Contact lenses containing light absorbing regions and methods for preparing same - Patents.com

Abstract

Contact lenses containing light-absorbing chromophores, the light-absorbing chromophores being concentrated in one or more selected regions of the lens, are described. Methods for making such contact lenses are also described.

Description

[Technical field]

[0001] (CROSS REFERENCE TO RELATED APPLICATIONS) This application claims priority to U.S. Patent Application No. 18 / 052,010, filed November 2, 2022, and U.S. Provisional Patent Application No. 63 / 265,705, filed December 20, 2021, both of which are incorporated by reference in their entireties.

[0002] FIELD OF THEINVENTION The present invention relates to contact lenses containing light-absorbing chromophores. More particularly, the present invention relates to contact lenses in which the light-absorbing chromophores are concentrated in one or more selected regions of the lens. The present invention also relates to methods of making such lenses. [Background technology]

[0003] Contact lenses have been used commercially to improve vision since the 1950s. Currently available contact lenses remain a cost-effective means of vision correction. The thin lenses are fitted over the cornea of ​​the eye to correct vision defects including myopia, hyperopia, astigmatism, i.e., asphericity of the cornea, and presbyopia, i.e., loss of the ability of the crystalline lens to accommodate.

[0004] In recent years, contact lenses have been developed that incorporate spectral filters that absorb specific wavelengths of visible and / or ultraviolet light, thus allowing the lenses to be tailored for a variety of applications, including protection of the cornea, lens, and retina from harmful or undesirable radiation wavelengths. For example, contact lenses have been disclosed that incorporate visible light absorbing chromophores, including high-energy visible light (HEVL) absorbers, green light absorbers, and the like. Additionally, both static and photochromic chromophores have been incorporated into contact lenses.

[0005] Typically, spectral filtering contact lenses are edge-to-edge, meaning that the absorbing chromophores are distributed throughout the lens. Although the distribution of chromophores throughout the lens facilitates the manufacture of the lens, it has drawbacks. For example, visible light absorbing chromophores can exhibit very noticeable colors themselves, so incorporating such materials edge-to-edge can be undesirable for cosmetic reasons.

[0006] One possible approach to alleviate the cosmetic problem is to localize the light absorbing chromophore in the central region of the lens so that it primarily covers the pupil of the eye. Although processes for making pupil-only light absorbing contact lenses have been previously published, such processes are typically complex, can add significant cost to the manufacturing process, and can distort or otherwise undesirably affect the optical and / or mechanical properties of the lens.

[0007] Therefore, it would be an advancement in the art to develop novel light absorbing contact lenses that have light absorbing chromophores localized to specific regions of the lens, and to develop a commercially viable process for making such contact lenses. Summary of the Invention [Means for solving the problem]

[0008] The present invention relates to contact lenses having light absorbing properties, such as the ability to absorb visible light of various wavelengths, including high energy visible light. The light absorbing materials, i.e., chromophores, within the lenses are concentrated in one or more selected regions of the lens, instead of being distributed substantially uniformly throughout the lens. Such selective concentration provides many advantages over incorporating chromophores throughout the lens, including, for example, improved aesthetics.

[0009] The inventors have discovered that contact lenses as described herein that contain visible light chromophores in selected regions of the lens, such as the central zone, can be prepared by facile manufacturing methods that are simple to employ and that minimize undesirable side effects such as lens distortion or adversely affecting the mechanical properties of the lens.

[0010] Thus, in one aspect, the invention provides a contact lens comprising: a first region, a second region, a visible light absorbing chromophore, and a derivative of the visible light absorbing chromophore, wherein the first region contains the visible light absorbing chromophore and the second region contains the derivative of the visible light absorbing chromophore, and the second region has a greater average transmittance than the first region over the wavelength range of 400 nm to 600 nm.

[0011] The present invention further provides a method for making a contact lens, comprising providing a lens precursor having a first region and a second region, the lens precursor containing a visible light absorbing chromophore in the first region and the second region, and selectively derivatizing the visible light absorbing chromophore in the second region to form a derivative of the visible light absorbing chromophore, the derivative having a greater average transmittance over a wavelength range of 400 nm to 600 nm than the visible light absorbing chromophore. [Brief description of the drawings]

[0012] [Figure 1] FIG. 1 shows the UV-VIS transmission spectra of exemplary contact lenses prepared according to Examples 1A-1C compared to a lens precursor that has not undergone derivatization. [Diagram 2] FIG. 1 shows the UV-VIS transmission spectra of a Precursor 2 lens (not underivatized) as described in the Examples, and an Example 2A lens and an Example 2B lens of the present invention (peripherally derivatized followed by central zone dyeing) for a minus 1 diopter lens. [Diagram 3]FIG. 1 shows the UV-VIS transmission spectra of a Precursor 2 lens (not underivatized) as described in the Examples, and an Example 2A lens and an Example 2B lens of the present invention (peripherally derivatized followed by central zone dyeing) for a minus 12 diopter lens. [Figure 4] FIG. 1 shows the UV-VIS transmission spectra of Precursor 3 and Example 3 lenses after sterilization. [Diagram 5] FIG. 1 shows the UV-VIS transmission spectra of Precursor 4 lens and Example 4 lens. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0013] It is to be understood that the invention is not limited to the details of construction or process steps set forth in the following description, as the invention is capable of other embodiments and of being practiced or carried out in various ways using the teachings set forth herein.

[0014] The following definitions are provided for terms used in this disclosure.

[0015] Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art to which this invention belongs. The definition of polymer is consistent with 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 herein are incorporated herein by reference.

[0016] As used herein, the term "(meth)" refers to optional methyl substitution. Thus, a term such as "(meth)acrylate" refers to both methacrylate and acrylate.

[0017] Wherever a chemical structure is depicted, it should be understood that the disclosed alternatives for the substituents in the structure may be combined in any combination. Thus, when a structure contains a substituent R * and R ** and each of these contains a list of three possible groups, then nine combinations are disclosed. The same is true for combinations of features.

[0018] General formula [ *** ] n When a subscript, such as "n" in: is used to denote the number of repeat units in a chemical formula for a polymer, the formula should be interpreted as representing the number average molecular weight of the polymer.

[0019] The term "individual" includes humans and vertebrate animals.

[0020] The term "biomedical device" refers to any article designed to be used either in or on mammalian tissue or fluid, preferably in or on human tissue or fluid. Examples of these devices include, but are not limited to, wound dressings, sealants, tissue prostheses, drug delivery systems, coatings, adhesion barriers, catheters, implants, stents, and ophthalmic devices such as intraocular lenses and contact lenses. The biomedical device may be an ophthalmic device, specifically a contact lens, most specifically a contact lens made from silicone hydrogels or conventional hydrogels.

[0021] The term "ocular surface" includes the superficial and glandular epithelium of the cornea, conjunctiva, lacrimal gland, accessory lacrimal gland, nasolacrimal duct, and meibomian gland, as well as their apical and basal matrices, puncta, and adjacent or associated structures including the eyelids, which are connected as a functional system by both the continuity of the epithelium through innervation and by the endocrine and immune systems.

[0022] The term "ophthalmic device" refers to any optical device present in or on the eye or any part of the eye (including the ocular surface). These devices may provide optical correction, appearance enhancement, vision enhancement, therapeutic effects (e.g., as a dressing), or delivery of active ingredients such as pharmaceutical and nutraceutical ingredients, or any combination of the foregoing. Examples of ophthalmic devices include, but are not limited to, lenses, optics, and ocular inserts (including, but not limited to, punctal plugs). "Lens" includes spectacle lenses, sunglass lenses, soft contact lenses, hard contact lenses, hybrid contact lenses, intraocular lenses, and overlay lenses. Ophthalmic devices may include contact lenses.

[0023] 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 light absorption, reduction of visible light or glare, or any combination thereof. A contact lens can be of any suitable material known in the art and can be a soft lens, a hard lens, or a hybrid lens that contains at least two separate portions with different physical, mechanical, or optical properties, such as modulus of elasticity, water content, light transmittance, or a combination thereof.

[0024] The biomedical devices, ophthalmic devices, and lenses of the present invention may be composed of silicone hydrogels or conventional hydrogels, which typically contain at least one hydrophilic monomer and at least one silicone-containing component covalently bonded to each other in the cured device.

[0025] "Target polymer" refers to a polymer that has been synthesized from a reactive monomer mixture that includes monomers, macromers, prepolymers, crosslinkers, initiators, additives, diluents, and the like.

[0026] The term "polymerizable compound" means a compound that contains one or more polymerizable groups. This term includes, for example, monomers, macromers, oligomers, prepolymers, crosslinkers, and the like.

[0027] A "polymerizable group" is a group capable of undergoing chain growth polymerization, such as a carbon-carbon double bond that can polymerize when subjected to radical polymerization initiation conditions, such as free radical and / or cationic polymerization, preferably free radical polymerization. Non-limiting examples of polymerizable groups include (meth)acrylate groups, styryl groups, (meth)acrylamide groups, and vinyl groups. Preferably, the polymerizable group is selected from (meth)acrylate functional groups, (meth)acrylamide functional groups, N-vinyl lactam functional groups, N-vinylamide functional groups, vinyl carbonate functional groups, vinyl ether functional groups, vinyl carbamate functional groups, and styryl functional groups. More preferably, the polymerizable group is selected from (meth)acrylate and (meth)acrylamide. The polymerizable group may be unsubstituted or substituted. For example, the nitrogen atom in (meth)acrylamide may be bonded to hydrogen or the hydrogen may be replaced by alkyl or cycloalkyl (which may themselves be further substituted).

[0028] Any type of free radical polymerization can be used, including but not limited to bulk, solution, suspension, and emulsion, as well as any of the controlled radical polymerization techniques, such as stable free radical polymerization, nitric oxide mediated living polymerization, atom transfer radical polymerization, reversible addition-fragmentation chain transfer polymerization, organotellurium mediated living radical polymerization, etc.

[0029] A "monomer" is a monofunctional molecule that can undergo chain growth polymerization, particularly free radical polymerization, thereby creating repeat units within the chemical structure of a target macromolecule. Some monomers have difunctional impurities that can act as crosslinkers. A "hydrophilic monomer" is also a monomer that, when mixed with deionized water at a concentration of 5 weight percent at 25°C, gives a clear, single-phase solution. A "hydrophilic component" is a monomer, macromer, prepolymer, initiator, crosslinker, additive, or polymer that, when mixed with deionized water at a concentration of 5 weight percent at 25°C, gives a clear, single-phase solution. A "hydrophobic component" is a monomer, macromer, prepolymer, initiator, crosslinker, additive, or polymer that is slightly soluble or insoluble in deionized water at 25°C.

[0030] A "polymer" is an organic compound having a number average molecular weight greater than 1500 and may be reactive or non-reactive.

[0031] A "macromonomer" or "macromer" is a polymer having one group capable of undergoing chain growth polymerization, particularly free radical polymerization, thereby creating repeat units within the chemical structure of a target macromolecule. Generally, the chemical structure of a macromer is different from the chemical structure of the target macromolecule, i.e., the repeat units of the pendant group of the macromer are different from the repeat units of the target macromolecule or its backbone. The only difference between a monomer and a macromer is one of the chemical structure of the pendant group, the molecular weight, and the molecular weight distribution. As a result, and as used herein, the patent literature sometimes defines a monomer as a polymerizable compound having a relatively low molecular weight of about 1,500 daltons or less, which essentially includes some macromers. Specifically, monomethacryloxypropyl terminated mono-n-butyl terminated polydimethylsiloxane (molecular weight = 500-1500 g / mol) (mPDMS) and mono-(2-hydroxy-3-methacryloxypropyl)-propyl ether terminated mono-n-butyl terminated polydimethylsiloxane (molecular weight = 500-1500 g / mol) (OH-mPDMS) may be referred to as monomers or macromers. Additionally, the patent literature sometimes defines macromers as having one or more polymerizable groups, essentially expanding the general definition of macromer to include prepolymers. As a result, and as used herein, difunctional and multifunctional macromers, prepolymers, and crosslinkers may be used interchangeably.

[0032] A "silicone-containing component" is a monomer, macromer, prepolymer, crosslinker, initiator, additive, or polymer in the reactive mixture that has at least one silicon-oxygen bond, usually in the form of a siloxy group, a siloxane group, a carbosiloxane group, and mixtures thereof.

[0033] Examples of silicone-containing components useful in the present invention are disclosed in U.S. Pat. Nos. 3,808,178, 4,120,570, 4,136,250, 4,153,641, 4,740,533, 5,034,461, 5,070,215, 5,244,981, 5,314,960, 5,331,067, 5,371,147, 5,760,100, 5,849,811, 5,96 No. 2,548, No. 5,965,631, No. 5,998,498, No. 6,367,929, No. 6,822,016, No. 6,943,203, No. 6,951,894, No. 7,052,131, No. No. 7,247,692, No. 7,396,890, No. 7,461,937, No. 7,468,398, No. 7,538,146, No. 7,553,880, No. 7,572,841, No. 7,666,921 , No. 7,691,916, No. 7,786,185, No. 7,825,170, No. 7,915,323, No. 7,994,356, No. 8,022,158, No. 8,163,206, No. 8,273, No. 802, No. 8,399,538, No. 8,415,404, No. 8,420,711, No. 8,450,387, No. 8,487,058, No. 8,568,626, No. 8,937,110, No. 8,9 37,111, 8,940,812, 8,980,972, 9,056,878, 9,125,808, 9,140,825, 9,156,934, 9,170,349, 9,217,813, 9,244,196, 9,244,197, 9,260,544, 9,297,928, 9,297,929, and European Patent No. 080539. These patents are incorporated herein by reference in their entirety.

[0034] A "polymer" is a target macromolecule made up of repeating units of the monomers used during polymerization.

[0035] A "homopolymer" is a polymer made from one monomer, a "copolymer" is a polymer made from two or more monomers, and a "terpolymer" is a polymer made from three monomers. A "block copolymer" consists of compositionally distinct blocks or segments. A diblock copolymer has two blocks. A triblock copolymer has three blocks. A "comb or graft copolymer" is made from at least one macromer.

[0036] A "repeating unit" is the smallest grouping of atoms in a polymer that corresponds to the polymerization of a particular monomer or macromer.

[0037] An "initiator" is a molecule that is decomposable into radicals that can subsequently react with monomers to initiate a free radical polymerization reaction. Thermal initiators decompose at a specific rate depending on the temperature, and typical examples are azo compounds such as 1,1'-azobisisobutyronitrile and 4,4'-azobis(4-cyanovaleric acid), peroxides such as benzoyl peroxide, tert-butyl peroxide, tert-butyl hydroperoxide, tert-butyl peroxybenzoate, dicumyl peroxide, and lauroyl peroxide, peracids such as peracetic acid and potassium persulfate, and various redox systems. Photoinitiators decompose by a photochemical process, and typical examples are derivatives of benzil, benzoin, acetophenone, benzophenone, camphorquinone, and mixtures thereof, as well as various monoacyl and bisacylphosphine oxides, and combinations thereof.

[0038] A "crosslinker" is a di- or polyfunctional monomer or macromer that can undergo free radical polymerization at two or more positions on the molecule, thereby creating branch points and polymer networks. Common examples are ethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, methylene bisacrylamide, triallyl cyanurate, etc.

[0039] A "prepolymer" is a reaction product of monomers that contain remaining polymerizable groups that can undergo further reaction to form a polymer.

[0040] A "polymer network" is a cross-linked polymer that can swell but cannot be dissolved in a solvent. A "hydrogel" is a polymer network that swells in water or an aqueous solution, typically absorbing at least 10% by weight of water. A "silicone hydrogel" is a hydrogel made from at least one silicone-containing component together with at least one hydrophilic component. The hydrophilic component may also include a non-reactive polymer.

[0041] "Conventional hydrogel" refers to a polymer network made from components that do not have any siloxy, siloxane, or carbosiloxane groups. Conventional hydrogels are prepared from reactive mixtures that include hydrophilic monomers. Examples include 2-hydroxyethyl methacrylate ("HEMA"), N-vinylpyrrolidone ("NVP"), N,N-dimethylacrylamide ("DMA"), or vinyl acetate. U.S. Patent Nos. 4,436,887, 4,495,313, 4,889,664, 5,006,622, 5,039459, 5,236,969, 5,270,418, 5,298,533, 5,824,719, 6,420,453, 6,423,761, 6,767,979, 7,934,830, 8,138,290, and 8,389,597 disclose the formation of conventional hydrogels. Commercially available conventional hydrogels include, but are not limited to, etafilcon, genfilcon, hilafilcon, lenefilcon, nesofilcon, omafilcon, polymacon, and vifilcon (including all variations thereof).

[0042] "Silicone hydrogel" refers to a polymer network made from at least one hydrophilic component and at least one silicone-containing component. Examples of suitable families of hydrophilic components that may be present in the reactive mixture 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)acrylates, styryls, vinyl ethers, (meth)acrylamides, N-vinyl lactams, N-vinyl amides, O-vinyl carbamates, O-vinyl carbonates, vinyl groups, or mixtures of the above), at least one siloxane group, and one or more linking groups (which may be chemical bonds) that connect the polymerizable group to the siloxane group. The silicone-containing component may, for example, contain 1 to 220 siloxane repeating units. The silicone-containing component may also contain at least one fluorine atom. The silicone hydrogel lens may include a coating, which may be the same or a different material as the substrate.

[0043] Examples of silicone hydrogels include acquafilcon, asmofilcon, balafilcon, comfilcon, delefilcon, enfilcon, fanfilcon, formofilcon, galyfilcon, lotrafilcon, narafilcon, and the like. In addition to cyclofilcon, riofilcon, samfilcon, senofilcon, somofilcon, and stenfilcon (including all variations thereof), 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, 5,760,1 No. 00, No. 5,776,999, No. 5,789,461, No. 5,849,811, No. 5,965,631, No. 6 ,367,929, 6,822,016, 6,867,245, 6,943,203, 7,247,692 No. 7,249,848, No. 7,553,880, No. 7,666,921, No. 7,786,185, No. 7,95 6,131, 8,022,158, 8,273,802, 8,399,538, 8,470,906, No. 8,450,387, No. 8,487,058, No. 8,507,577, No. 8,637,621, No. 8,703,8 No. 91, No. 8,937,110, No. 8,937,111, No. 8,940,812, No. 9,056,878, No. 9, No. 057,821, No. 9,125,808, No. 9,140,825, No. 9156,934, No. 9,170,349, No. 9,244,196, No. 9,244,197, No. 9,260,544, No. 9,297,928, No. 9,297,No. 929, and silicone hydrogels such as those prepared in WO 03 / 22321, WO 2008 / 061992, and U.S. Patent Application Publication No. 2010 / 0048847, which are incorporated herein by reference in their entireties.

