Polymerizable absorbers for uv and high-energy visible light

Abstract

The present invention relates to polymerizable absorbers of UV and high energy visible light. The present invention describes polymerizable high energy light absorbing compounds. The compounds absorb UV and / or high energy visible light of various wavelengths and are suitable for incorporation into various products such as biomedical devices and ophthalmic devices such as hydrogel contact lenses. The monomers have the following general formula I, wherein X is O, S, NR, SO, or SO2; Y is a linking group; Pg is a polymerizable group; and EWG is an electron withdrawing group.

Description

[0001] This application is a divisional application of the invention patent application filed on February 27, 2019, with application number 201980016821.5 and invention title "polymerizable absorber for UV and high-energy visible light".

[0002] Related applications

[0003] This application claims priority to U.S. Patent Application Serial No. 16 / 268,897, filed February 6, 2019; U.S. Provisional Patent Application Serial No. 62 / 691,112, filed June 28, 2018; and U.S. Provisional Patent Application Serial No. 62 / 637,505, filed March 2, 2018, the entire contents of each of which are incorporated herein by reference. Technical Field

[0004] This invention relates to UV and high-energy visible light absorbers. More specifically, this invention relates to compounds having polymerizable functionality that absorb various wavelengths of UV and / or high-energy visible light and remain visually transparent when incorporated into articles. Therefore, these compounds can be used in polymer articles, including biomedical devices such as ophthalmic devices. Background Technology

[0005] High-energy light from the sun, such as UV light and high-energy visible light, is known to cause cell damage. While most radiation with wavelengths below 280 nm is absorbed by the Earth's atmosphere, photons in the 280 nm to 400 nm range are associated with a variety of eye diseases, including corneal degenerative changes, age-related cataracts, and macular degeneration. (See American Optometric Association, "Statement on Ocular Ultraviolet Radiation Hazards in Sunlight," November 10, 1993). The human cornea absorbs some radiation with wavelengths up to 320 nm (with a transmittance of 30%) (Doutch, JJ, Quantock, AJ, Joyce, NC, Meek, KM, Biophys. J, 2012, 102, 1258-1264), but is ineffective in protecting the back of the eye from radiation in the 320 nm to 400 nm range.

[0006] The standard for contact lenses defines the upper limit of UV radiation wavelength as 380 nm. The current Class I UV absorption standard defined by the American Optometry Association requires contact lenses to absorb >99% of radiation between 280 nm and 315 nm (UV B) and >90% of radiation between 316 nm and 380 nm (UV A). While this standard effectively addresses corneal protection (UV B transmittance <1%), it pays little attention to lower-energy UV radiation (>380 nm and <400 nm) associated with retinal damage (Ham, WT, Mueller, HA, Sliney, DH Nature 1976; 260(5547): 153-5), or even less attention to high-energy visible radiation.

[0007] High-energy visible (HEV) radiation can cause visual discomfort or circadian rhythm disruption. For example, computer and electronic device screens, flat-screen TVs, energy-saving lamps, and LED lights are known to emit HEV light. Prolonged exposure to such HEV light sources can cause eye strain. It is also hypothesized that viewing HEV light-emitting devices at night can disrupt the natural circadian rhythm, leading to, for example, sleep deprivation.

[0008] Absorbing high-energy light radiation before it reaches the eye has always been a desired goal in ophthalmology. However, the degree to which specific wavelength ranges are absorbed is also important. For example, in the UV A and UV B range, it may be desirable to absorb as much radiation as possible. On the other hand, since HEV light forms part of the visible spectrum, complete absorption of HEV light may have adverse effects on vision. Therefore, for HEV light, partial absorption may be more desirable.

[0009] Materials are needed that provide targeted absorption of unwanted high-energy radiation wavelengths and can be processed into functional products. Compounds that absorb or attenuate high-energy radiation, when used in ophthalmic devices, can help protect the cornea and internal cells of the ocular environment from degradation, strain, and / or circadian rhythm disruption. Summary of the Invention

[0010] This invention relates to high-energy light-absorbing compounds that absorb UV and / or high-energy visible (HEV) light while being substantially transmissive at wavelengths longer than about 450 nm (e.g., transmittance greater than 80%). Therefore, these compounds effectively provide targeted absorption of high-energy light such as UV (UVA and UVB), low-energy UV light (385 nm to 400 nm), or HEV light (e.g., 400 nm to 450 nm).

[0011] The compound is also polymerizable and is generally compatible with other raw materials and polymerization and processing conditions commonly used in the manufacture of ophthalmic devices such as soft contact lenses. Therefore, the compound can be readily covalently incorporated into the final product without requiring significant modifications to existing manufacturing processes and equipment.

[0012] Therefore, in one aspect, the present invention provides a compound of formula I:

[0013]

[0014] in:

[0015] m and n are independently 0, 1, 2, 3 or 4;

[0016] T represents a chemical bond, O, or NR;

[0017] X is O, S, NR, SO, or SO2;

[0018] Y is a linking group;

[0019] P g It is a polymerizable group;

[0020] R is independently H, C1-C6 alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, or YP each time it appears. g ;

[0021] When R exists 1 and R 2 At that time, R 1 and R 2 Each time it appears, it is independently C1-C6 alkyl, C1-C6 alkoxy, C1-C6 alkylthio, C3-C7 cycloalkyl, aryl, halogen, hydroxyl, amino, NR 3 R 4 Or benzyl, where R 3 and R 4 Independently H or C1-C6 alkyl, or two adjacent R 1 Or R 2 The groups, together with the carbon atoms they are attached to, combine to form cycloalkyl or aryl rings; and

[0022] EWG is an electron-withdrawing group, such as cyano, amide, ester, ketone or aldehyde (preferably cyano).

[0023] 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 manufacturing the ophthalmic device; and a polymerizable high-energy light-absorbing compound comprising compounds of Formula I as described herein.

[0024] In another aspect, the present invention provides a method for manufacturing an ophthalmic device. The method includes: (a) providing a reactive mixture comprising a compound of formula I as described herein, one or more device-forming monomers, and a free radical initiator; and (b) polymerizing the reactive mixture to form the ophthalmic device.

[0025] In another aspect, the present invention provides an ophthalmic device that is the reaction product of a reactive mixture comprising: a polymerizable high-energy light-absorbing compound; and one or more monomers suitable for manufacturing an ophthalmic device, wherein the ophthalmic device transmits: 45% or less of light with wavelengths from 280 nm to 399 nm; 1% to 70% of light with wavelengths from 400 nm to 409 nm; and at least 80% of light with wavelengths from 450 nm to 800 nm.

[0026] In another aspect, the present invention provides an ophthalmic device that is a polymerization product of a reactive mixture comprising one or more reactive components (such as a hydrophilic component and an organosilicon-containing compound), wherein the polymerization product contains one or more chromophores of formula IV as covalently bonded substituents.

[0027]

[0028] Where m, n, X, R1, R2, R5 and EWG are as defined in this paper. Attached Figure Description

[0029] Figure 1 The UV-VIS transmission spectra of exemplary compounds (B), (C) and (E) in 0.2 mM solutions in methanol are shown.

[0030] Figure 2 The UV-VIS transmission spectra of compounds (G), (H), and (J) in methanol and compound (L) in dichloromethane are shown.

[0031] Figure 3 The UV-VIS transmission spectra of exemplary silicone hydrogel contact lenses 9A and 9B are shown.

[0032] Figure 4 The UV-VIS transmission spectra of exemplary silicone hydrogel contact lenses 9A and 9C are shown.

[0033] Figure 5 The UV-VIS transmission spectra of exemplary silicone hydrogel contact lenses 9A and 9D are shown.

[0034] Figure 6 The UV-VIS transmission spectra of exemplary silicone hydrogel contact lenses 10A and 10B are shown.

[0035] Figure 7 The UV-VIS transmission spectra of exemplary silicone hydrogel contact lenses 10A and 10C are shown.

[0036] Figure 8 The UV-VIS transmission spectra of exemplary silicone hydrogel contact lenses 10A and 10B are shown.

[0037] Figure 9 The UV-VIS transmission spectrum of a silicone hydrogel contact lens (11A) containing compound (B) after exposure to direct sunlight is shown.

[0038] Figure 10 The UV-VIS transmission spectrum of a silicone hydrogel contact lens (11B) containing compound (B) after exposure to indoor lighting is shown. Detailed Implementation

[0039] It should be understood that the present invention is not limited to the details of the construction or process steps set forth in the following description. Using the teachings herein, the present invention can have other embodiments and can be practiced or implemented in various ways.

[0040] As described above, in one aspect, the present invention provides a UV / HEV absorbing compound. This compound contains polymerizable functionality. It has been found that ophthalmic devices absorbing large amounts of UV light and some amounts of HEV light can be readily prepared, as described herein.

[0041] It was also found that light-absorbing compounds can be selected to provide targeted absorption of UV and / or high-energy visible light (e.g., increasing UV absorption and decreasing HEV absorption, or increasing HEV absorption, etc.). Such targeting can be achieved, for example, using compounds of formula I containing a heterocyclic core chromophore. For example, as described in more detail below, compounds of formula I where the heteroatom (X in formula I) is sulfur can absorb HEV light. On the other hand, compounds of formula I where the heteroatom is oxygen (X is O) can absorb less HEV light but more UV light. Therefore, the compound can be used to absorb selected regions of UV and / or HEV light, or they can be mixed together or mixed with other absorbing compounds to provide broad-spectrum protection (e.g., UV and HEV light). Advantageously, the compound exhibits transmission cutoff at visible wavelengths of 450 nm or longer (e.g., they absorb 20% or less).

[0042] Further investigation revealed that the compounds of Formula I are substantially photostable, meaning that the compounds do not undergo significant degradation over time when incorporated into ophthalmic devices and when exposed to lighting such as indoor or outdoor illumination. This photostable stability can be determined by measuring the UV / Vis transmission spectrum of the ophthalmic device over a test period, such as 21 weeks. Significant changes in the spectrum during the test period indicate a lack of photostable stability. As an example, ophthalmic devices (such as contact lenses) containing the compounds of the present invention exhibit an average transmittance change of 5% or less, preferably 2% or less, more preferably 0.5% or less, and even more preferably 0.4% or less in the wavelength range of 380 nm to 700 nm when exposed to indoor office lighting at room temperature for 21 weeks. As another example, ophthalmic devices (such as contact lenses) containing the compounds of the present invention exhibit an average transmittance change of 5% or less, preferably 2% or less, more preferably 1% or less, and even more preferably 0.7% or less in the wavelength range of 400 nm to 500 nm when exposed to indoor office lighting at room temperature for 21 weeks. Such changes can be calculated as the absolute value of the difference between the average transmittance at time 21 weeks and time zero (within a specified wavelength range).

