Polymerizable absorbers of UV and high-energy visible light

Abstract

To provide polymerizable high-energy light absorbing compounds.SOLUTION: Described are polymerizable high-energy light absorbing compounds. The compounds absorb various wavelengths of ultraviolet and / or high energy visible light and are suitable for incorporation in various products, such as biomedical devices and ophthalmic devices, such as a hydrogel contact lens. A monomer has the specified general formula I, where: X is O, S, NR, SO, or S02; Y is a linking group; Pg is a polymerizable group; and EWG is an electron-withdrawing group.SELECTED DRAWING: Figure 9

Description

[Technical Field]

[0001] (CROSS-REFERENCE TO RELATED APPLICATIONS) This application claims priority to U.S. Patent Application No. 16 / 268,897, filed February 6, 2019, U.S. Provisional Patent Application No. 62 / 691,112, filed June 28, 2018, and U.S. Provisional Patent Application No. 62 / 637,505, filed March 2, 2018, each of which is incorporated by reference in its entirety.

[0002] FIELD OF THE INVENTION The present invention relates to UV and high-energy visible light absorbers. More specifically, the present invention relates to compounds having polymerizable functional groups that absorb UV and / or high-energy visible light at various wavelengths and are optically transparent when incorporated into articles. Thus, the compounds can be used in polymeric articles, including biomedical devices such as ophthalmic devices. [Background technology]

[0003] High-energy light from the sun, such as UV light and high-energy visible light, is known to be involved in cell damage. While most radiation with wavelengths below 280 nm is absorbed by the Earth's atmosphere, photons with wavelengths in the 280-400 nm range have been linked to degenerative changes in the cornea and several eye disorders, including age-related cataracts and macular degeneration. (See Statement on Ocular Ultraviolet Radiation Hazards in Sunlight, American Optometric Association, November 10, 1993.) The human cornea absorbs some radiation up to 320 nm (30% transmission) (Doutch, JJ, Quantock, AJ, Joyce, NC, Meek, KM, Biophys. J, 2012, 102, 1258-1264), but is inefficient at protecting the back of the eye from radiation in the 320-400 nm wavelength range.

[0004] Contact lens standards define the upper ultraviolet wavelength at 380 nm. The current Class I UV absorption standard defined by the American Optometric Association requires that >99% of radiation between 280 and 315 nm (UV B) and >90% of radiation between 316 and 380 nm (UV A) be absorbed by contact lenses. While this standard effectively addresses corneal protection (<1% UV B transmittance), little attention is paid to lower-energy UV radiation (>380 and <400 nm) associated with retinal damage (Ham, W.T., Mueller, H.A., Sliney, D.H. Nature 1976;260(5547):153-5) or high-energy visible light.

[0005] High-energy visible (HEV) light can cause visual discomfort or disrupt circadian rhythms. For example, computer and electronic device screens, flat-screen televisions, energy-efficient lights, and LED lights are known to emit HEV light. Long-term exposure to such HEV light sources can cause eye strain. Viewing devices that emit HEV light at night is also thought to disrupt natural circadian rhythms, leading to, for example, sleep deprivation.

[0006] Absorption of high-energy light rays before they reach the eye remains a desirable goal in ophthalmology. However, the degree to which certain wavelength ranges are absorbed is also important. For example, in the UV-A and UV-B ranges, it may be desirable to absorb as much radiation as possible. On the other hand, because HEV light forms part of the visible spectrum, complete absorption of HEV light may have adverse effects on vision. Therefore, partial absorption of HEV light may be more desirable. Summary of the Invention [Problem to be solved by the invention]

[0007] There is a need for materials that provide targeted absorption of undesirable wavelengths of high-energy radiation and that can be processed into functional products. Compounds that absorb or attenuate high-energy radiation, when used in ophthalmic devices, can help protect the cornea, as well as internal cells in the ocular environment, from deterioration, fatigue, and / or circadian rhythm disruption. [Means for solving the problem]

[0008] The present invention relates to high-energy light absorbing compounds that absorb UV and / or high-energy visible (HEV) light but substantially transmit (e.g., greater than 80% transmittance) wavelengths longer than about 450 nm. The compounds are therefore effective in providing targeted absorption of high-energy light, such as UV (UV A and UV B), low-energy UV light (385 nm to 400 nm), or HEV light (e.g., 400 to 450 nm).

[0009] The compounds are also polymerizable and generally compatible with the polymerization and processing conditions typically used to make ophthalmic devices such as soft contact lenses, in addition to other raw materials, and therefore can be easily covalently incorporated into final products without requiring significant modifications to existing manufacturing processes and equipment.

[0010] Thus, in one aspect, the present invention provides a compound of formula I:

[0011] [ka] provide During the ceremony, m and n are independently 0, 1, 2, 3, or 4; T is a bond, O, or NR; X is O, S, NR, SO, or SO; 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 at each occurrence C1-C6 alkyl, C1-C6 alkoxy, C1-C6 thioalkyl, C3-C7 cycloalkyl, aryl, halo, hydroxy, amino, NR 3 R 4 or benzyl, where 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; The EWG is an electron-withdrawing group such as cyano, amide, ester, keto, or aldehyde (preferably cyano).

[0012] In another aspect, the present invention provides an ophthalmic device that is a free radical reaction product of a reactive mixture comprising one or more monomers suitable for making an ophthalmic device and a polymerizable high-energy light absorbing compound comprising a compound of Formula I described herein.

[0013] In a further aspect, the present invention provides a method of making an ophthalmic device, the method comprising: (a) providing a reactive mixture containing a compound of Formula I described herein, one or more device-forming monomers, and a radical initiator; and (b) polymerizing the reactive mixture to form the ophthalmic device.

[0014] In still a further aspect, the present invention provides an ophthalmic device that is a reaction product of a reactive mixture, the ophthalmic device comprising a polymerizable high-energy light absorbing compound and one or more monomers suitable for making an ophthalmic device, the ophthalmic device transmitting no more than 45 percent of light having a wavelength between 280 and 399 nm, between 1 percent and 70 percent of light having a wavelength between 400 and 409 nm, and at least 80 percent of light having a wavelength between 450 and 800 nm.

[0015] In a further aspect, the present invention provides an ophthalmic device that is a polymerization reaction product of a reactive mixture that includes one or more reactive components (such as a hydrophilic component and a silicone-containing compound), wherein the polymerization reaction product includes, as covalently attached substituents, one or more chromophores of Formula IV:

[0016] [ka] an ophthalmic device comprising: In the formula, m, n, X, R 1 , R 2 , R 5 , and EWG are as defined herein. [Brief explanation of the drawings]

[0017] [Figure 1] 1 shows UV-VIS transmission spectra of 0.2 mM solutions of exemplary compounds (B), (C), and (E) in methanol. [Figure 2] 1 shows the UV-VIS transmission spectra of 0.2 mM solutions of compounds (G), (H), and (J) in methanol and compound (L) in dichloromethane. [Figure 3] 1 shows the UV-VIS transmission spectra of exemplary silicone hydrogel contact lenses 9A and 9B. [Figure 4] 1 shows the UV-VIS transmission spectra of exemplary silicone hydrogel contact lenses 9A and 9C. [Figure 5] 1 shows the UV-VIS transmission spectra of exemplary silicone hydrogel contact lenses 9A and 9D. [Figure 6] 1 shows the UV-VIS transmission spectra of exemplary silicone hydrogel contact lenses 10A and 10B. [Figure 7] 1 shows the UV-VIS transmission spectra of exemplary silicone hydrogel contact lenses 10A and 10C. [Figure 8] 1 shows the UV-VIS transmission spectra of exemplary silicone hydrogel contact lenses 10A and 10B. [Figure 9] 1 shows the UV-VIS transmission spectrum of a silicone hydrogel contact lens (11A) containing compound (B) after exposure to direct sunlight. [Figure 10] 1 shows the UV-VIS transmission spectrum of a silicone hydrogel contact lens (11B) containing Compound (B) after exposure to room lighting. DETAILED DESCRIPTION OF THE INVENTION

[0018] 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.

[0019] As mentioned above, in one aspect, the present invention provides a UV / HEV absorbing compound. The compound contains a polymerizable functional group. It has been discovered that ophthalmic devices that absorb a significant amount of UV light as well as some amount of HEV light can be readily prepared as described herein.

[0020] It has also been discovered that light-absorbing compounds can be selected to provide targeted absorption of UV and / or high-energy visible light (e.g., increased UV absorption and decreased HEV absorption, or increased HEV absorption). Such targeting can be achieved, for example, using compounds of Formula I containing a heterotricyclic core chromophore. For example, as described in more detail below, compounds of Formula I in which the heteroatom (X in Formula I) is sulfur can absorb HEV light. On the other hand, compounds of Formula I in which the heteroatom is oxygen (X is O) can absorb less HEV light but more UV light. Thus, the compounds can be used to absorb selected regions of UV and / or HEV light, or can be mixed together or with other absorbing compounds to provide broad-spectrum protection (e.g., UV and HEV light). Advantageously, the compounds exhibit a transmission cutoff (e.g., absorb 20 percent or less) at visible wavelengths of 450 nm or greater.

[0021] The compounds of Formula I have further been found to be substantially photostable, meaning that when incorporated into an ophthalmic device, the compounds do not undergo significant degradation over time when exposed to lighting, such as indoor or outdoor lighting. Such photostability can be determined by measuring the UV / Vis transmittance spectrum of the ophthalmic device over a test period, such as 21 weeks. A significant change in the spectrum over the test period indicates a lack of photostability. By way of example, an ophthalmic device (such as a contact lens) containing a compound of the present invention exhibits a change in its average transmittance of no more than 5%, preferably no more than 2%, more preferably no more than 0.5%, and even more preferably no more than 0.4% over the wavelength range of 380-700 nm when exposed to indoor office lighting at room temperature for 21 weeks. As a further example, an ophthalmic device (such as a contact lens) containing a compound of the present invention exhibits a change in its average transmittance of no more than 5%, preferably no more than 2%, more preferably no more than 1%, and even more preferably no more than 0.7% over the wavelength range of 400-500 nm when exposed to indoor office lighting at room temperature for 21 weeks. Such changes can be calculated as the absolute difference between the mean transmittance (over a specified wavelength range) at 21 weeks and at time zero.

[0022] Thus, the compounds of the present invention are transparent in the visible spectrum but can successfully absorb UV (UVA, UVB) and / or HEV radiation, making them suitable for incorporation into a variety of products, including biomedical and ophthalmic devices.

[0023] The following definitions are provided for terms used in this disclosure.

[0024] 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 by reference.

[0025] As used herein, the term "(meth)" refers to any methyl substitution. Thus, a term such as "(meth)acrylate" refers to both methacrylate and acrylate.

[0026] Wherever a chemical structure is depicted, it should be understood that the disclosed options for substituents in the structure may be combined in any combination. * 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 properties.

[0027] General formula [ *** ] n When a subscript, such as "n" in {overscore (R)} is used to denote the number of repeating units in a chemical formula of a polymer, the formula should be interpreted as representing the number average molecular weight of the polymer.

[0028] The term "individual" includes humans and vertebrates.

[0029] The term "biomedical device" refers to any article designed to be used in or on mammalian tissue or fluid, preferably 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 a silicone hydrogel or a conventional hydrogel.

[0030] The term "ocular surface" includes the surface 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 epithelial continuity through innervation and by the endocrine and immune systems.

[0031] The term "ophthalmic device" refers to any apparatus that resides in or on the eye or any part of the eye (including the ocular surface). These devices can provide optical correction, appearance enhancement, vision enhancement, therapeutic effects (e.g., as a bandage), or delivery of active ingredients such as pharmaceutical and nutritional supplements, 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 soft contact lenses, hard contact lenses, hybrid contact lenses, intraocular lenses, and overlay lenses. Ophthalmic devices can include contact lenses.

[0032] The term "contact lens" refers to an ophthalmic device that can be placed on the cornea of ​​an individual's eye. Contact lenses can provide corrective, cosmetic, or therapeutic benefits, including wound healing, delivery of medications or nutritional supplements, diagnostic evaluation or monitoring, ultraviolet absorption, visible light or glare reduction, or any combination thereof. Contact lenses can be of any suitable material known in the art and can be soft lenses, hard lenses, or hybrid lenses containing at least two distinct portions with different physical, mechanical, or optical properties, such as modulus of elasticity, water content, light transmission, or a combination thereof.

[0033] 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 within the cured device.

[0034] "Target macromolecule" means a macromolecule that has been synthesized from a reactive monomer mixture, including monomers, macromers, prepolymers, crosslinkers, initiators, additives, diluents, and the like.

[0035] The term "polymerizable compound" means a compound containing one or more polymerizable groups. This term includes, for example, monomers, macromers, oligomers, prepolymers, crosslinkers, and the like.

[0036] 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 free radical and / or cationic polymerization, e.g., radical polymerization initiation conditions. Non-limiting examples of free radical reactive groups include (meth)acrylate, styrene, vinyl ether, (meth)acrylamide, N-vinyl lactam, N-vinyl amide, O-vinyl carbamate, O-vinyl carbonate, and other vinyl groups. Preferably, the free radical polymerizable group comprises (meth)acrylate, (meth)acrylamide, N-vinyl lactam, N-vinyl amide, and styryl functional groups, as well as mixtures of any of the foregoing. More preferably, the free radical polymerizable group comprises (meth)acrylate, (meth)acrylamide, and mixtures thereof. 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 substituted with alkyl or cycloalkyl (which may themselves be further substituted).

[0037] Any type of free radical polymerization can be used, including but not limited to bulk, solution, suspension, and emulsion, as well as any controlled radical polymerization method, such as stable free radical polymerization, nitroxide-mediated living polymerization, atom transfer radical polymerization, reversible addition-fragmentation chain transfer polymerization, organotellurium-mediated living radical polymerization, etc.

[0038] A "monomer" is a monofunctional molecule that can undergo chain growth polymerization, particularly free radical polymerization, thereby creating repeating 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% by weight 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% by weight 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.

[0039] A "macromolecule" is an organic compound having a number average molecular weight greater than 1500, and may be reactive or non-reactive.

[0040] A "macromonomer" or "macromer" is a macromolecule having one group capable of undergoing chain-growth polymerization, particularly free-radical polymerization, thereby creating repeating units within the chemical structure of a target macromolecule. Generally, the chemical structure of a macromer differs from that of a target macromolecule; i.e., the repeating units of the pendant group of the macromer differ from the repeating units of the target macromolecule or its backbone. The only differences between a monomer and a macromer are the chemical structure of the pendant group, the molecular weight, and the molecular weight distribution. Consequently, and as used herein, 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. Furthermore, the patent literature sometimes defines macromers as having one or more polymerizable groups, essentially expanding the general definition of macromer to include prepolymers. Consequently, and as used herein, difunctional and multifunctional macromers, prepolymers, and crosslinkers may be used interchangeably.

[0041] A "silicone-containing component" is a monomer, macromer, prepolymer, crosslinker, initiator, additive, or polymer in a 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.

[0042] 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.

[0043] A "polymer" is a target macromolecule made up of repeating units of the monomers used during polymerization.

[0044] 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.

[0045] A "repeating unit" is the smallest group within a polymer that corresponds to the polymerization of a particular monomer or macromer.

[0046] An "initiator" is a molecule that can decompose 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.

[0047] 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.

[0048] A "prepolymer" is a reaction product of monomers that contain remaining polymerizable groups that can undergo further reaction to form a polymer.

[0049] A "polymer network" is a cross-linked macromolecule 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.

[0050] "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.

[0051] "Silicone hydrogel" refers to a polymer network made from at least one hydrophilic component and at least one silicone-containing component. Examples of silicone hydrogels include acquafilcon, asmofilcon, balafilcon, comfilcon, delefilcon, enfilcon, fanfilcon, formofilcon, galyfilcon, lotrafilcon, narafilcon, and the like. In addition to rafilcon, 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, 6,087,411, and 6,117,416. No. 5, No. 5,760,100, No. 5,776,999, No. 5,789,461, No. 5,849,811, No. 5 ,965,631, 6,367,929, 6,822,016, 6,867,245, 6,943,2 No. 03, No. 7,247,692, No. 7,249,848, No. 7,553,880, No. 7,666,921, No. 7,666,921, No. No. 7,786,185, No. 7,956,131, No. 8,022,158, No. 8,273,802, No. 8,399,5 No. 38, No. 8,470,906, No. 8,450,387, No. 8,487,058, No. 8,507,577, No. No. 8,637,621, No. 8,703,891, No. 8,937,110, No. 8,937,111, No. 8,940, No. 812, No. 9,056,878, No. 9,057,821, No. 9,125,808, No. 9,140,825, No. 9,140,825, No. No. 9,156,934, No. 9,170,349, No. 9,244,196, No. 9,244,197, No. 9,260,544, 9,297,928, 9,297,929, as well as 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.