[0044] An "interpenetrating polymer network" comprises two or more networks that are at least partially entangled on a molecular scale, but are not covalently bonded to each other and cannot be separated without a blocking chemical bond. A "semi-interpenetrating polymer network" comprises one or more networks and one or more polymers that are characterized by some intermixing at the molecular level between at least one network and at least one polymer. A mixture of different polymers is a "polymer blend." Although semi-interpenetrating networks are technically polymer blends, in some cases the polymers are so entangled that they cannot be easily removed.

[0045] "Reactive components" are the polymerizable compounds (such as monomers, macromers, oligomers, prepolymers, and crosslinkers) in the reactive mixture (as defined below), as well as any other components in the reactive mixture that are intended to remain substantially in the resulting polymer network after polymerization and all work-up steps (such as extraction steps) and packaging steps are complete. The reactive components may be retained in the polymer network by covalent bonds, hydrogen bonds, electrostatic interactions, the formation of an interpenetrating polymer network, or any other means. Components that are intended to be released from the polymer network during use are still considered "reactive components". For example, a pharmaceutical or nutraceutical component in a contact lens that is intended to be released during wear is considered a "reactive component". Components that are intended to be removed from the polymer network during the manufacturing process (e.g., by extraction), such as diluents, are not "reactive components".

[0046] The terms "reactive mixture" and "reactive monomer mixture" refer to a mixture of components that, when mixed together and subjected to polymerization conditions, result in the formation of polymer networks (such as conventional or silicone hydrogels) and biomedical devices, ophthalmic devices, and contact lenses made therefrom. The reactive monomer mixture may include reactive components such as monomers, macromers, prepolymers, crosslinkers, and initiators, wetting agents, polymers, light absorbing compounds such as dyes, UV absorbers, pigments, dyes, and photochromic compounds, and additives such as pharmaceutical and nutraceutical compounds, all of which may be polymerizable or non-polymerizable but are capable of being retained in the resulting biomedical device (e.g., contact lens). The reactive mixture may also contain other components that are intended to be removed from the device before use, such as diluents. It will be understood that a wide range of additives may be added depending on the contact lens to be produced and the intended application. The concentrations of the components of the reactive mixture are therefore expressed as a weight percentage of all components in the reactive mixture, excluding the diluent. When diluents are used, their concentrations are expressed as weight percent based on the amounts of all components (including the diluent) in the reactive mixture.

[0047] The term "silicone hydrogel contact lenses" refers to hydrogel contact lenses made from at least one silicone-containing compound. Silicone hydrogel contact lenses generally have increased oxygen permeability compared to traditional hydrogels. Silicone hydrogel contact lenses utilize both their water content and polymer content to deliver oxygen to the eye.

[0048] The term "photochromic" refers to a material that, upon exposure to electromagnetic radiation of a particular wavelength, reversibly changes its absorption characteristics (i.e., color) caused by a photochemical reaction within the material. As an example, a photochromic material may exhibit a reversible change in average transmission of 5% or more, or 10% or more, or 20% or more in the visible portion of the electromagnetic spectrum (e.g., wavelength range from about 380 nm to about 760 nm) upon exposure to UV or HEV light. "Static" as used in reference to chromophores refers to a material that is not photochromic, and thus does not undergo a photochemical reaction that reversibly changes its color.

[0049] The term "visible light absorbing chromophore" or similar terms refers to a chemical moiety that limits the transmission of one or more wavelengths of visible light through a lens, for example, in the range of 380-760 nm, or preferably 400-600 nm. The ability of a material to absorb light of a particular wavelength may be determined by measuring its UV / Vis transmission spectrum. A material that exhibits no absorption at a particular wavelength exhibits substantially 100 percent transmission at that wavelength. Conversely, a material that is completely absorbing at a particular wavelength exhibits substantially 0% transmission at that wavelength. As used herein, "average transmission," "average transmittance," and related terms may be calculated as the average of the transmittance in 1 nm increments over the specified range (or, if no range is specified, over the range of 400-600 nm).

[0050] As used herein, the term "derivative" refers to a moiety derived from a parent moiety. For example, a "derivative" of a visible light absorbing chromophore refers to a moiety formed by derivatizing the visible light absorbing chromophore. The terms "derivatize," "derive," and similar terms, when used herein in the context of a visible light absorbing chromophore and its derivatives, indicate that the visible light absorbing chromophore is treated under conditions to form a derivative. Such treatment may be, for example, chemical, photochemical, electron beam, or other means (or a combination thereof). In the present invention, derivatization is preferably performed chemically, such as by chemical oxidation of one or more functional groups in the parent moiety.

[0051] As used herein, the term "central zone" refers to the central portion of a contact lens and may include the pupil region of the lens. The central zone may have a diameter ranging, for example, from about 3 mm to about 12 mm, preferably from about 5 mm to about 11 mm, and more preferably from about 7 mm to about 10 mm. "Peripheral zone" refers to the region of the lens circumferentially surrounding the central zone of the contact lens. The peripheral zone may extend to the edge of the lens.

[0052] The term "multifunctional" refers to a component having two or more polymerizable groups. The term "monofunctional" refers to a component having one polymerizable group.

[0053] The terms "halogen" or "halo" refer to fluorine, chlorine, bromine, and iodine.

[0054] "Alkyl" refers to an optionally substituted straight or branched chain alkyl group containing the specified number of carbon atoms. If no number is specified, the alkyl (including the optional substituents on the alkyl) may contain 1 to 16 carbon atoms. Preferably, the alkyl group contains 1 to 10 carbon atoms, alternatively 1 to 8 carbon atoms, alternatively 1 to 6 carbon atoms, alternatively 1 to 4 carbon atoms. Examples of alkyl include methyl, ethyl, propyl, isopropyl, butyl, iso-, sec-, and tert-butyl, pentyl, hexyl, heptyl, 3-ethylbutyl, and the like. Examples of substituents on alkyl include one, two, or three groups independently selected from hydroxy, amino, amido, oxa, carboxy, alkylcarboxy, carbonyl, alkoxy, thioalkyl, carbamate, carbonate, halogen, phenyl, benzyl, and combinations thereof. "Alkylene" means a divalent alkyl group, e.g., -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH2CH(CH3)CH2-, and -CH2CH2CH2CH2-.

[0055] "Haloalkyl" refers to an alkyl group, as defined above, substituted by one or more halogen atoms, where each halogen is independently F, Cl, Br, or I. A preferred halogen is F. Preferred haloalkyl groups contain 1 to 6 carbons, more preferably 1 to 4 carbons, and even more preferably 1 to 2 carbons. "Haloalkyl" includes perhaloalkyl groups such as -CF3- or -CF2CF3-. "Haloalkylene" refers to a divalent haloalkyl group, such as -CH2CF2-.

[0056] "Cycloalkyl" refers to an optionally substituted cyclic hydrocarbon containing the specified number of ring carbon atoms. If no number is specified, cycloalkyl may contain 3 to 12 ring carbon atoms. Preferred are C3-C8 cycloalkyl groups, C3-C7 cycloalkyl groups, more preferably C4-C7 cycloalkyl groups, and even more preferably C5-C6 cycloalkyl groups. Examples of cycloalkyl include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. Examples of substituents on cycloalkyl include one, two, or three groups independently selected from alkyl, hydroxy, amino, amido, oxa, carbonyl, alkoxy, thioalkyl, amido, carbamate, carbonate, halo, phenyl, benzyl, and combinations thereof. "Cycloalkylene" refers to a divalent cycloalkyl group, such as 1,2-cyclohexylene, 1,3-cyclohexylene, or 1,4-cyclohexylene.

[0057] "Heterocycloalkyl" refers to a cycloalkyl ring or ring system as defined above in which at least one ring carbon is replaced by a heteroatom selected from nitrogen, oxygen, and sulfur. The heterocycloalkyl ring is optionally fused or otherwise attached to other heterocycloalkyl rings and / or non-aromatic hydrocarbon rings and / or phenyl rings. Preferred heterocycloalkyl groups have 5 to 7 members. More preferred heterocycloalkyl groups have 5 or 6 members. Heterocycloalkylene refers to a divalent heterocycloalkyl group.

[0058] "Aryl" refers to an optionally substituted aromatic hydrocarbon ring system containing at least one aromatic ring. The aryl group contains the indicated number of ring carbon atoms. If no number is indicated, the aryl may contain 6 to 14 ring carbon atoms. The aromatic ring may be optionally fused or otherwise attached to other aromatic or non-aromatic hydrocarbon rings. Examples of aryl groups include phenyl, naphthyl, and biphenyl. Preferred examples of aryl groups include phenyl. Examples of substituents on an aryl include one, two, or three groups independently selected from alkyl, hydroxy, amino, amido, oxa, carboxy, alkylcarboxy, carbonyl, alkoxy, thioalkyl, carbamate, carbonate, halo, phenyl, benzyl, and combinations thereof. "Arylene" refers to a divalent aryl group, such as 1,2-phenylene, 1,3-phenylene, or 1,4-phenylene.

[0059] "Heteroaryl" refers to an aryl ring or ring system, as defined above, in which at least one ring carbon atom is replaced by a heteroatom selected from nitrogen, oxygen, and sulfur. The heteroaryl ring may be fused or otherwise bonded to one or more heteroaryl rings, aromatic or non-aromatic hydrocarbon rings, or heterocycloalkyl rings. Examples of heteroaryl groups include pyridyl, furyl, pyrazinyl, benzimidazolyl, and thienyl. "Heteroarylene" refers to a divalent heteroaryl group.

[0060] "Alkoxy" refers to an alkyl group attached to the parent molecular moiety through an oxygen bridge. Examples of alkoxy groups include, for example, methoxy, ethoxy, propoxy, and isopropoxy. "Thioalkyl" refers to an alkyl group attached to the parent moiety through a sulfur bridge. Examples of thioalkyl groups include, for example, methylthio, ethylthio, n-propylthio, and isopropylthio. "Selenoalkyl" refers to an alkyl group attached to the parent moiety through a selenium bridge. Examples of selenoalkyl groups include, for example, methylseleno, ethylseleno, n-propylseleno, and iso-propylseleno. "Aryloxy" refers to an aryl group attached to the parent molecular moiety through an oxygen bridge. Examples include phenoxy. "Cyclic alkoxy" refers to a cycloalkyl group attached to the parent moiety through an oxygen bridge.

[0061] "Alkylamine" refers to an alkyl group attached to the parent molecular moiety through an -NH bridge. Alkyleneamine refers to a divalent alkylamine group, such as -CHCHNH-.

[0062] "Siloxanyl" refers to a structure having at least one Si-O-Si bond. Thus, for example, a siloxanyl group refers to a group having at least one Si-O-Si group (i.e., a siloxane group), and a siloxanyl compound refers to a compound having at least one Si-O-Si group. "Siloxanyl" encompasses monomeric structures (e.g., Si-O-Si) as well as oligomeric / polymeric structures (e.g., -[Si-O]n-, where n is 2 or greater). Each silicon atom in a siloxanyl group is independently selected to complete their valences, R A Group(R A is replaced by (as defined in options (b) to (i) of formula A).

[0063] "Silyl" refers to a structure of formula RSi- and "siloxy" refers to a structure of formula RSi-O-, where each R in silyl or siloxy is independently selected from trimethylsiloxy, C1-C8 alkyl (preferably C1-C3 alkyl, more preferably ethyl or methyl), and C3-C8 cycloalkyl.

[0064] "Alkyleneoxy" refers to a group having the general formula -(alkylene-O-) p -or-(O-alkylene) p -, where alkylene is as defined above, p is 1-200, or 1-100, or 1-50, or 1-25, or 1-20, or 1-10, and each alkylene is independently optionally substituted with one or more groups independently selected from hydroxyl, halo (e.g., fluoro), amino, amido, ether, carbonyl, carboxyl, and combinations thereof. When p is greater than 1, each alkylene may be the same or different, and the alkyleneoxy may be in a block or random configuration. When the alkyleneoxy forms a terminal group in a molecule, the terminus of the alkyleneoxy may be, for example, a hydroxyl or alkoxy (e.g., HO-[CH2CHO] p - or CH3O-[CH2CH2O] pExamples of alkyleneoxy include polyethyleneoxy, polypropyleneoxy, polybutyleneoxy, and poly(ethyleneoxy-co-propyleneoxy).

[0065] "Oxaalkylene" refers to an alkylene group as defined above in which one or more non-adjacent CH groups are replaced by an oxygen atom, such as -CH2CH2OCH(CH3)CH2-. "Thiaalkylene" refers to an alkylene group as defined above in which one or more non-adjacent CH groups are replaced by a sulfur atom, such as -CH2CH2SCH(CH3)CH2-. "Selenoalkylene" refers to an alkylene group as defined above in which one or more non-adjacent CH groups are replaced by a selenium atom, such as -CH2CH2SeCH(CH3)CH2-.

[0066] The term "linking group" refers to a moiety that connects a polymerizable group to a parent molecule. The linking group may be any moiety that is compatible with the compound of which it is a part, does not undesirably interfere with the polymerization of the compound, and is stable under the polymerization conditions as well as the conditions of processing and storage of the final product. For example, the linking group may be a bond or may include one or more of alkylene, haloalkylene, amide, amine, alkyleneamine, carbamate, ester (-CO2-), arylene, heteroarylene, cycloalkylene, heterocycloalkylene, alkyleneoxy, oxaalkylene, thiaalkylene, haloalkyleneoxy (alkyleneoxy substituted with one or more halo groups, e.g., -OCF2-, -OCF2CF2-, -OCF2CH2-), siloxanyl, alkylenesiloxanyl, or combinations thereof. The linking group may be optionally substituted with one or more substituents. Suitable substituents can include those independently selected from alkyl, halo (e.g., fluoro), hydroxyl, HO-alkyleneoxy, MeO-alkyleneoxy, siloxanyl, siloxy, siloxy-alkyleneoxy-, siloxy-alkylene-alkyleneoxy- (wherein there can be more than one alkyleneoxy group, and each methylene in the alkylene and alkyleneoxy is independently optionally substituted with hydroxyl), ether, amine, carbonyl, carbamate, and combinations thereof. The linking group can also be substituted with a polymerizable group (in addition to the polymerizable group to which it is attached), such as (meth)acrylate.

[0067] Preferred linking groups include C1-C8 alkylene (preferably C2-C6 alkylene), C1-C8 oxaalkylene (preferably C2-C6 oxaalkylene), C1-C8 thiaalkylene, C1-C8 alkylene-carboxylate-C1-C8 alkylene, C1-C8 alkylene-amide-C1-C8 alkylene, and C1-C8 alkylene-amine-C1-C8 alkylene, each of which is substituted with one or two groups each independently selected from hydroxyl and siloxy.

[0068] When the linking group is composed of a combination of moieties as described above (e.g., alkylene and cycloalkylene), such moieties may be present in any order. For example, in the following formula A, when L is shown to be -alkylene-cycloalkylene-, Rg-L may be either Rg-alkylene-cycloalkylene- or Rg-cycloalkylene-alkylene-. Regardless, the order listed represents the preferred order in which the moieties appear in the compound, starting from the terminal polymerizable group (Rg or Pg) to which the linking group is attached. For example, in formula A, when L is shown to be alkylene-cycloalkylene, Rg-L is preferably Rg-alkylene-cycloalkylene-.

[0069] The linking group may be or may contain one or more oxidizable functional groups. Exemplary linking groups containing oxidizable functional groups include, for example, thiaalkylene, alkyleneamine, and selenoalkylene.

[0070] The term "light absorbing compound" refers to a chemical that absorbs light within the visible spectrum (e.g., in the range of 380-780 nm). The ability of a material to absorb light of a particular wavelength can be determined by measuring its UV / Vis transmission or absorbance spectrum.

[0071] When the compounds described herein contain olefinic double bonds or other centers of geometric asymmetry, unless otherwise specified, the compounds are intended to include the cis, trans, Z-, and E-configurations, as well as all tautomeric and salt forms.

[0072] The term "optional substituent" means that an underlying hydrogen atom is optionally replaced by a substituent. Any substituent that is sterically practical at the substitution site and synthetically feasible may be used. Identification of suitable optional substituents is within the ability of one of ordinary skill in the art. Examples of "optional substituents" include C1-C6 alkyl, C1-C6 alkoxy, C1-C6 thioalkyl, C1-C6 selenoalkyl, C3-C7 cycloalkyl, aryl, halo, hydroxy, amino, NR 4 R 5 , benzyl, SO3H, SO3Na, or -LP g In particular, but not limited to, 4 and R 5 are independently H or C1-C6 alkyl, L is a linking group, and P g is a polymerizable group. The aforementioned substituents may be optionally substituted with optional substituents (which are preferably not further substituted unless otherwise indicated). For example, alkyl may be substituted with halo (e.g., resulting in CF3).

[0073] The term "oxidizable functional group" refers to a functional group that can undergo oxidation, such as an increase in oxygen content. Preferred oxidizable functional groups include groups that contain oxidizable sulfur, selenium, and / or nitrogen atoms.

[0074] "Substructure" refers to a compound having a specified chemical structure, as well as any compound derived from the specified chemical structure, through the replacement of one or more hydrogen atoms with any other atom or group (wherein the atom or group may be bonded to other atoms or groups). The replacement may be, for example, one or more, preferably one or three, more preferably one or two hydrogen atoms with any independently selected substituent. Included in the definition of "substructure" are materials in which the specified chemical structure forms a fragment of a larger compound, such as a monomer (e.g., containing one or more polymerizable groups), polymer, macromolecule, or polymer network.