[0043] Therefore, the compounds of this invention can successfully absorb UV (UVA, UVB) and / or HEV while transmitting in the visible spectrum. These compounds are suitable for incorporation into a variety of products, including biomedical devices and ophthalmic devices.

[0044] The following definitions are provided relative to the terminology used in this disclosure.

[0045] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. The definition of a polymer conforms to those disclosed in the 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 Metanski. All publications, patent applications, patents, and other references mentioned herein are incorporated herein by reference.

[0046] As used herein, the term "(methyl)" refers to an optional methyl substitution. Therefore, terms such as "(meth)acrylate" refer to both methacrylate and acrylate.

[0047] Wherever the chemical structure is provided, it should be understood that any combination of alternatives to the substituents disclosed on the structure is permissible. Therefore, if the structure contains substituents R* and R**, each of which contains three lists of possible groups, disclosing nine combinations. The same applies to combinations of properties.

[0048] When the subscript is such as the general formula [***] n When "n" is used to describe the number of repeating units in the chemical formula of a polymer, the formula should be interpreted as representing the number-average molecular weight of the macromolecule.

[0049] The term "individual" includes both humans and vertebrates.

[0050] The term "biomedical device" refers to any article designed for use in or on mammalian tissues or body fluids, and preferably in or on human tissues or body fluids. Examples of such devices include, but are not limited to, wound dressings, sealants, tissue fillers, drug delivery systems, coatings, anti-adhesion barriers, catheters, implants, stents, and ophthalmic devices (such as intraocular lenses and contact lenses). Biomedical devices can be ophthalmic devices, specifically contact lenses, most specifically contact lenses made of silicone hydrogels or conventional hydrogels.

[0051] The term "ocular surface" includes the surface and glandular epithelial cells of the cornea, conjunctiva, lacrimal gland, accessory lacrimal gland, nasolacrimal duct, and meibomian gland, as well as their apical and basal stroma, lacrimal puncta, and adjacent or related structures, including the eyelids, which are connected by the continuity of epithelial cells, nerve innervation, and the endocrine and immune systems to form a functional system.

[0052] The term "ophthalmic device" refers to any device located in or on the eye or any part of the eye, including the surface of the eye. These devices can provide optical correction, cosmetic enhancement, improved vision, therapeutic benefits (e.g., as a bandage), or delivery of active ingredients, such as pharmaceutical and nutritional components, or any combination of the foregoing functions. 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, rigid contact lenses, hybrid contact lenses, intraocular lenses, and covering lenses. Ophthalmic devices may include contact lenses.

[0053] 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, drug or nutritional delivery, diagnostic evaluation or monitoring, ultraviolet light absorption, visible light or glare reduction, or any combination thereof. Contact lenses can be made 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, water content, light transmission, or combinations thereof.

[0054] The biomedical device, ophthalmic device, and lens of the present invention can be made of silicone hydrogel or conventional hydrogel. Silicone hydrogels typically contain at least one hydrophilic monomer and at least one silicone-containing component, which are covalently bonded to each other in a curing device.

[0055] "Target macromolecule" refers to a macromolecule synthesized from a mixture of reactive monomers, including monomers, macromonomers, prepolymers, crosslinking agents, initiators, additives, diluents, etc.

[0056] The term "polymerizable compound" refers to a compound containing one or more polymerizable groups. This term encompasses, for example, monomers, macromonomers, oligomers, prepolymers, crosslinking agents, etc.

[0057] A “polymerizable group” is a group that can undergo chain-growth polymerization (such as radical and / or cationic polymerization), for example, a carbon-carbon double bond that can polymerize when subjected to radical polymerization initiation conditions. Non-limiting examples of polymerizable groups include (meth)acrylates, styrene, vinyl ethers, (meth)acrylamide, N-vinyl lactam, N-vinylamide, O-vinyl carbamate, O-vinyl carbonate, and other vinyl groups. Preferably, polymerizable groups include (meth)acrylates, (meth)acrylamide, N-vinyl lactam, N-vinylamide, and styrene functional groups, as well as mixtures of any of the foregoing. More preferably, polymerizable groups include (meth)acrylates, (meth)acrylamide, and mixtures thereof. The polymerizable group can be unsubstituted or substituted. For example, the nitrogen atom in (meth)acrylamide may be bonded to hydrogen, or the hydrogen may be replaced by an alkyl or cycloalkyl group (which itself may be further substituted).

[0058] Any type of free radical polymerization can be used, including but not limited to bulk, solution, suspension and emulsion, as well as any of the controlled free radical polymerization methods, such as stable free radical polymerization, nitro oxygen-mediated living polymerization, atom transfer radical polymerization, reversible addition-fragmentation chain transfer polymerization, organotellurium-mediated living radical polymerization, etc.

[0059] "Monomer" is a monofunctional molecule that can undergo chain-growth polymerization (specifically free radical polymerization) to form a repeating unit in the chemical structure of a target macromolecule. Some monomers have difunctional impurities that can act as crosslinking agents. "Hydrophilic monomer" is also a monomer that produces a clear single-phase solution when mixed with deionized water at a concentration of 5% by weight at 25°C. "Hydrophilic component" is a monomer, macromonomer, prepolymer, initiator, crosslinking agent, additive, or polymer that produces a clear single-phase solution when mixed with deionized water at a concentration of 5% by weight at 25°C. "Hydrophobic component" is a monomer, macromonomer, prepolymer, initiator, crosslinking agent, additive, or polymer that is slightly soluble or insoluble in deionized water at 25°C.

[0060] "Macromolecules" are organic compounds with a number average molecular weight greater than 1500, and can be reactive or non-reactive.

[0061] A "maoromonomer" is a macromolecule having a repeating unit in its chemical structure that can undergo chain-growth polymerization (specifically, free radical polymerization) to form a target macromolecule. Typically, the chemical structure of a macromonomer differs from that of the target macromolecule; in other words, the repeating units of the macromonomer's side groups differ from those of the target macromolecule or its main chain. The difference between a monomer and a macromonomer lies solely in one of these: chemical structure, molecular weight, and the molecular weight distribution of the side groups. Therefore, and as used herein, patent literature occasionally defines a monomer as a polymerizable compound with a relatively low molecular weight of about 1,500 Daltons or less, which essentially includes some macromonomers. Specifically, monomethacryloyloxypropyl-terminated mono-n-butyl-terminated polydimethylsiloxane (mPDMS) (mM = 500-1500 g / mol) and mono-(2-hydroxy-3-methacryloyloxypropyl)-propyl ether-terminated mono-n-butyl-terminated polydimethylsiloxane (OH-mPDMS) can be referred to as monomers or macromonomers. Furthermore, patent literature occasionally defines a macromonomer as having one or more polymerizable groups, thus substantially extending the general definition of a macromonomer to include prepolymers. Therefore, and as used herein, bifunctional and multifunctional macromonomers, prepolymers, and crosslinking agents are used interchangeably.

[0062] "Components containing organosilicon" are monomers, macromonomers, prepolymers, crosslinking agents, initiators, additives or polymers having at least one siloxane bond in a reactive mixture, wherein the at least one siloxane bond is typically in the form of a silanoxy group, a siloxane group, a carbosiloxane group, or a mixture thereof.

[0063] Examples of organosilicon-containing components that can be used in this invention are found in U.S. Patent 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, and 5,849,81. 1, 5,962,548, 5,965,631, 5,998,498, 6,367,929, 6,822,016, 6,943,203, 6,951,894, 7,052,131, 7,247,692, 7,396,890, 7,461,937, 7,468,398, 7,538,146, 7,553,880, 7,572,841, 7,6 66,921, 7,691,916, 7,786,185, 7,825,170, 7,915,323, 7,994,356, 8,022,158, 8,163,206, 8,273,802, 8,399,538, 8,415,404, 8,420,711, 8,450,387, 8,487,058, 8,568,626, 8,937,11 The patents referred to herein are 0, 8,937,111, 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. The entire contents of these patents are incorporated herein by reference.

[0064] A "polymer" is a target macromolecule composed of repeating units of monomers used during polymerization.

[0065] A homopolymer is a polymer made from one monomer; a copolymer is a polymer made from two or more monomers; a terpolymer is a polymer made from three monomers. A block copolymer is composed of blocks or segments with different compositions. A diblock copolymer has two blocks. A triblock copolymer has three blocks. A comb-like or graft copolymer is made from at least one macromonomer.

[0066] A “repeating unit” is the smallest group of atoms in a polymer, which corresponds to the polymerization of a specific monomer or macromonomer.

[0067] An "initiator" is a molecule that can decompose into free radicals, which can then react with monomers to initiate free radical polymerization. Thermal initiators decompose at a rate depending on temperature; typical examples include azo compounds such as 1,1′-azobisisobutyronitrile and 4,4′-azobis(4-cyanopentanoic 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 via photochemical methods; typical examples include benzoyl, benzoin, acetophenone, benzophenone, camphorquinone, and mixtures thereof, as well as various monoacyl and diacylphosphine oxides and their combinations.

[0068] A "crosslinking agent" is a difunctional or polyfunctional monomer or macromonomer that can undergo free radical polymerization at two or more sites on a molecule to form branch points and polymer networks. Common examples include ethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, methylenebisacrylamide, and triallyl cyanurate.

[0069] "Prepolymer" is the reaction product of a monomer that contains residual polymerizable groups that can undergo further reactions to form a polymer.

[0070] A "polymer network" is a cross-linked macromolecule that can swell in a solvent but cannot dissolve. A "hydrogel" is a polymer network that swells in water or an aqueous solution, typically absorbing at least 10% by weight of water. An "organosilicon hydrogel" is a hydrogel made from at least one component containing organosilicon and at least one hydrophilic component. The hydrophilic component may also include a non-reactive polymer.

[0071] "Conventional hydrogels" refer to polymer networks made from components that do not contain any siloxy, siloxane, or carbosiloxane groups. Conventional hydrogels are prepared from reactive mixtures containing 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, 5,039,459, 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, etanercept, genifircept, hilafilcon, linifircept, nesofilcon, omafilcon, polymacon, and veficon, including all their variations.