[0052] 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 interlocking chemical bonds. A "semi-penetrating polymer network" comprises one or more networks and one or more polymers 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 a semi-penetrating network is technically a polymer blend, in some cases the polymers are entangled so that they cannot be easily removed.

[0053] The terms "reactive mixture" and "reactive monomer mixture" refer to a mixture of components (both reactive and non-reactive) that, when mixed together and subjected to polymerization conditions, form the biomedical devices, ophthalmic devices, and contact lenses made therefrom, in addition to conventional or inventive silicone hydrogels. Reactive monomer mixtures may include reactive components such as monomers, macromers, prepolymers, crosslinkers, and initiators; additives such as wetting agents, polymers, dyes; light-absorbing compounds such as UV absorbers, pigments, dyes, and photochromic compounds (all of which may be reactive or non-reactive but can be retained in the resulting biomedical devices, as well as pharmaceutical and nutraceutical compounds); and optional diluents. It will be understood that various additives may be added depending on the biomedical device being made and its intended use. The concentrations of the components of the reactive mixture are expressed as weight percentages of all components in the reactive mixture, excluding the diluent. If a diluent is used, their concentration is expressed as a weight percentage based on the amount of all components and diluent in the reactive mixture.

[0054] A "reactive component" is a component of the reactive mixture that becomes part of the chemical structure of the polymer network of the resulting hydrogel through covalent bonding, hydrogen bonding, electrostatic interactions, formation of an interpenetrating polymer network, or any other means.

[0055] The term "silicone hydrogel contact lenses" refers to hydrogel contact lenses made from at least one silicone-containing component. Silicone hydrogel contact lenses typically 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.

[0056] The term "multifunctional" refers to a component having two or more polymerizable groups. The term "monofunctional" refers to a component having one polymerizable group.

[0057] The terms "halogen" or "halo" refer to fluorine, chlorine, bromine, and iodine.

[0058] "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) can 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, or 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 such as -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH2CH(CH3)CH2-, and -CH2CH2CH2CH2-.

[0059] "Haloalkyl" refers to an alkyl group, as defined above, substituted with 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-.

[0060] "Cycloalkyl" refers to an optionally substituted cyclic hydrocarbon containing the specified number of ring carbon atoms. If no number is specified, the cycloalkyl may contain 3 to 12 ring carbon atoms. Preferred are C3-C8 cycloalkyl groups, C3-C7 cycloalkyl, more preferably C4-C7 cycloalkyl, and even more preferably C5-C6 cycloalkyl. 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.

[0061] "Heterocycloalkyl" refers to a cycloalkyl ring or ring system, as defined above, in which at least one ring carbon is replaced with 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.

[0062] "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 optionally be fused to 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 aryl groups 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.

[0063] "Heteroaryl" refers to an aryl ring or ring system, as defined above, in which at least one ring carbon atom is replaced with 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, and thienyl. "Heteroarylene" refers to a divalent heteroaryl group.

[0064] "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 molecular moiety through a sulfur bridge. Examples of thioalkyl groups include, for example, methylthio, ethylthio, n-propylthio, and isopropylthio. "Aryloxy" refers to an aryl group attached to the parent molecular moiety through an oxygen bridge. An example is phenoxy. "Cyclicalkoxy" refers to a cycloalkyl group attached to the parent moiety through an oxygen bridge.

[0065] "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 -CH2CH2NH-.

[0066] "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" refers to monomers (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 the siloxanyl group is independently selected to complete their valence. A group (where R A is as defined in options (b) to (i) of Formula A).

[0067] "Silyl" refers to a structure of formula R3Si-, and "siloxy" refers to a structure of formula R3Si-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.

[0068] "Alkyleneoxy" refers to a group having the general formula -(alkylene-O-) p -or -(O-alkylene) p " refers to the group -, where alkylene is as defined above, p is 1 to 200, or 1 to 100, or 1 to 50, or 1 to 25, or 1 to 20, or 1 to 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 alkyleneoxy forms a terminal group in a molecule, the terminus of the alkyleneoxy may be, for example, hydroxy or alkoxy (e.g., HO-[CHCHO] p - or CHO-[CHCHO] p Examples of alkyleneoxy include polyethyleneoxy, polypropyleneoxy, polybutyleneoxy, and poly(ethyleneoxy-co-propyleneoxy).

[0069] "Oxaalkylene" refers to an alkylene group as defined above in which one or more non-adjacent CH groups are replaced with an oxygen atom, such as -CHCHOCH(CH)CH-. "Thiaalkylene" refers to an alkylene group as defined above in which one or more non-adjacent CH groups are replaced with a sulfur atom, such as -CHCHSCH(CH)CH-.

[0070] 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 conditions of polymerization, as well as the processing and storage of the final product. For example, the linking group may be a bond or may contain one or more alkylene, haloalkylene, amide, amine, alkyleneamine, carbamate, ester (-CO-), arylene, heteroarylene, cycloalkylene, heterocycloalkylene, alkyleneoxy, oxaalkylene, thiaalkylene, haloalkyleneoxy (alkyleneoxy substituted with one or more halo groups, e.g., -OCF-, -OCFCF-, -OCFCH-), 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- (more than one alkyleneoxy group can be present, 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 linked), such as (meth)acrylate.

[0071] Preferred linking groups include C1-C8 alkylene (preferably C2-C6 alkylene) and C1-C8 oxaalkylene (preferably C2-C6 oxaalkylene), each of which is optionally substituted with one or two groups independently selected from hydroxyl and siloxy. Preferred linking groups also include carboxylate, amide, C1-C8 alkylene-carboxylate-C1-C8 alkylene, or C1-C8 alkylene-amide C1-C8 alkylene.

[0072] When the linking group is composed of a combination of the moieties described above (e.g., alkylene and cycloalkylene), the moieties may be present in any order. For example, in the following formula E, when L is shown to be -alkylene-cycloalkylene-, Rg-L may be either Rg-alkylene-cycloalkylene- or Rg-cycloalkylene-alkylene-. Regardless, the listed order 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 E, L and L 2 and -L are preferably Rg-alkylene-cycloalkylene-, and -L 2 -Rg is preferably -cycloalkylene-alkylene-Rg.

[0073] The term "electron-withdrawing group" (EWG) refers to a chemical group that withdraws electron density from the atom or group of atoms to which it is bonded. Examples of EWGs include, but are not limited to, cyano, amide, ester, keto, or aldehyde. A preferred EWG is cyano (CN).

[0074] The terms "high energy absorber," "UV / HEV absorber," or "high energy light absorbing compound" refer to chemicals that absorb various wavelengths of ultraviolet light, high energy visible light, or both. The ability of a material to absorb light of a particular wavelength can be determined by measuring its UV / Vis transmittance spectrum. A compound that exhibits no absorption at a particular wavelength will exhibit substantially 100 percent transmittance at that wavelength. Conversely, a compound that completely absorbs at a particular wavelength will exhibit substantially 0% transmittance at that wavelength. When the transmittance of a material is given as a percentage for a particular wavelength range, it is understood that the material exhibits transmittance at all wavelengths within that range.

[0075] Unless otherwise stated, ratios, percentages, parts, etc. are by weight.

[0076] Unless otherwise stated, a numerical range such as, for example, "2 to 10" is inclusive of the numbers defining the range (eg, 2 and 10).

[0077] As noted above, in one aspect, the present invention provides an ophthalmic device that is the reaction product of a reactive mixture comprising one or more polymerizable high-energy light absorbing compounds and one or more monomers suitable for fabricating the ophthalmic device, wherein the ophthalmic device transmits 45 percent or less of light having a wavelength between 280 and 399 nm, at least 1 percent and at most 70 percent of light having a wavelength between 400 and 409 nm, and at least 80 percent of light having a wavelength between 450 and 800 nm. Preferably, the ophthalmic device also transmits at least 10 percent and at most 95 percent of light having a wavelength between 410 and 424 nm. Also preferably, the ophthalmic device transmits at least 50 percent of light having a wavelength between 425 and 449 nm. Even more preferably, the ophthalmic device transmits 10 percent or less of light having a wavelength between 200 and 279 nm.

[0078] Preferably, the transmittance of the ophthalmic device from 200 to 279 nm is 5 percent or less, or 1 percent or less, or preferably, it is less than 1 percent.

[0079] Preferably, the transmittance of the ophthalmic device from 280 to 399 nm is 35 percent or less, or 25 percent or less, or 20 percent or less, or 10 percent or less, or 5 percent or less, or 1 percent or less.

[0080] Preferably, the transmittance of the ophthalmic device at 400-409 nm is at least 2 percent, at least 3 percent, or at least 4 percent, and more preferably, the transmittance of the ophthalmic device at 400-409 nm is at most 60 percent, at most 50 percent, at most 40 percent, at most 30 percent, or at most 20 percent.

[0081] Preferably, the transmittance of the ophthalmic device at 410-424 nm is at least 15 percent. Also preferably, the transmittance of the ophthalmic device at 410-424 nm is at most 85 percent, at most 75 percent, or at most 65 percent.

[0082] Preferably, the transmittance of the ophthalmic device between 425 and 449 nm is at least 60 percent.

[0083] Preferably, the transmittance of the ophthalmic device between 450 and 800 nm is at least 85 percent.

[0084] The preferred ophthalmic device is a contact lens, more preferably a soft hydrogel contact lens. The aforementioned transmission wavelengths and percentages can be measured on lenses of various thicknesses. For example, the center thickness can be 80-100 micrometers, or 90-100 micrometers, or 90-95 micrometers. Various concentrations of one or more polymerizable high-energy light-absorbing compounds can be used to achieve the aforementioned results. For example, the concentration can range from at least 0.1 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 range from 1 to 5 percent.

[0085] The present invention also provides a UV / HEV absorbing compound of formula I:

[0086] [ka] provide During the ceremony, m and n are independently 0, 1, 2, 3, or 4; T is a bond, O, or NR; X is O, S, NR, SO, or SO; 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 at each occurrence C1-C6 alkyl, C1-C6 alkoxy, C1-C6 thioalkyl, C3-C7 cycloalkyl, aryl (preferably unsubstituted phenyl or phenyl substituted with alkyl or halo), halo, hydroxy, amino, NR 3 R 4 or benzyl, where 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.

[0087] The compounds of formula I preferably contain one or two Y-Pg groups, more preferably the compounds contain one Y-Pg group.

[0088] Formula I-1. Compounds of formula I can include compounds of formula I-1, which are compounds of formula I where X is S.

[0089] I-2. Compounds of formula I can include compounds of formula I-2, which are compounds of formula I where X is O.

[0090] I-3. Compounds of formula I may include compounds of formula I-3, which are compounds of formula I where X is NR, preferably NH or N-alkyl.

[0091] I-4. Compounds of formula I can include compounds of formula I-4, which are compounds of formula I where X is SO.

[0092] I-5. Compounds of formula I can include compounds of formula I-5, which are compounds of formula I where X is SO2.

[0093] I-6. Compounds of Formula I, I-1, I-2, I-3, I-4, and I-5 can include compounds of Formula I-6, which are compounds of Formula I, I-1, I-2, I-3, I-4, or I-5 where m and n are independently 0 or 1, or both are 0.

[0094] I-7. Compounds of formula I, I-1, I-2, I-3, I-4, and I-5 are compounds wherein m is 1 and R 1 may include compounds of formula I-7, which are compounds of formula I, I-1, I-2, I-3, I-4 or I-5, wherein is C1-C6 alkyl, preferably ethyl or methyl.

[0095] I-8. Compounds of formula I, I-1, I-2, I-3, I-4, I-5, and I-7 are compounds wherein n is 1 and R 2 may include compounds of formula I-8, which are compounds of formula I, I-1, I-2, I-3, I-4, I-5, or I-7, wherein is C1-C6 alkyl, preferably ethyl or methyl.

[0096] I-9. Compounds of formula I, I-1, I-2, I-3, I-4, I-5, I-6, I-7, and I-8 may include compounds of formula I-9, which are compounds of formula I, I-1, I-2, I-3, I-4, I-5, I-6, I-7, or I-8, where R is H or C1-C6 alkyl. Preferably, R in the group T is H.

[0097] I-10. Compounds of formula I, I-1, I-2, I-3, I-4, I-5, I-6, I-7, I-8, and I-9 are P gThe compounds of formula I-10 may include compounds of formula I, I-1, I-2, I-3, I-4, I-5, I-6, I-7, I-8, or I-9, where (polymerizable group) independently at each occurrence is a styryl, vinyl carbonate, vinyl ether, vinyl carbamate, N-vinyl lactam, N-vinyl amide, (meth)acrylate, or (meth)acrylamide. The polymerizable group allows the compounds of the present invention to form covalent bonds when reacted with monomers, crosslinkers, and other components commonly used in the fabrication of polymeric devices. The compatibility of the compound with the reactive mixture can be controlled by the selection of the polymerizable group (and linking group). Preferred polymerizable groups include (meth)acrylate or (meth)acrylamide. A more preferred polymerizable group is methacrylate.

[0098] I-11. Compounds of Formula I, I-1, I-2, I-3, I-4, I-5, I-6, I-7, I-8, I-9, and I-10 can include compounds of Formula I-11, which are compounds of Formula I, I-1, I-2, I-3, I-4, I-5, I-6, I-7, I-8, I-9, or I-10, where Y (the linking group) is alkylene, cycloalkylene, heterocycloalkylene, arylene (e.g., phenylene), heteroarylene, oxaalkylene, alkylene-amide-alkylene, alkylene-amine-alkylene, or any combination of these 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 is C1-C8 alkylene, especially ethylene (-CH2CH2-). When T in a compound of Formula I 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(CH-2) x -(In the formula, R H are independently C1 to C6 alkyl (preferably independently methyl or ethyl), and x is 1 to 5).

[0099] I-12. Compounds of Formula I, I-1, I-2, I-3, I-4, I-5, I-6, I-7, I-8, I-9, I-10, and I-11 can include compounds of Formula I-12, which are compounds of Formula I, I-1, I-2, I-3, I-4, I-5, I-6, I-7, I-8, I-9, I-10, or I-11, wherein T is a bond or NR (preferably NH).

[0100] I-13. Compounds of formula I, I-1, I-2, I-3, I-4, I-5, I-6, I-7, I-8, I-9, I-10, I-11, and I-12 can include compounds of formula I-13, which are compounds of formula I, I-1, I-2, I-3, I-4, I-5, I-6, I-7, I-8, I-9, I-10, I-11, or I-12, in which EWG is cyano, amide, ester, keto, or aldehyde. Preferably, EWG is cyano.

[0101] Preferred compounds of formula I are compounds of formula II:

[0102] [ka] Including, During the ceremony, m and n are independently 0, 1, 2, 3, or 4; T is a bond, O, or NR; X is O, S, NR, SO, or SO; 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 2is, when present, independently at each occurrence C1-C6 alkyl, C1-C6 alkoxy, C1-C6 thioalkyl, C3-C7 cycloalkyl, aryl (preferably unsubstituted phenyl or phenyl substituted with alkyl or halo), halo, hydroxy, amino, NR 3 R 4 or benzyl, where 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 linked to form a cycloalkyl or aryl ring. Compounds of formula I preferably contain one or two Y-Pg groups. More preferably, the compounds contain one Y-Pg group.

[0103] Formula II-1. Compounds of formula II may include compounds of formula II-1, which are compounds of formula II where X is S.

[0104] II-2. Compounds of formula II may include compounds of formula II-2, which are compounds of formula II where X is O.

[0105] II-3. Compounds of formula II may include compounds of formula II-3, which are compounds of formula II where X is NR, preferably NH or N-alkyl.

[0106] II-4. Compounds of formula II may include compounds of formula II-4, which are compounds of formula II where X is SO.

[0107] II-5. Compounds of formula II can include compounds of formula II-5, which are compounds of formula II where X is SO2.

[0108] II-6. Compounds of Formula II, II-1, II-2, II-3, II-4, and II-5 can include compounds of Formula II-6, which are compounds of Formula II, II-1, II-2, II-3, II-4, or II-5 where m and n are independently 0 or 1, or both are 0.

[0109] II-7. Compounds of formula II, II-1, II-2, II-3, II-4, and II-5 are those in which m is 1 and R 1 is a C1-C6 alkyl, preferably ethyl or methyl.

[0110] II-8. Compounds of formula II, II-1, II-2, II-3, II-4, II-5, and II-7 are those in which n is 1 and R 2 is a C1-C6 alkyl, preferably ethyl or methyl.

[0111] II-9. Compounds of formula II, II-1, II-2, II-3, II-4, II-5, II-6, II-7 and II-8 may include compounds of formula II-9, which are compounds of formula II, II-1, II-2, II-3, II-4, II-5, II-6, II-7 or II-8, in which R is H or C1-C6 alkyl. Preferably, R in the group T is H.

