpyrrolidone) (ISP Ashland) TEGDMA: Tetraethylene glycol dimethacrylate (Esstech) Omnirad 1870: Blend of bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide, and mPDMS: Mono-n-butyl terminated monomethacryloxypropyl terminated polydimethylsiloxane (M n = 800 - 1500 daltons) (Gelest) SiMAA: 2-Propenoic acid, 2-methyl-2-hydroxy-3-[3-[1,3,3,3-tetramethyl-1-[(trimethylsilyl)oxy]disiloxanyl]propoxy]propyl ester (Toray), or 3-(3-(1,1,1,3,5,5,5-heptamethyltrisiloxan-3-yl)propoxy)-2-hydroxypropyl methacrylate Norbloc: 2-(2’-Hydroxy-5-methacryloyloxyethylphenyl)-2H-benzotriazole (Janssen) Blue HEMA: 1-Amino-4-[3-(4-(2-methacryloyloxy-ethoxy)-6-chlorotriazin-2-ylamino)-4-sulfophenylamino]anthraquinone-2-sulfonic acid (described in U.S. Patent No. 5,944,853) Borate buffer packing solution: 18.52 grams (300 mmol) of boric acid, 3.7 grams (9.7 mmol) of sodium borate decahydrate, and 28 grams (197 mmol) of sodium sulfate were dissolved in sufficient deionized water to fill a 2-liter volumetric flask. AIBN: Azobisisobutyronitrile FTIR: Fourier transform infrared spectroscopy DCA: Dynamic contact angle wettability DIW: Deionized water IPA: Isopropyl alcohol THF: Tetrahydrofuran D3O: 3,7-Dimethyl-3-octanol (Vigon) 1E2P: 1-Ethoxy-2-propanol 3E3P: 3-Ethyl 3-pentanol HEP: 1-(2-Hydroxyethyl)-2-pyrrolidone IPL: Isopropyl lactate

[0079] Borate buffer packing solution: 18.52 grams (300 mmol) of boric acid, 3.7 grams (9.7 mmol) of sodium borate decahydrate, and 28 grams (197 mmol) of sodium sulfate were dissolved in sufficient deionized water to fill a 2-liter volumetric flask.

[0080] Preparation 1 An AIBN solution was prepared by dissolving 4 grams of AIBN in 300 grams of 1-propanol. The AIBN solution was degassed with nitrogen gas for 15 - 20 minutes before use. A monomer solution was prepared by dissolving 98 grams of HEMA and 98 grams of mPDMS in 91 grams of 1-propanol. The monomer solution was degassed with nitrogen gas for 15 - 20 minutes before use.

[0081] A 2-liter jacketed reactor containing 279 grams of 1-propanol was heated to 70 °C under a nitrogen gas atmosphere using a water bath. Using a Watson-Marlow pump, the AIBN and monomer solutions were added to the reactor over 4 hours. After stirring the reaction mixture overnight, the temperature was lowered to 50 °C and monomer conversion was monitored by FTIR until the carbon-carbon double bond band disappeared. Complete conversion took approximately 24 hours.

[0082] The reaction mixture was transferred to a clear glass jar. The copolymer was isolated by precipitation into water, suction filtration, and vacuum drying to obtain approximately 182 grams of product (copolymer #1).

[0083] (Example 1) Ink compositions 1A - 1D were prepared by adding 9 wt% of a black iron oxide pigment (Sicovit® Black 85 E 172, Rockwood Italia SpA - Divisione Silo) to the clear coat solution listed in Table 1. The inks were mixed using a bench-scale ball mill (Ultra-Turrax® Tube Drive (UTTD) system, IKA). Additionally, the inks could be further manually mixed using a jar roller or an overhead mixer could be used at 700 - 1800 rpm for 30 minutes.

[0084]

Table 1

[0085] (Example 2) Using a laboratory-scale pad printer, a Vivid® clichéd pattern was printed on the front curve mold, first with a transparent coating (Clear Coat 1A - 1D) and then with Inks 1A - 1D. These printed front curve molds were degassed under nitrogen for at least 12 hours. Contact lenses were fabricated in a glove box with the oxygen gas concentration maintained at 0.5 - 5%. Approximately 100 microliters of RMM#1 listed in Table 2 was introduced onto the printed front curve mold at ambient temperature. The time between the introduction of RMM#1 and the placement of the BC is referred to as "Dwell 1". The nominal Dwell 1 time was 5 seconds or less unless otherwise specified. Next, the base curve mold was placed on top of RMM#1. Next, a transparent quartz plate was placed on the mold assembly. Then, the pallet containing the mold assembly was moved into a curing chamber at 60 - 70 °C. The time between the placement of the weight and the start of curing is referred to as "Dwell 2". The nominal Dwell 2 was 5 seconds or less unless otherwise specified. Curing was initiated by irradiating the pallet containing the mold assembly with a TL 20W / 03 T fluorescent lamp (Philips) and positioned to achieve an intensity of 4.0 mW / cm 2 for 8 minutes.