[0072] "Organosilicon hydrogel" refers to a polymer network made of at least one hydrophilic component and at least one component containing organosilicon. Examples of organosilicon hydrogels include acquafilcon, asmofilcon, balafilcon, comfilcon, delefilcon, enfilcon, fanfilcon, formofilcon, galyfilcon, lotrafilcon, narafilcon, riofilcon, samfilcon, senofilcon, somofilcon, and stenfilcon, including all their variants, as well as those such as those in U.S. Patent Nos. 4,659,782, 4,659,783, 5,244,981, 5,314,960, 5,331,067, 5,371,147, 5,998,498, 6,087,415, 5,760,100, 5,776,999, 5,789,461, 5,849,811, and 5,965,631. 6,367,929, 6,822,016, 6,867,245, 6,943,203, 7,247,692, 7,249,848, 7,553,880, 7,666,921, 7,786,185, 7,956.131, 8,022,158, 8,273,802, 8,399,538, 8,470,906, 8,450,387, 8,487,058, 8,507 Organosilicon hydrogels prepared as described in WO 03 / 22321, WO 2008 / 061992 and US 2010 / 0048847. The entire contents of these patents are incorporated herein by reference.

[0073] An "interpenetrating polymer network" comprises two or more networks that are at least partially interwoven at the molecular scale but not covalently bonded to each other and cannot be separated without hindering chemical bonding. A "semi-interpenetrating polymer network" comprises one or more networks and one or more polymers characterized by some mixing at the molecular level between at least one network and at least one polymer. A mixture of different polymers is a "polymer blend." Technically, a semi-interpenetrating network is a polymer blend, but in some cases, the polymers are entangled together such that they cannot be easily removed.

[0074] The terms "reactive mixture" and "reactive monomer mixture" refer to mixtures (both reactive and non-reactive) of components (mixed together and subjected to polymerization conditions) that form the conventional or silicone hydrogels of the present invention, as well as biomedical devices, ophthalmic devices, and contact lenses made therefrom. Reactive monomer mixtures may contain reactive components (such as monomers, macromonomers, prepolymers, crosslinking agents and initiators, additives (such as wetting agents), polymers, dyes, light-absorbing compounds (such as UV absorbers), pigments, dyes, and photochromic compounds, any of which may be reactive or non-reactive but are capable of being retained in the resulting biomedical device) as well as pharmaceutical and nutritional formulation compounds and any diluents. It should be understood that a wide range of additives may be added based on the resulting biomedical device and its intended use. The concentrations of the components in the reactive mixture are expressed as a weight percentage of all components in the reactive mixture (excluding diluents). When diluents are used, their concentrations are expressed as a weight percentage based on the amount of all components in the reactive mixture and the diluent.

[0075] "Reactive component" is a component in a reactive mixture that becomes part of the chemical structure of the polymer network of the resulting hydrogel through covalent bonding, hydrogen bonding, electrostatic interaction, the formation of interpenetrating polymer networks, or any other means.

[0076] The term "silicone hydrogel contact lens" refers to a hydrogel contact lens made from at least one compound containing organosilicon. Compared to conventional hydrogels, silicone hydrogel contact lenses typically have improved oxygen permeability. Silicone hydrogel contact lenses utilize both their water and polymer contents to deliver oxygen to the eye.

[0077] The term "multifunctional" refers to a component having two or more polymerizable groups. The term "monofunctional" refers to a component having only one polymerizable group.

[0078] The term "halogen" or "halogenated group" refers to fluorine, chlorine, bromine, and iodine.

[0079] "alkyl" means a straight-chain or branched alkyl group containing a specified number of carbon atoms with optional substitutions. If no number is specified, the alkyl group (including any optional substituents on the alkyl group) may contain 1 to 16 carbon atoms. Preferably, the alkyl group contains 1 to 10 carbon atoms, alternatively 1 to 8 carbon atoms, alternatively 1 to 6 carbon atoms, or alternatively 1 to 4 carbon atoms. Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl and tert-butyl, pentyl, hexyl, heptyl, 3-ethylbutyl, etc. Examples of substituents on the alkyl group include one, two, or three groups independently selected from: hydroxyl, amino, amide, oxa, carboxyl, alkylcarboxyl, carbonyl, alkoxy, alkylthio, carbamate, carbonate, halogen, phenyl, benzyl, and combinations thereof. "Alkylene" refers to divalent alkyl groups, such as -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH2CH(CH3)CH2-, and -CH2CH2CH2CH2-.

[0080] "Haloalkyl" refers to an alkyl group as defined above, substituted with one or more halogen atoms, wherein each halogen is independently F, Cl, Br, or I. The 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" means a divalent haloalkyl group, such as -CH2CF2-.

[0081] “Cycloalkyl” refers to a cyclic hydrocarbon with optional substitutions containing a specified number of cyclic carbon atoms. If no number is specified, a cycloalkyl group may contain 3 to 12 cyclic carbon atoms. Preferred are C3-C8 cycloalkyl groups, C3-C7 cycloalkyl groups, more preferably C4-C7 cycloalkyl groups, and even more preferably C5-C6 cycloalkyl groups. Examples of cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. Examples of substituents on a cycloalkyl group include one, two, or three groups independently selected from: alkyl, hydroxyl, amino, amide, oxa, carbonyl, alkoxy, alkylthio, amide, carbamate, carbonate, halogen, phenyl, benzyl, and combinations thereof. “Cycloalkylene” means a divalent cycloalkyl group, such as 1,2-cyclohexylene, 1,3-cyclohexylene, or 1,4-cyclohexylene.

[0082] "Heterocyclic alkyl" refers to a cycloalkyl ring or ring system as defined above, in which at least one ring carbon has been replaced by a heteroatom selected from nitrogen, oxygen, and sulfur. The heterocyclic alkyl ring may optionally be fused to or otherwise connected to other heterocyclic alkyl rings and / or non-aromatic hydrocarbon rings and / or benzene rings. Preferred heterocyclic alkyl groups have 5 to 7 members. More preferably, heterocyclic alkyl groups have 5 or 6 members. Heterocyclic alkylene refers to a divalent heterocyclic alkyl group.

[0083] "Aryl" refers to an optionally substituted aromatic hydrocarbon ring system containing at least one aromatic ring. An aryl group contains a specified number of ring carbon atoms. If no number is specified, an aryl group may contain 6 to 14 ring carbon atoms. The aromatic ring may optionally be fused or otherwise attached to other aromatic or non-aromatic hydrocarbon rings. Examples of aryl groups include phenyl, naphthyl, and biphenyl. Preferred examples of aryl groups include phenyl. Examples of substituents on the aryl group include one, two, or three groups independently selected from: alkyl, hydroxyl, amino, amide, oxa, carboxyl, alkylcarboxyl, carbonyl, alkoxy, alkylthio, carbamate, carbonate, halogen, phenyl, benzyl, and combinations thereof. "Arylene" means a divalent aryl group, such as 1,2-phenylene, 1,3-phenylene, or 1,4-phenylene.

[0084] "Heteroaryl" refers to an aryl ring or ring system as defined above, in which at least one ring carbon atom has been replaced by a heteroatom selected from nitrogen, oxygen, and sulfur. Heteroaryl rings may be fused or otherwise attached to one or more heteroaryl rings, aromatic or non-aromatic hydrocarbon rings, or heterocyclic alkyl rings. Examples of heteroaryl groups include pyridinyl, furanyl, and thiopheneyl. "Heteroarylene" refers to a divalent heteroaryl group.

[0085] "Alkoxy" refers to an alkyl group that is connected to the parent molecule via an oxygen bridge. Examples of alkoxy groups include, for example, methoxy, ethoxy, propoxy, and isopropoxy. "Alkthio" refers to an alkyl group that is connected to the parent molecule via a sulfur bridge. Examples of alkthio groups include, for example, methylthio, ethylthio, n-propylthio, and isopropylthio. "Aryloxy" refers to an aryl group that is connected to the parent molecule via an oxygen bridge. Examples include phenoxy. "Cycloalkoxy" refers to a cycloalkyl group that is connected to the parent molecule via an oxygen bridge.

[0086] "Alkylamine" refers to an alkyl group that is attached to the parent molecule via a -NH bridge. Alkylene amines refer to divalent alkylamine groups, such as -CH2CH2NH-.

[0087] "Siloxane" refers to a structure having at least one Si-O-Si bond. Therefore, for example, a siloxane group means a group having at least one Si-O-Si group (i.e., a siloxane group), and a siloxane compound means a compound having at least one Si-O-Si group. "Siloxane" encompasses 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 siloxane group is replaced by an independently selected RA group (where RA is defined as in options (b) to (i) of formula A) to complete its valence.

[0088] "Silyl" refers to the structure of formula R3Si-, and "siloxy" refers to the structure of formula R3Si-O-, wherein 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.

[0089] "Alkyloxy group" refers to a compound with the general formula -(alkylene-O-). p - or -(O-alkylene) p -A group, wherein the alkylene group is as defined above, and 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, wherein each alkylene group is independently and optionally substituted by one or more groups, which are independently selected from hydroxyl, halogen (e.g., fluorine), amino, amide, ether, carbonyl, carboxyl, and combinations thereof. If p is greater than 1, each alkylene group may be the same or different, and the alkoxide group may be block or random. When the alkoxide group forms a terminal group in the molecule, the terminal end of the alkoxide group may be, for example, a hydroxyl or alkoxy group (e.g., HO-[CH2CH2O)). p -or CH3O-[CH2CH2O] p Examples of alkene oxides include poly(ethylene oxide), poly(propylene oxide), poly(butylene oxide), and poly(ethylene oxide-co-propylene oxide).

[0090] "Oxyalkylene" refers to an alkylene group as defined above in which one or more non-adjacent CH2 groups have been replaced by an oxygen atom, such as -CH2CH2OCH(CH3)CH2-. "Thioalkylene" refers to an alkylene group as defined above in which one or more non-adjacent CH2 groups have been replaced by a sulfur atom, such as -CH2CH2SCH(CH3)CH2-.

[0091] The term "linking group" refers to the portion that connects a polymerizable group to a parent molecule. The linking group can be any portion compatible with the compound, which is part of the compound and does not undesirably interfere with the polymerization of the compound, and is stable under polymerization conditions and under conditions used for processing and storing the final product. For example, the linking group can be a chemical bond, or it can include one or more alkylene groups, haloalkylene groups, amides, amines, alkylamines, carbamates, esters (-CO2-), arylenes, heteroarylenes, cycloalkylenes, heterocycloalkylenes, alkoxy groups, oxaalkylenes, thiaalkylenes, haloalkoxy groups (alkoxy groups substituted with one or more halogen groups, such as -OCF2-, -OCF2CF2-, -OCF2CH2-), siloxanes, alkylsiloxanes, or combinations thereof. The linking group may optionally be substituted with one or more substituent groups. Suitable substituent groups may include those independently selected from alkyl, halogen (e.g., fluorine), hydroxyl, HO-alkeneoxy, MeO-alkeneoxy, siloxane, silanoxy, silanoxy-alkeneoxy-, silanoxy-alkylene-alkeneoxy- (wherein more than one alkeneoxy group may be present, and where each methylene group in the alkylene and alkeneoxy groups is independently and optionally substituted with a hydroxyl group), ether, amine, carbonyl, urethane, and combinations thereof. Linking groups may also be replaced by polymerizable groups such as (meth)acrylates (in addition to the polymerizable groups to which the linking group is attached).