[0112] II-10. Compounds of formula II, II-1, II-2, II-3, II-4, II-5, II-6, II-7, II-8, and II-9 are P gThe compounds of formula II-10 may include compounds of formula I, II-1, II-2, II-3, II-4, II-5, II-6, II-7, II-8, or II-9, where (polymerizable group) independently at each occurrence is a styryl, vinyl carbonate, vinyl ether, vinyl carbamate, N-vinyl lactam, N-vinyl amide, (meth)acrylate, or (meth)acrylamide. The polymerizable group allows the compounds of the present invention to form covalent bonds when reacted with monomers, crosslinkers, and other components commonly used in the fabrication of polymeric devices. The compatibility of the compound with the reactive mixture can be controlled by the selection of the polymerizable group (and linking group). Preferred polymerizable groups include (meth)acrylates or (meth)acrylamides. A more preferred polymerizable group is methacrylate.

[0113] II-11. Compounds of Formula II, II-1, II-2, II-3, II-4, II-5, II-6, II-7, II-8, II-9, and II-10 can include compounds of Formula II-11, which are compounds of Formula II, II-1, II-2, II-3, II-4, II-5, II-6, II-7, II-8, II-9, or II-10, where Y (the linking group) is alkylene, cycloalkylene, heterocycloalkylene, arylene (e.g., phenylene), heteroarylene, oxaalkylene, alkylene-amide-alkylene, alkylene-amine-alkylene, or any combination of these 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 II 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(CH-2) x -(In the formula, R Hare independently C1 to C6 alkyl (preferably independently methyl or ethyl), and x is 1 to 5).

[0114] II-12. Compounds of Formula II, II-1, II-2, II-3, II-4, II-5, II-6, II-7, II-8, II-9, II-10, and II-11 can include compounds of Formula II-12, which are compounds of Formula II, II-1, II-2, II-3, II-4, II-5, II-6, II-7, II-8, II-9, II-10, or II-11, where T is a bond or NR (preferably NH).

[0115] Preferred compounds of formula I and formula II include compounds of formula III:

[0116] [ka] are listed, During the ceremony, m and n are independently 0, 1, 2, 3, or 4; X is O, S, NR, SO, or SO; 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 at each occurrence C1-C6 alkyl, C1-C6 alkoxy, C1-C6 thioalkyl, C3-C7 cycloalkyl, aryl (preferably unsubstituted phenyl or phenyl substituted with alkyl or halo), halo, hydroxy, amino, NR 3 R 4 or benzyl, where R 3 and R 4 are independently H or C1-C6 alkyl, or two adjacent R 1 or R 2The groups, together with the carbon atoms to which they are attached, are linked to form a cycloalkyl or aryl ring. Compounds of formula II preferably contain one or two YP g More preferably, the compound contains one Y-Pg group.

[0117] Formula III-1. Compounds of formula III may include compounds of formula III-1, which are compounds of formula III where X is S.

[0118] III-2. Compounds of formula III may include compounds of formula III-2, which are compounds of formula III where X is O.

[0119] III-3. Compounds of formula III may include compounds of formula III-3, which are compounds of formula III where X is NR, preferably NH or N-alkyl.

[0120] III-4. Compounds of formula III may include compounds of formula III-4, which are compounds of formula III where X is SO.

[0121] III-5. Compounds of formula III can include compounds of formula III-5, which are compounds of formula III where X is SO2.

[0122] III-6. Compounds of formula III, III-1, III-2, III-3, III-4, and III-5 can include compounds of formula III-6, which are compounds of formula III, III-1, III-2, III-3, III-4, or III-5 where m and n are independently 0 or 1, or both are 0.

[0123] III-7. Compounds of formula III, III-1, III-2, III-3, III-4, and III-5 are those in which m is 1 and R 1 may include compounds of formula III-7, which are compounds of formula III, III-1, III-2, III-3, III-4, or III-5, where is C1-C6 alkyl, preferably ethyl or methyl.

[0124] III-8. Compounds of formula III, III-1, III-2, III-3, III-4, III-5, and III-7 are those in which n is 1 and R 2 is a C1-C6 alkyl, preferably ethyl or methyl, compound of formula III, III-1, III-2, III-3, III-4, III-5, or III-7.

[0125] III-9. Compounds of formula III, III-1, III-2, III-3, III-4, III-5, III-6, III-7, and III-8 may include compounds of formula III-9, which are compounds of formula III, III-1, III-2, III-3, III-4, III-5, III-6, III-7, or III-8, where R, in each occurrence, is independently H or C1-C6 alkyl. Preferably, R, in each occurrence, is H. Preferably, R in the group T is H.

[0126] III-10. Compounds of formula III, III-1, III-2, III-3, III-4, III-5, III-6, III-7, III-8, and III-9 are P g The compounds of formula III-10 may include compounds of formula III, III-1, III-2, III-3, III-4, III-5, III-6, III-7, III-8, or III-9, where (polymerizable group) independently at each occurrence is a styryl, vinyl carbonate, vinyl ether, vinyl carbamate, N-vinyl lactam, N-vinyl amide, (meth)acrylate, or (meth)acrylamide. The polymerizable group allows the compounds of the present invention to form covalent bonds when reacted with monomers, crosslinkers, and other components commonly used in the fabrication of polymeric devices. The compatibility of the compound with the reactive mixture can be controlled by the selection of the polymerizable group (and linking group). Preferred polymerizable groups include (meth)acrylates or (meth)acrylamides. A more preferred polymerizable group is methacrylate.

[0127] III-11. Compounds of Formula III, III-1, III-2, III-3, III-4, III-5, III-6, III-7, III-8, III-9, and III-10 can include compounds of Formula III-11, which are compounds of Formula III, III-1, III-2, III-3, III-4, III-5, III-6, III-7, III-8, III-9, or III-10, where Y (the linking group) is alkylene, cycloalkylene, heterocycloalkylene, arylene (e.g., phenylene), heteroarylene, oxaalkylene, alkylene-amide-alkylene, alkylene-amine-alkylene, or any combination of these 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 is C1-C8 alkylene, especially ethylene (-CH2CH2-).

[0128] Specific examples of compounds of Formula I include, but are not limited to, the compounds shown in Table 1.

[0129] [Table 1-1]

[0130] [Table 1-2]

[0131] [Table 1-3]

[0132] [Table 1-4]

[0133] [Table 1-5]

[0134] [Table 1-6]

[0135] The compounds of the present invention can be selected to provide targeted absorption of UV and / or high-energy visible light. Such targeting can be achieved, for example, by selecting the heteroatom (X in Formula I) of the core tricyclic structure. For example, compounds of Formula I-1 (where the heteroatom is sulfur) can absorb HEV light. On the other hand, compounds of Formula I-2 (where the heteroatom is oxygen) can absorb UV light and some HEV light, although to a lesser extent than compounds of Formula I-1.

[0136] The absorption characteristics for a given X in a compound of formula I can be modified, for example, by changing the substituent R 1 and R 2 The absorption spectrum can be further adjusted by adding or modifying the substituents. Electron-donating substituents can cause, for example, a red shift in the UV-VIS absorption spectrum, while electron-withdrawing groups can cause a blue shift. The magnitude of these shifts can depend on the electron-donating or -withdrawing ability and position of the substituent. For example, an alkoxy substituent can cause a smaller red shift than, for example, an amino or thioalkyl group at the same carbon center.

[0137] Preferred X groups in the compounds of the present invention are S, O, and NR, more preferably S and O. However, further oxidation states of sulfur, such as sulfoxides and sulfones, may also provide a means of modifying the UV-VIS spectrum of the compounds. Sulfoxides and sulfones have reduced electron density on the sulfur atom and can be used to impart a hypsochromic (blue) shift to the spectrum.

[0138] The compound of Formula I can be used in combination with other absorbing compounds to provide desirable absorption properties. For example, a preferred composition may include a compound of Formula I-1 (where X is S) and a second compound that absorbs UV. The second compound may be, for example, a compound of Formula I that absorbs in the UV region (such as a compound of Formula I-2 (where X is O)), or it may be another UV-absorbing compound. Suitable UV-absorbing compounds are known in the art and fall into several categories, including, but not limited to, benzophenones, benzotriazoles, triazines, substituted acrylonitriles, salicylic acid derivatives, benzoic acid derivatives, cinnamic acid derivatives, chalcone derivatives, dipnone derivatives, crotonic acid derivatives, or any mixture thereof. A preferred class of UV-absorbing compounds are benzotriazoles, such as Norbloc (2-(2'-hydroxy-5-methacrylyloxyethylphenyl)-2H-benzotriazole).

[0139] A particularly preferred composition comprises 2-(2-cyano-2-(9H-thioxanthen-9-ylidene)acetamido)ethyl methacrylate and 2-(2-cyano-2-(9H-xanthen-9-ylidene)acetamido)ethyl methacrylate. Another preferred composition comprises 2-(2-cyano-2-(9H-thioxanthen-9-ylidene)acetamido)ethyl methacrylate and 2-(2'-hydroxy-5-methacrylyloxyethylphenyl)-2H-benzotriazole. A further preferred composition comprises N-(2-(2-cyano-2-(10-methylacridin-9(10H)ylidene)acetamido)ethyl)methacrylamide.

[0140] Compounds of Formula I can be prepared by one skilled in the art using literature methods. By way of example, various compounds of Formula I in which EWG is cyano can be prepared as shown in Scheme 1 and the associated description. Exemplary reagents and procedures for these reactions are provided in the Examples.

[0141] [ka]

[0142] Scheme 1 shows a method for preparing exemplary compounds of the present invention. Thus, the carbonyl moiety of the starting material is converted to a reactive dihalide intermediate, which is further reacted with an activated methylene compound without further purification or isolation. The reactive mixture is protected from air and moisture until the reaction with the cyanomethylamide derivative is complete. Other compounds of the present invention can be prepared by one skilled in the art using procedures similar to those shown in Scheme 1 with appropriate substitution of reagents.

[0143] High-energy light-absorbing compounds, such as compounds of Formula I, can be included in reactive mixtures to form a variety of products, including biomedical and ophthalmic devices. Generally, the high-energy light-absorbing compound can be present in any amount up to its solubility limit. For example, the compound can be present in an amount ranging from about 0.1% to about 10% by weight, or from about 0.5 to about 5% by weight, or from about 0.75% to about 4% by weight. The upper limit is typically determined by the solubility of the compound with other comonomers and / or diluents in the reactive monomer mixture.

[0144] Preferably, the high-energy light absorbing compound of the present invention is contained in an ophthalmic device. A variety of ophthalmic devices can be prepared, including hard contact lenses, soft contact lenses, corneal onlays, corneal inlays, intraocular lenses, or overlay lenses. Preferably, the ophthalmic device is a soft contact lens, which can be made from a conventional or silicone hydrogel formulation.

[0145] The ophthalmic devices of the present invention comprise the free radical reaction product of a reactive mixture containing one or more polymerizable high-energy light-absorbing compounds, such as compounds of Formula I, one or more monomers suitable for making the desired ophthalmic device (also referred to herein as device-forming monomers or hydrogel-forming monomers), and optional ingredients. Thus, in addition to the polymerizable high-energy light-absorbing compounds described above, the reactive mixture may include 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.

[0146] hydrophilic component Examples of suitable families of hydrophilic monomers 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.

[0147] 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-hydroxypropyl)(meth)acrylamide, 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.

[0148] 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-acrylamidopropanoic 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- Examples include 8-aza-4-phosphanundec-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).

[0149] Non-limiting examples of hydrophilic N-vinyl lactam and N-vinyl amide monomers include N-vinylpyrrolidone (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-vinylacetamide (NVA), N-vinyl-N-methylacetamide (VMA), N-vinyl-N-ethylacetamide, N-vinyl-N-ethylformamide, N-vinylformamide, N-vinyl-N-methylpropionamide, N-vinyl-N-methyl-2-methylpropionamide, 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.

[0150] 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.

[0151] Other hydrophilic vinyl compounds include ethylene glycol vinyl ether (EGVE), di(ethylene glycol) vinyl ether (DEGVE), allyl alcohol, and 2-ethyloxazoline.

[0152] 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)acrylate, styrene, vinyl ether, (meth)acrylamide, N-vinylamide, etc. Macromers of these polyethers have one polymerizable group, and prepolymers may have two or more polymerizable groups.

[0153] 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.

[0154] Generally, there are no particular limitations 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, etc. 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, alternatively from about 1 to about 80 weight percent, alternatively from about 5 to about 65 weight percent, alternatively from about 40 to about 60 weight percent, or alternatively from about 55 to about 60 weight percent, based on the total weight of the reactive components in the reactive monomer mixture.

[0155] 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 repeating units, such as those defined below. The silicone-containing component may also contain at least one fluorine atom.

[0156] 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, one or more optionally repeating siloxane units, and one or more linking groups connecting the polymerizable groups to the siloxane units, which 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.

[0157] The silicone-containing component may independently comprise 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.

[0158] The silicone-containing component may independently comprise one or more polymerizable groups that are (meth)acrylate, (meth)acrylamide, 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.

[0159] Formula A. The silicone-containing component comprises one or more polymerizable compounds of Formula A:

[0160] [ka] may include During the ceremony, At least one R A is the formula R g -L group, where R g is a polymerizable group, L is a linking group, and the remaining R A are each 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) C3-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) C-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 polyethyleneoxyalkyl, polypropyleneoxyalkyl, or poly(ethyleneoxy-co-propyleneoxyalkyl); or (i) a monovalent siloxane chain comprising 1 to 100 siloxane repeating 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. 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.

[0161] 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.

[0162] Formula B. The silicone-containing component of Formula A is a monofunctional polymerizable compound of Formula B:

[0163] [ka] may be During the ceremony, Rg is a polymerizable group, L is a linking group, j1 and j2 each independently represent an integer of 0 to 220, provided that the sum of j1 and j2 is 1 to 220; R A1 , R A2 , R A3 , R A4 , R A5 , and R A7 is independently, at each occurrence, C1-C6 alkyl, C3-C 12 Cycloalkyl, C1-C6 alkoxy, C4-C 12cyclic alkoxy, alkoxy-alkyleneoxy-alkyl, aryl (e.g., phenyl), aryl-alkyl (e.g., benzyl), haloalkyl (e.g., partially or fully fluorinated alkyl), siloxy, fluoro, or combinations thereof, wherein each alkyl group in the foregoing groups is optionally substituted with one or more hydroxy, amino, amido, oxa, carboxy, alkylcarboxy, carbonyl, alkoxy, carbamate, carbonate, halo, phenyl, or benzyl; each cycloalkyl is optionally substituted with one or more alkyl, hydroxy, amino, amido, oxa, carbonyl, alkoxy, carbamate, carbonate, halo, phenyl, or benzyl; and each aryl is optionally substituted with one or more alkyl, hydroxy, amino, amido, oxa, carboxy, alkylcarboxy, carbonyl, alkoxy, carbamate, carbonate, halo, phenyl, or benzyl; R A6 is siloxy, C1-C8 alkyl (e.g., C1-C4 alkyl, or butyl, or methyl), or aryl (e.g., phenyl), where alkyl and aryl may be optionally substituted with one or more fluorine atoms.

[0164] Formula B-1. Compounds of formula B may include compounds of formula B-1, which are compounds of formula B, wherein j1 is 0 and j2 is 1 to 220, or j2 is 1 to 100, or j2 is 1 to 50, or j2 is 1 to 20, or j2 is 1 to 5, or j2 is 1.

[0165] B-2. Compounds of formula B may include compounds of formula B-2, which are compounds of formula B, wherein j1 and j2 are independently 4 to 100, or 4 to 20, or 4 to 10, or 24 to 100, or 10 to 100.

[0166] B-3. ​​Compounds of formula B, B-1, and B-2 may include compounds of formula B-3, wherein R A1 , R A2 , RA3 , and R A4 is independently at each occurrence a C1-C6 alkyl or siloxy. Preferred alkyl is a C1-C3 alkyl, or more preferably methyl. Preferred siloxy is trimethylsiloxy.

[0167] B-4. Compounds of formula B, B-1, B-2, and B-3 may include compounds of formula B-4, wherein R A5 and R A7 are independently alkoxy-alkyleneoxy-alkyl, preferably independently of the formula CH3O-[CH2CH2O] p A compound of formula B, B-1, B-2, or B-3, which is a methoxy-capped polyethyleneoxyalkyl of the formula -CH2CH2CH2 (where p is an integer from 1 to 50).

[0168] B-5. Compounds of formula B, B-1, B-2, and B-3 may include compounds of formula B-5, wherein R A5 and R A7 is a compound of formula B, B-1, B-2, or B-3, wherein is independently siloxy, such as trimethylsiloxy.