[0086]

Table 2

[0087] With most of the lenses attached to the FC, the printed lenses were manually demolded and demolded by immersing the lenses in 70% IPA for about 1 hour or 2 hours, followed by washing twice with 70% IPA, optionally twice with 25% IPA, twice with DI, and finally twice with boric acid buffer filling solution. Each washing step was continued for about 30 minutes. Those skilled in the art understand that the exact lens demolding process can be varied according to the lens formulation and mold material with respect to the concentration of the aqueous isopropanol solution, the number of washes with each solvent, and the duration of each step. The purpose of the lens demolding process is to demold all lenses without defects and to transfer from the network swollen with the diluent to the hydrogel swollen with the filling solution. After transferring the lenses into the vials, they were sterilized by autoclaving at 122 °C for 30 minutes. Sterile printed lenses (produced from 2A - 2D, ink compositions 1A - 1D respectively) were evaluated for haze, smear, durability, and shape, and the results are listed in Table 3 [Dowel 1 = 5 seconds, Dowel 2 = 300 seconds].

[0088]

Table 3

[0089] As shown in Table 3, the printed lenses 2B and 2D were transparent, round, did not exhibit printed-off rubbing, and exhibited only slight smear or no smear. The printed lens 2D was also wettable.

[0090] (Example 3) Ink compositions 3A - 3C were prepared by adding 9 wt% of black iron oxide pigment (Sicovit® Black 85 E 172, Rockwood Italia SpA - Divisione Silo) to the clear coat solutions listed in Table 4. The ink was mixed using a bench-scale ball mill (Ultra-Turrax® Tube Drive (UTTD) system, IKA). Additionally, the ink can be further mixed manually using a jar roller or an overhead mixer can be used at 700 - 1800 rpm for 30 minutes.

[0091]

Table 4

[0092] (Example 4) Using a laboratory-scale pad printer, a front curve mold was first printed with a transparent coating (Clear Coat 3A - 3C) and then with Ink 3A - 3C to a Vivid® clichéd pattern. These printed front curve molds were degassed under nitrogen for at least 12 hours. Contact lenses were fabricated in a glove box maintained at an oxygen gas concentration of 0.5 - 5%. Approximately 100 microliters of RMM#1 listed in Table 2 was introduced onto the printed front curve mold at ambient temperature. The time between the introduction of RMM#1 and the placement of BC is referred to as "Dwell 1". The nominal Dwell 1 time was 5 seconds or less unless otherwise specified. Next, the base curve mold was placed on top of RMM#1. Next, a transparent quartz plate was placed on the mold assembly. Then, the pallet containing the mold assembly was moved into a curing chamber at 60 - 70 °C. The time between the placement of the weight and the start of curing is referred to as "Dwell 2". The nominal Dwell 2 was 5 seconds or less unless otherwise specified. Curing was initiated by irradiating the pallet containing the mold assembly with a TL 20W / 03 T fluorescent lamp (Philips) and positioned to achieve an intensity of 4.0 mW / cm 2 for 8 minutes.

[0093] With most of the lenses adhered to the FC, the printed lenses were manually demolded, and the lenses were demolded by immersing them in 70% IPA for about 1 hour or 2 hours, followed by washing twice with 70% IPA, optionally twice with 25% IPA, twice with DI, and finally twice with boric acid buffer filling solution. Each washing step was continued for about 30 minutes. Those skilled in the art understand that the exact lens demolding process can be varied according to the lens formulation and the molding material with respect to the concentration of the aqueous isopropanol solution, the number of washings with each solvent, and the duration of each step. The purpose of the lens demolding process is to demold all lenses without defects and to transfer from the network swollen with the diluent to the hydrogel swollen with the filling solution. After transferring the lenses into the vials, they were sterilized by autoclaving at 122 °C for 30 minutes. Sterile printed lenses (produced from 4A - 4C, ink compositions 3A - 3C respectively) were evaluated for haze, smear, durability, and shape, and the results are listed in Table 5 [Dowell 1 = 5 seconds, Dowell 2 = 300 seconds].