[0092] Preferred linking groups include C1-C8 alkylene groups (preferably C2-C6 alkylene groups) and C1-C8 oxaalkylene groups (preferably C2-C6 oxaalkylene groups), each optionally substituted with one or two groups independently selected from hydroxyl and silanoxy groups. Preferred linking groups also include carboxylic esters, amides, C1-C8 alkylene-carboxylic ester-C1-C8 alkylene groups, or C1-C8 alkylene-amide-C1-C8 alkylene groups.

[0093] When the linking group is composed of a combination of moieties as described above (e.g., alkylene and cycloalkylene), the moieties can be present in any order. For example, if L indicates -alkylene-cycloalkylene- in formula E below, then Rg-L can be Rg-alkylene-cycloalkylene- or Rg-cycloalkylene-alkylene-. Nevertheless, the listed order indicates the preferred order in which the terminal polymerizable group (Rg or Pg) attached to the linking group first appears in the compound. For example, if in formula E, L and L 2 If both are indicated as alkylene-cycloalkylene, then Rg-L is preferably Rg-alkylene-cycloalkylene-and-L 2 -Rg is preferably -cycloalkylene-alkylene-Rg.

[0094] The term "electron-withdrawing group" (EWG) refers to a chemical group that withdraws electrons from the atom or group of atoms to which it is attached. Examples of EWGs include, but are not limited to, cyano, amide, ester, ketone, or aldehyde groups. A preferred EWG is a cyano (CN).

[0095] The terms "high-energy radiation absorber," "UV / HEV absorber," or "high-energy light absorbing compound" refer to chemical materials that absorb ultraviolet light, high-energy visible light, or both, at various wavelengths. A material's ability to absorb certain wavelengths of light can be determined by measuring its UV / Vis transmission spectrum. A compound that exhibits no absorption at a specific wavelength will exhibit essentially 100% transmittance at that wavelength. Conversely, a compound that completely absorbs light at a specific wavelength will exhibit essentially 0% transmittance at that wavelength. If the transmittance of a material is expressed as a percentage of a specific wavelength range, it should be understood that the material exhibits a percentage of transmittance at all wavelengths within that range.

[0096] Unless otherwise specified, ratios, percentages, parts, etc. are by weight.

[0097] Unless otherwise specified, a numerical range (e.g., "2 to 10") includes numbers within a defined range (e.g., 2 and 10).

[0098] As described above, one aspect of 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 manufacturing an ophthalmic device, wherein the ophthalmic device transmits: 45% or less of light with wavelengths from 280 nm to 399 nm; at least 1% and at most 70% of light with wavelengths from 400 nm to 409 nm; and at least 80% of light with wavelengths from 450 nm to 800 nm. Preferably, the ophthalmic device also transmits at least 10% and at most 95% of light with wavelengths from 410 nm to 424 nm. More preferably, the ophthalmic device transmits at least 50% of light with wavelengths from 425 nm to 449 nm. More preferably, the ophthalmic device transmits 10% or less of light with wavelengths from 200 nm to 279 nm.

[0099] Preferably, the ophthalmic device has a transmittance of 5% or less, or 1% or less, in the 200nm to 279nm range. Alternatively, preferably, the transmittance is less than 1%.

[0100] Preferably, the transmittance of the ophthalmic device in the 280nm to 399nm range is 35% or less, or 25% or less, or 20% or less, or 10% or less, or 5% or less, or 1% or less.

[0101] Preferably, the transmittance of the ophthalmic device in the 400 nm to 409 nm range is at least 2%, at least 3%, or at least 4%. More preferably, the transmittance of the ophthalmic device in the 400 nm to 409 nm range is at most 60%, at most 50%, at most 40%, at most 30%, or at most 20%.

[0102] Preferably, the ophthalmic device has a transmittance of at least 15% in the 410 nm to 424 nm range. More preferably, the ophthalmic device has a transmittance of at most 85%, at most 75%, or at most 65% in the 410 nm to 424 nm range.

[0103] Preferably, the ophthalmic device has a transmittance of at least 60% in the 425 nm to 449 nm range.

[0104] Preferably, the ophthalmic device has a transmittance of at least 85% in the 450 nm to 800 nm range.

[0105] The preferred ophthalmic device is a contact lens, more preferably a soft hydrogel contact lens. The aforementioned transmission wavelength and percentage can be measured on lenses of various thicknesses. For example, the center thickness can be 80 to 100 micrometers, or 90 to 100 micrometers, or 90 to 95 micrometers. One or more polymerizable high-energy light-absorbing compounds of various concentrations can be used to achieve the above results. For example, the concentration can be in the range of at least 0.1% or at least 2% and at most 10% or at most 5% based on the weight percentage of all components (excluding diluent) in the reactive mixture. Typical concentrations can be in the range of 1% to 5%.

[0106] This invention also provides a UV / HEV absorbing compound of formula I:

[0107]

[0108] in:

[0109] m and n are independently 0, 1, 2, 3 or 4;

[0110] T represents a chemical bond, O, or NR;

[0111] X is O, S, NR, SO, or SO2;

[0112] Y is a linking group;

[0113] P g It is a polymerizable group;

[0114] R is independently H, C1-C6 alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, or YP each time it appears. g ;

[0115] When R exists 1 and R2 At that time, R 1 and R 2 Each time it appears independently of C1-C6 alkyl, C1-C6 alkoxy, C1-C6 alkylthio, C3-C7 cycloalkyl, aryl (preferably unsubstituted phenyl or phenyl substituted with alkyl or halogen), halogen, hydroxyl, amino, NR 3 R 4 Or benzyl, where R 3 and R 4 Independently H or C1-C6 alkyl, or two adjacent R 1 Or R 2 The groups, together with the carbon atoms they are attached to, combine to form cycloalkyl or aryl rings; and

[0116] EWG is an electron-withdrawing group.

[0117] The compound of formula I preferably contains one or two YP. g More preferably, the compound contains a YP group. g Group.

[0118] Formula I-1. Compounds of Formula I may include compounds of Formula I-1, which are compounds of Formula I in which X is S.

[0119] I-2. Compounds of formula I may include compounds of formula I-2, which are compounds of formula I in which X is O.

[0120] I-3. Compounds of Formula I may include compounds of Formula I-3, wherein X is NR, preferably NH or N-alkyl, of Formula I.

[0121] I-4. Compounds of Formula I may include compounds of Formula I-4, which are compounds of Formula I in which X is SO.

[0122] I-5. Compounds of Formula I may include compounds of Formula I-5, which are compounds of Formula I in which X is SO2.

[0123] I-6. Compounds of formula I, I-1, I-2, I-3, I-4 and I-5 may include compounds of formula I-6, which are compounds of formula I, I-1, I-2, I-3, I-4 or I-5 in which m and n are independently 0 or 1, or alternatively both 0.

[0124] I-7. Compounds of formulas I, I-1, I-2, I-3, I-4, and I-5 may include compounds of formula I-7, wherein m is 1 and R 1 Compounds of formula I, I-1, I-2, I-3, I-4 or I-5 that are C1-C6 alkyl, preferably ethyl or methyl.

[0125] I-8. Compounds of formulas I, I-1, I-2, I-3, I-4, I-5, and I-7 may include compounds of formula I-8, wherein n is 1 and R 2 Compounds of formula I, I-1, I-2, I-3, I-4, I-5 or I-7 that are C1-C6 alkyl, preferably ethyl or methyl.

[0126] I-9. Compounds of formulas 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 formulas I, I-1, I-2, I-3, I-4, I-5, I-6, I-7, or 1-8 wherein R is H or a C1-C6 alkyl group. Preferably, R in group T is H.

[0127] I-10. Compounds of formulas I, I-1, I-2, I-3, I-4, I-5, I-6, I-7, I-8, and I-9 may include compounds of formula I-10, wherein P is... g The polymerizable group, each time appearing independently, comprises compounds of formula I, I-1, I-2, I-3, I-4, I-5, I-6, I-7, I-8, or I-9, consisting of styrene, vinyl carbonate, vinyl ether, vinyl carbamate, N-vinyl lactam, N-vinylamide, (meth)acrylate, or (meth)acrylamide. The polymerizable group allows the compounds of the present invention to form covalent bonds when reacting with monomers, crosslinking agents, and other components commonly used in the manufacture of polymer devices. The compatibility of the compound with reactive mixtures can be controlled by selecting the polymerizable group (and linking group). Preferred polymerizable groups include (meth)acrylate or (meth)acrylamide. More preferably, the polymerizable group is methacrylate.

[0128] 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 may include compounds of formula I-11, wherein Y (linking group) is an alkylene, cycloalkylene, heterocycloalkylene, aryl (e.g., phenylene), heteroaryl, oxaalkylene, alkylene-amide-alkylene, alkylene-amine-alkylene, or a combination of any of the above groups, and is a compound of formula I, I-1, I-2, I-3, I-4, I-5, I-6, I-7, I-8, I-9, or I-10. Preferred linking groups include C1-C8 alkylene (e.g., ethylene or propyleneene), C1-C8 oxaalkylene, C1-C8 alkylene-amide-C1-C8 alkylene, and C1-C8 alkylene-amine-C1-C8 alkylene. Particularly preferred are C1-C8 alkylene groups, especially ethylene (CH2CH2-). When T is O in a compound of formula I, it is preferred to have a carbon atom that hinders the linking group to which O is attached. For example, if T is O and Y is an alkylene group, then the preferred alkylene group is -C(R H )2(CH2) x -, where R H It is independently a C1-C6 alkyl group (preferably independently methyl or ethyl), and x is 1 to 5.

[0129] 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 may 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 in which T is a chemical bond or NR (preferably NH).

[0130] 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 may 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 a cyano, amide, ester, ketone, or aldehyde. Preferably, EWG is a cyano.