[0169] B-6. Compounds of formula B, B-1, B-2, and B-3 may include compounds of formula B-6, wherein R A5 and R A7 is independently C1-C6 alkyl, alternatively C1-C4 alkyl, or alternatively butyl or methyl.

[0170] B-7. Compounds of formula B, B-1, B-2, B-3, B-4, B-5, and B-6 are R A6 is a C1-C8 alkyl, preferably a C1-C6 alkyl, more preferably a C1-C4 alkyl (e.g., methyl, ethyl, n-propyl, or n-butyl).A6 is n-butyl.

[0171] B-8. The compounds of formula B, B-1, B-2, B-3, B-4, B-5, B-6, and B-7 may include compounds of formula B-8, which are compounds of formula B, B-1, B-2, B-3, B-4, B-5, B-6, or B-7, where Rg includes styryl, vinyl carbonate, vinyl ether, vinyl carbamate, N-vinyl lactam, N-vinyl amide, (meth)acrylate, or (meth)acrylamide. Preferably, Rg includes (meth)acrylate, (meth)acrylamide, or styryl. More preferably, Rg includes (meth)acrylate or (meth)acrylamide. When Rg is (meth)acrylamide, the nitrogen group is R A9 may be substituted with R A9 is H, C1-C8 alkyl (preferably C1-C4 alkyl, e.g., n-butyl, n-propyl, methyl, or ethyl), or C3-C8 cycloalkyl (preferably C5-C6 cycloalkyl), where the alkyl and cycloalkyl are optionally substituted with one or more groups independently selected from hydroxyl, amide, ether, silyl (e.g., trimethylsilyl), siloxy (e.g., trimethylsiloxy), alkyl-siloxanyl (wherein the alkyl is itself optionally substituted with fluoro), aryl-siloxanyl (wherein the aryl is itself optionally substituted with fluoro), and silyl-oxaalkylene (wherein the oxaalkylene is itself optionally substituted with hydroxyl).

[0172] B-9. Compounds of formula B, B-1, B-2, B-3, B-4, B-5, B-6, B-7, and B-8 may include compounds of formula B-9, wherein the linking group is selected from the group consisting of alkylene (preferably C1-C4 alkylene), cycloalkylene (preferably C5-C6 cycloalkylene), alkyleneoxy (preferably ethyleneoxy), haloalkyleneoxy (preferably haloethyleneoxy), amido, oxaalkylene (preferably containing 3 to 6 carbon atoms), ), siloxanyl, alkylenesiloxanyl, carbamate, alkyleneamine (preferably C1-C6 alkyleneamine), or a combination of two or more thereof, wherein the linking group is optionally substituted with one or more substituents independently selected from alkyl, hydroxyl, ether, amine, carbonyl, siloxy, and carbamate.

[0173] B-10. Compounds of formula B, B-1, B-2, B-3, B-4, B-5, B-6, B-7, B-8, and B-9 may include compounds of formula B-10, wherein the linking group is alkylene-siloxanyl-alkylene-alkyleneoxy- or alkylene-siloxanyl-alkylene-[alkyleneoxy-alkylene-siloxanyl] q -alkyleneoxy- (wherein q is 1 to 50).

[0174] B-11. Compounds of formula B, B-1, B-2, B-3, B-4, B-5, B-6, B-7, B-8, and B-9 may include compounds of formula B-11, which are compounds of formula B, B-1, B-2, B-3, B-4, B-5, B-6, B-7, B-8, or B-9, wherein the linking group is C1-C6 alkylene, preferably C1-C3 alkylene, more preferably n-propylene.

[0175] B-12. Compounds of formula B, B-1, B-2, B-3, B-4, B-5, B-6, B-7, B-8, and B-9 may include compounds of formula B-12, which are compounds of formula B, B-1, B-2, B-3, B-4, B-5, B-6, B-7, B-8, or B-9, where the linking group is alkylene-carbamate-oxaalkylene. Preferably, the linking group is CH2CH2N(H)-C(=O)-O-CH2CH2-O-CH2CH2CH2.

[0176] B-13. Compounds of formula B, B-1, B-2, B-3, B-4, B-5, B-6, B-7, B-8, and B-9 may include compounds of formula B-13, which are compounds of formula B, B-1, B-2, B-3, B-4, B-5, B-6, B-7, B-8, or B-9, in which the linking group is oxaalkylene. Preferably, the linking group is CH2CH2-O-CH2CH2CH2.

[0177] B-14. Compounds of formula B, B-1, B-2, B-3, B-4, B-5, B-6, B-7, B-8, and B-9 may include compounds of formula B-14, wherein the linking group is alkylene-[siloxanyl-alkylene] q -, where q is 1 to 50. An example of such a linking group is -(CH2)3-[Si(CH3)2-O-Si(CH3)2-(CH2)2] q -It is.

[0178] B-15. Compounds of Formula B, B-1, B-2, B-3, B-4, B-5, B-6, B-7, B-8, and B-9 may include compounds of Formula B-15, which are compounds of Formula B, B-1, B-2, B-3, B-4, B-5, B-6, B-7, B-8, or B-9, where the linking group is alkyleneoxy-carbamate-alkylene-cycloalkylene-carbamate-oxaalkylene, where the cycloalkylene is optionally substituted with one, two, or three independently selected alkyl groups (preferably C1-C3 alkyl, more preferably methyl). An example of such a linking group is -[OCH2CH2] q -OC(=O)-NH-CH2-[1,3-cyclohexylene]-NHC(=O)O-CH2CH2-O-CH2CH2-, where the cyclohexylene is substituted with three methyl groups at the 1- and 5-positions.

[0179] B-16. Compounds of formula B, B-1, B-2, B-3, B-4, B-5, B-6, B-7, B-8, and B-9 can include compounds of formula B-16, which are compounds of formula B, B-1, B-2, B-3, B-4, B-5, B-6, B-7, B-8, or B-9, where Rg comprises styryl and the linking group is a bond or alkyleneoxy, where each alkylene in the alkyleneoxy is independently optionally substituted with hydroxyl. An example of such a linking group is -O-(CH)-. Another example of such a linking group is -O-CHCH(OH)CH-O-(CH)-.

[0180] B-17. Compounds of formula B, B-1, B-2, B-3, B-4, B-5, B-6, B-7, B-8, and B-9 may include compounds of formula B-17, which are compounds of formula B, B-1, B-2, B-3, B-4, B-5, B-6, B-7, B-8, or B-9, where Rg comprises styryl and the linking group is an alkyleneamine. An example of such a linking group is -NH-(CH2)3-.

[0181] B-18. Compounds of formula B, B-1, B-2, B-3, B-4, B-5, B-6, B-7, B-8, and B-9 may include compounds of formula B-18, which are compounds of formula B, B-1, B-2, B-3, B-4, B-5, B-6, B-7, B-8, or B-9, where the linking group is an oxaalkylene optionally substituted with hydroxyl, siloxy, or silyl-alkyleneoxy (the alkyleneoxy is itself optionally substituted with hydroxyl). An example of such a linking group is -CHCH(G)CH-O-(CH)-, where G is hydroxyl. In another example, G is RSiO-, two R groups are trimethylsiloxy, and the third is C1-C8 alkyl (preferably C1-C3 alkyl, more preferably methyl), or the third is C3-C8 cycloalkyl. In a further example, G is RSi-(CH2)3-O-CH2CH(OH)CH2-O-, two R groups are trimethylsiloxy, and the third is C1-C8 alkyl (preferably C1-C3 alkyl, more preferably methyl) or C3-C8 cycloalkyl. In yet a further example, G is a polymerizable group such as (meth)acrylate. Such compounds can function as crosslinkers.

[0182] B-19. Compounds of formula B, B-1, B-2, B-3, B-4, B-5, B-6, B-7, B-8, and B-9 may include compounds of formula B-19, which are compounds of formula B, B-1, B-2, B-3, B-4, B-5, B-6, B-7, B-8, or B-9, where Rg comprises a styryl and the linking group is an amine-oxaalkylene optionally substituted with a hydroxyl. An example of such a linking group is -NH-CHCH(OH)CH-O-(CH)-.

[0183] B-20. Compounds of formula B, B-1, B-2, B-3, B-4, B-5, B-6, B-7, B-8, and B-9 may include compounds of formula B-20, which are compounds of formula B, B-1, B-2, B-3, B-4, B-5, B-6, B-7, B-8, or B-9, where Rg comprises styryl and the linking group is alkyleneoxy-carbamate-oxaalkylene. An example of such a linking group is -O-(CH)-N(H)C(=O)O-(CH)-O-(CH)-.

[0184] B-21. Compounds of formula B, B-1, B-2, B-3, B-4, B-5, B-6, B-7, B-8, and B-9 may include compounds of formula B-21, which are compounds of formula B, B-1, B-2, B-3, B-4, B-5, B-6, B-7, B-8, or B-9, where the linking group is alkylene-carbamate-oxaalkylene. An example of such a linking group is -(CH)-N(H)C(=O)O-(CH)-O-(CH)-.

[0185] Silicone-containing components of Formula C. Formula A, B, B-1, B-2, B-3, B-4, B-5, B-6, B-7, B-8, B-9, B-10, B-11, B-12, B-13, B-14, B-15, B-18, and B-21 may include compounds of Formula C, which are compounds of Formula A, B, B-1, B-2, B-3, B-4, B-5, B-6, B-7, B-8, B-9, B-10, B-11, B-12, B-13, B-14, B-15, B-18, or B-21 having the following structure:

[0186] [ka] and During the ceremony, R A8 is hydrogen or methyl, Z is O, S, or N(R A9 ) and L, j1, j2, R A1 , R A2 , R A3 , R A4 , RA5 , R A6 , R A7 , and R A9 is as defined in formula B or its various subformulas (e.g., B-1, B-2, etc.).

[0187] C-1. Compounds of formula C may include (meth)acrylates of formula C-1, which are compounds of formula C where Z is O.

[0188] C-2. Compounds of formula C may include (meth)acrylamides of formula C-2, where Z is N(R A9 ) and R A9 is H.

[0189] C-3. Compounds of formula C may include (meth)acrylamides of formula C-3, where Z is N(R A9 ) and R A9 is a C1-C8 alkyl that is unsubstituted or optionally substituted as described above. A9 Examples of R include CH3, -CH2CH(OH)CH2(OH), -(CH2)3-siloxanyl, -(CH2)3-SiR3, and -CH2CH(OH)CH2-O-(CH2)3-SiR3, where each R in the foregoing groups is independently selected from trimethylsiloxy, C1-C8 alkyl (preferably C1-C3 alkyl, more preferably methyl), and C3-C8 cycloalkyl. A9 Further examples include -(CH2)3-Si(Me)(SiMe3)2 and -(CH2)3-Si(Me2)-[O-SiMe2] 1~10 -CH3 is an example.

[0190] Formula D. The compound of formula C can be converted to a compound of formula D:

[0191] [ka] may include During the ceremony, R A8is hydrogen or methyl, Z 1 is O or N(R A9 ) and L 1 is an alkylene containing 1 to 8 carbon atoms or an oxaalkylene containing 3 to 10 carbon atoms, and L 1 is optionally substituted with hydroxyl; j2, R A3 , R A4 , R A5 , R A6 , R A7 , and R A9 is as defined in formula B or its various subformulas (e.g., B-1, B-2, etc.).

[0192] D-1. Compounds of formula D may include compounds of formula D-1, wherein L 1 is a C2-C5 alkylene optionally substituted with hydroxyl. 1 is n-propylene optionally substituted with hydroxyl.

[0193] D-2. Compounds of formula D may include compounds of formula D-2, wherein L 1 is an oxaalkylene containing 4 to 8 carbon atoms optionally substituted with hydroxyl. 1 is an oxaalkylene containing 5 or 6 carbon atoms optionally substituted with hydroxyl. Examples include -(CH)-O-(CH)- and -CHCH(OH)CH-O-(CH)-.

[0194] D-3. Compounds of formula D, D-1, and D-2 may include compounds of formula D-3, wherein Z 1 is O.

[0195] D-4. Compounds of formula D, D-1, and D-2 may include compounds of formula D-4, wherein Z1 is N(R A9 ) and R A9 is H.

[0196] D-5. Compounds of formula D, D-1, and D-2 may include compounds of formula D-5, wherein Z 1 is N(R A9 ) and R A9 is a C1-C4 alkyl optionally substituted with one or two substituents selected from hydroxyl, siloxy, and C1-C6 alkyl-siloxanyl-.

[0197] D-6. Compounds of formula D, D-1, D-2, D-3, D-4, and D-5 may include compounds of formula D-6, which are compounds of formula D, D-1, D-2, D-3, D-4, or D-5, where j2 is 1.

[0198] D-7. Compounds of formula D, D-1, D-2, D-3, D-4, and D-5 may include compounds of formula D-7, which are compounds of formula D, D-1, D-2, D-3, D-4, or D-5, wherein j2 is 2 to 220, or 2 to 100, or 10 to 100, or 24 to 100, or 4 to 20, or 4 to 10.

[0199] D-8. Compounds of formula D, D-1, D-2, D-3, D-4, D-5, D-6, and D-7 may include compounds of formula D-8, wherein R A3 , R A4 , R A5 , R A6 , and R A7 is independently C1-C6 alkyl or siloxy. A3 , R A4 , R A5 , R A6 , and R A7are independently selected from methyl, ethyl, n-propyl, n-butyl, and trimethylsiloxy. More preferably, R A3 , R A4 , R A5 , R A6 , and R A7 is independently selected from methyl, n-butyl, and trimethylsiloxy.

[0200] D-9. Compounds of formula D, D-1, D-2, D-3, D-4, D-5, D-6, and D-7 may include compounds of formula D-9, wherein R A3 and R A4 are independently C1-C6 alkyl (e.g., methyl or ethyl) or siloxy (e.g., trimethylsiloxy), and R A5 , R A6 , and R A7 is independently C1-C6 alkyl (e.g., methyl, ethyl, n-propyl, or n-butyl).

[0201] Formula E. The silicone-containing component used in the present invention may include a multifunctional silicone-containing component. Thus, for example, a silicone-containing component of Formula A may be combined with a difunctional material of Formula E:

[0202] [ka] may include During the ceremony, Rg, L, j1, j2, R A1 , R A2 , R A3 , R A4 , R A5 , and R A7 is as defined above for formula B or its various subformulas (e.g., B-1, B-2, etc.), L 2 is a linking group, Rg 1 is a polymerizable group.

[0203] E-1. Compounds of formula E may include compounds of formula E-1, wherein Rg and Rg 1 are compounds of formula E, which are vinyl carbonates of the structure CH2=CH-OC(=O)-O- or CH2=C(CH3)-OC(=O)-O-, respectively.

[0204] E-2. Compounds of formula E may include compounds of formula E-2, wherein Rg and Rg 1 are each (meth)acrylates.

[0205] E-3. Compounds of formula E may include compounds of formula E-3, wherein Rg and Rg 1 are (meth)acrylamides, and the nitrogen group is R A9 may be substituted with (R A9 is as defined above), a compound of formula E.

[0206] E-4. Suitable compounds of formulas E, E-1, E-2, and E-3 include compounds of formula E-4, which are compounds of formula E, E-1, E-2, or E-3, wherein j1 is 0 and j2 is 1 to 220, or j2 is 1 to 100, or j2 is 1 to 50, or j2 is 1 to 20.

[0207] E-5. Suitable compounds of formulas E, E-1, E-2, and E-3 include compounds of formula E-5, which are compounds of formula E, E-1, E-2, or E-3, wherein j1 and j2 are independently 4 to 100.

[0208] E-6. Suitable compounds of formulas E, E-1, E-2, E-3, E-4, and E-5 include compounds of formula E-6, wherein R A1 , R A2 , R A3 , R A4 , and R A5are independently at each occurrence C1-C6 alkyl, preferably they are independently C1-C3 alkyl, or preferably each is methyl.

[0209] E-7. Suitable compounds of formula E, E-1, E-2, E-3, E-4, E-5, and E-6 include compounds of formula E-7, wherein R A7 is an alkoxy-alkyleneoxy-alkyl, preferably of the formula CH3O-[CH2CH2O] p A compound of formula E, E-1, E-2, E-3, E-4, E-5, or E-6, which is a methoxy-capped polyethyleneoxyalkyl of the formula —CHCHCH, where p is an integer from 1 to 50, or from 1 to 30, or from 1 to 10, or from 6 to 10.

[0210] E-8. Suitable compounds of formula E, E-1, E-2, E-3, E-4, E-5, E-6, and E-7 include compounds of formula E-8, which are compounds of formula E, E-1, E-2, E-3, E-4, E-5, E-6, or E-7, wherein L comprises alkylene, carbamate, siloxanyl, cycloalkylene, amide, haloalkyleneoxy, oxaalkylene, or a combination of two or more thereof, and the linking group is optionally substituted with one or more substituents independently selected from alkyl, hydroxyl, ether, amine, carbonyl, and carbamate.