[0094]

Table 5

[0095] As shown in Table 5, the printed lenses 4B and 4C were transparent, round, did not exhibit print rubbing off, and exhibited only slight smear or no smear. The printed lens 4B was also wettable.

[0096] (Example 5) Ink compositions 5A - 5D were prepared by adding 9 wt% of black iron oxide pigment (Sicovit® Black 85 E 172, Rockwood Italia SpA - Divisione Silo) to the clear coat solutions listed in Table 6. The inks were mixed using a bench - scale ball mill (Ultra - Turrax® Tube Drive (UTTD) system, IKA). Additionally, the inks could be further manually mixed using a jar roller or an overhead mixer could be used at 700 - 1800 rpm for 30 minutes.

[0097]

Table 6

[0098] (Example 6) Using a laboratory-scale pad printer, a front curve mold was first printed with a transparent coating (Clear Coat 5A - 5D) and then a Vivid (registered trademark) clichéd pattern was printed using Inks 5A - 5D. These printed front curve molds were degassed under nitrogen for at least 12 hours. Printed contact lenses were fabricated within a glove box maintained at an oxygen gas concentration of 0.5 - 5%. Approximately 100 microliters of RMM#1 listed in Table 2 was introduced into the printed front curve mold at ambient temperature. The time between the introduction of RMM#1 and the placement of BC is referred to as "Dwell 1". The nominal Dwell 1 time was 5 seconds or less unless otherwise stated. Next, the base curve mold was placed on top of RMM#1. Next, a transparent quartz plate was placed on the mold assembly. Then, the pallet containing the mold assembly was moved into a curing chamber at 60 - 70°C. The time between the placement of the weight and the start of curing is referred to as "Dwell 2". The nominal Dwell 2 was 5 seconds or less unless otherwise stated. Curing was initiated by irradiating the pallet containing the mold assembly with a TL 20W / 03 T fluorescent lamp (Philips) and positioned to achieve an intensity of 4.0 mW / cm 2 for 8 minutes.

[0099] With most of the lenses attached to the FC, the printed lenses were manually demolded, and the lenses were demolded by immersing them in 70% IPA for about 1 hour or 2 hours, followed by washing twice with 70% IPA, optionally twice with 25% IPA, twice with DI, and finally twice with a boric acid buffered filling solution. Each washing step was continued for about 30 minutes. Those skilled in the art understand that the exact lens demolding process can be varied according to the lens formulation and mold material with respect to the concentration of the aqueous isopropanol solution, the number of washings with each solvent, and the duration of each step. The purpose of the lens demolding process is to demold all the lenses without defects and to transfer from the network swollen with the diluent to the hydrogel swollen with the filling solution. After transferring the lenses into the vials, they were sterilized by autoclaving at 122 °C for 30 minutes. Sterile printed lenses (6A - 6D, prepared from ink compositions 5A - 5D respectively) were evaluated for haze, smear, durability, and shape, and the results are listed in Table 7 [Dowell 1 = 5 seconds, Dowell 2 = 300 seconds].

[0100]

Table 7

[0101] As shown in Table 7, the printed lenses 6C and 6D were transparent, round, showed no printed wear-off, and showed only mild smearing. The printed lenses 6C and 6D were also wettable.

[0102] (Example 7) The ink composition 7A was prepared by adding 9 wt% of black iron oxide pigment (Sicovit® Black 85 E 172, Rockwood Italia SpA - Divisione Silo) to the clear coat solution listed in Table 8. The ink set composition 7B was prepared by adding combinations of various concentrations of black, blue, and white pigments in the range of 3.8 - 9.0 wt% to the clear coat solution listed in Table 8 to create a set of three - color inks. One cosmetic ink design for the printed lens 7B was created using a set of three inks. The inks were mixed using a bench - scale ball mill (Ultra - Turrax® Tube Drive (UTTD) system, IKA). Additionally, the inks could be further manually mixed using a jar roller or an overhead mixer could be used at 700 - 1800 rpm for 30 minutes.