[0131] Preferred compounds of formula I include compounds of formula II:

[0132]

[0133] in:

[0134] m and n are independently 0, 1, 2, 3 or 4;

[0135] T represents a chemical bond, O, or NR;

[0136] X is O, S, NR, SO, or SO2;

[0137] Y is a linking group;

[0138] P g It is a polymerizable group;

[0139] R is independently H, C1-C6 alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, or YP each time it appears. g ;and

[0140] When R exists 1 and R 2 At that time, R 1 and R 2 Each time it appears independently of C1-C6 alkyl, C1-C6 alkoxy, C1-C6 alkylthio, C3-C7 cycloalkyl, aryl (preferably unsubstituted phenyl or phenyl substituted with alkyl or halogen), halogen, hydroxyl, amino, NR 3 R 4 Or benzyl, wherein R 3 and R 4 Independently H or C1-C6 alkyl, or two adjacent R 1 Or R 2 The groups, together with the carbon atoms they are attached to, combine to form cycloalkyl or aryl rings. Compounds of Formula I preferably contain one or two YP groups. g More preferably, the compound contains a YP group. g Group.

[0141] Formula II-1. Compounds of Formula II may include compounds of Formula II-1, which are compounds of Formula II in which X is S.

[0142] II-2. Compounds of formula II may include compounds of formula II-2, which are compounds of formula II in which X is O.

[0143] II-3. Compounds of formula II may include compounds of formula II-3, wherein X is NR, preferably NH or N-alkyl of formula II.

[0144] II-4. Compounds of formula II may include compounds of formula II-4, which are compounds of formula II in which X is SO.

[0145] II-5. Compounds of formula II may include compounds of formula II-5, which are compounds of formula II in which X is SO2.

[0146] II-6. Compounds of formula II, II-1, II-2, II-3, II-4 and II-5 may include compounds of formula II-6, which are compounds of formula II, II-1, II-2, II-3, II-4 or II-5 in which m and n are independently 0 or 1, or alternatively both 0.

[0147] II-7. Compounds of formulas II, II-1, II-2, II-3, II-4, and II-5 may include compounds of formula II-7, wherein m is 1 and R 1 Compounds of formula II, II-1, II-2, II-3, II-4 or II-5 that are C1-C6 alkyl, preferably ethyl or methyl.

[0148] II-8. Compounds of formulas II, II-1, II-2, II-3, II-4, II-5, and II-7 may include compounds of formula II-8, wherein n is 1 and R 2 Compounds of formula II, II-1, II-2, II-3, II-4, II-5 or II-7 that are C1-C6 alkyl, preferably ethyl or methyl.

[0149] II-9. Compounds of formulas 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, wherein R is a H or a C1-C6 alkyl group of formula II, II-1, II-2, II-3, II-4, II-5, II-6, II-7, or II-8. Preferably, R in group T is H.

[0150] II-10. Compounds of formulas II, II-1, II-2, II-3, II-4, II-5, II-6, II-7, II-8, and II-9 may include compounds of formula II-10, wherein P is... g The polymerizable group, each time appearing independently, comprises compounds of formula II, II-1, II-2, II-3, II-4, II-5, II-6, II-7, II-8, or II-9, consisting of styrene, vinyl carbonate, vinyl ether, vinyl carbamate, N-vinyl lactam, N-vinylamide, (meth)acrylate, or (meth)acrylamide. The polymerizable group allows the compounds of the present invention to form covalent bonds when reacting with monomers, crosslinking agents, and other components commonly used in the manufacture of polymer devices. The compatibility of the compound with reactive mixtures can be controlled by selecting the polymerizable group (and linking group). Preferred polymerizable groups include (meth)acrylate or (meth)acrylamide. More preferably, methacrylate is a polymerizable group.

[0151] 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 may include compounds of formula II-11, wherein Y (linking group) is an alkylene, cycloalkylene, heterocycloalkylene, aryl (e.g., phenylene), heteroaryl, oxaalkylene, alkylene-amide-alkylene, alkylene-amine-alkylene, or a combination of any of the above groups, and is a compound of formula II, II-1, II-2, II-3, II-4, II-5, II-6, II-7, II-8, II-9, or II-10. Preferred linking groups include C1-C8 alkylene (e.g., ethylene or propylene), C1-C8 oxaalkylene, C1-C8 alkylene-amide-C1-C8 alkylene, and C1-C8 alkylene-amine-C1-C8 alkylene. Particularly preferred are C1-C8 alkylene groups, especially ethylene (CH2CH2-). When T is O in the compound of formula II, it is preferred to be a carbon atom that hinders the linking group to which O is attached. For example, if T is O and Y is an alkylene group, then the preferred alkylene group is -C(R H )2(CH2) x -, where R H It is independently a C1-C6 alkyl group (preferably independently methyl or ethyl), and x is 1 to 5.

[0152] 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 may 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 in which T is a chemical bond or NR (preferably NH).

[0153] Preferred compounds of formula I and II include compounds of formula III:

[0154]

[0155] in:

[0156] m and n are independently 0, 1, 2, 3 or 4;

[0157] X is O, S, NR, SO, or SO2;

[0158] Y is a linking group;

[0159] P g It is a polymerizable group;

[0160] R is independently H, C1-C6 alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, or YP each time it appears. g ;and

[0161] When R exists 1 and R 2 At that time, R 1 and R 2 Each time it appears independently of C1-C6 alkyl, C1-C6 alkoxy, C1-C6 alkylthio, C3-C7 cycloalkyl, aryl (preferably unsubstituted phenyl or phenyl substituted with alkyl or halogen), halogen, hydroxyl, amino, NR 3 R 4 Or benzyl, where R 3 and R 4 Independently H or C1-C6 alkyl, or two adjacent R 1 Or R 2 The groups, together with the carbon atoms they are attached to, combine to form cycloalkyl or aryl rings. Compounds of Formula II preferably contain one or two YP groups. g More preferably, the compound contains a YP group. g Group.

[0162] Formula III-1. Compounds of Formula III may include compounds of Formula III-1, which are compounds of Formula III in which X is S.

[0163] III-2. Compounds of formula III may include compounds of formula III-2, which are compounds of formula III in which X is O.

[0164] III-3. Compounds of formula III may include compounds of formula III-3, wherein X is NR, preferably NH or N-alkyl of formula III.

[0165] III-4. Compounds of formula III may include compounds of formula III-4, which are compounds of formula III in which X is SO.

[0166] III-5. Compounds of formula III may include compounds of formula III-5, which are compounds of formula III in which X is SO2.

[0167] III-6. Compounds of formula III, III-1, III-2, III-3, III-4 and III-5 may include compounds of formula III-6, which are compounds of formula III, III-1, III-2, III-3, III-4 or III-5 in which m and n are independently 0 or 1, or alternatively both 0.

[0168] III-7. Compounds of formulas III, III-1, III-2, III-3, III-4, and III-5 may include compounds of formula III-7, wherein m is 1 and R 1 Compounds of formula III, III-1, III-2, III-3, III-4 or III-5 that are C1-C6 alkyl, preferably ethyl or methyl.

[0169] III-8. Compounds of formulas III, III-1, III-2, III-3, III-4, III-5, and III-7 may include compounds of formula III-8, wherein n is 1 and R 2 Compounds of formula III, III-1, III-2, III-3, III-4, III-5 or III-7 that are C1-C6 alkyl, preferably ethyl or methyl.

[0170] III-9. Compounds of formulas 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, wherein R is independently H or a C1-C6 alkyl group in each occurrence. Preferably, R is H in each occurrence. Preferably, R in group T is H.

[0171] III-10. Compounds of formulas III, III-1, III-2, III-3, III-4, III-5, III-6, III-7, III-8, and III-9 may include compounds of formula III-10, wherein P is... g The polymerizable group, each time appearing independently, comprises a compound of formula III, III-1, III-2, III-3, III-4, III-5, III-6, III-7, III-8, or III-9, consisting of styrene, vinyl carbonate, vinyl ether, vinyl carbamate, N-vinyl lactam, N-vinylamide, (meth)acrylate, or (meth)acrylamide. The polymerizable group allows the compounds of the present invention to form covalent bonds when reacting with monomers, crosslinking agents, and other components commonly used in the manufacture of polymer devices. The compatibility of the compound with reactive mixtures can be controlled by selecting the polymerizable group (and linking group). Preferred polymerizable groups include (meth)acrylate or (meth)acrylamide. More preferably, the polymerizable group is methacrylate.

[0172] III-11. Compounds of formulas III, III-1, III-2, III-3, III-4, III-5, III-6, III-7, III-8, III-9, and III-10 may include compounds of formula III-11, wherein Y (linking group) is an alkylene, cycloalkylene, heterocycloalkylene, aryl (e.g., phenylene), heteroaryl, oxaalkylene, alkylene-amide-alkylene, alkylene-amine-alkylene, or a combination of any of the above groups, and is a compound of formulas III, III-1, III-2, III-3, III-4, III-5, III-6, III-7, III-8, III-9, or III-10. Preferred linking groups include C1-C8 alkylene (e.g., ethylene or propylene), C1-C8 oxaalkylene, C1-C8 alkylene-amide-C1-C8 alkylene, and C1-C8 alkylene-amine-C1-C8 alkylene. C1-C8 alkylene groups are particularly preferred, especially ethylene (CH2CH2-).

[0173] Specific examples of compounds of Formula I include, but are not limited to, the compounds shown in Table 1.

[0174] Table 1

[0175]

[0176]

[0177]

[0178]

[0179]

[0180]

[0181]

[0182] 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 of the core tricyclic structure (X in Formula I). ​​For example, the compound of Formula I-1 (with sulfur as the heteroatom) can absorb HEV light. On the other hand, the compound of Formula 1-2 (with oxygen as the heteroatom) can absorb UV light and some HEV light, but to a lesser extent than the compound of Formula I-1.

[0183] By adding or changing the substituent R 1 and R 2This allows for, for example, obtaining long or short shifts, thereby providing additional tuning of the absorption properties of a given X in a compound of Formula I. Electron-donating substituents can, for example, cause 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 electron-withdrawing ability of the substituent and its position. For example, alkoxy substituents can result in a smaller red shift than, for example, an amino or alkylthio group at the same carbon center.

[0184] In the compounds of the present invention, the preferred X groups are S, O, and NR, with S and O being more preferred. However, additional oxidation states of sulfur, such as sulfoxides and sulfones, can also provide ways to modify the UV-VIS spectra of the compounds. Sulfoxides and sulfones have reduced electron density on sulfur atoms and can be used to produce short-shift (blue-shift) spectra.

[0185] Compounds of Formula I can be used in combination with other absorbing compounds to provide desired absorption properties. For example, a preferred composition may comprise a compound of Formula I-1 (where X is S) and a second compound that absorbs UV. The second compound may also 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 are classified into several classes, including but not limited to benzophenone, benzotriazole, triazine, substituted acrylonitrile, salicylic acid derivatives, benzoic acid derivatives, cinnamic acid derivatives, chalcone derivatives, diphenyl ethyl ketone derivatives, crotonic acid derivatives, or any mixture thereof. One class of preferred UV absorbing compounds is benzotriazole, such as Norbloc (2-(2′-hydroxy-5-methacryloyloxyethylphenyl)-2H-benzotriazole).