[0075] "Visible light absorption maximum" means the wavelength within the visible light wavelength range (380 nm to 760 nm) at which the absorbance of light is greatest. The definition includes materials that exhibit an overall absorption maximum outside the visible light range, such as in the UV region.

[0076] As noted above, in one aspect, the present invention provides a contact lens comprising a first region, a second region, a visible light absorbing chromophore, and a derivative of the visible light absorbing chromophore, wherein the first region contains the visible light absorbing chromophore and the second region contains the derivative of the visible light absorbing chromophore, and the second region has a greater average transmittance than the first region over a wavelength range of 400 nm to 600 nm.

[0077] The contact lens defines at least a first region and a second region. The first region and the second region may correspond to different portions of the lens. For example, the first region may correspond to a central zone of the lens, including the pupil region of the lens, and the second region may correspond to a peripheral zone of the lens. Alternatively, the second region may correspond to the central zone and the first region may correspond to the peripheral zone.

[0078] According to the invention, the lens comprises a visible light absorbing chromophore in a first region and a derivative of the visible light absorbing chromophore in a second region. The derivative of the visible light absorbing chromophore exhibits a greater average light transmission over the wavelength range of 400-600 nm than the visible light absorbing chromophore. As a result, the average transmission of the second region of the lens over the range of 400-600 nm is greater than the average percent transmission of the first region. Thus, if the first region corresponds to the central zone of the lens and the second region corresponds to the peripheral zone, the light absorbing chromophore (which itself can exhibit a visible color) will be concentrated primarily in the central region, resulting in a lens that can exhibit less color in the peripheral zone. In this way, a more cosmetically pleasing lens can be achieved than would be obtained if the visible light absorbing chromophore were uniformly distributed throughout the lens.

[0079] The visible light absorbing chromophore of the lens of the present invention preferably absorbs light in the wavelength range of 380 nm to 760 nm, or 400 to 600 nm, or 400 to 500 nm, or 400 to 470 nm. For example, the average transmittance of the visible light absorbing chromophore over the range of 400 to 600 nm may be 95 percent or less, or 85 percent or less. As a further example, the average transmittance of the visible light absorbing chromophore over the range of 400 to 500 nm may be 95 percent or less, or 85 percent or less, or 70 percent or less. As a further example, the average transmittance of the visible light absorbing chromophore over the range of 400 to 460 nm may be 95 percent or less, or 85 percent or less, or 70 percent or less, or 60 percent or less. As a further example, the average transmittance of the visible light absorbing chromophore over the range of 380 to 450 nm may be 95 percent or less, or 85 percent or less, or 70 percent or less, or 65 percent or less, or 60 percent or less.

[0080] The visible light absorbing chromophore preferably comprises an oxidizable functional group, which is preferably an S, Se, or amine group.

[0081] The visible light absorbing chromophore may be photochromic or static. Exemplary chromophores include light absorbing functional groups selected from, for example, chromenes, spiropyrans, oxazines, mercury dithizonates, fulgides, fulgimides, organometallic dithiozonates, naphthacenediones, benzotriazoles, acetophenones, benzophenones, azos, diphenyldiazines, alkoxyanilines, tetrahydronaphthalenes, anthraquinones, anthracenes, dihydroanthracenes, selenoxanthenes, thioxanthenes, acridines, derivatives thereof, or mixtures of two or more thereof.

[0082] The visible light absorbing chromophore can be, for example, represented by the following formula I:

[0083] [ka] may have the substructure In the formula, R B is -C(=O)H or EWG, X is NR, S, or Se, R is H, C1-C6 alkyl, cycloalkyl, heterocycloalkyl, aryl, or heteroaryl, and EWG at each occurrence is independently an electron withdrawing group (e.g., cyano).

[0084] Preferred substructures of formula I include those where X is S.

[0085] Preferred substructures of formula I include those where X is NR.

[0086] Preferred substructures of formula I include those where X is Se.

[0087] Preferred substructures of formula I include R B is an EWG, preferably cyano. More preferably, each occurrence of the EWG is cyano.

[0088] Preferred substructures of formula I include R B is -C(=O)H.

[0089] Typically, the chromophores described herein absorb visible light and therefore may exhibit a noticeable color to the observer. One advantage of the present invention is that by concentrating the visible light absorbing chromophore in selected regions of the lens, such as the central zone, and reducing its concentration in other regions, such as the peripheral zone, the presence of the chromophore becomes less noticeable.

[0090] In the lenses of the invention, the visible light absorbing chromophore is derivatized to a form that exhibits a greater average visible light transmission than the parent chromophore in the region where it is desired to reduce or eliminate the color of the chromophore, for example in the range of 400-600 nm. Thus, the derivative may exhibit a less noticeable color to the observer, or even no color. For example, the average transmission of the derivative over the wavelength range of 400-600 nm (or 400-500 nm, or 400-460 nm, or 380-450 nm) may be at least 5 percent greater, or at least 10 percent greater, or at least 15 percent greater, or at least 20 percent greater, or at least 30 percent greater, or at least 40 percent greater, or at least 50 percent greater than the average transmission of the visible light absorbing chromophore over the same wavelength range.

[0091] The derivative of the visible light absorbing chromophore may be an oxidized derivative of the visible light absorbing chromophore. For example, the derivative may be an oxidized derivative of the visible light absorbing chromophore. + RO - , SO, SO2, SeO, or SeO2, where R is, for example, H, C1-C6 alkyl, cycloalkyl, heterocycloalkyl, aryl, or heteroaryl.

[0092] The derivative may be, for example, a compound of the formula II below, in which case the visible light absorbing chromophore present in the lens has the substructure of formula I as shown above:

[0093] [ka] may have the substructure In the formula, R B is -C(=O)H or EWG, and X' is N + RO - , SO, SO2, SeO, or SeO2, R is H, C1-C6 alkyl, cycloalkyl, heterocycloalkyl, aryl, or heteroaryl, and EWG at each occurrence is independently an electron withdrawing group (e.g., cyano).

[0094] Preferred substructures of formula II include those where X' is SO.

[0095] Preferred substructures of formula II include those where X' is SO2.

[0096] Preferred substructures of formula II include those where X' is a mixture of SO and SO2.

[0097] Preferred substructures of formula II include those where X' is SeO.

[0098] Preferred substructures of formula II include those where X' is SeO2.

[0099] Preferred substructures of formula II include those where X' is a mixture of SeO and SeO2. Preferred substructures of formula II include those where X' is N + RO - Examples of such items include:

[0100] Preferred substructures of formula II include R B is an EWG, preferably cyano. More preferably, each occurrence of the EWG is cyano.

[0101] Preferred substructures of formula II include R B is -C(=O)H.

[0102] As noted above, the present invention also provides a method for making a contact lens as described herein, the method comprising providing a lens precursor having a first region and a second region, the lens precursor containing a visible light absorbing chromophore in the first region and the second region, and selectively derivatizing the visible light absorbing chromophore in the second region to form a derivative of the visible light absorbing chromophore, the derivative having a greater average transmittance over the wavelength range of 400 nm to 600 nm than the visible light absorbing chromophore.

[0103] The lens precursor for use in the method may simply be any of the contact lenses mentioned above that further contain a visible light absorbing chromophore.For example, the lens precursor may be a material selected from any of the following (and contain a visible light absorbing chromophore): etafilcon, genfilcon, hilafilcon, lenefilcon, nesofilcon, omafilcon, polymacon, bifilcon, aquafilcon, asmofilcon, balafilcon, comfilcon, delefilcon, enfilcon, funfilcon, formofilcon, galifilcon, lotrafilcon, narafilcon, lyofilcon, samfilcon, senofilcon, somofilcon, and stenfilcon, or any of their variants.Preferably, the lens precursor is either a conventional hydrogel containing a visible light absorbing chromophore or a silicone hydrogel containing a visible light absorbing chromophore.More preferably, it is a silicone hydrogel containing a visible light absorbing chromophore.

[0104] A lens precursor for use in the present invention may be a polymerization reaction product of a reactive mixture including (a) a chromophore-containing monomer; and (b) a monomer suitable for making a contact lens precursor. Exemplary contact lens precursors that may be used in the present invention, as well as chromophore-containing monomers, are described in U.S. Pat. No. 10,935,695, U.S. Patent Application Publication Nos. 2020 / 0407324 and 2020 / 0407337, and applicant's co-pending U.S. Patent Application No. 17 / 456,659, filed Nov. 29, 2021, each of which is incorporated herein by reference in its entirety.

[0105] For example, the chromophore-containing monomer may be represented by the following formula III:

[0106] [ka] may contain compounds of During the ceremony, m and n are independently 0, 1, 2, 3, or 4; R CEWC or formula-TYP g T is a bond, O, or NR; Y is a linking group; P g is a polymerizable group, X is O, NR, S, or Se; R, at each occurrence, is independently H, C1-C6 alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, or YP g and R 1 and R 2 is, when present, independently selected from C1-C6 alkyl, C1-C6 alkoxy, C1-C6 thioalkyl, C1-C6 selenoalkyl, C3-C7 cycloalkyl, aryl, halo, hydroxy, amino, NR 3 R 4 , benzyl, or -YP g and R 3 and R 4 are independently H or C1-C6 alkyl, or two adjacent R 1 Or R 2 the groups, together with the carbon atoms to which they are attached, are joined to form a cycloalkyl or aryl ring; EWG, for each occurrence, is independently an electron-withdrawing group, The compound of formula III comprises at least one P g group and at least one oxidizable functional group.

[0107] The chromophore-containing monomer has formula IV:

[0108] [ka] may contain compounds of During the ceremony, m and n are independently 0, 1, 2, 3, or 4; R C EWC or formula-TYP g T is a bond, O, or NR; Y is a linking group; P g is a polymerizable group, X is NR, S, or Se; R, at each occurrence, is independently H, C1-C6 alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, or YP g and R 1 and R 2 is, when present, independently selected from C1-C6 alkyl, C1-C6 alkoxy, C1-C6 thioalkyl, C1-C6 selenoalkyl, C3-C7 cycloalkyl, aryl, halo, hydroxy, amino, NR 3 R 4 , benzyl, or -YP g and R 3 and R 4 are independently H or C1-C6 alkyl, or two adjacent R 1 Or R 2 the groups, together with the carbon atoms to which they are attached, are joined to form a cycloalkyl or aryl ring; EWG, for each occurrence, is independently an electron-withdrawing group, The compound of formula III has at least one P g Contains a group.

[0109] The chromophore-containing monomer has the following formula V:

[0110] [ka] may contain compounds of During the ceremony, m and n are independently 0, 1, 2, 3, or 4; T is a bond, O, or NR; X is NR, S, or Se; Y is a linking group; P g is a polymerizable group, R, at each occurrence, is independently H, C1-C6 alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, or YP g and R 1 and R2 is, when present, independently selected from C1-C6 alkyl, C1-C6 alkoxy, C1-C6 thioalkyl, C1-C6 selenoalkyl, C3-C7 cycloalkyl, aryl, halo, hydroxy, amino, NR 3 R 4 or benzyl, R 3 and R 4 are independently H or C1-C6 alkyl, or two adjacent R 1 Or R 2 the groups, together with the carbon atoms to which they are attached, are joined to form a cycloalkyl or aryl ring; EWG is an electron withdrawing group.

[0111] Preferred compounds of formula V include those where Y, at each occurrence, is independently alkylene, cycloalkylene, heterocycloalkylene, arylene, heteroarylene, oxaalkylene, alkylene-amide-alkylene, alkylene-amine-alkylene, or combinations thereof.

[0112] Preferred compounds of formula V include P g Examples of the vinyl ether include styryl, vinyl carbonate, vinyl ether, vinyl carbamate, N-vinyl lactam, N-vinyl amide, (meth)acrylate, or (meth)acrylamide.

[0113] Preferred compounds of formula V include those where X is N.

[0114] Preferred compounds of formula V include those where X is S.

[0115] Preferred compounds of formula V include those in which EWG at each occurrence is independently cyano, amide, ester, keto, or aldehyde. More preferably, EWG at each occurrence is cyano.

[0116] Preferred compounds of formula V include those where m and n are each zero.

[0117] The chromophore-containing monomer has the following formula VI:

[0118] [ka] may contain compounds of wherein EWG, at each occurrence, is independently an electron withdrawing group; R 1 YP g Y is a linking group, and P g is a polymerizable group.

[0119] Preferred compounds of formula VI include P g The (polymerizable group) may include styryl, vinyl carbonate, vinyl ether, vinyl carbamate, N-vinyl lactam, N-vinyl amide, (meth)acrylate, or (meth)acrylamide. A preferred polymerizable group may include (meth)acrylate or (meth)acrylamide. A more preferred polymerizable group is methacrylate.

[0120] Preferred compounds of formula VI include those in which Y (the linking group) is alkylene, cycloalkylene, heterocycloalkylene, arylene (e.g., phenylene), heteroarylene, oxaalkylene, alkylene-amide-alkylene, alkylene-amine-alkylene, or any combination of the foregoing groups. Preferred linking groups include C1-C8 alkylene (e.g., ethylene or propylene), C1-C8 oxaalkylene, C1-C8 alkylene-amide-C1-C8 alkylene, and C1-C8 alkylene-amine-C1-C8 alkylene. Particularly preferred are C1-C8 oxaalkylene, C2-C4 oxaalkylene, or oxaethylene (-O-CH2CH2-).

[0121] Preferred compounds of formula VI include those where EWG, at each occurrence, is independently cyano, amide, ester, keto, or aldehyde. EWG, at each occurrence, may be cyano.

[0122] The chromophore-containing monomer has the following formula VII:

[0123] [ka] may contain compounds of During the ceremony, T is a bond, O, or NR 6 and R 6 is H, C1-C6 alkyl, cycloalkyl, heterocycloalkyl, aryl, or heteroaryl; R is H, C1-C6 alkyl, cycloalkyl, heterocycloalkyl, aryl, or heteroaryl; Y is a linking group; P g is a polymerizable group; R 7 is H, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 thioalkyl, C1-C6 selenoalkyl, C3-C7 cycloalkyl, aryl (preferably unsubstituted phenyl or phenyl substituted by alkyl or halo), halo, hydroxy, amino, NR 3 R 4 , benzyl, SO3H, or SO3M (where M is a monovalent cation such as sodium or potassium), and R 3 and R 4 is independently H or C1-C6 alkyl; and EWG is an electron withdrawing group.

[0124] Preferred compounds of formula VII include those in which R 7 is H.

[0125] Preferred compounds of formula VII include those in which R 7 is C1 to C6 alkyl, C1 to C6 alkoxy, or C1 to C6 thioalkyl.

[0126] Preferred compounds of formula VII include those in which R 7For example, C1 to C6 alkoxy such as ethoxy or methoxy, preferably methoxy.

[0127] Preferred compounds of formula VII include those where R is H or C1-C6 alkyl. Preferably, R is C1-C6 alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, t-butyl, or sec-butyl. Preferably, R is n-propyl or n-butyl.

[0128] Preferred compounds of formula VII include those in which T is NR 6 and R 6 is H or C1 to C6 alkyl. Particularly preferred are those where R 6 is H.

[0129] Preferred compounds of formula VII include P g The (polymerizable group) may, at each occurrence, independently include styryl, vinyl carbonate, vinyl ether, vinyl carbamate, N-vinyl lactam, N-vinyl amide, (meth)acrylate, or (meth)acrylamide. Preferred polymerizable groups include (meth)acrylate or (meth)acrylamide. More preferred polymerizable groups are methacrylate.

[0130] Preferred compounds of formula VII include those in which Y (the linking group) is alkylene, cycloalkylene, heterocycloalkylene, arylene (e.g., phenylene), heteroarylene, oxaalkylene, alkylene-amido-alkylene, alkylene-amine-alkylene, or any combination of the foregoing groups. Preferred linking groups include C1-C8 alkylene (e.g., ethylene or propylene), C1-C8 oxaalkylene, C1-C8 alkylene-amido-C1-C8 alkylene, and C1-C8 alkylene-amine-C1-C8 alkylene. Particularly preferred are C1-C8 alkylenes, especially ethylene (-CH2CH2-). When T in a compound of formula VI is O, it is preferred that the carbon atom of the linking group to which O is attached is interrupted. For example, when T is O and Y is alkylene, a preferred alkylene is -C(R H )2(CH2) x - and R H is independently C1 to C6 alkyl (preferably, independently, methyl or ethyl), and x is 1 to 5.

[0131] Preferred compounds of formula VII include those in which T is a bond or NR 6 (preferably NH).

[0132] Preferred compounds of formula VII include those where EWG is cyano, amide, ester, keto, or aldehyde. Preferably, EWG is cyano.

[0133] The chromophore-containing monomer has the following formula VIII:

[0134] [ka] may contain compounds of During the ceremony, m and n are independently 0, 1, 2, 3, or 4; T is a bond, O, or NR; X is O or S; Y is a linking group; P g is a polymerizable group, R, at each occurrence, is independently H, C1-C6 alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, or YP g and R 1 and R 2 is, when present, independently selected from C1-C6 alkyl, C1-C6 alkoxy, C1-C6 thioalkyl, C1-C6 selenoalkyl, C3-C7 cycloalkyl, aryl, halo, hydroxy, amino, NR 3 R 4 or benzyl, R 3 and R 4 are independently H or C1-C6 alkyl, or two adjacent R 1 Or R 2 The groups, together with the carbon atom to which they are attached, are joined to form a cycloalkyl or aryl ring, provided that R 1 and R 2 At least one of the groups contains an oxidizable functional group; EWG is an electron withdrawing group.

[0135] Preferred compounds of formula VIII include those where Y, at each occurrence, is independently alkylene, thiaalkylene, selenoalkylene, alkyleneamine, cycloalkylene, heterocycloalkylene, arylene, heteroarylene, oxaalkylene, alkylene-amide-alkylene, alkylene-amine-alkylene, or combinations thereof.