[0103]

Table 8

[0104] Using a pad printer, a front curve forming mold was first printed with a transparent coating (clear coats 7A and 7B), and then a clichéd pattern was printed using ink 7A or 7B. Contact lenses were fabricated in a pilot facility manufacturing line where the oxygen gas level was maintained at 0.5 - 5%. Approximately 100 microliters of RMM#2 listed in Table 9 was introduced onto the printed front curve forming mold at ambient temperature. The time between the introduction of RMM#2 and the placement of BC is referred to as "dwell 1". The nominal dwell 1 time was 5 seconds or less, unless otherwise specified. Next, the base curve forming mold was placed on top of RMM#2. Then, an early curing weight was placed on the mold assembly. Next, the pallet containing the mold assembly was moved into a heated early curing tunnel at approximately 30°C. The time between the placement of the weight and the start of curing is referred to as "dwell 2". The nominal dwell 2 was 5 seconds or less, unless otherwise specified. Curing was initiated by irradiating the pallet containing the mold assembly with a TL 20W / 03 T fluorescent lamp (Philips) and positioned to achieve an intensity of 4.0 mW / cm 2 for 8 minutes.

[0105]

Table 9

[0106] With most of the lenses attached to the FC, the printed lenses were demolded, and the lenses were demolded by immersing them in 70% IPA for about 1 hour or 2 hours, followed by washing twice with 70% IPA, optionally twice with 25% IPA, twice with DI, and finally once with a boric acid buffer filling solution. Each washing step was continued for about 30 minutes. Those skilled in the art understand that the exact lens demolding process can be varied according to the lens formulation and mold material with respect to the concentration of the aqueous isopropanol solution, the number of washings with each solvent, and the duration of each step. The purpose of the lens demolding process is to demold all the lenses without defects and to transfer from the network swollen with the diluent to the hydrogel swollen with the filling solution. After inspecting the lenses and packaging them in heat-sealed blisters, they were sterilized by autoclaving at 121 °C for 18 minutes. Sterile printed lenses (7A - 7B, prepared from ink compositions 7A - 7B respectively) were evaluated for haze, smear, durability, shape, and wettability, and the results are listed in Table 3 (Well 1 = 5 seconds, Well 2 = 300 seconds).

[0107]

Table 10

[0108] As shown in Table 10, the printed lenses 7A and 7B were transparent, round, showed no print rubbing off or smearing, and were wettable.

[0109] (Example 8) Combinations of black, blue, and white pigments at various concentrations from 3.8 to 9.0% by weight were added to the ink base solution listed in Table 8 to prepare an ink set composition 8A by creating a set of three inks. Using the set of three inks, one cosmetic ink design for the printed lens 8A was created. The inks were mixed using a bench-scale ball mill (Ultra-Turrax® Tube Drive (UTTD) system, IKA). Additionally, the inks can be further manually mixed using a jar roller or an overhead mixer can be used at 700 - 1800 rpm for 30 minutes.

[0110]

Table 11

[0111] Using a pad printer, a front curve mold was first coated with a transparent coating (clear coat 7B from Example 7), and then a clichéd pattern was printed using the ink set 8A. Printed contact lenses were fabricated on a pilot production line where the oxygen gas level was maintained at 0.5 - 5%. Approximately 100 microliters of RMM#2 listed in Table 9 was introduced onto the printed front curve mold at ambient temperature. The time between the introduction of RMM#2 and the placement of the BC is referred to as "dwell 1". The nominal dwell 1 time was 5 seconds or less unless otherwise stated. Next, the base curve mold was placed on top of the RMM#2. Then, an early curing weight was placed on the mold assembly. Next, the pallet containing the mold assembly was moved into a heated early curing tunnel at approximately 30°C. The time between the placement of the weight and the start of curing is referred to as "dwell 2". The nominal dwell 2 was 5 seconds or less unless otherwise stated. Curing was initiated by irradiating the pallet containing the mold assembly with a TL 20W / 03 T fluorescent lamp (Philips) and positioned to achieve an intensity of 4.0 mW / cm 2 for 8 minutes.

[0112] With most lenses attached to the FC, the printed lenses were demolded, and the lenses were demolded by immersing them in 70% IPA for about 1 hour or 2 hours, followed by washing twice with 70% IPA, optionally twice with 25% IPA, twice with DI, and finally once with a boric acid buffered filling solution. Each washing step was continued for about 30 minutes. Those skilled in the art understand that the exact lens demolding process can be varied according to the lens formulation and mold material with respect to the concentration of the aqueous isopropanol solution, the number of washings with each solvent, and the duration of each step. The purpose of the lens demolding process is to demold all lenses without defects and to transfer from a network swollen with a diluent to a hydrogel swollen with a filling solution. After inspecting the lenses and packaging them in heat-sealed blisters, they were sterilized by autoclaving at 121 °C for 18 minutes. Sterile printed lenses (each made from 78A, clear coat 7B, and ink composition set 8A) were evaluated for haze, smearing, durability, shape, and wettability, and the results are listed in Table 3 (well 1 = 5 seconds, well 2 = 300 seconds).