[0211] E-9. Suitable compounds of formula E, E-1, E-2, E-3, E-4, E-5, E-6, E-7, and E-8 include compounds of formula E-9, wherein L 2comprises alkylene, carbamate, siloxanyl, cycloalkylene, amide, haloalkyleneoxy, oxaalkylene, or a combination of two or more thereof, and the linking group is optionally substituted with one or more substituents independently selected from alkyl, hydroxyl, ether, amine, carbonyl, and carbamate.

[0212] Examples of silicone-containing components suitable for use in the present invention include, but are not limited to, the compounds listed in Table 2. When a compound in Table 2 contains a polysiloxane group, the number of SiO repeat units in such a compound is preferably 3 to 100, more preferably 3 to 40, or even more preferably 3 to 20, unless otherwise specified.

[0213] [Table 2-1]

[0214] [Table 2-2]

[0215] Additional non-limiting examples of suitable silicone-containing components are listed in Table 3. 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 or j2, the sum of j1 and j2 is preferably 2 to 100, more preferably 3 to 40, or even more preferably 3 to 15.

[0216] [Table 3-1]

[0217] [Table 3-2]

[0218] Mixtures of silicone-containing components can also be used.For example, suitable mixtures 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 containing 4 and 15 SiO repeat units; mixtures of OH-mPDMS (for example, containing 4 and 15 repeat SiO repeat units) with silicone-based crosslinkers such as bis-3-acryloxy-2-hydroxypropyloxypropyl polydimethylsiloxane (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.

[0219] The silicone-containing component used in the present invention can have an average molecular weight of from about 400 to about 4000 daltons.

[0220] The silicone-containing component(s) may be present in an amount of up to about 95% by weight, or from about 10 to about 80% by weight, or from about 20 to about 70% by weight of the reactive mixture (excluding diluent), based on all reactive components.

[0221] polyamide The reactive mixture may include at least one polyamide. As used herein, the term "polyamide" refers to polymers and copolymers containing repeating units containing amide groups. Polyamides 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 that are capable of association with hydroxyl groups. Cyclic polyamides include cyclic amide groups that are capable of association with hydroxyl groups.

[0222] Examples of suitable acyclic polyamides include polymers and copolymers comprising repeating units of formulae G1 and G2:

[0223] [ka] are listed, In the formula, X is a direct bond, —(CO)—, or —(CONHR 44 )-, wherein R 44 is a C1-C3 alkyl group, and R 40 is selected from H, a linear or branched, substituted or unsubstituted C1-C4 alkyl group, and R 41 is selected from H, straight or branched chain 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 methyl, ethoxy, hydroxyethyl, and hydroxymethyl; R 43 is selected from H, a linear or branched, substituted or unsubstituted C1-C4 alkyl group, or methyl, ethoxy, hydroxyethyl, and hydroxymethyl; R 40 and R 41 the total number of carbon atoms in R is 8 or less, including 7, 6, 5, 4, 3, or less; 42 and R 43 The total number of carbon atoms in R is 8 or less, including 7, 6, 5, 4, 3, or less. 40 and R 41 The total number of carbon atoms in R may be 6 or less, or 4 or less. 42 and R 43 The total number of carbon atoms in the alkyl group may be up to 6. 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 a combination thereof.

[0224] R 40 and R 41may 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 R 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.

[0225] The acyclic polyamides of the present invention may comprise a majority of repeating units of Formula LV or Formula LVI, or the acyclic polyamides may comprise at least 50 mol %, such as at least about 70 mol %, and at least 80 mol %, of repeating units of Formula G or Formula G1. Specific examples of repeating 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 repeating units derived from the acyclic amides of Formulas G2 and G3.

[0226] [ka]

[0227] 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 polymers and copolymers comprising repeating units of formula G4:

[0228] [ka] are listed, 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)-, where 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, including 5, 4, 3, 2, or 1. In Formula G4, f can be 2 to 8, including 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).

[0229] The cyclic polyamides of the present invention may comprise 50 mol % or more of repeating units of formula G4, or the cyclic polyamides may comprise at least 50 mol % of repeating units of formula G4, such as at least 70 mol %, and at least 80 mol %.

[0230] Polyamides may also be copolymers containing both cyclic and non-cyclic amide repeating units. The additional repeating 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 repeating units. Specific examples of additional monomers that can 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 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-propanaminium, 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-phosphanundec-10-ene-1-aminium, 4-hydroxy-N,N,N-trimethyl-9-oxo-, inner salt, 4-oxide(9CI) (PBT, phosphobetaine, CAS 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).

[0231] The reactive monomer mixture may include both acyclic polyamides and cyclic polyamides or copolymers thereof. The acyclic polyamide may be any of the acyclic polyamides or copolymers thereof described herein, and the cyclic polyamide may be any of the cyclic polyamides or copolymers thereof described herein. The polyamide may be selected from the group consisting of polyvinylpyrrolidone (PVP), polyvinylmethylacetamide (PVMA), polydimethylacrylamide (PDMA), polyvinylacetamide (PNVA), poly(hydroxyethyl(meth)acrylamide), polyacrylamide, and copolymers and mixtures thereof. The polyamide may be a mixture of PVP (e.g., PVP K90) and PVMA (e.g., a cyclic polyamide having an M of about 570 KDa). w The compound may be a mixture of

[0232] 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 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.

[0233] 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.

[0234] When a polyamide is incorporated into 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, or from about 300,000 to about 1,800,000 daltons. High molecular weight polyamides can be used if they are compatible with the reactive monomer mixture.

[0235] Crosslinking agent It is generally desirable to add one or more crosslinking agents, also referred to as crosslinking monomers, multifunctional macromers, and prepolymers, to the reactive mixture. The crosslinking agent may be selected from difunctional, trifunctional, 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, methylenebisacrylamide (MBA), and polyethylene glycol dimethacrylate, where the polyethylene glycol has a molecular weight of up to about 5000 daltons. The crosslinking agent is 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, if present, do not require the addition of additional crosslinkers to the reactive mixture 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 prepare the silicone hydrogels of the present invention.

[0236] It may be desirable to select a crosslinker that has similar reactivity with 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 of the 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.

[0237] To further increase the modulus and maintain tensile strength, multifunctional silicone-containing components, including macromers, crosslinkers, and prepolymers, may also be included. 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, when present, does not require the addition of a crosslinking monomer to the reactive mixture, is α,ω-bismethacryloylpropyl polydimethylsiloxane. Another example is bis-3-acryloxy-2-hydroxypropyloxypropyl polydimethylsiloxane (ac-PDMS).

[0238] Crosslinkers with rigid chemical structures and polymerizable groups capable of undergoing free radical polymerization can 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. The rigid crosslinkers can be present in an amount of about 0.5 to about 15, or about 2 to 10, or 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 can be optimized for specific applications by adjusting the components in the reactive mixture.

[0239] Non-limiting examples of silicone crosslinkers also include the multifunctional silicone-containing components described above, such as compounds of Formula E (and subformulas thereof) and the multifunctional compounds shown in Table 3.

[0240] 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, copolymeric dyes, non-polymeric dyes, mold release agents, and combinations thereof.

[0241] Suitable types of diluents for silicone hydrogel reactive mixtures 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. Diluents can be primary, secondary, and tertiary alcohols.

[0242] 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 classes for silicone hydrogel reactive mixtures include alcohols having 2 to 20 carbon atoms, amides having 10 to 20 carbon atoms derived from primary amines, and carboxylic acids having 8 to 20 carbon atoms. Primary and tertiary alcohols can be used. Preferred classes include alcohols having 5 to 20 carbon atoms and carboxylic acids having 10 to 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 suitable diluents include alcohol, 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, and mixtures thereof. Examples of amide diluents include N,N-dimethylpropionamide and dimethylacetamide.

[0243] 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.

[0244] 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.

[0245] When a diluent is present, there is generally no particular limit as to 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 weight percent, such as from about 5 to about 50 weight percent and from about 15 to about 40 weight percent, based on the total weight of the reactive mixture (including reactive and non-reactive formulations). Mixtures of diluents may also be used.

[0246] A polymerization initiator may be used in the reactive mixture, and may include at least one of those that generate free radicals at moderately high temperatures, such as lauryl peroxide, benzoyl peroxide, isopropyl percarbonate, azobisisobutyronitrile, and photoinitiator systems, such as aromatic α-hydroxyketones, alkoxyoxybenzoins, acetophenones, acylphosphine oxides, bisacylphosphine oxides, and tertiary amines plus diketones, and 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.

[0247] Commercially available visible light initiator systems (manufactured by IGM Resins BV, The Netherlands) include Irgacure® 819, Irgacure® 1700, Irgacure® 1800, Irgacure® 819, Irgacure® 1850, and Lucrin® TPO initiators. Commercially available UV photoinitiators (manufactured by IGM Resins BV) include Darocur® 1173 and Darocur® 2959. These and other photoinitiators that can be used are disclosed in Volume III, Photoinitiators for Free Radical Cationic & Anionic Photopolymerization, 2nd Edition by J.V. 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, 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, preferred initiators are bisacylphosphine oxides, 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).

[0248] The reactive mixture for making the ophthalmic devices of the present invention may include any of the polymerizable compounds and optional ingredients described above in addition to the high-energy light absorbing compound.

[0249] A preferred reactive mixture may include a high energy light absorbing compound, such as a compound of Formula I, and a hydrophilic component.

[0250] A preferred reactive mixture may include a high-energy light absorbing compound, such as a compound of Formula I, and a hydrophilic component selected from DMA, NVP, HEMA, VMA, NVA, methacrylic acid, and mixtures thereof. A mixture of HEMA and methacrylic acid is preferred.

[0251] A preferred reactive mixture can include a high-energy light absorbing compound, such as a compound of Formula I, a hydrophilic component, and a silicone-containing component.

[0252] A preferred reactive mixture may include a high-energy light absorbing compound, such as a compound of Formula I, a hydrophilic component, and a silicone-containing component including a compound of Formula D (or subformulas D-1, D-2, etc.).

[0253] A preferred reactive mixture may include a high-energy light absorbing compound such as a compound of formula I, a hydrophilic component selected from DMA, NVP, HEMA, VMA, NVA, and mixtures thereof, a silicone-containing component including a compound of formula D (or subformulas D-1, D-2, etc.), and an internal wetting agent.

[0254] A preferred reactive mixture may include a high-energy light absorbing compound such as a compound of Formula I, a hydrophilic component selected from DMA, HEMA, and mixtures thereof, 2-hydroxy-3-[3-methyl-3,3-di(trimethylsiloxy)silylpropoxy]-propyl methacrylate (SiMAA), mono-methacryloxypropyl-terminated mono-n-butyl-terminated polydimethylsiloxane (mPDMS), mono-(2-hydroxy-3-methacryloxypropyl)-propyl ether-terminated mono-n-butyl-terminated polydimethylsiloxane (OH-mPDMS), and mixtures thereof, and a wetting agent (preferably PVP or PVMA). For the hydrophilic component, a mixture of DMA and HEMA is preferred. For the silicone-containing component, a mixture of SiMAA and mPDMS is preferred.

[0255] A preferred reactive mixture may include a high-energy light absorbing compound, such as a compound of Formula I, a hydrophilic component including a mixture of DMA and HEMA, and a silicone-containing component including a mixture of OH-mPDMS having 2 to 20 repeating units (preferably a mixture of 4 and 15 repeating units). Preferably, the reactive mixture further includes a silicone-containing crosslinker, such as ac-PDMS. Also preferably, the reactive mixture includes a wetting agent, preferably DMA, PVP, PVMA, or a mixture thereof.

[0256] A preferred reactive mixture comprises a high-energy light absorbing compound, such as a compound of Formula I, from about 1 to about 15 weight percent of at least one polyamide (e.g., an acyclic polyamide, a cyclic polyamide, or a mixture thereof), at least one first monofunctional hydroxyl-substituted poly(disubstituted siloxane) having 4 to 8 siloxane repeat units (e.g., OH-mPDMS, where n is 4 to 8, preferably n is 4), and at least one second hydroxyl-substituted poly(disubstituted siloxane) that is a monofunctional hydroxyl-substituted poly(disubstituted siloxane) having 10 to 200, or 10 to 100, or 10 to 50, or 10 to 20 siloxane repeat units (e.g., OH-mPDMS, where n is 10 to 20). 00, or 10-100, or 10-50, or 10-20, preferably n is 15), about 5 to about 35 weight percent of at least one hydrophilic monomer, and optionally a multifunctional hydroxyl-substituted poly(disubstituted siloxane) (e.g., ac-PDMS) having 10-200 or 10-100 siloxane repeat units. Preferably, the first monofunctional hydroxyl-substituted poly(disubstituted siloxane) and the second hydroxyl-substituted poly(disubstituted siloxane) are present in concentrations to provide a ratio of weight percent of the first monofunctional hydroxyl-substituted poly(disubstituted siloxane) to weight percent of the second hydroxyl-substituted poly(disubstituted siloxane) of 0.4 to 1.3 or 0.4 to 1.0.

[0257] The reactive mixture may contain optional ingredients such as, but not limited to, one or more initiators, internal wetting agents, crosslinkers, other UV or HEV absorbers, and diluents.

[0258] When copolymerized with other reactive components, compounds of Formula I provide polymerization products containing chromophore substituents. Such chromophore substituents can provide products with desirable light absorption properties, as described above. For example, ophthalmic devices, such as contact lenses, containing chromophore substituents can block undesirable high-energy light, as described in detail above. Accordingly, the present invention provides an ophthalmic device that is the polymerization reaction product of a reactive mixture (e.g., including a hydrophilic component and a silicone-containing compound), wherein the polymerization reaction product contains, as a covalently bonded substituent, one or more chromophores of Formula IV:

[0259] [ka] and an ophthalmic device comprising: wherein m and n are independently 0, 1, 2, 3, or 4; X is O, S, NR, SO, or SO; R, in each occurrence, is independently H, C1-C6 alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, or a bond to a polymerization reaction product; and R 1 and R 2 is, when present, independently at each occurrence C1-C6 alkyl, C1-C6 alkoxy, C1-C6 thioalkyl, C3-C7 cycloalkyl, aryl, halo, hydroxy, amino, NR 3 R 4 or benzyl, where 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 linked to form a cycloalkyl or aryl ring, and R 5is the bond to the polymerization reaction product, and EWG is an electron withdrawing group (preferably cyano).

[0260] In Formula IV, X is preferably O or S. In Formula IV, the bond to the polymerization reaction product preferably includes a residue of a polymerizable group and one or more of an alkylene group, a cycloalkylene group, a heterocycloalkylene group, an arylene group, a heteroarylene group, an oxaalkylene group, an alkylene-amide-alkylene group, or an alkylene-amine-alkylene group. Preferred polymerizable groups include styryl, vinyl carbonate, vinyl ether, vinyl carbamate, N-vinyl lactam, N-vinyl amide, (meth)acrylate, or (meth)acrylamide.

[0261] Preferred polymerization reaction products may further comprise one or more covalently bound UV-absorbing chromophores in addition to the chromophore of Formula IV. Preferred UV-absorbing chromophores include residues of benzophenones, benzotriazoles, triazines, substituted acrylonitriles, salicylic acid derivatives, benzoic acid derivatives, cinnamic acid derivatives, chalcone derivatives, dipnone derivatives, crotonic acid derivatives, or mixtures thereof.

[0262] Curing of Hydrogels and Lens Fabrication The reactive mixture may be formed by any method known in the art, such as by shaking or stirring, and used to form a polymeric article or device by known methods. The reactive components are mixed together, either with or without a diluent, to form the reactive mixture.

[0263] For example, an ophthalmic device can be prepared by mixing the reactive components and optionally diluent(s) with a polymerization initiator and curing under appropriate conditions to form a product that can later be formed into a suitable shape by lathing, cutting, etc. Alternatively, the reactive mixture can be placed in a mold and then cured into a suitable article.

[0264] A method of making a molded ophthalmic device such as a silicone hydrogel contact lens 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 a contact lens.

[0265] The reactive mixture may be cured via any known process for shaping reactive mixtures in the production of contact lenses, including rotational molding and static molding. Rotational molding processes are disclosed in U.S. Patent Nos. 3,408,429 and 3,660,545, and static molding processes are disclosed in U.S. Patent Nos. 4,113,224 and 4,197,266. The contact lenses of the present invention may also be formed by direct molding of silicone hydrogels, which is economical and allows for precise control of the final shape of the hydrated lens. 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.

[0266] After curing, the lens may be subjected to extraction to remove unreacted components and remove the lens from the lens mold. Extraction may be performed using conventional extraction fluids, such as organic solvents such as alcohols, or may be extracted using aqueous solutions.