[0136] Preferred compounds of formula VIII include P g Examples of the vinyl ether include styryl, vinyl carbonate, vinyl ether, vinyl carbamate, N-vinyl lactam, N-vinyl amide, (meth)acrylate, or (meth)acrylamide.

[0137] Preferred compounds of formula VIII include those where X is N.

[0138] Preferred compounds of formula VIII include those where X is S.

[0139] Preferred compounds of formula VIII include those where X is O.

[0140] Preferred compounds of formula VIII include those where m is 0 and n is 1.

[0141] Preferred compounds of formula VIII include those in which m is 0, n is 1, and R 2 Preferably, R 2 includes S, Se, NH, thiaalkyl, selenoalkyl, alkylamine, thiaalkylene, selenoalkylene, or alkyleneamine.

[0142] Preferred compounds of formula VIII include those in which EWG at each occurrence is independently cyano, amide, ester, keto, or aldehyde. More preferably, EWG at each occurrence is cyano.

[0143] Preferred chromophore-containing monomers include the following, including mixtures of two or more of these:

[0144] [Table 1]

[0145] Other chromophore-containing monomers that can be used in making the lens precursors of the present invention include, but are not limited to, chromenes (such as naphthopyrans, benzopyrans, indenonaphthopyrans, and phenanthropyrans); spiropyrans (such as spiro(benzoindoline)naphthopyrans, spiro(indoline)benzopyrans, spiro(indoline)naphthopyrans, spiro(indoline)quinonones, and spiro(indoline)pyranoses); oxazines (such as spiro(indoline)naphthoxazines, spiro(indoline)pyridobenzoxazines, spiro(benzoindoline)pyridabenzoxazines, spiro(benzoindoline)naphthoxazines, and spiro(indoline)benzoxazines); mercury dithizonates, fulgides, fulgimides, and mixtures of such monomers.

[0146] Additional suitable chromophore-containing monomers include, but are not limited to: (arylazo)-thioformic acid arylhydrazides, such as mercury dithizone; and organometallic dithiozonates, such as fulgides and fulgimides, naphthoxazines, spirobenzopyrans; polymeric spirobenzopyrans and spirobenzopyrans; polymeric fulgides; polymeric naphcenediones; polymeric spirooxazines; and polymeric polyalkoxylated naphthiolanes. The monomers may be used alone or in combination with one or more other chromophore-containing monomers.

[0147] Other chromophore-containing monomers are disclosed in U.S. Patent No. 7,556,750, the disclosure of which is incorporated herein by reference. Non-limiting examples of suitable monomers include naphthopyrans. These monomers may contain polymerizable functional groups so that they are copolymerized with the resulting contact lens. Examples of polymerizable functional groups include (meth)acrylates, (meth)acrylamides, vinyls, and the like.

[0148] Still other useful chromophore-containing monomers include indeno-fused naphthopyrans selected from indeno[2',3':3,4]naphtho[1,2-b]pyran and indeno[1',2':4,3]naphco[2,1-b]pyran, which are more specifically disclosed in U.S. Patent Application Publication Nos. 2009 / 0072206 and 2006 / 0226401, and are cited in U.S. Patent No. 7,364,291, and combinations thereof. A preferred chromophore-containing monomer is 4-[4-[3,13-dihydro-6-methoxy-13,13-dimethyl-3-phenyl-7-(1-piperidinyl)benzo[3,4]fluoreno[2,1-b]pyran-3-yl]phenyl]-γ-oxo, 2-[(2-methyl-1-oxo-2-propen-1-yl)oxy]ethyl ester 1-piperazinebutanoic acid (Registry No. 1339922-40-5), shown below.

[0149] [ka]

[0150] The chromophore-containing monomer may comprise a mixture of two or more of the aforementioned compounds. For example, the chromophore-containing monomer may comprise a mixture of a compound of formula III where X is S and a compound of formula III where X is NR. As a further example, the chromophore-containing monomer may comprise a mixture of a compound of formula V where X is S and a compound of formula VII. Alternatively, the chromophore-containing monomer may comprise a mixture of 2-(2-cyano-2-(9H-thioxanthen-9-ylidene)acetamido)ethyl methacrylate and 2-(2-(10-butyl-2-methoxyacridin-9(10H)-ylidene)-2-cyanoacetamido)ethyl methacrylate. Alternatively, the chromophore-containing monomer may comprise a mixture of 2-(2-cyano-2-(9H-thioxanthen-9-ylidene)acetamido)ethyl methacrylate and N-(2-(2-cyano-2-(10-methylacridin-9(10H)-ylidene)acetamido)ethyl)methacrylamide.

[0151] Formation of Contact Lens Precursor To form a contact lens precursor for use in the present invention, a chromophore-containing monomer is copolymerized with one or more monomers suitable for making a contact lens precursor. The monomers can generally be added to the reactive mixture from which the polymer network is formed. The chromophore-containing monomer can be present in the reactive mixture in any amount up to its solubility limit. For example, the chromophore-containing monomer can be present in a concentration of at least 0.1 percent, at least 1 percent, or at least 2 percent, and up to 10 percent or up to 5 percent, based on the weight percent of all components in the reactive mixture excluding the diluent. Typical concentrations can be in the range of 1 to 5 percent. The upper limit is typically determined by the solubility of the compound with other comonomers and / or diluents in the reactive monomer mixture.

[0152] Copolymerization conditions for forming the contact lens precursors described herein, including typical types of monomers, initiators, diluents, etc., are well known to those skilled in the art and are described, for example, in the patents referenced above.

[0153] A contact lens precursor for use in the present invention may comprise a free radical reaction product of a reactive mixture containing one or more monomers suitable for making a contact lens precursor (also referred to herein as device-forming monomers or hydrogel-forming monomers), one or more chromophore-containing monomers, and optional ingredients. Upon polymerization, the reactive mixture results in the formation of a polymer network in which the contact lens precursor may be comprised. The polymer network may be, for example, a hydrogel (e.g., a conventional hydrogel or a silicone hydrogel).

[0154] Non-limiting examples of polymer networks into which the chromophore-containing monomers may be incorporated (e.g., as monomers) include the materials described above, such as etafilcon, genfilcon, hilafilcon, lenefilcon, nesofilcon, omafilcon, polymafilcon, bifilcon, aquafilcon, asmofilcon, balafilcon, comfilcon, delefilcon, enfilcon, funfilcon, formofilcon, galyfilcon, lotrafilcon, narafilcon, lyofilcon, samfilcon, senofilcon, somofilcon, and stenfilcon, or any of their variants.

[0155] As a further example, the polymer network may be made from a reactive mixture that includes one or more of a hydrophilic component, a hydrophobic component, a silicone-containing component, a wetting agent such as a polyamide, a crosslinker, and additional components such as a diluent and an initiator. As mentioned above, the reactive mixture also includes a chromophore-containing monomer. Examples of various monomers and other materials for making the polymer network from which the lens precursor of the present invention can be constructed are as follows:

[0156] hydrophilic component Examples of suitable families of hydrophilic monomers that may be present in the reactive mixture 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.

[0157] Non-limiting examples of hydrophilic (meth)acrylate and (meth)acrylamide monomers include acrylamide, N-isopropylacrylamide, N,N-dimethylaminopropyl(meth)acrylamide, N,N-dimethylacrylamide (DMA), 2-hydroxyethyl methacrylate (HEMA), 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 ... N-hydroxypropyl)(meth)acrylamide, N-(2-hydroxybutyl)(meth)acrylamide, N-(3-hydroxybutyl)(meth)acrylamide, N-(4-hydroxybutyl)(meth)acrylamide, 2-aminoethyl(meth)acrylate, 3-aminopropyl(meth)acrylate, 2-aminopropyl(meth)acrylate, N-2-aminoethyl(meth)acrylamide), N-3-aminopropyl(meth)acrylamide, N-2-aminopropyl(meth)acrylamide, N,N-bis-2-aminoethyl(meth)acrylamide, N,N-bis-3-aminopropyl(meth)acrylamide), N,N-bis-2-aminopropyl(meth)acrylamide, glycerol methacrylate, polyethylene glycol monomethacrylate, (meth)acrylic acid, vinyl acetate, acrylonitrile, and mixtures thereof.

[0158] The hydrophilic monomers may also be ionic, such as anionic, cationic, zwitterionic, betaine, and mixtures thereof. Non-limiting examples of such charged monomers include (meth)acrylic acid, N-[(ethenyloxy)carbonyl]-β-alanine (VINAL), 3-acrylamidopropanoic acid (ACA1), 5-acrylamidopentanoic acid (ACA2), 3-acrylamido-3-methylbutanoic acid (AMBA), 2-(methacryloyloxy)ethyltrimethylammonium chloride (Q salt or METAC), 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-phosphanedec-10-ene-1-aminium, 4-hydroxy-N,N,N-trimethyl-9-oxo-, inner salt, 4-oxide (9CI) (PBT), 2-methacryloyloxyethyl phosphorylcholine, 3-(dimethyl(4-vinylbenzyl)ammonio)propane-1-sulfonate (DMVBAPS), 3-((3-acrylamidopropyl)dimethylammonio)propane-1-sulfonate (AMPDAPS), 3-((3-methacrylamidopropyl)dimethylammonio)propane-1-sulfonate (MAMPDAPS), 3-((3-(acryloyloxy)propyl)dimethylammonio)propane-1-sulfonate (APDAPS), and methacryloyloxy)propyl)dimethylammonio)propane-1-sulfonate (MAPDAPS).

[0159] Non-limiting examples of hydrophilic N-vinyl lactam and N-vinyl amide monomers include N-vinyl pyrrolidone (NVP), N-vinyl-2-piperidone, N-vinyl-2-caprolactam, N-vinyl-3-methyl-2-caprolactam, N-vinyl-3-methyl-2-piperidone, N-vinyl-4-methyl-2-piperidone, N-vinyl-4-methyl-2-caprolactam, N-vinyl-3-ethyl-2-pyrrolidone, N-vinyl-4,5-dimethyl-2-pyrrolidone, N-vinyl acetamide (NVA), N-vinyl-N-methyl acetamide (VMA), N-vinyl-N-ethyl acetamide, N-vinyl-N-ethyl formamide, N-vinyl formamide, N-vinyl-N-methyl propionamide, N-vinyl-N-methyl-2-methyl propionamide, N-vinyl ... N-methylpropionamide, N-vinyl-N,N'-dimethylurea, 1-methyl-3-methylene-2-pyrrolidone, 1-methyl-5-methylene-2-pyrrolidone, 5-methyl-3-methylene-2-pyrrolidone; 1-ethyl-5-methylene-2-pyrrolidone, N-methyl-3-methylene-2-pyrrolidone, 5-ethyl-3-methylene-2-pyrrolidone, 1-N-propyl-3-methylene-2-pyrrolidone, 1-N-propyl-5-methylene-2-pyrrolidone, 1-isopropyl-3-methylene-2-pyrrolidone, 1-isopropyl-5-methylene-2-pyrrolidone, N-vinyl-N-ethylacetamide, N-vinyl-N-ethylformamide, N-vinylformamide, N-vinylisopropylamide, N-vinylcaprolactam, N-vinylimidazole, and mixtures thereof.

[0160] Non-limiting examples of hydrophilic O-vinyl carbamate and O-vinyl carbonate monomers include N-2-hydroxyethyl vinyl carbamate and N-carboxy-β-alanine N-vinyl ester. Further examples of hydrophilic vinyl carbonate or vinyl carbamate monomers are disclosed in U.S. Patent No. 5,070,215. Hydrophilic oxazolone monomers are disclosed in U.S. Patent No. 4,910,277.

[0161] Other hydrophilic vinyl compounds include ethylene glycol vinyl ether (EGVE), di(ethylene glycol) vinyl ether (DEGVE), allyl alcohol, and 2-ethyloxazoline.

[0162] The hydrophilic monomer may also be a macromer or prepolymer of linear or branched poly(ethylene glycol), poly(propylene glycol), or statistical random or block copolymers of ethylene oxide and propylene oxide, having polymerizable moieties such as (meth)acrylates, styrenes, vinyl ethers, (meth)acrylamides, N-vinyl amides, etc. Macromers of these polyethers have one polymerizable group and prepolymers may have two or more polymerizable groups.

[0163] Preferred hydrophilic monomers of the present invention are DMA, NVP, HEMA, VMA, NVA, and mixtures thereof. Preferred hydrophilic monomers include mixtures of DMA and HEMA. Other suitable hydrophilic monomers will be apparent to those skilled in the art.

[0164] Generally, there is no particular limitation regarding the amount of hydrophilic monomer present in the reactive monomer mixture. The amount of hydrophilic monomer can be selected based on the desired properties of the resulting hydrogel, including water content, transparency, wettability, protein uptake, and the like. Wettability can be measured by contact angle, with desirable contact angles being less than about 100°, less than about 80°, and less than about 60°. The hydrophilic monomer can be present in an amount ranging from about 0.1 to about 100 weight percent, or from about 1 to about 80 weight percent, or from about 5 to about 65 weight percent, or from about 40 to about 60 weight percent, or from about 55 to about 60 weight percent, based on the total weight of the reactive components in the reactive monomer mixture.

[0165] Silicone-containing ingredients Silicone-containing components suitable for use in the present invention include one or more polymerizable compounds, each compound independently including at least one polymerizable group, at least one siloxane group, and one or more linking groups connecting the polymerizable group(s) to the siloxane group(s). The silicone-containing component may contain, for example, 1 to 220 siloxane repeat units, such as those defined below. The silicone-containing component may also contain at least one fluorine atom.

[0166] The silicone-containing component may comprise one or more polymerizable groups as defined above, one or more optionally repeating siloxane units, and one or more linking groups connecting the polymerizable groups to the siloxane units. The silicone-containing component may comprise one or more polymerizable groups that are independently (meth)acrylate, styryl, vinyl ether, (meth)acrylamide, N-vinyl lactam, N-vinyl amide, O-vinyl carbamate, O-vinyl carbonate, vinyl groups, or mixtures thereof, one or more optionally repeating siloxane units, and one or more linking groups connecting the polymerizable groups to the siloxane units.

[0167] The silicone-containing component may include, independently, one or more polymerizable groups that are (meth)acrylate, (meth)acrylamide, N-vinyl lactam, N-vinyl amide, styryl, or mixtures of the foregoing; one or more optionally repeating siloxane units; and one or more linking groups connecting the polymerizable groups to the siloxane units.

[0168] The silicone-containing component may independently comprise one or more polymerizable groups that are (meth)acrylate, (meth)acrylamide, or a mixture of the foregoing, one or more optionally repeating siloxane units, and one or more linking groups connecting the polymerizable groups to the siloxane units.

[0169] The silicone-containing component has the formula A:

[0170] [ka] and During the ceremony, At least one R A is the formula R g -L-, where R g is a polymerizable group, L is a linking group, and the remaining R A are, independently: (a)R g -L-, (b) C1-C optionally substituted with one or more hydroxy, amino, amido, oxa, carboxy, alkylcarboxy, carbonyl, alkoxy, amido, carbamate, carbonate, halo, phenyl, benzyl, or combinations thereof. 16 Alkyl, (c) C-C optionally substituted with one or more alkyl, hydroxy, amino, amido, oxa, carbonyl, alkoxy, amido, carbamate, carbonate, halo, phenyl, benzyl, or combinations thereof. 12 Cycloalkyl, (d) C6-C optionally substituted with one or more alkyl, hydroxy, amino, amido, oxa, carboxy, alkylcarboxy, carbonyl, alkoxy, amido, carbamate, carbonate, halo, phenyl, benzyl, or combinations thereof. 14 Aryl groups, (e) halo, (f) alkoxy, cyclic alkoxy, or aryloxy, (g) siloxy, (h) alkyleneoxy-alkyl or alkoxy-alkyleneoxy-alkyl, such as, for example, polyethyleneoxyalkyl, polypropyleneoxyalkyl, or poly(ethyleneoxy-co-propyleneoxyalkyl), or (i) a monovalent siloxane chain comprising 1 to 100 siloxane repeat units optionally substituted with alkyl, alkoxy, hydroxy, amino, oxa, carboxy, alkylcarboxy, alkoxy, amido, carbamate, halo, or combinations thereof; n is 0 to 500, or 0 to 200, or 0 to 100, or 0 to 20, and when n is other than 0, it is understood that n is a distribution having a mode equivalent to the indicated value. When n is 2 or more, the SiO units may be the same or different R A may carry substituents, different R A When substituents are present, the n groups may be in a random or block configuration.

[0171] In formula A, three R A may each contain a polymerizable group, alternatively two R A may each contain a polymerizable group, or alternatively one R A may contain a polymerizable group.

[0172] Examples of silicone-containing components suitable for use in the present invention include, but are not limited to, the compounds listed in Table B. When the compounds in Table B contain polysiloxane groups, the number of SiO repeat units in such compounds is preferably 3 to 100, more preferably 3 to 40, or even more preferably 3 to 20, unless otherwise specified.

[0173] [Table 2-1]

[0174] [Table 2-2]

[0175] Additional non-limiting examples of suitable silicone-containing components are listed in Table C. Unless otherwise specified, where applicable, j2 is preferably 1 to 100, more preferably 3 to 40, or even more preferably 3 to 15. In compounds containing j1 and j2, the sum of j1 and j2 is preferably 2 to 100, more preferably 3 to 40, or even more preferably 3 to 15.

[0176] [Table 3-1]

[0177] [Table 3-2]

[0178] Mixtures of silicone-containing components may also be used.For example, suitable mixtures may include, but are not limited to, mixtures of mono-(2-hydroxy-3-methacryloxypropyloxy)-propyl-terminated mono-n-butyl-terminated polydimethylsiloxanes (OH-mPDMS) with different molecular weights, such as mixtures of OH-mPDMS with 4 and 15 repeating SiO units, mixtures of OH-mPDMS with different molecular weights (e.g., containing 4 and 15 repeating SiO units) with silicone-based crosslinkers, such as bis-3-acryloxy-2-hydroxypropyloxypropyl polydimethylsiloxanes (ac-PDMS), mixtures of 2-hydroxy-3-[3-methyl-3,3-di(trimethylsiloxy)silylpropoxy]-propyl methacrylate (SiMAA) with mono-methacryloxypropyl-terminated mono-n-butyl-terminated polydimethylsiloxanes (mPDMS), such as mPDMS1000.