[0113]

Table 12

[0114] As shown in Table 12, the printed lens 8A using the heterogeneous ink layer composition was transparent, round, did not exhibit printing wear or smearing, and was wettable.

[0115] 〔Embodiment〕 (1) An ink composition for producing a cosmetic contact lens, the ink composition comprising (a) a colorant, (b) a non-reactive hydrophilic polymer, and optionally (c) a binder polymer. (2) The ink composition according to Embodiment 1, wherein the non-reactive hydrophilic polymer comprises a polyamide. (3) The non-reactive hydrophilic polymer of the ink composition according to Embodiment 1, comprising dextran, poly(ethylene oxide), polyvinyl alcohol (PVA), poly(N-isopropylacrylamide), poly(oligoethylene oxide), polyethylene glycol (PEG), poly(N,N-dimethylaminoethyl acrylate), poly(imine), poly(acrylic acid), or a mixture of two or more of these. (4) The ink composition according to any one of Embodiments 1 to 3, wherein the optional binder polymer comprises a hydrophilic monomer containing a functional group selected from the group consisting of hydroxyalkyl, aminoalkyl, and mixtures thereof, a silicone-containing macromer, and a copolymer formed from a silicone-containing monomer optionally. (5) (d) The ink composition according to any one of Embodiments 1 to 4, further comprising a solvent.

[0116] (6) The ink composition according to Embodiment 5, wherein the solvent comprises ethanol, 1-propanol, 2-propanol, 1-ethoxy-2-propanol (1E2P), t-butyl alcohol, t-amyl alcohol, and 3,7-dimethyl-1,7-octanediol (D3O), tripropylene glycol methyl ether (TPME), isopropyl lactate (IPL), 1-(2-hydroxyethyl)-2-pyrrolidone (HEP), glycerol, or a mixture of two or more of these. (7) The ink composition according to any one of Embodiments 1 to 6, wherein the non-reactive hydrophilic polymer comprises a cyclic polyamide. (8) The ink composition according to any one of Embodiments 1 to 7, wherein the colorant comprises phthalocyanine blue, phthalocyanine green, carbazole violet, vat orange #1, iron oxide black, iron oxide brown, iron oxide yellow, iron oxide red, titanium dioxide, dichlorotriazine, vinyl sulfone-based dyes, or a mixture of two or more of these. (9) An ink composition according to any one of embodiments 1-8, comprising 0.1 to about 25% by weight of the colorant, about 1 to about 50% by weight of the non-reactive hydrophilic polymer, about 1 to 60% by weight of the binder polymer, and about 50 to about 95% by weight of the solvent, based on the total weight of each ink composition. (10) The ink composition according to any one of embodiments 1-9, wherein the binder polymer has a weight average molecular weight in the range of about 1.66×10 -23 to about 1.66×10 -22 kg (about 10 to about 100 kDa).

[0117] (11) The ink composition according to any one of embodiments 1-10, wherein the non-reactive hydrophilic polymer is poly(vinylpyrrolidone). (12) The ink composition according to embodiment 4, wherein the hydrophilic monomer comprises 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2,3-dihydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, N-(2-hydroxyethyl)(meth)acrylamide, N,N-bis(2-hydroxyethyl)(meth)acrylamide, N-(2-hydroxypropyl)(meth)acrylamide, N,N-bis(2-hydroxypropyl)(meth)acrylamide, N-(3-hydroxypropyl)(meth)acrylamide, N-(2-hydroxybutyl)(meth)acrylamide, N-(3-hydroxybutyl)(meth)acrylamide, N-(4-hydroxybutyl)(meth)acrylamide, or a mixture thereof. (13) The ink composition according to embodiment 12, wherein the hydrophilic monomer is 2-hydroxyethyl (meth)acrylate. (14) The silicone-containing macromer is the ink composition according to any one of Embodiments 4 to 13, which contains a polymerizable functional group selected from the group consisting of (meth)acrylate, (meth)acrylamide, styryl, vinyl, N-vinyl lactam, N-vinyl amide, O-vinyl ether, O-vinyl carbonate, and O-vinyl carbonate. (15) The silicone-containing macromer contains a chemical structure represented by Formula I,