[0186] Particularly preferred compositions include ethyl 2-(2-cyano-2-(9H-thioxanthoxy-9-ylidene)acetamido)methacrylate and ethyl 2-(2-cyano-2-(9H-thioxanthoxy-9-ylidene)acetamido)methacrylate. Another preferred composition includes ethyl 2-(2-cyano-2-(9H-thioxanthoxy-9-ylidene)acetamido)methacrylate and 2-(2′-hydroxy-5-methacryloyloxyethylphenyl)-2H-benzotriazole. Yet another preferred composition includes N-(2-(2-cyano-2-(10-methylacridin-9(10H)ylidene)acetamido)ethyl)methacrylamide.

[0187] Compounds of Formula I can be prepared by those skilled in the art using methods described in the literature. By way of example, various compounds of Formula I in which EWG is a cyano group can be prepared as shown in Scheme 1 and the related description. Exemplary reagents and procedures for these reactions are shown in the working examples.

[0188]

[0189] Scheme 1 illustrates a method for preparing exemplary compounds of the present invention. Thus, the carbonyl moiety of the starting material is converted into a reactive dihalide intermediate, which reacts further with the active methylene compound without further purification or separation. The reaction 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 those skilled in the art using a process similar to that shown in Scheme 1 by appropriately substituting reagents.

[0190] 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 devices 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 amounts ranging from about 0.1 wt% to about 10 wt%, or from about 0.5 wt% to about 5 wt%, or from about 0.75 wt% to about 4 wt%. The upper limit is typically determined by the solubility of the compound in the reactive monomer mixture with other comonomers and / or diluents.

[0191] Preferably, the ophthalmic device contains the high-energy light-absorbing compound of the present invention. Various ophthalmic devices can be prepared, including rigid contact lenses, soft contact lenses, corneal inlays, corneal implants, intraocular lenses, or covering lenses. Preferably, the ophthalmic device is a soft contact lens that can be made from conventional or silicone hydrogel formulations.

[0192] The ophthalmic device of the present invention comprises a 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 manufacturing the desired ophthalmic device (also referred to herein as device-forming monomers or hydrogel-forming monomers), and optional components. Therefore, in addition to the polymerizable high-energy light-absorbing compounds as described above, the reactive mixture may also contain, for example, one or more of the following: hydrophilic components, hydrophobic components, silicone-containing components, wetting agents (such as polyamides), crosslinking agents, and other components (such as diluents and initiators).

[0193] hydrophilic components

[0194] Examples of suitable types of hydrophilic monomers include (meth)acrylates, styrene, vinyl ethers, (meth)acrylamide, N-vinyl lactam, N-vinylamide, N-vinylimide, N-vinyl urea, O-vinyl carbamate, O-vinyl carbonate, other hydrophilic vinyl compounds, and mixtures thereof.

[0195] Non-limiting examples of hydrophilic (meth)acrylates 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)... (Methacrylamide), N-(2-hydroxybutyl)methacrylamide, N-(3-hydroxybutyl)methacrylamide, N-(4-hydroxybutyl)methacrylamide, 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, glyceryl methacrylate, polyethylene glycol monomethacrylate, (meth)acrylic acid, vinyl acetate, acrylonitrile, and mixtures thereof.

[0196] Hydrophilic monomers can also be ionic, including anionic, cationic, amphoteric, betaine, and mixtures thereof. Non-limiting examples of such charged monomers include (meth)acrylic acid, N-[(ethoxy)carbonyl]-β-alanine (VINAL), 3-acrylamidopropionic acid (ACA1), 5-acrylamidovalerate (ACA2), 3-acrylamido-3-methylbutyric acid (AMBA), 2-(methacryloyloxy)ethyltrimethylammonium chloride (Q salt or METAC), 2-acrylamido-2-methylpropanesulfonic acid (AMPS), N-(2-carboxyethyl)-N,N-dimethyl-3-[(1-oxo-2-propen-1-yl)amino]-1-propaneammonium inner salt (CBT), N,N-dimethyl-N-[3-[(1-oxo-2-propen-1-yl)amino]propyl]-3-sulfo-1-propaneammonium inner salt (SBT), 4-hydroxy-N,N,N- Trimethyl-9-oxo-4-oxide 3,5-dioxa-8-aza-4-phospha-undeca-10-en-1-ammonium inner salt (9CI) (PBT), 2-methacryloyloxyethyl phosphocholine, 3-(dimethyl(4-vinylbenzyl)ammonium)propane-1-sulfonate (DMVBAPS), 3-((3-acrylamidopropyl)dimethylammonium)propane-1-sulfonate (AMPDAPS), 3-((3-methacrylamidopropyl)dimethylammonium)propane-1-sulfonate (MAMPDAPS), 3-((3-(acryloyloxy)propyl)dimethylammonium)propane-1-sulfonate (APDAPS), and 3-((3-(methacryloyloxy)propyl)dimethylammonium)propane-1-sulfonate (MAPDAPS).

[0197] Non-limiting examples of hydrophilic N-vinyl lactams and N-vinylamide monomers include: N-vinylpyrrolidone (NVP), N-vinyl-2-piperidinone, N-vinyl-2-caprolactam, N-vinyl-3-methyl-2-caprolactam, N-vinyl-3-methyl-2-piperidinone, N-vinyl-4-methyl-2-piperidinone, 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-2-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-vinylimidazolium, and mixtures thereof.

[0198] Non-limiting examples of hydrophilic O-vinylcarbamate and O-vinyl carbonate monomers include N-2-hydroxyethylvinylcarbamate and N-carboxy-β-alanine N-vinyl ester. Other examples of hydrophilic ethylene carbonate or vinyl carbamate monomers are disclosed in U.S. Patent 5,070,215. Hydrophilic azole monomers are disclosed in U.S. Patent 4,910,277.

[0199] Other hydrophilic vinyl compounds include ethylene glycol vinyl ether (EGVE), di(ethylene glycol) vinyl ether (DEGVE), allyl alcohol, and 2-ethyloxazoline.

[0200] The hydrophilic monomers can also be linear or branched macromonomers or prepolymers of poly(ethylene glycol) and poly(propylene glycol), or statistically random or block copolymers of ethylene oxide and propylene oxide, having polymerizable portions such as (meth)acrylates, styrene, vinyl ethers, (meth)acrylamide, N-vinylamide, etc. These polyether macromonomers have one polymerizable group; prepolymers may have two or more polymerizable groups.

[0201] 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.

[0202] Generally, there are no particular limitations on the amount of hydrophilic monomers present in the reactive monomer mixture. The amount of hydrophilic monomers can be selected based on the desired characteristics of the resulting hydrogel, including water content, transmittance, wettability, protein uptake, etc. Wetting ability can be measured by the contact angle, and the desired contact angle is less than about 100°, less than about 80°, and less than about 60°. Based on the total weight of the reactive components in the reactive monomer mixture, the hydrophilic monomers can be present, for example, in the range of about 0.1 wt% to about 100 wt%, alternatively in the range of about 1 wt% to about 80 wt%, alternatively in the range of about 5 wt% to about 65 wt%, alternatively in the range of about 40 wt% to about 60 wt%, or alternatively in the range of about 55 wt% to about 60 wt%.

[0203] Components containing organosilicon

[0204] The organosilicon-containing components applicable to the present invention comprise one or more polymerizable compounds, wherein each compound independently comprises at least one polymerizable group, at least one siloxane group, and one or more linking groups connecting the one or more polymerizable groups to the one or more siloxane groups. The organosilicon-containing components may, for example, contain 1 to 220 repeating siloxane units, such as groups as defined below. The organosilicon-containing components may also contain at least one fluorine atom.

[0205] The organosilicon-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 that connect the polymerizable group to the siloxane unit. The organosilicon-containing component may comprise: one or more polymerizable groups, which are independently (meth)acrylates, styrene, vinyl ethers, (meth)acrylamide, N-vinyl lactam, N-vinylamide, O-vinylcarbamate, O-vinyl carbonate, vinyl groups, or mixtures thereof; one or more optionally repeating siloxane units; and one or more linking groups that connect the polymerizable group to the siloxane unit.

[0206] The component containing organosilicon may include: one or more polymerizable groups, which are independently (meth)acrylate, (meth)acrylamide, N-vinyl lactam, N-vinylamide, styrene, or a mixture of the foregoing; one or more optionally repeating siloxane units; and one or more linking groups that connect the polymerizable groups to the siloxane units.

[0207] The component containing organosilicon may include: one or more polymerizable groups, which are independently (meth)acrylate, (meth)acrylamide, or a mixture of the foregoing; one or more optionally repeating siloxane units; and one or more linking groups that connect the polymerizable groups to the siloxane units.

[0208] Formula A. The component containing organosilicon may include one or more polymerizable compounds of Formula A:

[0209]

[0210] in:

[0211] At least one R A For formula R g -L- groups, where R g The group is a polymerizable group and L is a linking group, and the remaining R is a polymerizable group. A Each independently is:

[0212] (a)R g -L-,

[0213] (b) C1-C groups optionally substituted with one or more hydroxyl, amino, amide, oxo, carboxyl, alkylcarboxyl, carbonyl, alkoxy, amide, carbamate, carbonate, halogen, phenyl, benzyl, or combinations thereof 16 alkyl,

[0214] (c) C3-C groups optionally substituted with one or more alkyl, hydroxyl, amino, amide, oxo, carbonyl, alkoxy, amide, carbamate, carbonate, halogen, phenyl, benzyl, or combinations thereof 12 cycloalkyl,

[0215] (d) C6-C groups optionally substituted with one or more alkyl, hydroxyl, amino, amide, oxo, carboxyl, alkylcarboxyl, carbonyl, alkoxy, amide, carbamate, carbonate, halogen, phenyl, benzyl, or combinations thereof. 14 aryl group,

[0216] (e) Halogens,

[0217] (f) Alkoxy, cyclic alkoxy, or aryloxy groups,

[0218] (g)silyloxy,

[0219] (h) Alkylene-alkyl or alkoxy-alkylene-alkyl, such as poly(ethyleneoxyalkylene), poly(propyleneoxyalkylene), or poly(ethyleneoxy-co-propyleneoxyalkylene), or

[0220] (i) a monovalent siloxane chain comprising 1 to 100 repeating siloxane units, wherein the repeating siloxane units are optionally substituted with alkyl, alkoxy, hydroxyl, amino, oxa, carboxyl, alkylcarboxyl, alkoxy, amide, carbamate, halogen, or combinations thereof; and

[0221] n can be 0 to 500, or 0 to 200, or 0 to 100, or 0 to 20. It should be understood that when n is not 0, n is a distribution with a mode equal to the specified value. When n is 2 or greater, the SiO unit can have the same or different RA substituents, and if different RA substituents are present, the n group can be random or block configuration.