[0267] An aqueous solution is a solution containing water. The aqueous solution of the present invention may contain at least about 20% by weight water, or at least about 50% by weight water, or at least about 70% by weight water, or at least about 95% by weight water. The aqueous solution may also contain additional water-soluble ingredients, such as inorganic salts or release agents, wetting agents, slip agents, pharmaceutical ingredients, and nutritional supplements, or 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 without the release agent. The aqueous solution may not require special handling, such as purification, recycling, or special disposal.

[0268] Extraction can be accomplished, for example, by immersing the lens in an aqueous solution or by exposing the lens to a stream of 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 lens release; mechanically or ultrasonically agitating the lens; and incorporating at least one filter aid or extraction aid into the aqueous solution to a concentration sufficient to facilitate adequate removal of unreacted components from the lens. The foregoing, with or without the addition of heat, vibration, or both, can be carried out in a batch or continuous process.

[0269] 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.

[0270] The lenses may be sterilized by known means, such as, but not limited to, autoclaving.

[0271] As noted above, the preferred ophthalmic device is a contact lens, more preferably a soft hydrogel contact lens. The transmission wavelengths and percentages described herein can be measured on lenses of various thicknesses, for example, using the methods described in the Examples. For example, preferred center thicknesses for measuring transmission spectra in soft contact lenses can be 80-100 micrometers, 90-100 micrometers, or 90-95 micrometers. Measurements can typically be performed at the center of the lens, using, for example, an instrument slit width of 4 nm. Various concentrations of one or more polymerizable high-energy light-absorbing compounds can be used to achieve the above transmission characteristics. For example, concentrations can range from 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 range from 3 to 5%.

[0272] Silicone hydrogel ophthalmic devices (e.g., contact lenses) according to the present invention preferably exhibit the following properties. All values ​​are preceded by "about," and the device can 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. Pregrant Publication No. 2018 / 0037690, which is incorporated herein by reference.

[0273] Water concentration %: at least 20%, or at least 25% and at most 80%, or at most 70% Haze: 30% or less, or 10% or less Kruss dynamic contact angle (°): 100° or less, or 50° or less Tensile modulus (psi): 120 or less, or 80 to 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 With regard to ionic silicone hydrogels, the following properties (in addition to those mentioned above) may also be desirable: 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 Some embodiments of the present invention will now be described in detail in the following examples. [Example]

[0274] Test Method The UV-visible spectra of 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 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 transmittance or absorbance, and baseline correction was selected. For the Cary instrument, the scan range was 200-800 nm, the scan speed was 600 nm / min, the slit width was 2 nm, the mode was set to transmittance or absorbance, and baseline correction was selected. Baseline correction was performed before analyzing samples using the autozero function.

[0275] The ultraviolet-visible spectra of partially formed contact lenses 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. The instruments were allowed to thermally equilibrate for at least 30 minutes before use. The Perkin Elmer instrument had a scan range of 200-800 nm, a scan speed of 960 nm per minute, a slit width of 4 nm, and the mode set to transmission, with baseline correction 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 consistent sample thickness, all lenses were fabricated using the same mold. The central thickness of the contact lenses was measured using an electronic thickness gauge. The reported central thickness and transmittance spectra are obtained by averaging data from three individual lenses.

[0276] 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.

[0277] The following abbreviations are used throughout the examples and figures and have the following meanings: BC: Back or base curve plastic mold FC: Front curve plastic molding mold DMA: N,N-dimethylacrylamide (Jarchem) HEMA: 2-hydroxyethyl methacrylate (Bimax) PVP: Poly(N-vinylpyrrolidone) (ISP Ashland) PDMA: Polydimethylacrylamide PVMA: Polyvinylmethylacetamide EGDMA: Ethylene glycol dimethacrylate (Esstech) TEGDMA: Tetraethylene glycol dimethacrylate (Esstech) Irgacure 819: Bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (BASF or Ciba Specialty Chemicals) Irgacure 1870: a blend of bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide and 1-hydroxycyclohexyl phenyl ketone (BASF or Ciba Specialty Chemicals) mPDMS: mono-n-butyl terminated, monomethacryloxypropyl terminated polydimethylsiloxane (M n =800-1000 Daltons) (Gelest) HO-mPDMS: mono-n-butyl terminated mono-(2-hydroxy-3-methacryloxypropyloxy)-propyl terminated polydimethylsiloxane (M n =400-1500 Daltons) (Ortec or DSM-Polymer Technology Group) ac-PDMS: bis-3-acryloxy-2-hydroxypropyloxypropyl polydimethylsiloxane (Tegomer V-Si 2250 from Evonik) Blue HEMA: 1-amino-4-[3-(4-(2-methacryloyloxyethoxy)-6-chlorotriazin-2-ylamino)-4-sulfophenylamino]anthraquinone-2-sulfonic acid, as described in U.S. Pat. No. 5,944,853 Da: Daltons or g / mol kDa: kilodalton, or atomic mass unit equal to 1,000 daltons 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 RB247: 1,4-bis[2-methacryloxyethylamino]-9,10-anthraquinone BHT: Butylated hydroxytoluene DO: 3,7-dimethyl-3-octanol (Vigon) DIW: Deionized water MeOH: Methanol IPA: Isopropyl alcohol HCl: Hydrochloric acid CH2Cl2 or DCM: methylene chloride or dichloromethane SOCl2: Thionyl chloride mCPBA: m-chloroperbenzoic acid EtOAc: ethyl acetate NH2CH2CH2OH: Ethanolamine or 2-aminoethanol Norbloc: 2-(2'-hydroxy-5-methacrylyloxyethylphenyl)-2H-benzotriazole (Janssen) 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 TL03 Light: Phillips TLK 40W / 03 bulb LED: Light-emitting diode 1 N NMR: Proton nuclear magnetic resonance spectroscopy UV-VIS: Ultraviolet-visible spectroscopy L: Liter mL: milliliter Equiv. or eq.: equivalent weight kg: kilogram g: grams mol: mole mmol: millimolar min:minutes nm: nanometer TLC: Thin Layer Chromatography Borate Buffer Packing Solution: 18.52 grams (300 mmol) of boric acid, 3.7 grams (9.7 mmol) of sodium borate decahydrate, and 28 grams (197 mmol) of sodium sulfate were dissolved in enough deionized water to fill a 2-liter volumetric flask.

[0278] Example 1 - Synthesis of 2-(2-cyanoacetamido)ethyl methacrylate (A) and 2-(2-cyano-2-(9H-thioxanthen-9-ylidene)acetamido)ethyl methacrylate (B) as shown in Scheme 2

[0279] [ka]

[0280] Methyl cyanoacetate (40 grams, 0.4037 moles) and 25 mL of dichloromethane were stirred in a three-necked 500 mL round-bottom flask equipped with a reflux condenser under a nitrogen atmosphere. After 2-aminoethanol (23.8 grams, 0.3897 moles, ∼0.97 equivalents) was added to the solution via an addition funnel, the temperature rose and the methylene chloride began to reflux. After the exotherm subsided, external heat was applied to maintain gentle reflux for a total of 2 hours, after which no ethanolamine was observed by thin-layer chromatography.

[0281] The reaction may also be carried out at room temperature and is complete within a few hours.

[0282] The mixture was cooled to room temperature, and all methylene chloride was evaporated under reduced pressure. The residual oil was washed three times with 50 mL of ethyl acetate to remove unreacted starting material and nonpolar impurities. The residual ethyl acetate was then removed under reduced pressure, and the resulting oil was used for acylation without further purification.

[0283] The crude N-2-hydroxyethylacetamide derivative was dissolved in 150 mL of dichloromethane containing 40 grams of pyridine (~0.5 moles) in a three-neck round-bottom flask equipped with a reflux condenser, an addition funnel, and a magnetic stir bar. The flask was immersed in an ice bath and cooled to approximately 0°C. Methacryloyl chloride (45.76 g, ~0.44 moles) was added dropwise through the addition funnel, and the resulting reactive mixture was allowed to warm to room temperature while constantly stirring the system. Methanol (20 mL) was added to the flask to quench any unreacted methacryloyl chloride. Volatile components were removed by rotary evaporation under reduced pressure, and the crude product was dissolved in 800 mL of dilute aqueous HCl. The resulting aqueous solution was extracted three times with 100 mL of hexane in a separatory funnel to remove any nonpolar impurities. The organic layer was discarded. Sodium chloride was added to the aqueous layer, which was then extracted three times with 300 mL of ethyl acetate. Approximately 50 milligrams of BHT was added as an inhibitor to the combined organic fractions, and the ethyl acetate was removed by rotary evaporation under reduced pressure. The crude product crystallized from solution during solvent removal. When approximately 100 mL of ethyl acetate remained in the flask, 250 mL of hexane was added, and the crude product was isolated by vacuum filtration using a fritted glass funnel. Thin-layer chromatography indicated the presence of a single compound. The filter cake was washed twice with 150 mL of hexane and then dried under vacuum at 40°C to yield 53 grams (approximately 70% yield) of 2-(2-cyanoacetamido)ethyl methacrylate (A). 1 H NMR(500MHz,CDCl3)δ 1.93(3H,s,CH3),3.36(2H,s,CNCH2),3.60(2H,dd,CH2NH),4.26(2H,t,CH2OC=O),5.59(1H,m,vinylic),6.11(1H,bs,vinylic),6.52(1H,bs,NH).

[0284] A mixture of 9H-thioxanthen-9-one (2.12 grams, 0.01 mole) and thionyl chloride (5 mL, 8.2 grams, ∼0.07 mole) was refluxed in a 50 mL round-bottom flask under a nitrogen atmosphere with constant stirring. After 2 hours, the red solution was evaporated to dryness to ensure all unreacted thionyl chloride was removed from the system. 2-(2-cyanoacetamido)ethyl methacrylate (A) (2.3 grams, 0.0117 mole, ∼1.17 equivalents) and 15 mL of dichloromethane were added, and the resulting reactive mixture was heated to reflux under a nitrogen blanket. The reaction was monitored by thin-layer chromatography. After 2 hours, no change in the chromatogram was observed, so the reactive mixture was cooled to room temperature. After passage through a short silica gel column (CHCl, followed by 8 wt% EtOAc in CHCl), 2-(2-cyano-2-(9H-thioxanthen-9-ylidene)acetamido)ethyl methacrylate (B) was isolated as yellow crystals (3.2 grams, 82% yield). The UV-VIS transmission spectrum of a 0.2 mM solution of compound B in methanol is shown in Figure 1. 1 H NMR(500MHz,CDCl3)δ 1.84(3H,s,CH3),3.47(2H,m,CH2NH),4.01(2H,t,CH2OC=O),5.55(1H,m,vinylic),5.91(1H,bs,NH),5.98(1H,bs,vinylic),7.2 4(1H,t,Ar-H),7.31(1H,t,Ar-H),7.39(2H,m,Ar-H),7.49(1H,d,Ar-H),7.55(1H,m,Ar-H),7.61(1H,d,Ar-H),8.04(1H,m,Ar-H).

[0285] Example 2 - Synthesis of 2-(2-cyano-2-(9H-xanthen-9-ylidene)acetamido)ethyl methacrylate (C) as shown in Scheme 3

[0286] [ka]

[0287] A mixture of 9H-xanthen-9-one (5.0 grams, 0.0255 moles) and thionyl chloride (10 mL, 16.4 grams, 0.138 moles) was refluxed in a 50 mL round-bottom flask under a nitrogen atmosphere with constant stirring. After 3 hours, the red solution was evaporated to dryness to ensure all unreacted thionyl chloride was removed from the system. 2-(2-cyanoacetamido)ethyl methacrylate (A) (6.0 grams, 0.0306 moles, ∼1.2 equivalents) and 20 mL of dichloromethane were added, and the resulting reactive mixture was heated to reflux under a nitrogen blanket. The reaction was monitored by thin-layer chromatography. After 2.5 hours, the mixture was cooled to room temperature and passed through a short silica gel column (CHCl and ethyl acetate in CHCl) to purify 2-(2-cyano-2-(9H-xanthen-9-ylidene)acetamido)ethyl methacrylate (C). The off-white precipitate formed during rotary evaporation is washed with hexane and dried overnight in a vacuum oven at 40 °C. The UV-VIS transmission spectrum of compound (C) in a 0.2 mM methanol solution is shown in Figure 1. 1 H NMR(500MHz,CDCl3)δ 1.85(3H,s,CH3),3.60(2H,dd,CH2NH),4.2(2H,t,CH2OC=O),5.53(1H,t,vinylic),5.99(1H,bs,vinylic),6.17(1H,t,NH),7 .12(1H,t,Ar-H),7.29-7.34(3H,m,Ar-H),7.45(1H,ddd,Ar-H),7.52(1H,ddd,Ar-H),7.67(1H,dd,Ar-H),8.41(1H,dd,Ar-H).

[0288] Example 3 - Synthesis of 2-(2-cyano-2-(10-methylacridin-9(10H)-ylidene)acetamido)ethyl methacrylate (D) as shown in Scheme 4 (not supporting data)

[0289] [ka]

[0290] A mixture of 10-methylacridin-9(10H)-one (2.09 grams, 0.01 mole) and thionyl chloride (5 mL, 8.2 grams, ∼0.07 mole) was refluxed in a 50 mL round-bottom flask under a nitrogen atmosphere with constant stirring. After 2 hours, the solution was evaporated to dryness to ensure all unreacted thionyl chloride was removed from the system. 2-(2-cyanoacetamido)ethyl methacrylate (A) (2.3 grams, 0.0117 mole, ∼1.17 equivalents) and 15 mL of dichloromethane were added, and the resulting reactive mixture was heated to reflux under a nitrogen blanket. The reaction was monitored by thin-layer chromatography. When no change in the chromatogram was observed, the reactive mixture was cooled to room temperature. 2-(2-cyano-2-(10-methylacridin-9(10H)-ylidene)acetamido)ethyl methacrylate (D) can be isolated by known methods, for example, after passing through a short silica gel column.

[0291] Example 4 - Synthesis of 2-(2-cyano-2-(10,10-dioxido-9H-thioxanthen-9-ylidene)acetamido)ethyl methacrylate (E) as shown in Scheme 5

[0292] [ka]

[0293] To a cold solution of 2-(2-cyano-2-(9H-thioxanthen-9-ylidene)acetamido)ethyl methacrylate (B) (2.0 grams, 5.2 mmol) in dichloromethane was added 2.32 grams of m-chloroperbenzoic acid (75% purity, ∼2 equivalents, mCPBA). The mixture was stirred cold for 1 hour and then warmed to room temperature. The solution lost its yellow color as the reaction proceeded, and a white solid crystallized or precipitated from the solution. The volatiles were evaporated under reduced pressure. The residue was redissolved in ethyl acetate and extracted with dilute aqueous base, followed by dilution with saline solution. The organic layer was separated, and the solvent was removed by rotary evaporation under reduced pressure. The residue was washed with hexane on a fritted glass funnel and dried under vacuum. The UV-VIS transmission spectrum of a 0.2 mM solution of Compound E in methanol is shown in Figure 1. 1 H NMR(500MHz,CDCl3)δ 1.85(3H,s,CH3),3.35(1H,m,CH2NH),3.61(1H,m,CH2NH),3.81(1H,m,CH2OC=O),4.05(1H,m,CH2OC=O),5.55(1H,m ,vinylic),5.95(1H,m,vinylic),6.35(1H,bs,NH),7.5-7.75(5H,m,Ar-H),8.03(2H,t,Ar-H),8.12(1H,d,Ar-H).

[0294] Example 5 - Synthesis of 2-(2-cyanoacetamido)ethyl methacrylate (F) and N-(2-(2-cyano-2-(9H-thioxanthen-9-ylidene)acetamido)ethyl)methacrylamide (G) as shown in Scheme 6

[0295] [ka]

[0296] Methyl cyanoacetate (22 grams, 0.22 moles) and 250 mL of dichloromethane were stirred in a three-necked 500 mL round-bottom flask equipped with a reflux condenser under a nitrogen atmosphere. The solution was cooled in a water bath, and 1,2-diaminoethane (12 grams, 0.2 moles, ∼0.9 equivalents) was added to the mixture. As the reaction progressed, the mixture appeared increasingly heterogeneous, and the product crashed out of solution. After stirring at room temperature for 4 hours, the volatiles were evaporated under reduced pressure, and the residue was washed with ethyl acetate on a fritted glass funnel and dried at 50°C before further use. 1 H NMR(500MHz,D2O)δ 2.74(2H,t,CH2NH2),3.29(2H,t,CH2NH),3.38(2H,s,CH2CN).