Chemical formula

[0118] (16) The silicone-containing macromer is selected from the group consisting of monoalkyl-terminated, mono(meth)acrylate-terminated poly(dialkylsiloxane), monoalkyl-terminated, monoalkyl-terminated, mono(meth)acrylate-terminated poly(diarylsiloxane), monoalkyl-terminated, mono(meth)acrylate-terminated poly(alkylarylsiloxane), and mixtures thereof, the ink composition according to any one of Embodiments 4 to 15. (17) The silicone-containing macromer is mono-n-butyl-terminated monomethacryloxypropyl-terminated polydimethylsiloxane, the ink composition according to Embodiment 16. (18) The silicone-containing macromer includes a chemical structure represented by Formula VIII, [Chemical formula] wherein Z is selected from O, N, S, or NCH 2 CH 2 O, R 1 is independently a hydrogen atom or a methyl group, R 2 , R 3 , and R 4is, independently, a hydrogen atom, or a linear, branched, or cyclic alkyl group containing from 1 to 8 carbon atoms, any of which may be further substituted with at least one hydroxy group and optionally substituted with an amide group, an ether group, an amino group, a carboxyl group, a carbonyl group, and combinations thereof, and in the cases of Z = O and S, R 2 is unnecessary, n is the number of siloxane repeating units and is from 4 to 200, and R 5 is a linear or branched C 1 ~C 8 alkyl group, and the ink composition according to any one of Embodiments 4 to 17. (19) The ink composition according to any one of Embodiments 4 to 18, wherein the silicone-containing macromer is mono-n-butyl-terminated mono-(2-hydroxy-3-methacryloxypropyl)-propyl ether-terminated polydimethylsiloxane. (20) The ink composition according to any one of Embodiments 4 to 19, wherein the silicone-containing macromer is selected from the group consisting of mono-n-butyl-terminated monomethacryloxypropyl-terminated polydimethylsiloxane, mono-n-butyl-terminated mono-(2-hydroxy-3-methacryloxypropyl)-propyl ether-terminated polydimethylsiloxane, and mixtures thereof.

[0119] (21) The ink composition according to any one of Embodiments 4 to 20, wherein the silicone-containing macromer has a number average molecular weight greater than 8.30×10 -25 kilograms (500 Daltons). (22) The ink composition according to any one of Embodiments 4 to 20, wherein the silicone-containing macromer has a number average molecular weight of about 8.30×10 -25 kilograms to about 3.32×10 -23 kilograms (about 500 Daltons to about 20,000 Daltons). (23) The ink composition according to any one of Embodiments 4 to 22, wherein the repeating units of the silicone-containing macromer are present in the range of about 30 to about 80% by weight of the total weight of the binder polymer. (24) The silicone-containing monomer is selected from the group consisting of 3-methacryloxypropyltris(trimethylsiloxy)silane, 3-acryloxypropyltris(trimethylsiloxy)silane, 3-methacrylamidopropyltris(trimethylsiloxy)silane, 3-acrylamidopropyltris(trimethylsiloxy)silane, tris(trimethylsiloxy)silylstyrene, 2-methyl-2-hydroxy-3-[3-[1,3,3,3-tetramethyl-1-[(trimethylsilyl)oxy]disiloxanyl]propoxy]propyl ester, N-(2,3-dihydroxylpropyl)N-(3-tetra(dimethylsiloxy)dimethylbutylsilane)propyl)acrylamide, and mixtures thereof, and the ink composition according to any one of Embodiments 4 to 23. (25) A method for producing a cosmetic contact lens, comprising: (i) applying a clear coat to the lens-forming surface of a first lens-forming mold; (ii) applying the ink composition according to any one of Embodiments 1 to 24 to the clear coat; (iii) optionally repeating step (i), step (ii), or both step (i) and step (ii); (iv) dispensing a lens material into the first lens-forming mold; (v) applying a second lens-forming mold; and (vi) curing the lens material to form the cosmetic contact lens.

[0120] (26) A cosmetic contact lens comprising a contact lens having the ink composition according to any one of Embodiments 1 to 24 applied thereon. (27) The cosmetic contact lens according to Embodiment 26, which is a cosmetic silicone hydrogel contact lens. (28) The cosmetic contact lens according to Embodiment 27, further comprising an internal wetting agent. (29) The cosmetic contact lens according to any one of Embodiments 26 to 28, wherein the lens comprises a plurality of layers of the ink composition, and the plurality of layers of the ink composition may be the same or different. The cosmetic contact lens according to any one of Embodiments 26 to 29, further comprising an ink layer that does not contain a non-reactive hydrophilic polymer.