[0179] The silicone-containing component used in the present invention can have an average molecular weight of from about 400 to about 4000 Daltons.

[0180] The silicone-containing component(s) may be present in an amount up to about 95%, or from about 10 to about 80%, or from about 20 to about 70% by weight of the reactive mixture (excluding diluent), based on all reactive components.

[0181] polyamide The reactive mixture may include at least one polyamide. As used herein, the term "polyamide" refers to polymers and copolymers that include repeating units that contain amide groups. The polyamide may include cyclic amide groups, non-cyclic amide groups, and combinations thereof, and may be any polyamide known to those skilled in the art. Non-cyclic polyamides include pendant non-cyclic amide groups and are capable of association with hydroxyl groups. Cyclic polyamides include cyclic amide groups and are capable of association with hydroxyl groups.

[0182] Examples of suitable acyclic polyamides include those of formulae G1 and G2:

[0183] [ka] and polymers and copolymers comprising the repeat unit In the formula, X is a direct bond, -(CO)-, or -(CONHR 44 )- and R 44 is a C1-C3 alkyl group, and R 40 is selected from H, linear or branched, substituted or unsubstituted C1-C4 alkyl groups, R 41 is selected from H, straight or branched, substituted or unsubstituted C1-C4 alkyl groups, amino groups having up to 2 carbon atoms, amido groups having up to 4 carbon atoms, and alkoxy groups having up to 2 carbon atoms; R 42 is selected from H, a linear or branched, substituted or unsubstituted C1-C4 alkyl group, or selected from methyl, ethoxy, hydroxyethyl, and hydroxymethyl; R 43 is selected from H, a linear or branched, substituted or unsubstituted C1-C4 alkyl group, or selected from methyl, ethoxy, hydroxyethyl, and hydroxymethyl; R 40 and R 41 The number of carbon atoms in R is 8 or less, including 7, 6, 5, 4, 3, or fewer, in total; 42 and R 43 The number of carbon atoms in R is 8 or less in total, including 7, 6, 5, 4, 3, or fewer. 40and R 41 The total number of carbon atoms in R may be 6 or less, or 4 or less. 42 and R 43 may have a total of up to 6 carbon atoms. As used herein, a substituted alkyl group includes an alkyl group substituted with an amine group, an amide group, an ether group, a hydroxyl group, a carbonyl group, or a carboxyl group, or combinations thereof.

[0184] R 40 and R 41 may be independently selected from H, a substituted or unsubstituted C1-C2 alkyl group; X may be a direct bond, and R 40 and R 41 may be independently selected from H, a substituted or unsubstituted C1-C2 alkyl group. 42 and R 43 may be independently selected from H, substituted or unsubstituted C1-C2 alkyl groups, methyl, ethoxy, hydroxyethyl, and hydroxymethyl.

[0185] The acyclic polyamides of the invention may comprise a majority of repeat units of formula LV or formula LVI, or the acyclic polyamides may comprise at least 50 mole percent of repeat units of formula G or formula G1, such as at least about 70 mole percent and at least 80 mole percent. Specific examples of repeat units of formula G and formula G1 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 repeat units derived from acrylamide of formulas G2 and G3 below:

[0186] [ka]

[0187] Examples of suitable cyclic amides that can be used to form the cyclic polyamides include α-lactams, β-lactams, γ-lactams, δ-lactams, and ε-lactams. Examples of suitable cyclic polyamides include those represented by formula G4:

[0188] [ka] and polymers and copolymers comprising the repeat unit In the formula, R 45 is a hydrogen atom or a methyl group, f is a number from 1 to 10, and X is a direct bond, -(CO)-, or -(CONHR 46 )- and R 46 is a C1-C3 alkyl group. In formula LIX, f can be 8 or less, including 7, 6, 5, 4, 3, 2, or 1. In formula G4, f can be 6 or less, for example, 5, 4, 3, 2, or 1. In formula G4, f can be 2-8, for example, 2, 3, 4, 5, 6, 7, or 8. In formula LIX, f can be 2 or 3. When X is a direct bond, f can be 2. In such cases, the cyclic polyamide can be polyvinylpyrrolidone (PVP).

[0189] The cyclic polyamides of the present invention may comprise 50 mole percent or more of repeat units of formula G4, or the cyclic polyamides may comprise at least 50 mole percent of repeat units of formula G4, such as at least 70 mole percent, and at least 80 mole percent.

[0190] Polyamides may also be copolymers containing both cyclic and non-cyclic amide repeat units. The additional repeat units may be formed from monomers selected from hydroxyalkyl (meth)acrylates, alkyl (meth)acrylates, other hydrophilic monomers, and siloxane-substituted (meth)acrylates. Any of the monomers listed as suitable hydrophilic monomers may be used as comonomers to form the additional repeat units. Specific examples of additional monomers that may be used to form polyamides include 2-hydroxyethyl (meth)acrylate, vinyl acetate, acrylonitrile, hydroxypropyl (meth)acrylate, methyl (meth)acrylate and hydroxybutyl (meth)acrylate, dihydroxypropyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, and the like, and mixtures thereof. Ionic monomers may also be included.Examples of ionic monomers include (meth)acrylic acid, N-[(ethenyloxy)carbonyl]-β-alanine (VINAL, CAS#148969-96-4), 3-acrylamidopropanoic acid (ACA1), 5-acrylamidopentanoic acid (ACA2), 3-acrylamido-3-methylbutanoic acid (AMBA), 2-(methacryloyloxy)ethyltrimethylammonium chloride (Q salt or METAC), 2-acrylamido-2-methylpropanesulfonic acid (AMPS), 1-propaneaminium, N-(2-carboxyethyl)-N,N-dimethyl-3- [(1-oxo-2-propen-1-yl)amino]-, inner salt (CBT, carboxybetaine; CAS#79704-35-1), 1-propanaminium,N,N-dimethyl-N-[3-[(1-oxo-2-propen-1-yl)amino]propyl]-3-sulfo-, inner salt (SBT, sulfobetaine; CAS#80293-60-3), 3,5-dioxa-8-aza-4-phosphane-10-en-1-aminium,4-hydroxy-N,N,N-trimethyl-9-oxo-, inner salt, 4-oxide (9CI) (PBT, phosphobetaine; CAS#80293-60-3). 163674-35-9, 2-methacryloyloxyethyl phosphorylcholine, 3-(dimethyl(4-vinylbenzyl)ammonio)propane-1-sulfonate (DMVBAPS), 3-((3-acrylamidopropyl)dimethylammonio)propane-1-sulfonate (AMPDAPS), 3-((3-methacrylamidopropyl)dimethylammonio)propane-1-sulfonate (MAMPDAPS), 3-((3-(acryloyloxy)propyl)dimethylammonio)propane-1-sulfonate (APDAPS), methacryloyloxy)propyl)dimethylammonio)propane-1-sulfonate (MAPDAPS).

[0191] The reactive monomer mixture may include both acyclic and cyclic polyamides or copolymers thereof. The acyclic polyamide may be any of the acyclic polyamides or copolymers thereof described herein, while the cyclic polyamide may be any of the cyclic polyamides or copolymers thereof described herein. The polyamide may be selected from the group of polyvinylpyrrolidone (PVP), polyvinylmethylacetamide (PVMA), polydimethylacrylamide (PDMA), polyvinylacetamide (PNVA), poly(hydroxyethyl(meth)acrylamide), polyacrylamide, and copolymers and mixtures thereof. The polyamide may be a combination of PVP (e.g., PVP K90) and PVMA (e.g., PVMA with an M of about 570 KDa). w It may be a mixture with

[0192] The total amount of all polyamides in the reactive mixture can be in the range of 1% to about 35% by weight, such as in the range of 1% to about 15% by weight, and such as in the range of about 5% to about 15% by weight, in all cases based on the total weight of the reactive components of the reactive monomer mixture.

[0193] Without being bound by theory, when used with silicone hydrogels, polyamides function as internal wetting agents. The polyamides of the present invention may be non-polymeric, in which case they are incorporated into the silicone hydrogel as a semi-interpenetrating network. The polyamides are encapsulated or physically held within the silicone hydrogel. Alternatively, the polyamides of the present invention may be polymeric, for example as polyamide macromers or prepolymers, in which case they are covalently incorporated into the silicone hydrogel. Mixtures of polymeric and non-polymeric polyamides may also be used.

[0194] When a polyamide is incorporated within the reactive monomer mixture, the polyamide may have a weight average molecular weight of at least 100,000 Daltons, greater than about 150,000, from about 150,000 to about 2,000,000 Daltons, from about 300,000 Daltons to about 1,800,000 Daltons. Higher molecular weight polyamides can be used if compatible with the reactive monomer mixture.

[0195] Crosslinking Agent Generally, it is desirable to add one or more crosslinking agents, also referred to as crosslinking monomers, multifunctional macromers, and prepolymers, to the reactive mixture. The crosslinking agents may be selected from difunctional crosslinkers, trifunctional crosslinkers, tetrafunctional crosslinkers, and mixtures thereof, including silicone-containing and non-silicone-containing crosslinkers. Non-silicone-containing crosslinkers include ethylene glycol dimethacrylate (EGDMA), tetraethylene glycol dimethacrylate (TEGDMA), trimethylolpropane trimethacrylate (TMPTMA), triallyl cyanurate (TAC), glycerol trimethacrylate, methacryloxyethyl vinyl carbonate (HEMAVc), allyl methacrylate, methylene bisacrylamide (MBA), and polyethylene glycol dimethacrylate, where the polyethylene glycol has a molecular weight of up to about 5000 Daltons. The crosslinking agents are used in the reactive mixture in conventional amounts, for example, from about 0.000415 to about 0.0156 moles per 100 grams of reactive formulation. Alternatively, if the hydrophilic monomer and / or silicone-containing component is multifunctional due to molecular design or impurities, adding a crosslinker to the reactive mixture is optional. Examples of hydrophilic monomers and macromers that can act as crosslinkers and do not require the addition of additional crosslinkers to the reactive mixture when present include (meth)acrylate and (meth)acrylamide end-capped polyethers. Other crosslinkers will be known to those skilled in the art and can be used to make the silicone hydrogel of the present invention.

[0196] It may be desirable to select a crosslinker that has a similar reactivity to one or more of the other reactive components in the formulation. In some cases, it may be desirable to select a mixture of crosslinkers with different reactivities to control some physical, mechanical, or biological properties of the resulting silicone hydrogel. The structure and morphology of the silicone hydrogel may also be affected by the diluent(s) and curing conditions used.

[0197] Multifunctional silicone-containing components, including macromers, crosslinkers, and prepolymers, may also be included to further increase modulus and maintain tensile strength. Silicone-containing crosslinkers may be used alone or in combination with other crosslinkers. An example of a silicone-containing component that can act as a crosslinker and does not require the addition of a crosslinking monomer to the reactive mixture when present includes α,ω-bismethacryloylpropylpolydimethylsiloxane. Another example is bis-3-acryloxy-2-hydroxypropyloxypropylpolydimethylsiloxane (ac-PDMS).

[0198] Crosslinkers with rigid chemical structures and polymerizable groups that undergo free radical polymerization may also be used. Non-limiting examples of suitable rigid structures include crosslinkers containing phenyl and benzyl rings, such as 1,4-phenylenediacrylate, 1,4-phenylenedimethacrylate, 2,2-bis(4-methacryloxyphenyl)-propane, 2,2-bis[4-(2-acryloxyethoxy)phenyl]propane, 2,2-bis[4-(2-hydroxy-3-methacryloxypropoxy)phenyl]propane, and 4-vinylbenzyl methacrylate, and combinations thereof. Rigid crosslinkers may be included in an amount of about 0.5 to about 15, or about 2 to 10, 3 to 7, based on the total weight of all reactive components. The physical and mechanical properties of the silicone hydrogels of the present invention may be optimized for a particular application by adjusting the components in the reactive mixture.

[0199] Non-limiting examples of silicone crosslinkers also include the multifunctional silicone-containing components set forth in Table D above.

[0200] Further components The reactive mixture may contain additional components such as, but not limited to, diluents, initiators, UV absorbers, visible light absorbers, photochromic compounds, pharmaceuticals, nutritional supplements, antimicrobial substances, colorants, pigments, copolymerizable dyes, non-polymerizable dyes, release agents, and combinations thereof.

[0201] Suitable types of diluents for the silicone hydrogel reactive mixture include alcohols having 2 to 20 carbon atoms, amides derived from primary amines having 10 to 20 carbon atoms, and carboxylic acids having 8 to 20 carbon atoms. The diluents can be primary, secondary, and tertiary alcohols.

[0202] Generally, the reactive components are mixed in a diluent to form a reactive mixture. Suitable diluents are known in the art. For silicone hydrogels, suitable diluents are disclosed in WO 03 / 022321 and U.S. Pat. No. 6,020,445, the disclosures of which are incorporated herein by reference. Suitable diluent types for silicone hydrogel reactive mixtures include alcohols having 2-20 carbons, amides having 10-20 carbon atoms derived from primary amines, and carboxylic acids having 8-20 carbon atoms. Primary and tertiary alcohols may be used. Preferred types include alcohols having 5-20 carbons and carboxylic acids having 10-20 carbon atoms. Specific diluents that may be used include 1-ethoxy-2-propanol, diisopropylaminoethanol, isopropanol, 3,7-dimethyl-3-octanol, 1-decanol, 1-dodecanol, 1-octanol, 1-pentanol, 2-pentanol, 1-hexanol, 2-hexanol, 2-octanol, 3-methyl-3-pentanol, tert-amyl alcohol, tert-butanol, 2-butanol, 1-butanol, 2-methyl-2 ... Examples of diluents include ethanol, 2-propanol, 1-propanol, ethanol, 2-ethyl-1-butanol, (3-acetoxy-2-hydroxypropyloxy)-propylbis(trimethylsiloxy)methylsilane, 1-tert-butoxy-2-propanol, 3,3-dimethyl-2-butanol, tert-butoxyethanol, 2-octyl-1-dodecanol, decanoic acid, octanoic acid, dodecanoic acid, 2-(diisopropylamino)ethanol, mixtures thereof, and the like. Examples of amide diluents include N,N-dimethylpropionamide and dimethylacetamide.

[0203] Preferred diluents include 3,7-dimethyl-3-octanol, 1-dodecanol, 1-decanol, 1-octanol, 1-pentanol, 1-hexanol, 2-hexanol, 2-octanol, 3-methyl-3-pentanol, 2-pentanol, t-amyl alcohol, tert-butanol, 2-butanol, 1-butanol, 2-methyl-2-pentanol, 2-ethyl-1-butanol, ethanol, 3,3-dimethyl-2-butanol, 2-octyl-1-dodecanol, decanoic acid, octanoic acid, dodecanoic acid, mixtures thereof, and the like.

[0204] More preferred diluents include 3,7-dimethyl-3-octanol, 1-dodecanol, 1-decanol, 1-octanol, 1-pentanol, 1-hexanol, 2-hexanol, 2-octanol, 1-dodecanol, 3-methyl-3-pentanol, 1-pentanol, 2-pentanol, t-amyl alcohol, tert-butanol, 2-butanol, 1-butanol, 2-methyl-2-pentanol, 2-ethyl-1-butanol, 3,3-dimethyl-2-butanol, 2-octyl-1-dodecanol, mixtures thereof, and the like. When a diluent is present, there is generally no particular restriction on the amount of diluent present. When a diluent is used, the diluent may be present in an amount ranging from about 2 to about 70 percent by weight, such as from about 5 to about 50 percent by weight and from about 15 to about 40 percent by weight, based on the total weight of the reactive mixture (including reactive and non-reactive compounds). A mixture of diluents may be used.

[0205] A polymerization initiator may be used in the reactive mixture. The polymerization initiator may include at least one of those that generate free radicals at moderately high temperatures, such as lauryl peroxide, benzoyl peroxide, iso-propyl percarbonate, azobisisobutyronitrile, and photoinitiator systems, such as aromatic α-hydroxyketones, alkoxyoxybenzoins, acetophenones, acylphosphine oxides, bisacylphosphine oxides, and tertiary amines + diketones, mixtures thereof. Specific examples of photoinitiators include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, bis(2,6-dimethoxybenzoyl)-2,4-4-trimethylpentylphosphine oxide (DMBAPO), bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (Irgacure 819), 2,4,6-trimethylbenzyldiphenylphosphine oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide, benzoin methyl ester, and a combination of camphorquinone and ethyl 4-(N,N-dimethylamino)benzoate.

[0206] Commercially available visible light initiator systems (from IGM Resins BV, The Netherlands) include Irgacure® 819, Irgacure® 1700, Irgacure® 1800, Irgacure® 819, Irgacure® 1850, and Lucrin® TPO initiators. Commercially available UV photoinitiators (from IGM Resins BV) include Darocur® 1173 and Darocur® 2959. These and other photoinitiators that may be used are disclosed in Volume III, Photoinitiators for Free Radical Cationic & Anionic Photopolymerization, 2nd Edition by JV Crivello & K. Dietliker; edited by G. Bradley; John Wiley and Sons; New York; 1998. The initiator is used in the reactive mixture in an amount effective to initiate photopolymerization of the reactive mixture, for example, from about 0.1 to about 2 parts by weight per 100 parts of the reactive monomer mixture. Polymerization of the reactive mixture can be initiated using heat or visible or ultraviolet light or other means, appropriately selected depending on the polymerization initiator used. Alternatively, initiation can be carried out using an electron beam without a photoinitiator. However, when a photoinitiator is used, the preferred initiator is a bisacylphosphine oxide, such as bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (Irgacure® 819), or a combination of 1-hydroxycyclohexyl phenyl ketone and bis(2,6-dimethoxybenzoyl)-2,4-4-trimethylpentylphosphine oxide (DMBAPO).