[0297] 2-Aminoethylcyanoacetamide (12.7 g, 0.1 mol) and 12.0 grams of sodium carbonate are stirred in 150 mL of methanol while cooling in an ice bath. Methacryloyl chloride (11.5 g, 1.1 equivalents) is added dropwise to the suspension, keeping the reaction temperature below 30°C. Upon completion of the reaction, all volatiles are evaporated under reduced pressure, the product is redissolved in acetonitrile, and the solution is filtered to remove any salts present. The acetonitrile is evaporated under reduced pressure, and the resulting solid is washed with ethyl acetate on a fritted glass funnel to give the desired 2-(2-cyanoacetamido)ethylmethacrylamide (F). 1 H NMR(500MHz,CD3OD)δ 1.86(3H,s,CH3),3.22-3.26(4H,m,NH,CH2CN),3.29(4H,m,CH2NH),5.31(1H,m,vinylic),5.63(1H,m,vinylic).

[0298] A mixture of thioxanthone (4.24 g, 0.02 mol) and 8 mL of thionyl chloride (13.12 g, ~0.11 mol) was gently refluxed under a nitrogen atmosphere with constant stirring. After heating for 2 hours, the solution was evaporated to dryness under reduced pressure to ensure all unreacted thionyl chloride was removed. 2-(2-cyanoacetamido)ethylmethacrylamide (F) (4.2 g, ~1.1 eq) and 20 mL of degassed methylene chloride were added to the flask, and the mixture was gently refluxed under a nitrogen atmosphere for 3 hours while monitoring progress by TLC. The volatiles were evaporated under reduced pressure, and the organics were washed with ethyl acetate. A large amount of precipitate, containing the major product, was observed. The suspension was filtered, and the remaining solid was washed with ethyl acetate before drying in a vacuum oven. The UV-VIS transmission spectrum of a 0.2 mM solution of compound G in methanol is shown in Figure 2. 1 H NMR(500MHz,CDCl3)δ 1.89(3H,s,CH3),3.26(2H,m,CH2NH),3.32(2H,m,CH2NH),5.33(1H,m,vinylic),5.68(1H,m,vinylic),6.63(1H,m,NH) ,6.49(1H,m,NH),7.25(1H,m,Ar-H),7.33(1H,dt,Ar-H),7.39(2H,m,Ar-H),7.51-7.59(3H,m,Ar-H),8.05(1H,m,Ar-H).

[0299] Example 6 - N-(2-(2-cyano-2-(10-methylacridin-9(10H)ylidene)acetamido)ethyl)methacrylamide (H) as shown in Scheme 7

[0300] [ka]

[0301] N-(2-aminoethyl)-2-cyanoacetamide (2): Compound 1 (30 g, 303 mmol, 1.0 equiv.) was added to a solution of ethylenediamine (54.5 g, 909 mol, 3 equiv.) in dichloromethane (600 mL) at −20° C. over 30 minutes. The reaction was allowed to warm to room temperature over 2 hours and stirred for 3 hours, at which point LC-MS indicated the reaction was complete. The resulting precipitate was filtered and washed with dichloromethane (2×100 mL) to give compound 2 (25 g, 66% yield, >95% purity) as a white solid.

[0302] N-(2-(2-cyanoacetamido)ethyl)methacrylamide (3): A solution of methylacrylic anhydride (41 g, 264 mmol, 1.3 equiv.) and triethylamine (40 mL, 287 mmol, 1.3 equiv.) in dichloromethane (300 mL) was stirred at room temperature for 1 h. The reaction was cooled to 0 °C, and compound 2 (28 g, 220 mmol, 1.0 equiv.) was added portionwise to the reactive mixture at 0 °C. The reaction was allowed to warm to room temperature and stirred for 5 h, at which point LC-MS indicated the reaction was complete. The resulting precipitate was filtered and washed with dichloromethane (2 × 100 mL) to give compound 3 (25.1 g, 60% yield, >95% purity) as a white solid.

[0303] 9,9-Dichloro-10-methyl-9,10-dihydroacrylidine (5): Compound 4 (10 g, 4.85 mmol, 1.0 equiv.) in thionyl chloride (200 mL, 2.75 mol, 55 equiv.) was stirred at 60° C. for 2 hours, at which point 1 H-NMR showed the reaction was complete. Thionyl chloride was removed under reduced pressure. The residue was azeotroped with toluene (2×20 mL) to give crude compound 5 (12.5 g) as a yellow solid, which was used subsequently.

[0304] N-(2-(2-cyano-2-(10-methylacridin-9(10H)-ylidene)acetamido)ethyl)methacrylamide (H): Triethylamine (20 mL, 143 mmol, 3.0 equiv) was added dropwise over 30 minutes to a solution of crude compound 5 (12.5 g, 48.5 mmol, 1.0 equiv) and compound 3 (9.33 g, 48.5 mmol, 1.0 equiv) in a 1:1 mixture of dichloromethane and acetonitrile (200 mL) at 0° C. The reaction was allowed to warm to room temperature and stirred for 2 hours, at which point LC-MS indicated the reaction was complete. The mixture was passed through a plug of silica gel (150 g) and eluted with dichloromethane (500 mL). The organics were concentrated under reduced pressure. The residue was purified on silica gel (800 g) and eluted with ethyl acetate to give compound (H) as a yellow solid. The solid was triturated with methyl tert-butyl ether (2 x 200 mL) for 2 hours, collected by filtration, and triturated with chloroform (50 mL) for 30 minutes to give pure compound (H) (11.9 g, 60% yield over two steps, 97.5% purity) as a yellow solid.

[0305] The UV-VIS transmission spectrum of a 0.2 mM methanol solution of Compound H is shown in FIG. 1 H NMR(500MHz,DMSO-d6)δ 1.87(3H,m,CH3),3.15-3.20(4H,m,CH2NH),3.72(3H,s,CH3N),5.36(1H,s,vinylic),5.68(1H, m,vinylic),7.14(1H,bt,NH),7.29(1H,bt,NH,7.49-7.65(4H,m,Ar-H),8.02-8.81(4H,Ar-H).

[0306] Example 7 - Synthesis of 2-(2-cyanoacetamido)ethylacrylamide (I) and N-(2-(2-cyano-2-(9H-xanthen-9-ylidene)acetamido)ethyl)acrylamide (J) as shown in Scheme 8

[0307] [ka]

[0308] 2-(2-cyanoacetamido)ethyl acrylamide (I) was prepared by the same method used for 2-(2-cyanoacetamido)ethyl methacrylate (F). 2-Aminoethylcyanoacetamide (12.7 g, 0.1 mol) and 12.0 grams of sodium carbonate were stirred in 150 mL of methanol while cooling in an ice bath. Acryloyl chloride (9.9 g, 1.1 equivalents) was added dropwise to the suspension, maintaining the reaction temperature below 30°C. Upon completion of the reaction, all volatiles were evaporated under reduced pressure, the product was redissolved in acetonitrile, and the solution was filtered to remove any salts present. The acetonitrile was evaporated under reduced pressure, and the resulting solid was washed with ethyl acetate on a fritted glass funnel to yield the desired 2-(2-cyanoacetamido)ethyl acrylamide (I). 1 H NMR(500MHz,CD3OD)δ 3.22-3.31(8H,m,NH,CH2),5.59(1H,dd,vinylic),6.14(2H,dd,vinylic).

[0309] A mixture of xanthone (3.92 g, 0.02 mol) and 5 mL of thionyl chloride (8.2 g, ∼0.07 mol) in 10 mL of toluene was gently refluxed with constant stirring under a nitrogen atmosphere. After heating for 6 hours, the solution was cooled and the volatiles were evaporated under reduced pressure to ensure all unreacted thionyl chloride was removed from the system. 2-(2-cyanoacetamido)ethylacrylamide (I) (3.8 g, ∼1.05 eq) and 20 mL of methylene chloride were added to the flask, and the mixture was gently refluxed under a nitrogen atmosphere for 3 hours while monitoring progress by TLC. The volatile components were evaporated under reduced pressure. The residue was washed with warm ethyl acetate and filtered through a fritted glass funnel. The filter cake was washed with additional ethyl acetate, followed by water. The bright yellow solid was dried in a vacuum oven. The UV-VIS transmission spectrum of a 0.2 mM solution of compound J in methanol is shown in Figure 2. 1H NMR(500MHz,DMSO-d6)δ 3.15-3.25(4H,m,CH2),5.62(1H,dd,vinylic),6.08-6.23(2H,m,vinylic),7.32-7.75(1H ,dt,Ar-H),7.46-7.72(6H,Ar-H),8.17(1H,bt,NH),8.34(1H,dd,Ar-H),8.88(1H,bt,NH).

[0310] Example 8 - Synthesis of 2-(2-cyanoacetoxy)ethyl methacrylate (K) and 2-(2-cyano-2-(9H-thioxanthen-9-ylidene)acetoxy)ethyl methacrylate (L) as shown in Scheme 9

[0311] [ka]

[0312] 2-(2-cyanoacetoxy)ethyl methacrylate (K) was prepared by coupling cyanoacetic acid with 2-hydroxyethyl methacrylate as follows: Cyanoacetic acid (9 g, 0.106 mol) and 13 g of 2-hydroxyethyl methacrylate (HEMA) were stirred in 250 mL of dichloromethane, and ethyl dimethylaminopropylcarbodiimide hydrochloride (EDC) was added to the suspension in four batches of 5 g each (20 g, 0.104 mol). The mixture gradually became more homogeneous as less polar derivatives were formed. After completion of the reaction, the volatiles were evaporated under reduced pressure. The product was redissolved in a 25:75 (by weight) mixture of ethyl acetate and hexane and extracted several times with deionized water to remove any residual salts and unreacted HEMA. A small amount of 4-methoxyhydroquinone (<20 mg) was added to the organic layer, and the pure product was obtained after evaporating the solvent under reduced pressure. 1 H NMR(500MHz,CDCl3)δ 1.92(3H,m,CH3),3.47(2H,S,NCCH2),4.36(2H,m,OCH2),4.44(2H,m,OCH2),4.59(1H,m,vinylic),6.10(1H,m,vinylic).

[0313] A mixture of thioxanthone (4.24 g, 0.02 mol) and 8 mL of thionyl chloride (13.12 g, ∼0.11 mol) was gently refluxed under a nitrogen atmosphere with constant stirring. After heating for 2 hours, the solution was evaporated to dryness under reduced pressure to ensure all unreacted thionyl chloride was removed. A solution of 2-(2-cyanoacetoxy)ethyl methacrylate (K) (4.33 g, ∼1.1 equivalents) in 20 mL of degassed methylene chloride was added to the flask, and the mixture was gently refluxed under a nitrogen atmosphere for 3 hours while monitoring progress by TLC. The residue was washed with methanol to remove most of the unreacted starting thioxanthone, reconcentrated, and the crude product was purified by chromatography on a silica gel plug and dried overnight under vacuum. The UV-VIS transmission spectrum of a 0.2 mM solution of compound L in dichloromethane is shown in Figure 2. 1 H NMR(500MHz,CDCl3)δ 1.92(3H,s,CH3),4.36(2H,m,CH2),4.44(2H,m,CH2),5.59(1H,m,vinylic),6.10(1H,m,vinylic),7.24-7.62(7H,m,Ar-H),8.1(1H,m,Ar-H).

[0314] Example 9 - Silicone Hydrogel Formulations Containing Compound (B) Reactive monomer mixtures were prepared consisting of 77 weight percent of the formulation listed in Table 4 and 23 weight percent of diluent DO. The reactive monomer mixtures were individually filtered under pressure through 3 μm filters using stainless steel syringes.

[0315] [Table 4]

[0316] Formulations 9A-9D were degassed at ambient temperature by applying a vacuum (40 Torr) for 45 minutes. Then, in a glove box containing a nitrogen gas atmosphere and less than about 0.1-0.2 percent oxygen gas, approximately 75 μL of the reactive mixture was dispensed at room temperature using an Eppendorf pipette onto a FC made with a 90:10 (w / w) Zeonor / TT blend. A BC made with a 90:10 (w / w) Zeonor / TT blend was then placed onto the FC. The molds were equilibrated in the glove box for a minimum of 12 hours before pouring. Each pallet containing the eight mold assemblies was transferred to an adjacent glove box maintained at 65°C, with a luminance of approximately 2 mW / cm at the tray position. 2 The adhesive was cured from the top and bottom for 15 minutes using a 435 nm LED light with an intensity of 1000 uV.

[0317] With most of the lenses still attached to the FC, the lenses were manually removed from the molds and released by floating them in approximately 1 liter of 70 percent IPA for approximately 1 hour, followed by two 30-minute baths in fresh 70 percent IPA, two 15-minute baths in fresh DIW, and two 30-minute baths in packing solution. The lenses were equilibrated and stored in the borate-buffered packing solution. Those skilled in the art will appreciate that the exact lens demolding process, with respect to the concentration of the aqueous isopropanol, the number of washes with each solvent, and the duration of each step, can vary depending on the lens formulation and mold material. The objective of the lens demolding process is to demold all of the lenses without damage and to transition them from a diluent-swollen network to a packing-solution-swollen hydrogel. The average center thickness of each lens set was measured: 9A = 87.7 micrometers, 9B = 85.3 micrometers, 9C = 87.3 micrometers, and 9D = 85.7 micrometers.

[0318] Figures 3-5 show the UV-VIS spectra of lenses made from formulations 9A-9D, which demonstrate that compound (B) or a combination of compound (B) and Norbloc® can provide complete or near complete absorption from 300 nm to 400 nm, while providing some absorption in the high-energy visible region from 400 nm to 450 nm.

[0319] Example 10 - Silicone Hydrogel Formulations Containing Compounds (B) and (C) Reactive monomer mixtures were prepared consisting of 77 weight percent of the formulation listed in Table 5 and 23 weight percent of diluent DO. The reactive monomer mixtures were individually filtered under pressure through 3 μm filters using stainless steel syringes.

[0320] [Table 5]

[0321] Formulations 10A-10D were degassed at ambient temperature by applying a vacuum (40 Torr) for 45 minutes. Approximately 75 μL of the reactive mixture was then dispensed into a FC made with a 90:10 (w / w) Zeonor / TT blend using an Eppendorf pipette at room temperature in a glove box containing a nitrogen gas atmosphere and less than about 0.1-0.2 percent oxygen gas. A BC made with a 90:10 (w / w) Zeonor / TT blend was then placed on the FC. The molds were equilibrated in the glove box for a minimum of 12 hours before pouring. Each pallet containing the eight mold assemblies was transferred to an adjacent glove box maintained at 65°C, with a luminance of approximately 2 mW / cm at the tray position. 2 The adhesive was cured from the top and bottom for 15 minutes using a 435 nm LED light with an intensity of 1000 uV.

[0322] With most of the lenses still attached to the FC, the lenses were manually removed from the molds and released by floating them in approximately 1 liter of 70 percent IPA for approximately 1 hour, followed by two 30-minute soaks in fresh 70 percent IPA, two 15-minute soaks in fresh DIW, and two 30-minute soaks in packing solution. The lenses were equilibrated and stored in the borate-buffered packing solution. Those skilled in the art will appreciate that the exact lens demolding process, with respect to the concentration of the aqueous isopropanol, the number of washes with each solvent, and the duration of each step, can vary depending on the lens formulation and mold material. The goal of the lens demolding process is to release all of the lenses without damage and allow them to transition from a diluent-swollen network to a packing-solution-swollen hydrogel. The average center thickness of each lens set was measured: 10A = 93.7 micrometers, 10B = 93.7 micrometers, 10C = 95.3 micrometers, and 10D = 92.3 micrometers.

[0323] Figures 6-8 show UV-VIS spectra of lenses made from formulations 10A-10D, demonstrating that the combination of compounds (B) and (C) can provide complete or near complete absorption from 300 nm to 400 nm, while also providing some absorption in the high-energy visible region from 400 nm to 450 nm. The figures also show that compound (C) alone provides absorption in various wavelength ranges.

[0324] Example 11 Lenses were fabricated using a reactive monomer mix containing the components listed as 9D in Table 4 and the same curing and hydration process, except that the oxygen gas concentration in the glove box was less than 0.5%. The lenses were packaged in glass vials containing PS and then placed on a windowsill exposed to direct sunlight (11A) or on top of a cabinet with only indoor lighting and no exposure to direct sunlight (11B). Controls were stored in the dark. After 3, 5, 9, 15, and 21 weeks of exposure, the UV-visible transmittance spectra of the lenses were measured, as shown in Figures 9 and 10.

[0325] For lenses exposed to direct sunlight, the absorption of high-energy visible light between 400 and 450 nm did not change over time. The UV-VIS transmission spectrum between 450 and 700 nm changed only slightly (approximately 1%) over the test period.

[0326] For lenses exposed to indoor lighting, the absorption of high-energy visible light between 400 nm and 450 nm did not change over time. Over the test period, the UV-VIS transmission spectrum did not change by more than about 2% or 3% from 450 nm to 700 nm.