Claims

1. An ink composition for making a cosmetic contact lens, comprising: (a) a colorant; and (b) a clear coat, The clearcoat comprises a non-reactive hydrophilic polymer and a binder polymer; the non-reactive hydrophilic polymer is poly(vinylpyrrolidone); the binder polymer comprises a hydrophilic monomer comprising a functional group selected from the group consisting of hydroxyalkyl, aminoalkyl, and mixtures thereof, a silicone-containing macromer, and optionally a copolymer formed from a silicone-containing monomer; An ink composition, wherein the concentration of said binder polymer is from 5 to 7.5% by weight, based on the total weight of said clearcoat.

2. 2. The ink composition of claim 1, wherein the concentration of the non-reactive hydrophilic polymer is from 14.7 to 22.5% by weight, based on the total weight of the clearcoat.

3. The ink composition of claim 1 or 2, wherein the clear coat further comprises a solvent.

4. 4. The ink composition of claim 3, wherein the solvent comprises ethanol, 1-propanol, 2-propanol, 1-ethoxy-2-propanol (1E2P), t-butyl alcohol, t-amyl alcohol, and 3,7-dimethyl-1,7-octanediol (DO), tripropylene glycol methyl ether (TPME), isopropyl lactate (IPL), 1-(2-hydroxyethyl)-2-pyrrolidone (HEP), glycerol, or a mixture of two or more thereof.

5. 5. The ink composition of claim 1, wherein the colorant comprises phthalocyanine blue, phthalocyanine green, carbazole violet, vat orange #1, iron oxide black, iron oxide brown, iron oxide yellow, iron oxide red, titanium dioxide, dichlorotriazine, vinyl sulfone dyes, and mixtures of two or more thereof.

6. The binder polymer is about 1.66×10 －２３ ~Approx. 1.66×10 －２２ The ink composition according to any one of claims 1 to 5, having a weight average molecular weight in the range of about 10 to about 100 kDa.

7. 7. The ink composition according to claim 1, wherein the hydrophilic monomer comprises 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2,3-dihydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, N-(2-hydroxyethyl)(meth)acrylamide, N,N-bis(2-hydroxyethyl)(meth)acrylamide, N-(2-hydroxypropyl)(meth)acrylamide, N,N-bis(2-hydroxypropyl)(meth)acrylamide, N-(3-hydroxypropyl)(meth)acrylamide, N-(2-hydroxybutyl)(meth)acrylamide, N-(3-hydroxybutyl)(meth)acrylamide, N-(4-hydroxybutyl)(meth)acrylamide, or a mixture thereof.

8. 8. The ink composition according to claim 7, wherein the hydrophilic monomer is 2-hydroxyethyl (meth)acrylate.

9. 9. The ink composition of claim 1, wherein the silicone-containing macromer comprises a polymerizable functional group selected from the group consisting of (meth)acrylate, (meth)acrylamide, styryl, vinyl, N-vinyl lactam, N-vinyl amide, O-vinyl ether, and O-vinyl carbonate.

10. The silicone-containing macromer comprises the chemical structure shown in Formula I: 【Chemistry 1】 In the formula, Z is O, N, S, or NCH ２ CH ２ O, and when Z=O or S, R ２ is unnecessary, and R １ is a hydrogen atom or methyl, n is an integer from 1 to 200, and R ３ is an alkylene segment (CH ２ ) ｙ where y is an integer from 1 to 6, and each methylene group may be optionally further and independently replaced with a group selected from the group consisting of ether, amine, ester, ketone, carbonyl, carboxylate, and carbamate, or when y is 2 or greater, a non-terminal methylene group may be optionally replaced with a carbamate group, or R ３ is an oxyalkylene segment O(CH ２ ) ｚ where z is an integer from 1 to 3, or R ３ is a mixture of alkylene and oxyalkylene segments, the sum of y and z is 1 to 9, and R ２ and R ４ are independently a hydrogen atom, a linear, branched, or cyclic alkyl group containing 1 to 6 carbon atoms, a linear, branched, or cyclic alkoxy group containing 1 to 6 carbon atoms, a linear or branched polyethyleneoxyalkyl group, an alkyl-siloxanyl-alkyl group, a phenyl group, a benzyl group, a substituted or unsubstituted aryl group, a fluoroalkyl group, a partially fluorinated alkyl group, a perfluoroalkyl group, a fluorine atom, a mono-, di-, or tri-hydroxyalkyl group containing 1 to 6 carbon atoms, or a combination thereof; R ５ 10. The ink composition according to claim 1, wherein is a substituted or unsubstituted linear, branched, or cyclic alkyl group having 1 to 8 carbon atoms, or an aryl group, any of which may be further substituted with one or more fluorine atoms or trimethylsiloxy groups.