[0207] Curing and Manufacturing of Contact Lens Precursors The reactive mixture may be formed by any method known in the art, such as by shaking or stirring, and used to form a polymer network or device by known methods. The reactive components are mixed together, either with or without a diluent, to form the reactive mixture.

[0208] For example, an ophthalmic device can be prepared by mixing the reactive components and optionally a diluent(s) with a polymerization initiator and curing under appropriate conditions to form a product that can later be molded into a suitable shape by lathing, cutting, etc. Alternatively, the reactive mixture can be placed into a mold and then cured into a suitable article.

[0209] A method of making a molded ophthalmic device, such as a silicone hydrogel contact lens precursor for use in the present invention may include preparing a reactive monomer mixture, transferring the reactive monomer mixture to a first mold, placing a second mold over the first mold filled with the reactive monomer mixture, and curing the reactive monomer mixture by free radical copolymerization to form a silicone hydrogel in the shape of the contact lens precursor.

[0210] The reactive mixture may be cured through any known process for shaping reactive mixtures in making contact lenses, including rotational molding and static molding. Rotational molding methods are disclosed in U.S. Patents 3,408,429 and 3,660,545, and static molding methods are disclosed in U.S. Patents 4,113,224 and 4,197,266. The contact lens precursor of the present invention may be formed by direct molding of silicone hydrogel, which is economical and allows precise control of the final shape of the lens precursor. In this method, the reactive mixture is placed into a mold having the shape of the desired final silicone hydrogel, and the reactive mixture is subjected to conditions that polymerize the monomers, thereby producing a polymer of the approximate shape of the desired final product.

[0211] Localization of visible light absorbing chromophores In the present invention, the visible light absorbing chromophore introduced into the lens precursor via the chromophore-containing monomer is concentrated in the desired regions of the lens. Localized concentration of the visible light absorbing chromophore is achieved by selectively derivatizing the chromophore in areas where its light absorbing properties are not needed or desired. Selective derivatization is preferably achieved chemically. More preferably, the derivatization is by chemical oxidation of one or more functional groups in the visible light absorbing chromophore, the oxidation resulting in a material that has greater visible light transmittance than the parent chromophore, for example over the range of 400-460 nm.

[0212] When derivatization is by chemical oxidation, the visible light absorbing chromophore preferably contains a functional group that can easily undergo oxidation reaction under conditions that result in a material with higher light transmittance than the parent.Exemplary functional groups for such oxidation include S, NR, and Se.Thus, preferred visible light absorbing chromophores include materials such as those described above that contain oxidizable functional groups, such as oxidizable sulfur, selenium, or amine moieties.

[0213] Chemical oxidation can be performed, for example, by bleaching, for example, as described in the Examples below. A variety of reagents can be used for oxidation, including, but not limited to, hypochlorite, Oxone®, dimethyldioxirane, hydrogen peroxide, and / or chlorite.

[0214] To form a derivative of the visible light absorbing chromophore in a selected region (e.g., a second region) of the Lens Precursor, a first region of the Lens Precursor where derivatization is not desired is masked from the derivatization conditions. For example, if derivatization is by chemical means (e.g., chemical oxidation), the first region of the Lens Precursor can be masked from the derivatization reagent, for example, using a cup appropriately sized to exclude the derivatization reagent from the first region. Preferably, such a cup is formed from a material (e.g., silicone) that provides adequate masking of the first region but does not damage the underlying Lens Precursor. Other masking techniques or devices can be readily used.

[0215] Once the first region of the lens precursor is properly masked, a derivatization step is then performed. For example, if the derivatization is by chemical means, a derivatization reagent can be applied to contact the second region without significantly contacting the first region. Contact of the reagent with the second region can be continued until a desired level of derivatization is achieved. The reagent is then removed, for example, by washing. An exemplary method is described in the Examples. The resulting contact lens contains a visible light absorbing chromophore in the first region of the lens and a derivative of the chromophore in the second region of the lens. Thus, the method provides a contact lens in which the visible light absorbing chromophore is concentrated in the desired region of the lens, for example the central zone, and a less absorbing derivative, which may be less visually noticeable to the observer, is concentrated in the peripheral zone of the lens.

[0216] Derivatization as described above is preferably carried out while the Contact Lens Precursor is still in the mold (preferably one of the mold halves is removed, thus allowing access to the Lens Precursor in the other mold half). After derivatization, the resulting contact lens may be subjected to processing methods typically used in the manufacture of contact lenses, including extraction to remove unreacted components and release of the lens from the lens mold. Extraction may be carried out using conventional extraction fluids, such as organic solvents such as alcohols, or may be extracted using aqueous solutions.

[0217] An aqueous solution is a solution that includes water. The aqueous solution of the present invention may include at least about 20 percent by weight water, or at least about 50 percent by weight water, or at least about 70 percent by weight water, or at least about 95 percent by weight water. The aqueous solution may also include additional water-soluble ingredients, such as inorganic salts or release agents, wetting agents, slip agents, pharmaceutical ingredients and nutritional supplements, combinations thereof. A release agent is a compound or mixture of compounds that, when combined with water, reduces the time required to remove a contact lens from a mold compared to the time required to remove a contact lens using an aqueous solution that does not include a release agent. The aqueous solution may not require special handling, such as purification, recycling, or special waste disposal.

[0218] Extraction can occur, for example, via immersing the lens in an aqueous solution or exposing the lens to a stream of an aqueous solution. Extraction can also include, for example, one or more of heating the aqueous solution, agitating the aqueous solution, increasing the concentration of a release agent in the aqueous solution to a level sufficient to cause release of the lens, subjecting the lens to mechanical or ultrasonic agitation, and incorporating at least one leaching or extraction aid into the aqueous solution to a concentration sufficient to facilitate adequate removal of unreacted components from the lens. The foregoing steps, with or without the addition of heat, vibration, or both, may be performed in a batch or continuous process.

[0219] To facilitate leaching and demolding, it may be desirable to apply physical agitation. For example, the lens mold part to which the lens is attached can be vibrated or moved back and forth in the aqueous solution. Other methods may include passing ultrasound through the aqueous solution.

[0220] The lenses may be sterilized by known means, such as, but not limited to, high pressure steam treatment.

[0221] As indicated above, the preferred contact lenses are soft hydrogel contact lenses. The transmission wavelengths and percentages described herein can be measured on lenses of various thicknesses, for example, using the methods described in the Examples. By way of example, the preferred center thickness for measuring the transmission spectrum in the first region can be 80-100 microns, or 90-100 microns, or 90-95 microns, if the first region of the soft contact lens corresponds to the central region. Typically, in such cases, the measurement can be performed in the center of the lens, for example, using an instrument slit width of 4 nm. Alternatively, the measurement can be performed in a second region, such as the peripheral zone, also using a slit width of 4 nm. For the purposes of the present invention, it should be understood that the difference in transmission between the first and second regions of the lens can be apparent to an observer without the need to collect a transmission spectrum. For example, if the second region is observed to have less coloration than the first region, this may indicate that the second region has a greater average transmittance in the visible spectrum than the first region, for example in the range of 380 nm to 760 nm, or in the range of 400 nm to 600 nm.

[0222] When the contact lenses of the present invention are silicone hydrogel contact lenses, the lenses may preferably exhibit the following properties: All values ​​are preceded by "about" and the lenses may have any combination of the listed properties. Properties can be determined by methods known to those skilled in the art, for example, as described in U.S. Patent Application Publication No. 2018 / 0037690, which is incorporated herein by reference.

[0223] Percentage of water: at least 20%, or at least 25% and at most 80%, or at most 70% Haze: 30% or less, or 10% or less Advancing dynamic contact angle (Wilhelmy plate method): 100° or less, 80° or less, or 50° or less Tensile modulus (psi): 120 or less, or 80-120 Oxygen permeability (Dk, Barrer): at least 80, or at least 100, or at least 150, or at least 200 Elongation at break: at least 100

[0224] With respect to ionic silicone hydrogels, the following properties (in addition to those mentioned above) may also be preferred: Lysozyme uptake (μg / lens): at least 100, or at least 150, or at least 500, or at least 700 Polyquaternium 1 (PQ1) uptake (%): 15 or less, or 10 or less, or 5 or less

[0225] The compound of the present invention may be used with other products in addition to ophthalmic devices.For example, the compound may be used in windows (for example, vehicle or building windows), or optical instruments such as binoculars and cameras.In such use, the compound may be coated, for example, on the surface of the device.The compound may be dissolved in a solvent to facilitate coating.

[0226] Some embodiments of the present invention are described in detail in the following examples. EXAMPLES

[0227] Test Method The water content (WC) was determined gravimetrically. The lenses were equilibrated in the packing solution for 24 hours. Three test lenses were each removed from the packing solution using a sponge-tipped swab and placed on a blotting wipe that had been moistened with packing solution. Both sides of the lens were contacted with the wipe. Using tweezers, the test lenses were placed in a pre-weighed weighing dish and weighed. Two additional sets of samples were prepared and weighed. All weight measurements were performed in triplicate and the average of these values ​​was used in the calculations. The wet weight is defined as the combined weight of the weighing dish and wet lens minus the weight of the weighing dish alone.

[0228] Dry weight was measured by placing the sample pan in a vacuum oven preheated to 60° C. for 30 minutes. Vacuum was applied until a pressure of at least 1 inch Hg was reached, although lower pressures are acceptable. The vacuum valve and pump were turned off and the lenses were allowed to dry for at least 12 hours (usually overnight). The purge valve was opened, allowing dry air or dry nitrogen gas in. The oven was allowed to reach atmospheric pressure. The weighing pan was removed and weighed. Dry weight is defined as the total weight of the weighing pan and dry lens minus the weight of the weighing pan alone. The water content of the test lenses was calculated as follows: percent water content=(wet weight-dry weight) / wet weight×100. The mean and standard deviation of the water content were calculated and the mean value was reported as the percent water content of the test lenses.

[0229] The wettability of the lenses was measured using the seismic drop technique with a KRUSS DSA-100™ instrument at room temperature and using deionized water as the probe solution (seismic drop). The lenses to be tested were rinsed in deionized water to remove the packing solution. Each test lens was placed on a lint-free blotting paper moistened with packing solution. Both sides of the lens were contacted with the blotting paper to remove surface water without drying the lens. To ensure proper flattening, the lens was placed "dish side down" on the convex surface of a contact lens plastic mold. The plastic mold and lens were placed in a drop fixture holder to ensure proper center syringe alignment. A 3-4 microliter drop of deionized water was formed on the tip of the syringe using DSA 100-Drop Shape Analysis software to ensure the drop would hang away from the lens. The drop was smoothly expelled onto the surface of the lens by moving the needle down. The needle was immediately withdrawn after dispensing the drop. The drop was allowed to equilibrate on the lens for 5-10 seconds and the contact angle was measured between the drop image and the lens surface. Typically, 3-5 lenses were evaluated and the average contact angle was reported.

[0230] The mechanical properties of the contact lenses were measured using an Instron model 1122 or 5542 tensile tester equipped with a load cell and pneumatic grip controls. A minus-1 diopter lens is the preferred lens geometry due to its uniform thickness profile at its center. Dog-bone shaped specimens cut from a -1 diopter lens, with a length of 0.522 inches, an "ear" width of 0.276 inches, and a "neck" width of 0.213 inches, were placed in the grips and stretched to break at a constant strain rate of 2 inches per minute. The center thickness of the dog-bone specimens was measured using an electronic thickness gauge prior to testing. The initial gauge length (L o ) and the specimen length at break (L f At least five specimens of each composition were measured and the average value was used to calculate the percent elongation to break. Percent Elongation = [(L f -L o ) / L o ]×100. Tensile modulus (M) was calculated as the slope of the initial linear portion of the stress-strain curve and the units of modulus are pounds per square inch or psi. Tensile strength (TS) was calculated from the peak load and the original cross-sectional area. Tensile strength is the peak load divided by the original cross-sectional area and the units of tensile strength are psi. Toughness was calculated from the energy to break and the original volume of the specimen. Toughness is the energy to break divided by the original volume of the specimen and the units of toughness are in-lbs / in 3 The elongation to break (ETB) was also recorded as a percentage of the strain at break.

[0231] The UV-visible spectra of the compounds in solution were measured on a Perkin Elmer Lambda 45 or Agilent Cary 6000i UV / VIS scanning spectrometer. The instruments were allowed to thermally equilibrate for at least 30 minutes before use. For the Perkin Elmer instruments, the scan range was 200-800 nm, the scan speed was 960 nm per minute, the slit width was 4 nm, the mode was set to transmission or absorbance, and baseline correction was selected. For the Cary instruments, the scan range was 200-800 nm, the scan speed was 600 nm / min, the slit width was 2 nm, the mode was transmission or absorbance, and baseline correction was selected. Baseline correction was performed before analyzing the samples using the autozero function.

[0232] The UV-visible spectra of contact lenses partially formed from the claimed compositions were measured using packing solutions on a Perkin Elmer Lambda 45 UV / VIS or Agilent Cary 6000i UV / VIS scanning spectrometer. Prior to use, the instrument was allowed to thermally equilibrate for at least 30 minutes. For the Perkin Elmer instrument, the scan range was 200-800 nm, the scan speed was 960 nm per minute, the slit width was 4 nm, the mode was set to transmission, and baseline correction was selected. Baseline correction was performed using a plastic two-piece lens holder and a cuvette containing the same solvent. These two-piece contact lens holders were designed to hold the sample in the quartz cuvette at a position traversed by the incident light beam. A reference cuvette also housed the two-piece holder. To ensure that the sample thickness was consistent, all lenses were made using the same mold. The center thickness of the contact lenses was measured using an electronic thickness gauge. The reported center thickness and transmission spectra are obtained by averaging three individual lens data.

[0233] It is important to ensure that the exterior of the cuvette is completely clean and dry and that there are no air bubbles within the cuvette. Measurement reproducibility is improved when the reference cuvette and its lens holder remain constant and all samples use the same sample cuvette and its lens holder, ensuring that both cuvettes are properly inserted into the instrument.

[0234] A calibrated dual interferometry was used to measure contact lens parameters in packing solution. These parameters include equivalent spherical power (diopters or D) at multiple apertures, cylindrical power (diopters or D) at multiple apertures, diameter (millimeters or mm), central thickness (millimeters or mm), sagittal height (millimeters or mm), and root-mean-square (RMS) optical path wavefront deviation from lens design target in micrometers or micrometers (μm) with sphere / cylinder power and removed coma aberration when measured using a 6.5 mm aperture. The instrument consists of a custom propionate interferometer for measurement of wavefront parameters and a Lumetrics OptiGauge® II low coherence interferometer for measurement of dimensional parameters of sagittal height and central thickness. The two individual instruments combined are similar to Lumetrics Clearwave™ Plus and the software is similar to Lumetrics OptiGauge Control Center v7.0 or later. The Clearwave™ Plus uses a camera to find the lens edge and then calculates the lens center, which is then used to align a 1310 nanometer interferometer probe to the lens center to measure sagittal height and central thickness. The transmitted wavefront is also continuously collected using a wavefront sensor (Shack-Hartmann sensor). Multiple parameters from the transmitted wavefront of the contact lens are measured and other parameters are calculated from these measurements.

[0235] Difference terms are calculated by comparing measurements from the targets from the collected data, including the root mean square path wavefront deviation (RMS_65) from the lens design target (sphere / cylinder and removed coma) in μm when measured using a 6.5 mm aperture, the second equivalent spherical power deviation (PW2EQD) from the lens design target in diopters (D) when measured using a 5 mm aperture, the deviation from the lens design target diameter (DMD) in mm, the lens design target base curve radius and deviation from the lens diameter (BCD) in mm, and the deviation from the lens design target central thickness (CTD) in mm, calculated from the sagittal height measured per ISO 18369-3.