[0327] Examples 12 to 25 are not supported by experimental data. Example 12: (Z)-2-(2-cyano-2-(3-hydroxyacridin-9(10H)-ylidene)acetamido)ethyl methacrylate The title compound can be synthesized by a similar procedure as above, starting from 3-hydroxyacridone (CAS Registry Number 20168-55-2).

[0328] Example 13: 2-(2-cyano-2-(10-methylacridin-9(10H)-ylidene)acetamido)ethyl methacrylate The title compound can be synthesized by a similar procedure as above, starting from N-methylacridone (719-54-0).

[0329] Example 14: 2-(2-cyano-2-(3,6-dihydroxyacridin-9(10H)-ylidene)acetamido)ethyl methacrylate The title compound can be synthesized by a similar procedure as above starting from 3,6-dihydroxyacridone (122105-95-7).

[0330] Example 15: (E)-2-(2-(7H-benzo[c]xanthen-7-ylidene)-2-cyanoacetamido)ethyl methacrylate The title compound can be synthesized by a similar procedure as above, starting from benzo[C]xanthone (63154-69-8).

[0331] Example 16: (Z)-2-(2-cyano-2-(3-methoxy-9H-xanthen-9-ylidene)acetamido)ethyl methacrylate The title compound can be synthesized by a similar procedure as above, starting from 3-methoxyxanthone (3722-52-9).

[0332] Example 17: 2-(2-cyano-2-(3,6-dihydroxy-9H-xanthen-9-ylidene)acetamido)ethyl methacrylate The title compound can be synthesized by a similar procedure as above, starting from 3,6-dihydroxyxanthone (1214-24-0).

[0333] Example 18: (E)-2-(2-cyano-2-(2-methyl-9H-xanthen-9-ylidene)acetamido)ethyl methacrylate The title compound can be synthesized by a similar procedure as above, starting from 2-methylxanthone (2680-45-1).

[0334] Example 19: (E)-2-(2-cyano-2-(1-hydroxy-9H-xanthen-9-ylidene)acetamido)ethyl methacrylate The title compound can be synthesized by a similar procedure as above, starting from 1-hydroxyxanthone (19-41-5).

[0335] Example 20: (E)-2-(2-cyano-2-(2,4-dichloro-9H-thioxanthen-9-ylidene)acetamido)ethyl methacrylate The title compound can be synthesized by a similar procedure as above, starting from 2,4-dichlorothioxanthone.

[0336] Example 21: (E)-2-(2-(2-chloro-9H-thioxanthen-9-ylidene)-2-cyanoacetamido)ethyl methacrylate The title compound can be synthesized by a similar procedure as above, starting from 2-chlorothioxanthone.

[0337] Example 22: (E)-2-(2-cyano-2-(2-isopropyl-9H-thioxanthen-9-ylidene)acetamido)ethyl methacrylate and (E)-2-(2-cyano-2-(4-isopropyl-9H-thioxanthen-9-ylidene)acetamido)ethyl methacrylate The title compound can be synthesized as a mixture by a similar procedure as above, starting from a mixture of 2 and 4-isopropylthioxanthone.

[0338] Examples 23 to 25 Contact lenses can be prepared from the silicone hydrogel formulations shown in Table 6 using procedures similar to those described in Example 6. In these examples, 77 weight percent of the formulation listed in Table 6 is diluted with 23 weight percent of a diluent (e.g., DO).

[0339] [Table 6]

[0340] [Embodiment] (1) A compound of formula I, [ka] During the ceremony, m and n are independently 0, 1, 2, 3, or 4; T is a bond, O, or NR; X is O, S, NR, SO, or SO; 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 1and R 2 is, when present, independently at each occurrence C1-C6 alkyl, C1-C6 alkoxy, C1-C6 thioalkyl, C3-C7 cycloalkyl, aryl, halo, hydroxy, amino, NR 3 R 4 or benzyl, where 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 in the compound. (2) The compound of embodiment 1, wherein m and n are each independently 0 or 1. (3) The compound of embodiment 1 or 2, wherein Y, at each occurrence, is independently alkylene, cycloalkylene, heterocycloalkylene, arylene, heteroarylene, oxaalkylene, alkylene-amido-alkylene, alkylene-amine-alkylene, or a combination thereof. (4) P g comprises a styryl, vinyl carbonate, vinyl ether, vinyl carbamate, N-vinyl lactam, N-vinyl amide, (meth)acrylate, or (meth)acrylamide. (5) The compound of any one of embodiments 1 to 4, wherein X is O.

[0341] (6) The compound of any one of embodiments 1 to 4, wherein X is S. (7) The compound of any one of embodiments 1 to 6, wherein EWG is cyano, amide, ester, keto, or aldehyde. (8) The compound of any one of embodiments 1-7, wherein EWG is cyano. (9) The following: 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-cyano-2-(9H-xanthen-9-ylidene)acetamido)ethyl methacrylate; 2-(2-cyano-2-(9H-xanthen-9-ylidene)acetamido)ethyl acrylate; N-(2-(2-cyano-2-(9H-xanthen-9-ylidene)acetamido)ethyl)methacrylamide; N-(2-(2-cyano-2-(9H-xanthen-9-ylidene)acetamido)ethyl)acrylamide; 2-(2-cyano-N-methyl-2-(9H-xanthen-9-ylidene)acetamido)ethyl methacrylate; 2-cyano-N-(2-(N-vinylacetamido)ethyl)-2-(9H-xanthen-9-ylidene)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; 2-(2-cyano-2-(9H-xanthen-9-ylidene)acetoxy)-2-methylpropyl acrylate; (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-(7H-benzo[c]xanthen-7-ylidene)-2-cyanoacetamido)ethyl methacrylate; (Z)-2-(2-cyano-2-(3-methoxy-9H-xanthen-9-ylidene)acetamido)ethyl methacrylate; 2-(2-cyano-2-(3,6-dihydroxy-9H-xanthen-9-ylidene)acetamido)ethyl methacrylate; (E)-2-(2-cyano-2-(2-methyl-9H-xanthen-9-ylidene)acetamido)ethyl methacrylate; (E)-2-(2-cyano-2-(1-hydroxy-9H-xanthen-9-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; or The compound according to embodiment 1, which is 2-(2-cyano-2-(9H-thioxanthen-9-ylidene)acetoxy)ethyl methacrylate. (10) An ophthalmic device that is a free radical reaction product of a reactive mixture comprising one or more monomers suitable for making the ophthalmic device and a polymerizable high-energy light absorbing compound comprising the compound of any one of embodiments 1-9.

[0342] (11) The ophthalmic device of embodiment 10, further comprising a second polymerizable high-energy light-absorbing compound. (12) The ophthalmic device of embodiment 11, wherein the second polymerizable high-energy light-absorbing compound is a UV-absorbing compound. 13. The ophthalmic device of claim 12, wherein the UV absorbing compound comprises a compound of Formula I, a benzophenone, a benzotriazole, a triazine, a substituted acrylonitrile, a salicylic acid derivative, a benzoic acid derivative, a cinnamic acid derivative, a chalcone derivative, a dipnone derivative, a crotonic acid derivative, or a mixture thereof. (14) The ophthalmic device of any one of embodiments 10 to 13, wherein the polymerizable high-energy light absorption compound comprises a mixture of a compound of Formula I, wherein X is S, and a compound of Formula I, wherein X is O. (15) The ophthalmic device of any one of embodiments 10 to 13, wherein the polymerizable high-energy light absorbing compound comprises a mixture of a compound of Formula I, wherein X is S, and a benzotriazole UV absorbing compound.

[0343] (16) The ophthalmic device of any one of embodiments 10 to 15, wherein the monomer suitable for making the ophthalmic device comprises a hydrophilic component, a silicone-containing component, or a mixture thereof. (17) The ophthalmic device according to any one of embodiments 10 to 16, which is a contact lens, a corneal onlay, a corneal inlay, an intraocular lens, or an overlay lens. (18) The ophthalmic device according to any one of embodiments 10 to 17, which is a hydrogel contact lens. (19) A method for making an ophthalmic device, comprising: (a) providing a reactive mixture comprising a compound of any one of embodiments 1-9, one or more device-forming monomers, and a radical initiator; (b) polymerizing the reactive mixture to form the ophthalmic device. (20) An ophthalmic device that is a reaction product of a reactive mixture, comprising: a polymerizable high-energy light absorbing compound; one or more monomers suitable for making an ophthalmic device; the ophthalmic device comprising: Not more than 45 percent of light has a wavelength between 280 and 399 nm; Between 1 percent and 70 percent of light with wavelengths between 400 and 409 nm, and At least 80 percent of light has a wavelength between 450 and 800 nm An ophthalmic device that penetrates the eye.

[0344] (21) 10 percent to 95 percent of light having a wavelength of 410 to 424 nm; and At least 50 percent of light has a wavelength between 425 and 449 nm An ophthalmic device as described in embodiment 20, which further transmits (22) Not more than 20 percent of light having a wavelength of 280 to 399 nm; Between 3 percent and 70 percent of light with wavelengths between 400 and 409 nm, and At least 85 percent of light has a wavelength between 450 and 800 nm 22. An ophthalmic device according to embodiment 20 or 21, which is transparent. (23) The polymerizable high-energy light-absorbing compound is a compound of Formula I: [ka] Including, During the ceremony, m and n are independently 0, 1, 2, 3, or 4; T is a bond, O, or NR; X is O, S, NR, SO, or SO; 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 at each occurrence C1-C6 alkyl, C1-C6 alkoxy, C1-C6 thioalkyl, C3-C7 cycloalkyl, aryl, halo, hydroxy, amino, NR 3 R 4 or benzyl, where R 3 and R 4 are independently H or C1-C6 alkyl, or two adjacent R 1 or R 2the groups, together with the carbon atoms to which they are attached, are joined to form a cycloalkyl or aryl ring; An ophthalmic device as described in embodiment 20, wherein the EWG is an electron-withdrawing group. (24) The ophthalmic device of embodiment 23, further comprising a second polymerizable high-energy light-absorbing compound. (25) The ophthalmic device of embodiment 24, wherein the second polymerizable high-energy light-absorbing compound is a UV-absorbing compound.

[0345] 26. The ophthalmic device of claim 25, wherein the UV absorbing compound comprises a compound of Formula I, a benzophenone, a benzotriazole, a triazine, a substituted acrylonitrile, a salicylic acid derivative, a benzoic acid derivative, a cinnamic acid derivative, a chalcone derivative, a dipnone derivative, a crotonic acid derivative, or a mixture thereof. (27) The ophthalmic device of any one of embodiments 23 to 26, wherein the polymerizable high-energy light absorption compound comprises a mixture of a compound of Formula I, wherein X is S, and a compound of Formula I, wherein X is O. 28. The ophthalmic device of any one of claims 23 to 26, wherein the polymerizable high-energy light absorbing compound comprises a mixture of a compound of Formula I, wherein X is S, and a benzotriazole UV absorbing compound. (29) The ophthalmic device of any one of embodiments 23 to 28, wherein m and n in the compound of formula I, at each occurrence, are each 0. (30) The ophthalmic device of any one of embodiments 23-29, wherein Y in the compound of Formula I, at each occurrence, is independently alkylene, cycloalkylene, heterocycloalkylene, arylene, heteroarylene, oxaalkylene, alkylene-amide-alkylene, alkylene-amine-alkylene, or a combination thereof.

[0346] (31) P in the compound of formula I gwherein each occurrence independently comprises styryl, vinyl carbonate, vinyl ether, vinyl carbamate, N-vinyl lactam, N-vinyl amide, (meth)acrylate, or (meth)acrylamide. (32) The ophthalmic device of any one of embodiments 20 to 31, wherein the ophthalmic device is a silicone hydrogel contact lens, the silicone hydrogel contact lens having a contact angle of about 70° or less, a water content of at least 25 percent, and an oxygen permeability of at least 80 barrers. (33) An ophthalmic device that is a polymerization reaction product of a reactive mixture comprising a hydrophilic component and a silicone-containing compound, said polymerization reaction product comprising, as covalently attached substituents, one or more chromophores of Formula IV: [ka] Contains During the ceremony, m and n are independently 0, 1, 2, 3, or 4; X is O, S, NR, SO, or SO; R, in each occurrence, is independently H, C1-C6 alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, or a bond to said polymerization reaction product; R 1 and R 2 is, when present, independently at each occurrence C1-C6 alkyl, C1-C6 alkoxy, C1-C6 thioalkyl, C3-C7 cycloalkyl, aryl, halo, hydroxy, amino, NR 3 R 4 or benzyl, where 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; R 5 is a bond to the polymerization reaction product, EWG is an electron-withdrawing group for ophthalmic devices. (34) The ophthalmic device of embodiment 33, wherein X is O. (35) The ophthalmic device of embodiment 34, wherein X is S.

[0347] (36) The ophthalmic device of any one of embodiments 33 to 35, wherein the polymerization reaction product further comprises one or more UV-absorbing chromophores covalently attached thereto. (37) The ophthalmic device of embodiment 36, wherein the UV-absorbing chromophore is a residue of a benzophenone, a benzotriazole, a triazine, a substituted acrylonitrile, a salicylic acid derivative, a benzoic acid derivative, a cinnamic acid derivative, a chalcone derivative, a dipnone derivative, a crotonic acid derivative, or a mixture thereof. (38) The ophthalmic device of any one of embodiments 33 to 37, wherein the bond to the polymerization reaction product comprises a residue of a polymerizable group and one or more of an alkylene group, a cycloalkylene group, a heterocycloalkylene group, an arylene group, a heteroarylene group, an oxaalkylene group, an alkylene-amide-alkylene group, or an alkylene-amine-alkylene group. (39) The ophthalmic device of embodiment 38, wherein the polymerizable group comprises styryl, vinyl carbonate, vinyl ether, vinyl carbamate, N-vinyl lactam, N-vinyl amide, (meth)acrylate, or (meth)acrylamide. (40) A silicone hydrogel contact lens that is the reaction product of a reactive mixture comprising a polymerizable high-energy light absorbing compound and one or more monomers suitable for making an ophthalmic device, wherein the contact lens has a contact angle of about 70° or less, a water content of at least 25 percent, and an oxygen permeability of at least 80 Barrers, and the contact lens is substantially photostable.

[0348] 41. The silicone hydrogel contact lens of claim 40, wherein the lens transmits between 1 percent and 70 percent of light having a wavelength between 400 and 409 nm and at least 80 percent of light having a wavelength between 450 and 800 nm. (42) The polymerizable high-energy light-absorbing compound is a compound of formula I: [ka] and During the ceremony, m and n are independently 0, 1, 2, 3, or 4; T is a bond, O, or NR; X is O, S, NR, SO, or SO; 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 at each occurrence C1-C6 alkyl, C1-C6 alkoxy, C1-C6 thioalkyl, C3-C7 cycloalkyl, aryl, halo, hydroxy, amino, NR 3 R 4 or benzyl, where 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; 42. The silicone hydrogel contact lens of embodiment 40 or 41, wherein the EWG is an electron-withdrawing group. (43) The ophthalmic device of any one of embodiments 23 to 32, wherein the EWG is cyano. (44) The ophthalmic device of any one of embodiments 33 to 39, wherein the EWG is cyano. (45) The silicone hydrogel contact lens of embodiment 42, wherein the EWG is cyano.

[0349] (46) A silicone hydrogel, a high-energy light absorbing compound; about 1 to about 15 weight percent of at least one polyamide; at least one first monofunctional hydroxyl-substituted poly(disubstituted siloxane) having 4 to 8 siloxane repeat units; at least one second hydroxyl-substituted poly(disubstituted siloxane) that is a monofunctional hydroxyl-substituted poly(disubstituted siloxane) having 10 to 200 siloxane repeat units; about 5 to about 35 weight percent of at least one hydrophilic monomer; 1. A silicone hydrogel formed from a reactive mixture comprising: 47. The silicone hydrogel of embodiment 46, wherein the high-energy light absorbing compound is a compound of formula I:

Claims

[Claim 1] A compound of formula I, 【Chemical 1】 During the ceremony, m and n are independently 0, 1, 2, 3, or 4; T is a bond, O, or NR; X is O, S, NR, SO, or SO ２ and Y is a linking group; P ｇ is a polymerizable group, R, in each occurrence, is independently H, C １ ~C ６ Alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, or Y-P ｇ and R １ and R ２ When present, each occurrence independently represents C １ ~C ６ Alkyl, C １ ~C ６ Alkoxy, C １ ~C ６ Thioalkyl, C ３ ~C ７ Cycloalkyl, aryl, halo, hydroxy, amino, NR ３ R ４ or benzyl, where 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, are joined to form a cycloalkyl or aryl ring; EWG is an electron withdrawing group, compound.

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