11. 11. The ink composition of claim 1, wherein the silicone-containing macromer is selected from the group consisting of monoalkyl-terminated, mono(meth)acrylate-terminated poly(dialkylsiloxanes), monoalkyl-terminated, monoalkyl-terminated, mono(meth)acrylate-terminated poly(diarylsiloxanes), monoalkyl-terminated, mono(meth)acrylate-terminated poly(alkylarylsiloxanes), and mixtures thereof.

12. The ink composition of claim 11, wherein the silicone-containing macromer is mono-n-butyl terminated monomethacryloxypropyl terminated polydimethylsiloxane.

13. The silicone-containing macromer comprises the chemical structure shown in Formula VIII: 【Chemistry 2】 In the formula, Z is O, N, S, or NCH ２ CH ２ O; R １ are independently a hydrogen atom or a methyl group, R ２ , R ３ , and R ４ are independently a hydrogen atom or a straight, branched, or cyclic alkyl group containing 1 to 8 carbon atoms, any of which may be further substituted with at least one hydroxy group and optionally substituted with amide groups, ether groups, amino groups, carboxyl groups, carbonyl groups, and combinations thereof; when Z=O and S, R ２ is not required, n is the number of siloxane repeat units and is 4 to 200, R ５ is a linear or branched chain C １ ~C ８ The ink composition according to any one of claims 1 to 12, wherein the alkyl group is selected from the group consisting of aryl, aryl, and alkyl groups.

14. The ink composition of any one of claims 1 to 13, wherein the silicone-containing macromer is a mono-n-butyl terminated mono-(2-hydroxy-3-methacryloxypropyl)-propyl ether terminated polydimethylsiloxane.

15. 15. The ink composition of claim 1, wherein the silicone-containing macromer is selected from the group consisting of mono-n-butyl terminated monomethacryloxypropyl terminated polydimethylsiloxane, mono-n-butyl terminated mono-(2-hydroxy-3-methacryloxypropyl)-propyl ether terminated polydimethylsiloxane, and mixtures thereof.

16. The silicone-containing macromer is 8.30×10 －２５ The ink composition of any one of claims 1 to 15, having a number average molecular weight of greater than 500 Daltons.

17. The silicone-containing macromer is about 8.30×10 －２５ Kilograms to approx. 3.32 x 10 －２３ The ink composition of any one of claims 1 to 15, having a number average molecular weight of from about 500 Daltons to about 20,000 Daltons.

18. The ink composition of any one of claims 1 to 17, wherein the silicone-containing macromer repeat units are present in the range of about 30 to about 80 weight percent of the total weight of the binder polymer.

19. 19. The ink composition of claim 1, wherein the silicone-containing monomer is selected from the group consisting of 3-methacryloxypropyl tris(trimethylsiloxy)silane, 3-acryloxypropyl tris(trimethylsiloxy)silane, 3-methacrylamidopropyl tris(trimethylsiloxy)silane, 3-acrylamidopropyl tris(trimethylsiloxy)silane, tris(trimethylsiloxy)silylstyrene, 2-methyl-2-hydroxy-3-[3-[1,3,3,3-tetramethyl-1-[(trimethylsilyl)oxy]disiloxanyl]propoxy]propyl ester, N-(2,3-dihydroxypropyl)N-(3-tetra(dimethylsiloxy)dimethylbutylsilane)propyl)acrylamide, and mixtures thereof.

20. 20. A method for making a cosmetic contact lens, the method comprising: (i) applying a clear coat to a lens forming surface of a first lens forming mold; (ii) applying the ink composition of any one of claims 1 to 19 to the clear coat; (iii) optionally repeating step (i), step (ii), or both steps (i) and (ii); (iv) dispensing lens material into the first lens forming mold; (v) applying a second lens forming mold; and (vi) curing the lens material to form the cosmetic contact lens.

21. A cosmetic contact lens comprising a contact lens having the ink composition of any one of claims 1 to 19 applied thereon.

22. 22. The cosmetic contact lens of claim 21 which is a cosmetic silicone hydrogel contact lens.

23. 23. The cosmetic contact lens of claim 22, further comprising an internal wetting agent.

24. The cosmetic contact lens of any one of claims 21 to 23, wherein the contact lens comprises multiple layers of ink compositions, and the multiple layers of ink compositions can be the same or different.

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