[0236] The following abbreviations are used throughout the examples and have the following meanings: DMA: N,N-dimethylacrylamide (Jarchem) HEMA: 2-hydroxyethyl methacrylate (Bimax) PVP K90: Poly(N-vinylpyrrolidone) (ISP Ashland) EGDMA: Ethylene glycol dimethacrylate (Esstech) TEGDMA: Tetraethylene glycol dimethacrylate (Esstech) 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 mPDMS: mono-n-butyl terminated monomethacryloxypropyl terminated polydimethylsiloxane, (M n =800-1500 grams / mole) (Gelest) Tegomer MA: Bis-3-methacryloxy-2-hydroxypropyloxypropyl polydimethylsiloxane (M n = 2000 g / mol, n = 20) (Shin Etsu)

[0237] [ka] HO-mPDMS: mono-n-butyl terminated mono-(2-hydroxy-3-methacryloxypropyloxy)-propyl terminated polydimethylsiloxane (M n =400-1400g / mol) (Ortec or DSM-Polymer Technology Group) OH-mPDMS (n=4):

[0238] [ka] OH-mPDMS (n=15):

[0239] [ka] Omnirad403: Bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide (IGM Resins) Omnirad819: Bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (IGM Resins) Omnirad 1173: 2-Hydroxy-2-methyl-1-phenylpropanone (IGM Resins) Omnirad 1700: a mixture of 25% by weight Omnirad 403 and 75% by weight Omnirad 1173 (IGM Resins) Omnirad 1870: a mixture of 70% by weight Omnirad 403 and 30% by weight Omnirad 1173 (IGM Resins) Norbloc: 2-(2'-hydroxy-5-methacrylyloxyethylphenyl)-2H-benzotriazole (Janssen) RB247: 1,4-Bis[2-methacryloxyethylamino]-9,10-anthraquinone (CAS#109561-07-1) Dye 1: 2-((9-(dicyanomethylene)-9H-thioxanthen-2-yl)oxy)ethyl methacrylate;

[0240] [ka] Dye 2: 2-(2-(10-butyl-2-methoxyacridin-9(10H)-ylidene)-2-cyanoacetamido)ethyl methacrylate;

[0241] [ka] Dye 3: 2-(2-cyano-2-(9H-thioxanthen-9-ylidene)acetamido)ethyl methacrylate

[0242] [ka] Dye 4: N-(2-(2-cyano-2-(10-methylacridin-9(10H)ylidene)acetamido)ethyl)methacrylamide

[0243] [ka] 3E3P: 3-ethyl 3-pentanol D3O: 3,7-dimethyl-3-octanol (Vigon) DIW: Deionized water IPA: Isopropyl alcohol PG: 1,2-propylene glycol HCl: Hydrochloric acid NaOCl: Sodium hypochlorite. M: Molar concentration (mol / L) N: Normality (equivalent / L) PS: Borate Buffer Package 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 enough deionized water to fill a 2 liter volumetric flask. BC: Base curve plastic mold made from PP, TT, Z, or blends thereof FC: Front curve plastic mold made from PP, TT, Z, or blends thereof PP: Polypropylene, a homopolymer of propylene TT: Tuftec (Asahi Kasei Chemicals), a hydrogenated styrene butadiene block copolymer Z: Zeonor (Nippon Zeon Co Ltd), a polycycloolefin thermoplastic polymer RMM: reactive monomer mixture LED: Light Emitting Diode UV-VIS: Ultraviolet-Visible g: grams mg: milligram kg: kilogram L: Liters mL: milliliter μL: microliter m: meters cm: centimeters mm: millimeters μm: micrometer or micron nm: nanometer in:inches lb: pound s or sec: seconds min:minutes hr: time "W": Watts mW: milliwatt D: Diopter Wt%: Weight%

[0244] Contact lens precursor (dyeing) Precursor 1 Lens: The reactive components listed in Table 1 were mixed with 3M3P to form a reactive monomer mixture such that the weight ratio of reactive components to 3M3P was 77:23 (w / w). In this case, the formulation components except PVP K90 and 3M3P were combined in dichloromethane solution, and then the required amount of PVP K90 and 3M3P was added to form the final reactive monomer mixture after removing the dichloromethane under reduced pressure in a rotary evaporator. The formulation was filtered through a 3 μm filter using a stainless steel syringe and degassed by applying a vacuum (about 40 mmHg). About 75 μL of the reactive mixture was loaded onto a FC made of 90:10 (w / w) Zeonor / TT blend using an Eppendorf pipette at room temperature in a glove box with a nitrogen gas atmosphere and less than about 0.2 percent oxygen gas. A BC made of 90:10 (w / w) Z:PP blend was then placed onto the FC. The target spherical power of the mold design was nominally minus 1 diopter. The molds were allowed to equilibrate for a minimum of 12 hours in the glove box prior to dispensing. Pallets, each containing eight mold assemblies, were transferred into an adjacent glove box maintained at 65°C and illuminated at approximately 1.5 mW / cm at the tray location. 2 3 min using a 420 nm light-emitting diode light with a brightness of 5 mW / cm2 and then at the tray location. 2 The lenses were cured from top to bottom for 5 minutes using 420 nm light emitting diode light with a brightness of 100 nm. The resulting lenses [Precursor 1 lenses] were mechanically released from the base curve mold, leaving the Precursor 1 lenses attached to the front curve mold. The Precursor 1 lenses attached to the front curve mold were then placed back into the pallet, which was subsequently selectively masked by applying a silicone cup to protect the central zone of each lens precursor for the selective bleaching step.

[0245] Precursor 2 Lens Precursor 1 Lens: The reactive components listed in Table 1 were mixed with D3O to form a reactive monomer mixture such that the weight ratio of reactive components to D3O was 62:38 (w / w). The blend was filtered through a 3 μm filter using a stainless steel syringe and degassed by applying a vacuum (about 40 mmHg). About 75 μL of the reactive mixture was dispensed into a FC made of 90:10 (w / w) Zeonor / TT blend using an Eppendorf pipette at room temperature in a glove box with a nitrogen gas atmosphere and less than about 0.2 percent oxygen gas. A BC made of 90:10 (w / w) Z:PP blend was then placed on the FC. The target spherical power of the mold design was nominally minus 1 diopter. The mold was allowed to equilibrate in the glove box for a minimum of 12 hours before dispensing. The pallets, each containing eight mold assemblies, were then transferred into an adjacent glove box maintained at approximately 65°C and exposed to approximately 2 mW / cm 2 The lenses were cured from top to bottom for approximately 10 minutes using 405 nm light emitting diode light with an intensity of 100 nm. The resulting lenses [Precursor 2 lenses] were mechanically demolded from the base curve mold, leaving the Precursor 2 lenses attached to the front curve mold. The Precursor 2 lenses attached to the front curve mold were then placed back into the palette, which was subsequently masked by applying a silicone cup to protect the central zone of each lens precursor for the selective bleaching step. Two sets of Precursor 2 lenses were produced: one set had a nominal spherical power of minus 1 diopter, and the other set had a nominal spherical power of minus 12 diopters.

[0246] Precursor 3 Lens: The reactive components listed in Table 1 were mixed with D3O to form a reactive monomer mixture such that the weight ratio of reactive components to D3O was 77:23 (w / w). The blend was filtered through a 3 μm filter using a stainless steel syringe and degassed by applying a vacuum (about 40 mmHg). About 75 μL of the reactive mixture was dispensed into a FC made of 90:10 (w / w) Zeonor / TT blend using an Eppendorf pipette at room temperature in a glove box with a nitrogen gas atmosphere and less than about 0.2 percent oxygen gas. A BC made of 90:10 (w / w) Z:PP blend was then placed on the FC. The target spherical power of the mold design was nominally minus 1 diopter. The mold was allowed to equilibrate in the glove box for a minimum of 12 hours before dispensing. The pallets, each containing eight mold assemblies, were then transferred into an adjacent glove box maintained at approximately 65°C and approximately 2mW / cm at the tray location. 2 The lenses were cured from top to bottom for approximately 10 minutes using 405 nm light emitting diode light having an intensity of 100 nm. The resulting lenses [Precursor 3 lenses] were mechanically released from the base curve mold, leaving the Precursor 3 lenses attached to the front curve mold. The Precursor 3 lenses attached to the front curve mold were then placed back into the pallet, which was subsequently masked by applying a silicone cup to protect the central zone of each lens precursor for the selective bleaching step.

[0247] [Table 4]

[0248] Example 1 A pallet was set up containing Precursor 1 lenses adhered to the front curve mold, and the central zone of each lens precursor was masked from the oxidizer solution using soft silicone cups. The diameter of the soft silicone cups was 10 mm. The lenses adhered to the front curve mold had a diameter greater than 10 mm. The array of soft silicone cups was lowered onto the lenses such that there was just enough compression between the cups and the lenses to prevent the oxidizer solution from reaching the central portion of the lenses, thereby allowing only the periphery of the lenses to be exposed to the oxidizer solution.

[0249] Approximately 1 mL of 0.5 wt% aqueous sodium hypochlorite solution neutralized to pH 7.2 was added to each front curve mold. The oxidizing solution was prepared by diluting 5 wt% aqueous sodium hypochlorite solution with 9 parts deionized water and then adjusting the pH to 7.2 with 3N aqueous HCl. After exposure to 0.5 wt% aqueous sodium hypochlorite for 5 seconds (Example 1A lenses), 30 seconds (Example 1B lenses), and 60 seconds (Example 1C lenses), the center-stained lenses were removed and immediately rinsed with DIW. The oxidized lenses were then removed by immersion in 70% (v / v) aqueous IPA (about 1 hour), extracted twice with 70% (v / v) aqueous IPA for 30 minutes, hydrated with deionized water for 30 minutes, and then equilibrated with packing solution. The resulting lenses were stored in the packing solution in a vial. After 5 seconds, significant peripheral bleaching was observed. As shown in Figure 1, the UV-VIS spectra measured in the central unbleached zone of these lenses of Examples 1A-1C were identical to the original fully dyed lenses of Precursor 1. Furthermore, the sphere and lens diameter of the lenses of Examples 1A-1C were substantially unaffected by peripheral oxidation, as listed in Table 2.

[0250] [Table 5]

[0251] Example 2 Example 1 was essentially repeated using a 7 millimeter diameter soft silicone cup instead of the 10 millimeter diameter cup, thereby bleaching a larger perimeter, and using only one exposure time to the 0.5 weight percent aqueous sodium hypochlorite solution. The exposure time was 60 seconds.

[0252] A pallet was set up containing Precursor 2 lenses adhered to the front curve mold, and the central zone of each lens precursor was masked from the oxidizer solution using soft silicone cups. The diameter of the soft silicone cups was 7 mm. The lenses adhered to the front curve mold had a diameter greater than 10 millimeters. The array of soft silicone cups was lowered onto the lenses such that there was just enough compression between the cups and the lenses to prevent the oxidizer solution from reaching the central portion of the lenses, thereby allowing only the periphery of the lenses to be exposed to the oxidizer solution.

[0253] Approximately 1 mL of 0.5 wt% sodium hypochlorite aqueous solution neutralized to pH 7.2 was added to each front curve mold. After 60 seconds of exposure to the 0.5 wt% sodium hypochlorite aqueous solution, the center-stained lenses were removed and immediately rinsed with DIW. The oxidized lenses were then removed by immersion in 70% (v / v) aqueous IPA (approximately 1 hour), extracted twice for 30 minutes with 70% (v / v) aqueous IPA, hydrated for 30 minutes with deionized water, and then equilibrated with packing solution. The lenses were stored in the packing solution in vials.

[0254] Various physical properties, mechanical properties, and lens parameters of these lenses were measured before and after the bleaching process and are listed in Table 3. Example 2A lenses were made by bleaching the periphery of Precursor 2 lenses with a spherical power of minus 1 diopter. Example 2B lenses were made by bleaching the periphery of Precursor 2 lenses with a spherical power of minus 12 diopter. None of the observed changes in properties and parameters after peripheral bleaching were statistically significant. The data for the minus 12 diopter lenses before and after bleaching were more variable than the data for the minus 1 diopter lenses. The periphery of the lenses of Examples 2A and 2B was clear, i.e., appeared undyed compared to the dyed areas. The UV-VIS transmission spectra of Precursor 2 lenses (unbleached) and Examples 2A and 2B lenses (dyed central zone after peripheral bleaching) are shown in Figure 2 for the minus 1 diopter lenses and in Figure 3 for the minus 12 diopter lenses. UV-VIS spectra showed that the peripheral bleaching process had an acceptably small effect on the visible light transmission profile of the lens.

[0255] [Table 6]

[0256] Example 3 Pallets containing Precursor 3 lenses bonded to the front curve mold for Precursor 3 lenses were treated with 0.5 weight percent aqueous sodium hypochlorite solution neutralized to pH 7.2 for 3 minutes at ambient temperature. The lenses were completely bleached throughout. These oxidized lenses were immediately rinsed with DIW. The oxidized lenses were then removed by immersion in 70% (v / v) aqueous IPA (about 1 hour), extracted twice with 70% (v / v) aqueous IPA for 30 minutes, hydrated with deionized water for 30 minutes, and then equilibrated with packing solution. The oxidized lenses [Example 3 lenses] were stored in the packing solution in vials. Some Precursor 3 lenses and some Example 3 lenses were sterilized by autoclaving at 121° C. for 30 minutes. As shown in FIG. 4, the UV-VIS spectra of both Precursor 3 lenses and Example 3 lenses were essentially unchanged by sterilization. Additionally, when Precursor 3 lenses were oxidized to produce Example 3 lenses, the average transmittance from 400 nm to 600 nm increased both pre- and post-sterilization. The data is shown in Table 4. If Example 3 had been performed using a soft silicone cup to isolate the central zone of the Precursor 3 lens from the oxidizer solution, allowing only the periphery to oxidize, a similar difference in transmittance would be expected between the central zone and the periphery. Any difference would likely be caused by differences in the thickness profile at the location being measured.

[0257] [Table 7]

[0258] Precursor 4 Lens Precursor 5 Lenses: The reactive components listed in Table 1 were mixed with 3M3P to form a reactive monomer mixture such that the weight ratio of reactive components to 3M3P was 77:23 (w / w). The blend was filtered through a 3 μm filter using a stainless steel syringe and degassed by applying a vacuum (approximately 40 mmHg) before use. Using this reactive monomer mixture, Precursor 4 lenses were prepared on a pilot line consisting of a two-zone curing tunnel with irradiation from the top and bottom of the tunnel under a nitrogen gas atmosphere (less than 3.0±0.5% oxygen gas). Pallets containing eight mold assemblies were moved down the tunnel, respectively. The mold assemblies were made by dosing the reactive monomer mixture into a front curve mold made from a 90:10 (w / w) Zeonor / TT blend, followed by placing a base curve mold made from the same polymer blend on top of the dosed front curve, thereby forming a lens-shaped cavity between them. The first zone in the curing tunnel had a radiation intensity of approximately 5 mW / cm2 as measured on the pallet supporting the mold assembly. 2 The second zone used a 435 nm LED lamp with an intensity of about 12 mW / cm2 when measured on the pallet supporting the mold assembly. 2 The temperature was kept constant at 65° C. in both zones. The pallets were exposed to light for 6 minutes in the first zone of the curing tunnel and 3 minutes in the second zone, for a total curing time of 9 minutes.

[0259] The resulting Precursor 4 lenses were mechanically removed from the base curve molds, leaving the lenses attached to the front curve molds. The Precursor 4 lenses attached to the front curve molds were then placed back into the pallet, which was subsequently masked by applying a silicone cup to protect the central zone of each Precursor 4 lens for the selective bleaching step.

[0260] [Table 8]

[0261] Example 4 A pallet containing lenses adhered to the front curve mold was set up and the central zone of each lens precursor was masked from the oxidizer solution using soft silicone cups. The diameter of the soft silicone cups was 10 mm. The lenses adhered to the front curve mold had a diameter greater than 10 millimeters. Using a mechanical fixture, the array of soft silicone cups was lowered onto the lenses so that there was just enough compression between the cups and the lenses to prevent the oxidizer solution from reaching the central portion of the lenses, thereby allowing only the periphery of the lenses to be exposed to the oxidizer solution.

[0262] The secondary container was filled with 0.5 wt% aqueous sodium hypochlorite solution neutralized to pH 7.2. The oxidizing solution was prepared by diluting 5 wt% aqueous sodium hypochlorite solution with 9 parts deionized water, and then adjusting the pH to 7.2 with 3N aqueous HCl. The mechanical fixture containing the contact lens protected by a silicone cup was submerged in the oxidizing solution. After 180 seconds of exposure to the 0.5 wt% aqueous sodium hypochlorite solution, the center-stained lens (Example 4 lens) was removed and immediately rinsed with DIW. The Example 4 lens was then removed by immersion in 70% (v / v) aqueous IPA (about 1 hour), extracted twice with 70% (v / v) aqueous IPA for 30 minutes, hydrated with deionized water for 30 minutes, and then equilibrated with packing solution. The resulting lens was stored in the packing solution in a vial.

[0263] Various physical properties, mechanical properties, and lens parameters of these lenses were measured before and after the bleaching process and are listed in Table 6. Example 4 lenses were made by bleaching the periphery of Precursor 4 lenses with a spherical power of minus 1 diopter. After peripheral bleaching, there was a small change in properties and parameters. As shown in Figure 5, the UV-VIS spectrum of Example 4 lenses (average of 5 lenses) measured in the central unbleached zone was only slightly different from the UV-VIS spectrum of the original fully dyed Precursor 4 lenses (average of 3 lenses).

[0264] [Table 9]

[0265] [Embodiment] (1) The first area; A second area; and a visible light absorbing chromophore; A derivative of the visible light absorbing chromophore; A contact lens comprising: the first region comprises the visible light absorbing chromophore and the second region comprises the derivative of the visible light absorbing chromophore; A contact lens, wherein the second region has a greater average transmittance than the first region over a wavelength range of 400 nm to 600 nm. (2) The contact lens of claim 1, wherein the average transmittance of the second region is at least 5 percent greater than the average transmittance of the first region. (3) The contact lens of embodiment 1 or 2, wherein the average transmittance of the visible light absorbing chromophore over the wavelength range of 400 to 600 nm is 95 percent or less. (4) The contact lens of claim 1, wherein the visible light absorbing chromophore contains an oxidizable functional group. (5) The contact lens of claim 1, wherein the derivative is an oxidized derivative of the visible light absorbing chromophore.

[0266] (6) The contact lens of embodiment 1, wherein the visible light absorbing chromophore is a static chromophore or a photochromic chromophore. (7) The contact lens of claim 1, wherein the first region comprises a central zone of the contact lens and the second region comprises a peripheral zone of the contact lens. (8) The contact lens of embodiment 1, wherein the visible light absorbing chromophore comprises one or more light absorbing functional groups selected from benzotriazole, acetophenone, benzophenone, azo, diphenyldiazine, alkoxyaniline, tetrahydronaphthalene, anthraquinone, anthracene, dihydroanthracene, selenoxanthene, thioxanthene, and acridine. (9) The contact lens of embodiment 1, wherein the visible light absorbing chromophore comprises one or more light absorbing functional groups selected from chromene, spiropyran, oxazine, mercury dithizonate, fulgide, fulgimide, organo-metal dithiozonate, and naphthacenedione. (10) The visible light absorbing chromophore is represented by formula I: [ka] The substructure has In the formula, R B is -C(=O)H or EWG; X is NR, S, or Se; R is H, C1-C6 alkyl, cycloalkyl, heterocycloalkyl, aryl, or heteroaryl; and EWG, at each occurrence, is independently an electron withdrawing group.