[0222] In Formula A, each of the three RAs may contain a polymerizable group, or alternatively, two RAs may each contain a polymerizable group, or alternatively, one RA may contain a polymerizable group.

[0223] Formula B. The organosilicon-containing component of Formula A can be a monofunctional polymerizable compound of Formula B:

[0224]

[0225] in:

[0226] Rg is a polymerizable group;

[0227] L is a linking group;

[0228] j1 and j2 are each independent integers from 0 to 220, provided that the sum of j1 and j2 is from 1 to 220;

[0229] R A1 R A2 R A3 R A4 R A5 and R A7 Each time it appears, it is independently a C1-C6 alkyl group or a C3-C alkyl group. 12 Cycloalkyl, C1-C6 alkoxy, C4-C 12Cyclic alkoxy groups, alkoxy-alkyleneoxy-alkyl groups, aryl groups (e.g., phenyl), aryl-alkyl groups (e.g., benzyl), haloalkyl groups (e.g., partially or fully fluorinated alkyl groups), silyloxy groups, fluorine groups, or combinations thereof, wherein each alkyl group in the foregoing groups is optionally substituted with one or more hydroxyl, amino, amide, oxa, carboxyl, alkylcarboxyl, carbonyl, alkoxy, carbamate, carbonate, halogen, phenyl, or benzyl groups; each cycloalkyl group is optionally substituted with one or more alkyl, hydroxyl, amino, amide, oxa, carbonyl, alkoxy, carbamate, carbonate, halogen, phenyl, or benzyl groups; and each aryl group is optionally substituted with one or more alkyl, hydroxyl, amino, amide, oxa, carboxyl, alkylcarboxyl, carbonyl, alkoxy, carbamate, carbonate, halogen, phenyl, or benzyl groups; and

[0230] R A6 It is siloxy, C1-C8 alkyl (e.g., C1-C4 alkyl or butyl or methyl) or aryl (e.g., phenyl), wherein the alkyl and aryl groups may optionally be substituted with one or more fluorine atoms.

[0231] Formula B-1. A compound of Formula B may include a compound of Formula B-1, wherein j1 is zero 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.

[0232] B-2. Compounds of formula B may include compounds of formula B-2, 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.

[0233] B-3. ​​Compounds of formula B, B-1, and B-2 may include compounds of formula B-3, wherein R is... A1 R A2 R A3 and R A4 Each occurrence is independently a compound of formula B, B-1, or B-2, which is a C1-C6 alkyl or siloxy group. Preferred alkyl groups are C1-C3 alkyl groups, or more preferably methyl groups. Preferred siloxy groups are trimethylsiloxy groups.

[0234] B-4. Compounds of formulas B, B-1, B-2, and B-3 may include compounds of formula B-4, wherein R is... A5 and R A7 Independently alkoxy-alkeneoxy-alkyl, preferably they independently have the formula CH3O-[CH2CH2O] p Compounds of formula B, B-1, B-2 or B-3 of methoxy-terminated poly(ethyleneoxyalkyl) compounds of formula B, B-1, B-2 or B-3 (where p is an integer from 1 to 50).

[0235] B-5. Compounds of formulas B, B-1, B-2, and B-3 may include compounds of formula B-5, wherein R is... A5 and R A7 Compounds of formula B, B-1, B-2 or B-3 that are independently siloxy groups (such as trimethylsiloxy groups).

[0236] B-6. Compounds of formulas B, B-1, B-2, and B-3 may include compounds of formula B-6, wherein R is... A5 and R A7 Compounds of formula B, B-1, B-2 or B-3 that are independently C1-C6 alkyl, alternatively C1-C4 alkyl, or alternatively butyl or methyl.

[0237] B-7. Compounds of formulas B, B-1, B-2, B-3, B-4, B-5, and B-6 may include compounds of formula B-7, wherein R is... A6 Compounds of formula B, B-1, B-2, B-3, B-4, B-5, or B-6, which are C1-C8 alkyl, preferably C1-C6 alkyl, more preferably C1-C4 alkyl (e.g., methyl, ethyl, n-propyl, or n-butyl). More preferably, R A6 It is n-butyl.

[0238] B-8. Compounds of formulas B, B-1, B-2, B-3, B-4, B-5, B-6, and B-7 may include compounds of formula B-8, wherein Rg comprises a styrene group, a vinyl carbonate, a vinyl ether, a vinyl carbamate, an N-vinyl lactam, an N-vinylamide, a (meth)acrylate, or a (meth)acrylamide. Preferably, Rg comprises a (meth)acrylate, a (meth)acrylamide, or a styrene group. More preferably, Rg comprises a (meth)acrylate or a (meth)acrylamide. When Rg is a (meth)acrylamide, the nitrogen group may be R... A9 Replace, where R A9 The alkyl group is H, C1-C8 alkyl (preferably C1-C4 alkyl, such as n-butyl, n-propyl, methyl or ethyl), or C3-C8 cycloalkyl (preferably C5-C6 cycloalkyl), wherein the alkyl and cycloalkyl groups are optionally substituted by one or more groups, said groups being independently selected from hydroxyl, amide, ether, silyl (e.g., trimethylsilyl), siloxy (e.g., trimethylsiloxy), alkyl-siloxane (wherein the alkyl group is optionally substituted by fluorine), aryl-siloxane (wherein the aryl group is optionally substituted by fluorine), and silyl-oxaalkylene (wherein the oxaalkylene is optionally substituted by hydroxyl).

[0239] 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 comprises an alkylene group (preferably C1-C4 alkylene), a cycloalkylene group (preferably C5-C6 cycloalkylene), an alkoxide group (preferably ethyloxide), a haloalkoxide group (preferably haloethyloxide), an amide, an oxaalkylene group (preferably containing 3 to 6 carbon atoms), a siloxane group, an alkylsiloxane group, a carbamate, an alkylamine group (preferably C1-C6 alkylamine), or a combination of two or more thereof (wherein the linking group is optionally substituted by one or more substituents independently selected from alkyl, hydroxyl, ether, amine, carbonyl, siloxy, and carbamate).

[0240] 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, 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 alkylene-siloxane-alkylene-alkoxy- or alkylene-siloxane-alkylene-[alkoxy-alkylene-siloxane]q-alkoxy- (where q is 1 to 50).

[0241] 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, wherein the linking group is a C1-C6 alkylene group, preferably a C1-C3 alkylene group, more preferably a n-propylene group, of formula B, B-1, B-2, B-3, B-4, B-5, B-6, B-7, B-8, or B-9.

[0242] 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 wherein the linking group is alkylene-carbamate-oxaalkylene. Preferably, the linking group is CH2CH2N(H)-C(=O)-O-CH2CH2-O-CH2CH2CH2.

[0243] 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, wherein the linking group is an oxaalkylene group of formula B, B-1, B-2, B-3, B-4, B-5, B-6, B-7, B-8, or B-9. Preferably, the linking group is CH2CH2-O-CH2CH2CH2.

[0244] B-14. Compounds of formulas 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 an alkylene group (-[siloxane-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 -

[0245] 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 wherein the linking group is an alkoxy-carbamate-alkylene-cycloalkylene-carbamate-oxaalkylene (wherein the cycloalkylene is optionally substituted by 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-, wherein the cyclohexylene is substituted by three methyl groups at positions 1 and 5.

[0246] 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 may include compounds of formula B-16, wherein Rg comprises a styrene group and the linking group is a chemical bond or an alkene group (wherein each alkylene group in the alkene group is independently and optionally substituted with a hydroxyl group). An example of such a linking group is -O-(CH2)3-. Another example of such a linking group is -O-CH2CH(OH)CH2-O-(CH2)3-.

[0247] B-17. Compounds of formulas 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, wherein Rg comprises a styrene group and the linking group is an alkyleneamine, and the compounds of formulas B, B-1, B-2, B-3, B-4, B-5, B-6, B-7, B-8, or B-9 are such that the linking group is -NH-(CH2)3-.

[0248] 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 in which the linking group is an oxaalkylene group (wherein the alkoxide itself is optionally substituted with a hydroxyl group, a silanoxy group, or a silyl-alkoxide group) substituted with a hydroxyl group. An example of such a linking group is CH2CH(G)CH2-O-(CH2)3-, where G is a hydroxyl group. In another example, G is R3SiO-, where two R groups are trimethylsilanoxy groups, and the third is a C1-C8 alkyl group (preferably C1-C3 alkyl, more preferably methyl) or a C3-C8 cycloalkyl group. In another example, G is R3Si-(CH2)3-O-CH2CH(OH)CH2-O-, wherein two R groups are trimethylsilyloxy and the third is a C1-C8 alkyl (preferably C1-C3 alkyl, more preferably methyl) or C3-C8 cycloalkyl. In yet another example, G is a polymerizable group, such as (meth)acrylate. Such compounds can be used as crosslinking agents.

[0249] B-19. Compounds of formulas 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, wherein Rg comprises a styrene group and the linking group is an amine-oxaene alkyl group optionally substituted with a hydroxyl group. An example of such a linking group is -NH-CH2CH(OH)CH2-O-(CH2)3-.

[0250] 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, wherein Rg comprises a styrene group and the linking group is an alkoxy-urethane-oxaalkylene group of formula B, B-1, B-2, B-3, B-4, B-5, B-6, B-7, B-8, or B-9. An example of such a linking group is -O-(CH2)2-N(H)C(=O)O-(CH2)2-O-(CH2)3-.

[0251] 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 wherein the linking group is an alkylene-urethane-oxaalkylene group. An example of such a linking group is -(CH2)2-N(H)C(=O)O-(CH2)2-O-(CH2)3-.

[0252] Formula C. Organosilicon-containing components of formulas 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 formulas 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 structures:

[0253]

[0254] in

[0255] R A8 It can be hydrogen or methyl;

[0256] Z is O, S, or N(R) A9 );and

[0257] L, j1, j2, R A1 R A2 R A3 R A4 R A5 R A6 R A7 and R A9 As defined in equation B or its various sub-equations (e.g., B-1, B-2, etc.).

[0258] C-1. Compounds of formula C may include (meth)acrylates of formula C-1, which are compounds of formula C in which Z is O.