[0267] (11) The derivative of the visible light absorbing chromophore has formula II: [ka] The substructure has In the formula, X' is N + RO -, SO, SO2, SeO, or SeO2. (12) A method for producing the contact lens of claim 1, said method comprising: providing a lens precursor having a first region and a second region, the lens precursor containing visible light absorbing chromophores in the first region and the second region; selectively derivatizing the visible light absorbing chromophore in the second region to form a derivative of the visible light absorbing chromophore, the derivative having a greater average transmittance than the visible light absorbing chromophore over a wavelength range of 400 nm to 600 nm; and A method comprising: 13. The method of claim 12, wherein the lens precursor is a polymerization reaction product of a reactive mixture comprising: (a) a chromophore-containing monomer; and (b) a monomer suitable for making the contact lens precursor. (14) The chromophore-containing monomer is represented by formula IV: [ka] is a compound of During the ceremony, m and n are independently 0, 1, 2, 3, or 4; R C However, EWC or formula -TYP g wherein T is a bond, O, or NR; Y is a linking group; and P g is a polymerizable group; X is NR, S, or Se; R, at each occurrence, is independently H, C1-C6 alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, or YP g and; R 1 and R 2 is independently, when present, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 thioalkyl, C1-C6 selenoalkyl, C3-C7 cycloalkyl, aryl, halo, hydroxy, amino, NR 3 R 4, benzyl, or -YP g and R 3 and R 4 are independently H or C1-C6 alkyl, or two adjacent R 1 Or R 2 the groups, together with the carbon atoms to which they are attached, combine to form a cycloalkyl or aryl ring; EWG, for each occurrence, is independently an electron-withdrawing group, The compound of formula I comprises at least one P g 14. The method of embodiment 13, wherein the R 1 -R 2 -R 3 -R 4 -R 5 -R 6 -R 7 -R 8 -R 9 -R 10 - (15) The method of embodiment 14, wherein m and n are each independently 0 or 1.

[0268] (16) The method of embodiment 14 or 15, wherein Y is, independently at each occurrence, alkylene, cycloalkylene, heterocycloalkylene, arylene, heteroarylene, oxaalkylene, alkylene-amide-alkylene, alkylene-amine-alkylene, or a combination thereof. (17) P g The method of embodiment 14, wherein each occurrence independently comprises styryl, vinyl carbonate, vinyl ether, vinyl carbamate, N-vinyl lactam, N-vinyl amide, (meth)acrylate, or (meth)acrylamide. (18) The method of embodiment 14, wherein X is S or NR. (19) The method of embodiment 14, wherein each occurrence of EWG is cyano. (20) The chromophore-containing monomer is represented by formula III: [ka] is a compound of During the ceremony: m and n are independently 0, 1, 2, 3, or 4; R C However, EWC or formula -TYP g wherein T is a bond, O, or NR; Y is a linking group; and P gis a polymerizable group; X is O, NR, S, or Se; R is, independently at each occurrence, H, C1-C6 alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, or YP g and; R 1 and R 2 is independently, when present, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 thioalkyl, C1-C6 selenoalkyl, C3-C7 cycloalkyl, aryl, halo, hydroxy, amino, NR 3 R 4 , benzyl, or -YP g and R 3 and R 4 are independently H or C1-C6 alkyl, or two adjacent R 1 Or R 2 the groups, together with the carbon atoms to which they are attached, combine to form a cycloalkyl or aryl ring; EWG, at each occurrence, is independently an electron withdrawing group; The compound of formula III comprises at least one P g 14. The method of embodiment 13, wherein the aryl group and at least one oxidizable functional group are present.

[0269] (21) The chromophore-containing monomer is: 2-(2-cyano-2-(9H-thioxanthen-9-ylidene)acetamido)ethyl methacrylate; 2-(2-cyano-2-(9H-thioxanthen-9-ylidene)acetamido)ethyl acrylate; N-(2-(2-cyano-2-(9H-thioxanthen-9-ylidene)acetamido)ethyl)methacrylamide; N-(2-(2-cyano-2-(9H-thioxanthen-9-ylidene)acetamido)ethyl)acrylamide; 2-(2-cyano-N-methyl-2-(9H-thioxanthen-9-ylidene)acetamido)ethyl methacrylate; 2-Cyano-2-(9H-thioxanthen-9-ylidene)-N-(2-(N-vinylacetamido)ethyl)acetamide; 2-(2-(acridin-9(10H)-ylidene)-2-cyanoacetamido)ethyl acrylate; N-(2-(2-(acridin-9(10H)-ylidene)-2-cyanoacetamido)ethyl)methacrylamide; N-(2-(2-(acridin-9(10H)-ylidene)-2-cyanoacetamido)ethyl)acrylamide; 2-(2-(acridin-9(10H)-ylidene)-2-cyano-N-methylacetamido)ethyl methacrylate; 2-(acridin-9(10H)-ylidene)-2-cyano-N-(2-(N-vinylacetamido)ethyl)acetamide; 2-(2-cyano-2-(9H-thioxanthen-9-ylidene)acetamido)-2-methylpropyl methacrylate; (Z)-2-(2-cyano-2-(3-hydroxyacridin-9(10H)-ylidene)acetamido)ethyl methacrylate; 2-(2-cyano-2-(10-methylacridin-9(10H)-ylidene)acetamido)ethyl methacrylate; 2-(2-cyano-2-(3,6-dihydroxyacridin-9(10H)-ylidene)acetamido)ethyl methacrylate; (E)-2-(2-cyano-2-(2,4-dichloro-9H-thioxanthen-9-ylidene)acetamido)ethyl methacrylate; (E)-2-(2-(2-chloro-9H-thioxanthen-9-ylidene)-2-cyanoacetamido)ethyl methacrylate; (E)-2-(2-cyano-2-(2-isopropyl-9H-thioxanthen-9-ylidene)acetamido)ethyl methacrylate; (E)-2-(2-cyano-2-(4-isopropyl-9H-thioxanthen-9-ylidene)acetamido)ethyl methacrylate; 2-(3-oxo-2-(9H-thioxanthen-9-ylidene)propanamido)ethyl methacrylate; 2-(3-oxo-2-(9H-thioxanthen-9-ylidene)butanamido)ethyl methacrylate; 2-(3-Methoxy-3-oxo-2-(9H-thioxanthen-9-ylidene)propanamido)ethyl methacrylate; 2-(3-amino-3-oxo-2-(9H-thioxanthen-9-ylidene)propanamido)ethyl methacrylate; 2-(2-cyano-2-(10,10-dioxido-9H-thioxanthen-9-ylidene)acetamido)ethyl methacrylate; N-(2-(2-cyano-2-(10-methylacridin-9(10H)ylidene)acetamido)ethyl)methacrylamide; 2-(2-cyano-2-(9H-thioxanthen-9-ylidene)acetoxy)ethyl methacrylate; 2-(2-cyano-2-(2-methoxy-10-propylacridin-9(10H)-ylidene)acetamido)ethyl methacrylate; N-(2-(2-cyano-2-(10-methylacridin-9(10H)-ylidene)acetamido)ethyl)methacrylamide; 2-(2-(10-butyl-2-methoxyacridin-9(10H)-ylidene)-2-cyanoacetamido)ethyl methacrylate; 2-((9-(dicyanomethylene)-9H-thioxanthen-2-yl)oxy)ethyl methacrylate; 2-(2-cyano-2-(3-(propylthio)-9H-thioxanthen-9-ylidene)acetamido)ethyl methacrylate; 2-(2-cyano-2-(3-(propylthio)-9H-xanthen-9-ylidene)acetamido)ethyl methacrylate; 3-((9-(1-cyano-2-((2-(methacryloyloxy)ethyl)amino)-2-oxoethylidene)-9H-thioxanthen-3-yl)thio)propyl methacrylate; 3-((9-(1-cyano-2-((2-(methacryloyloxy)ethyl)amino)-2-oxoethylidene)-9H-xanthen-3-yl)thio)propyl methacrylate; 3-((9-(dicyanomethylene)-9H-thioxanthen-3-yl)thio)propyl methacrylate; 3-((9-(dicyanomethylene)-9H-xanthen-3-yl)thio)propyl methacrylate; or Mixtures of two or more of these, 14. The method of embodiment 13, comprising: 22. The method of claim 13, wherein the monomer suitable for making the contact lens precursor comprises a hydrophilic component, a silicone-containing component, or a mixture thereof.

Claims

1. A first region; and A second region; and a visible light absorbing chromophore; A derivative of the visible light absorbing chromophore; A contact lens comprising: the first region comprises the visible light absorbing chromophore and the second region comprises the derivative of the visible light absorbing chromophore; A contact lens, wherein the second region has a greater average transmittance over the wavelength range of 400 nm to 600 nm than the first region.

2. The contact lens of claim 1 , wherein the average transmittance of the second region is at least 5 percent greater than the average transmittance of the first region.

3. 3. The contact lens of claim 1, wherein the average transmittance of the visible light absorbing chromophore over the wavelength range of 400 to 600 nm is 95 percent or less.

4. The contact lens of claim 1 , wherein the visible light absorbing chromophore contains an oxidizable functional group.

5. The contact lens of claim 1 , wherein the derivative is an oxidized derivative of the visible light absorbing chromophore.

6. The contact lens of claim 1 , wherein the visible light absorbing chromophore is a static chromophore or a photochromic chromophore.

7. The contact lens of claim 1 , wherein the first region comprises a central zone of the contact lens and the second region comprises a peripheral zone of the contact lens.

8. 2. The contact lens of claim 1, wherein the visible light absorbing chromophore comprises one or more light absorbing functional groups selected from benzotriazole, acetophenone, benzophenone, azo, diphenyldiazine, alkoxyaniline, tetrahydronaphthalene, anthraquinone, anthracene, dihydroanthracene, selenoxanthene, thioxanthene, and acridine.

9. The contact lens of claim 1 , wherein the visible light absorbing chromophore comprises one or more light absorbing functional groups selected from chromenes, spiropyrans, oxazines, mercury dithizonates, fulgides, fulgimides, organometallic dithiozonates, and naphthacenediones.

10. The visible light absorbing chromophore has formula I: 【Chemistry 1】 The substructure has In the formula, R Ｂ is -C(=O)H or EWG; X is NR, S, or Se; R is H, C １ ~C ６ 2. The contact lens of claim 1, wherein EWG is, independently at each occurrence, an electron withdrawing group.

11. The derivative of the visible light absorbing chromophore has formula II: 【Chemistry 2】 The substructure has In the formula, X′ is N ＋ RO － , SO, SO ２ , SeO, or SeO ２ 2. The contact lens of claim 1 ,

12. 10. A method for manufacturing a contact lens according to claim 1, said method comprising: providing a lens precursor having a first region and a second region, the lens precursor containing visible light absorbing chromophores in the first region and the second region; selectively derivatizing the visible light absorbing chromophore in the second region to form a derivative of the visible light absorbing chromophore, the derivative having a greater average transmittance than the visible light absorbing chromophore over a wavelength range of 400 nm to 600 nm; A method comprising:

13. 13. The method of claim 12, wherein the Lens Precursor is a polymerization reaction product of a reactive mixture comprising: (a) a chromophore-containing monomer; and (b) a monomer suitable for making the contact lens precursor.

14. The chromophore-containing monomer has Formula IV: 【Chemistry 3】 is a compound of During the ceremony, m and n are independently 0, 1, 2, 3, or 4; R Ｃ is EWC or the formula -TY-P ｇ where T is a bond, O, or NR, Y is a linking group, and P ｇ is a polymerizable group; X is NR, S, or Se; R, for each occurrence, independently represents H, C １ ~C ６ Alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, or Y-P ｇ and R １ and R ２ is present, and independently for each occurrence, C １ ~C ６ Alkyl, C １ ~C ６ Alkoxy, C １ ~C ６ Thioalkyl, C １ ~C ６ Selenoalkyl, C ３ ~C ７ Cycloalkyl, aryl, halo, hydroxy, amino, NR ３ R ４ , benzyl, or -Y-P ｇ and R ３ and R ４ are independently H or C １ ~C ６ alkyl or two adjacent R １ Or R ２ the groups, together with the carbon atoms to which they are attached, combine to form a cycloalkyl or aryl ring; EWG, at each occurrence, is independently an electron withdrawing group; The compound of formula I comprises at least one P ｇ The method of claim 13, comprising a group.

15. 15. The method of claim 14, wherein m and n are each independently 0 or 1.

16. 16. The method of claim 14 or 15, wherein Y is, independently at each occurrence, alkylene, cycloalkylene, heterocycloalkylene, arylene, heteroarylene, oxaalkylene, alkylene-amide-alkylene, alkylene-amine-alkylene, or combinations thereof.

17. P ｇ The method of claim 14, wherein each occurrence independently comprises styryl, vinyl carbonate, vinyl ether, vinyl carbamate, N-vinyl lactam, N-vinyl amide, (meth)acrylate, or (meth)acrylamide.

18. 15. The method of claim 14, wherein X is S or NR.

19. 15. The method of claim 14, wherein each occurrence of EWG is cyano.

20. The chromophore-containing monomer has Formula III: 【Chemistry 4】 is a compound of During the ceremony: m and n are independently 0, 1, 2, 3, or 4; R Ｃ is EWC or the formula -TY-P ｇ where T is a bond, O, or NR, Y is a linking group, and P ｇ is a polymerizable group; X is O, NR, S, or Se; R, independently for each occurrence, １ ~C ６ Alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, or Y-P ｇ and R １ and R ２ is present, and independently for each occurrence, C １ ~C ６ Alkyl, C １ ~C ６ Alkoxy, C １ ~C ６ Thioalkyl, C １ ~C ６ Selenoalkyl, C ３ ~C ７ Cycloalkyl, aryl, halo, hydroxy, amino, NR ３ R ４ , benzyl, or -Y-P ｇ and R ３ and R ４ are independently H or C １ ~C ６ alkyl or two adjacent R １ Or R ２ the groups, together with the carbon atoms to which they are attached, combine to form a cycloalkyl or aryl ring; EWG, at each occurrence, is independently an electron withdrawing group; The compound of formula III comprises at least one P ｇ The method of claim 13, comprising a group and at least one oxidizable functional group.

21. The chromophore-containing monomer is: 2-(2-cyano-2-(9H-thioxanthen-9-ylidene)acetamido)ethyl methacrylate; 2-(2-cyano-2-(9H-thioxanthen-9-ylidene)acetamido)ethyl acrylate; N-(2-(2-cyano-2-(9H-thioxanthen-9-ylidene)acetamido)ethyl)methacrylamide; N-(2-(2-cyano-2-(9H-thioxanthen-9-ylidene)acetamido)ethyl)acrylamide; 2-(2-cyano-N-methyl-2-(9H-thioxanthen-9-ylidene)acetamido)ethyl methacrylate; 2-cyano-2-(9H-thioxanthen-9-ylidene)-N-(2-(N-vinylacetamido)ethyl)acetamide; 2-(2-(acridin-9(10H)-ylidene)-2-cyanoacetamido)ethyl acrylate; N-(2-(2-(acridin-9(10H)-ylidene)-2-cyanoacetamido)ethyl)methacrylamide; N-(2-(2-(acridin-9(10H)-ylidene)-2-cyanoacetamido)ethyl)acrylamide; 2-(2-(acridin-9(10H)-ylidene)-2-cyano-N-methylacetamido)ethyl methacrylate; 2-(acridin-9(10H)-ylidene)-2-cyano-N-(2-(N-vinylacetamido)ethyl)acetamide; 2-(2-cyano-2-(9H-thioxanthen-9-ylidene)acetamido)-2-methylpropyl methacrylate; (Z)-2-(2-cyano-2-(3-hydroxyacridin-9(10H)-ylidene)acetamido)ethyl methacrylate; 2-(2-cyano-2-(10-methylacridin-9(10H)-ylidene)acetamido)ethyl methacrylate; 2-(2-cyano-2-(3,6-dihydroxyacridin-9(10H)-ylidene)acetamido)ethyl methacrylate; (E)-2-(2-cyano-2-(2,4-dichloro-9H-thioxanthen-9-ylidene)acetamido)ethyl methacrylate; (E)-2-(2-(2-chloro-9H-thioxanthen-9-ylidene)-2-cyanoacetamido)ethyl methacrylate; (E)-2-(2-cyano-2-(2-isopropyl-9H-thioxanthen-9-ylidene)acetamido)ethyl methacrylate; (E)-2-(2-cyano-2-(4-isopropyl-9H-thioxanthen-9-ylidene)acetamido)ethyl methacrylate; 2-(3-oxo-2-(9H-thioxanthen-9-ylidene)propanamido)ethyl methacrylate; 2-(3-oxo-2-(9H-thioxanthen-9-ylidene)butanamido)ethyl methacrylate; 2-(3-methoxy-3-oxo-2-(9H-thioxanthen-9-ylidene)propanamido)ethyl methacrylate; 2-(3-amino-3-oxo-2-(9H-thioxanthen-9-ylidene)propanamido)ethyl methacrylate; 2-(2-cyano-2-(10,10-dioxido-9H-thioxanthen-9-ylidene)acetamido)ethyl methacrylate; N-(2-(2-cyano-2-(10-methylacridin-9(10H)ylidene)acetamido)ethyl)methacrylamide; 2-(2-cyano-2-(9H-thioxanthen-9-ylidene)acetoxy)ethyl methacrylate; 2-(2-cyano-2-(2-methoxy-10-propylacridin-9(10H)-ylidene)acetamido)ethyl methacrylate; N-(2-(2-cyano-2-(10-methylacridin-9(10H)-ylidene)acetamido)ethyl)methacrylamide; 2-(2-(10-butyl-2-methoxyacridin-9(10H)-ylidene)-2-cyanoacetamido)ethyl methacrylate; 2-((9-(dicyanomethylene)-9H-thioxanthen-2-yl)oxy)ethyl methacrylate; 2-(2-cyano-2-(3-(propylthio)-9H-thioxanthen-9-ylidene)acetamido)ethyl methacrylate; 2-(2-cyano-2-(3-(propylthio)-9H-xanthen-9-ylidene)acetamido)ethyl methacrylate; 3-((9-(1-cyano-2-((2-(methacryloyloxy)ethyl)amino)-2-oxoethylidene)-9H-thioxanthen-3-yl)thio)propyl methacrylate; 3-((9-(1-cyano-2-((2-(methacryloyloxy)ethyl)amino)-2-oxoethylidene)-9H-xanthen-3-yl)thio)propyl methacrylate; 3-((9-(dicyanomethylene)-9H-thioxanthen-3-yl)thio)propyl methacrylate; 3-((9-(dicyanomethylene)-9H-xanthen-3-yl)thio)propyl methacrylate; or Mixtures of two or more of these, The method of claim 13, comprising:

22. The method of claim 13 , wherein the monomer suitable for making the contact lens precursor comprises a hydrophilic component, a silicone-containing component, or a mixture thereof.

Images