[0259] C-2. Compounds of formula C may include (meth)acrylamide of formula C-2, wherein Z is N(R A9 And R A9 Compounds of formula C with H.

[0260] C-3. Compounds of formula C may include (meth)acrylamide of formula C-3, wherein Z is N(R A9 And R A9 Compounds of formula C1-C8 alkyl groups, as described above, without or optionally with substituted alkyl groups. R A9 Examples include CH3, -CH2CH(OH)CH2(OH), -(CH2)3-siloxane, -(CH2)3-SiR3 and -CH2CH(OH)CH2-O-(CH2)3-SiR3, wherein each R in the aforementioned groups is independently selected from trimethylsiloxy, C1-C8 alkyl (preferably C1-C3 alkyl, more preferably methyl) and C3-C8 cycloalkyl. A9 Other examples include: -(CH2)3-Si(Me)(SiMe3)2 and -(CH2)3-Si(Me2)-[O-SiMe2] 1-10 -CH3.

[0261] Compounds of formula D and formula C may include compounds of formula D:

[0262]

[0263] in

[0264] R A8 It can be hydrogen or methyl;

[0265] Z 1 For O or N(R) A9 );

[0266] L 1 It is an alkylene group containing 1 to 8 carbon atoms, or an oxaalkylene group containing 3 to 10 carbon atoms, wherein L 1 Optionally substituted with a hydroxyl group; and

[0267] j2、R A3 R A4 R A5 R A6 R A7 and R A9 As defined in equation B or its various sub-equations (e.g., B-1, B-2, etc.).

[0268] D-1. Compounds of formula D may include compounds of formula D-1, wherein L is... 1 Compounds of formula D, optionally substituted with hydroxyl groups and comprising C2-C5 alkylene groups. Preferably, L 1 The n-propylidene group is optionally substituted with a hydroxyl group.

[0269] D-2. Compounds of formula D may include compounds of formula D-2, wherein L is... 1 Compounds of formula D containing 4 to 8 carbon atoms, optionally substituted with hydroxyl groups. Preferred L... 1 It is an oxaalkylene group containing five or six carbon atoms, optionally substituted with a hydroxyl group. Examples include -(CH2)2-O-(CH2)3- and -CH2CH(OH)CH2-O-(CH2)3-.

[0270] D-3. Compounds of formulas D, D-1, and D-2 may include compounds of formula D-3, wherein Z is... 1 Compounds of formula D, D-1 or D-2 with O.

[0271] D-4. Compounds of formulas D, D-1, and D-2 may include compounds of formula D-4, wherein Z is... 1 For N(R) A9 And R A9 Compounds of formula D, D-1 or D-2 with H.

[0272] D-5. Compounds of formulas D, D-1, and D-2 may include compounds of formula D-5, wherein Z is... 1 For N(R) A9 And R A9 A compound of formula D, D-1 or D-2 of C1-C4 alkyl group, optionally substituted with one or two substituents (selected from hydroxyl, siloxy, and C1-C6 alkyl-siloxane-).

[0273] D-6. Compounds of formulas D, D-1, D-2, D-3, D-4 and D-5 may include compounds of formula D-6, which are compounds of formulas D, D-1, D-2, D-3, D-4 or D-5 in which j2 is 1.

[0274] D-7. Compounds of formulas D, D-1, D-2, D-3, D-4 and D-5 may include compounds of formula D-7, which are compounds of formulas 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.

[0275] D-8. Compounds of formulas 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 is... A3 R A4 R A5 R A6 and R A7 Compounds of formula D, D-1, D-2, D-3, D-4, D-5, D-6, or D-7 that are independently C1-C6 alkyl or silanoxy groups. Preferably, R A3 R A4 R A5 R A6 and R A7 Independently selected from methyl, ethyl, n-propyl, n-butyl, and trimethylsilyloxy. More preferably, R A3 R A4 R A5 R A6 and R A7 It is independently selected from methyl, n-butyl and trimethylsiloxy.

[0276] 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 is... A3 and R A4 Independently C1-C6 alkyl (e.g., methyl or ethyl) or siloxy (e.g., trimethylsiloxy) and R A5 R A6 and R A7 Compounds of formula D, D-1, D-2, D-3, D-4, D-5, D-6 or D-7 that are independently C1-C6 alkyl (e.g. methyl, ethyl, n-propyl or n-butyl).

[0277] Formula E. The organosilicon-containing component used in this invention may comprise a multifunctional organosilicon-containing component. Therefore, for example, the organosilicon-containing component of Formula A may comprise a bifunctional material of Formula E:

[0278]

[0279] in

[0280] Rg, L, j1, j2, R A1 R A2 R A3 R A4 R A5 and R A7 As defined above for expression B or its various subexpressions (e.g., B-1, B-2, etc.);

[0281] L 2 It is a linking group; and

[0282] Rg 1 It is a polymerizable group.

[0283] E-1. Compounds of formula E may include compounds of formula E-1, wherein Rg and Rg are... 1 Compounds of formula E that are vinyl carbonates with the structure CH2=CH-OC(=O)-O- or CH2=C(CH3)-OC(=O)-O- respectively.

[0284] E-2. Compounds of formula E may include compounds of formula E-2, wherein Rg and Rg are... 1 Compounds of formula E that are each (meth)acrylates.

[0285] E-3. Compounds of formula E may include compounds of formula E-3, wherein Rg and Rg are... 1 Each is (meth)acrylamide (where the nitrogen group can be RA) 9 (where R) A9 Compounds of formula E that are substituted (as defined above).

[0286] E-4. Suitable compounds of formula 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 in which j1 is zero and j2 is 1 to 220 or j2 is 1 to 100 or j2 is 1 to 50 or j2 is 1 to 20.

[0287] E-5. Suitable compounds of formula E, E-1, E-2 and E-3 include compounds of formula E-5, wherein j1 and j2 are independently 4 to 100 of formula E, E-1, E-2 or E-3.

[0288] 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 is... A1 R A2 R A3 R A4 and R A5 Compounds of formula E, E-1, E-2, E-3, E-4 or E-5 that are independently C1-C6 alkyl, preferably independently C1-C3 alkyl, or preferably methyl, each when they appear independently.

[0289] E-7. Suitable compounds of formulas E, E-1, E-2, E-3, E-4, E-5, and E-6 include compounds of formula E-7, wherein R is... A7 It is an alkoxy-alkeneoxy-alkyl group, preferably of the formula CH3O-[CH2CH2O]. pCompounds of formula E, E-1, E-2, E-3, E-4, E-5 or E-6 of methoxy-terminated poly(ethyleneoxyalkyl) compounds of formula E, E-1, E-2, E-3, E-4 or E-6 (where p is an integer from 1 to 50, or 1 to 30, or 1 to 10, or 6 to 10).

[0290] 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 in which L includes alkylene, urethane, siloxane, cycloalkylene, amide, haloalkoxy, oxaalkylene, or a combination of two or more of these (wherein the linking group is optionally substituted by one or more substituents independently selected from alkyl, hydroxyl, ether, amine, carbonyl, and urethane).

[0291] E-9. Suitable compounds of formulas 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 2 Compounds of formula E-1, E-2, E-3, E-4, E-5, E-6, E-7, or E-8, including alkylene, urethane, siloxane, cycloalkylene, amide, haloalkoxy, oxaalkylene, or combinations thereof (wherein the linking group is optionally substituted by one or more substituents independently selected from alkyl, hydroxyl, ether, amine, carbonyl, and urethane).

[0292] Examples of organosilicon-containing components suitable for use in this invention include, but are not limited to, the compounds listed in Table 2. In the case of compounds in Table 2 containing polysiloxane groups, unless otherwise specified, the number of SiO repeating units in such compounds is preferably 3 to 100, more preferably 3 to 40, or even more preferably 3 to 20.

[0293] Table 2

[0294]

[0295]

[0296]

[0297] Additional non-limiting examples of suitable organosilicon-containing components are listed in Table 3. Unless otherwise specified, j2 is preferably 1 to 100, more preferably 3 to 40, or even more preferably 3 to 15, where applicable. In compounds containing j1 and j2, the sum of j1 and j2 is preferably 2 to 100, more preferably 3 to 40, or even more preferably 3 to 15.

[0298] Table 3

[0299]

[0300]

[0301] Mixtures containing organosilicon components may be used. Suitable mixtures may include, but are not limited to: mixtures of mono-(2-hydroxy-3-methacryloxypropoxy)-propyl-terminated mono-n-butyl-terminated polydimethylsiloxanes (OH-mPDMS) with different molecular weights, such as mixtures of OH-mPDMS containing 4 and 15 SiO repeating units; mixtures of OH-mPDMS with different molecular weights (e.g., containing 4 and 15 repeating SiO repeating units) with organosilicon-based crosslinking agents (such as bis-3-acryloxy-2-hydroxypropoxypropyl polydimethylsiloxane (ac-PDMS)); and mixtures of 2-hydroxy-3-[3-methyl-3,3-di(trimethylsiloxy)silylpropoxy]-propyl methacrylate (SiMAA) and mono-methacryloxypropyl-terminated mono-n-butyl-terminated polydimethylsiloxanes (mPDMS) (such as mPDMS 1000).

[0302] The organosilicon-containing components used in this invention may have an average molecular weight of about 400 Daltons to about 4000 Daltons.

[0303] Based on all reactive components (excluding diluents) of the reactive mixture, one or more organosilicon-containing components may be present in amounts of up to about 95% by weight, or about 10% by weight to about 80% by weight, or about 20% by weight to about 70% by weight.

[0304] polyamide

[0305] The reactive mixture may contain at least one polyamide. As used herein, the term "polyamide" refers to polymers and copolymers comprising repeating units containing amide groups. Polyamides may include cyclic amide groups, acyclic amide groups, and combinations thereof, and may be any polyamide known to those skilled in the art. Acyclic polyamides contain acyclic amide side groups and are capable of bonding with hydroxyl groups. Cyclic polyamides contain cyclic amide groups and are capable of bonding with hydroxyl groups.

[0306] Examples of suitable acyclic polyamides include polymers and copolymers containing repeating units of formula G1 and G2:

[0307]

[0308]

[0309] Where X is a direct bond, -(CO)- or -(CONHR)- 44 )-, where R 44 It is a C1 to C3 alkyl group; R 40 Selected from H, straight-chain or branched substituted or unsubstituted C1 to C4 alkyl groups; R 41 Selected from H, straight-chain or branched substituted or unsubstituted C1 to C4 alkyl groups, amino groups having up to two carbon atoms, amide groups having up to four carbon atoms, and alkoxy groups having up to two carbon atoms; R 42 Selected from H, straight-chain or branched substituted or unsubstituted C1 to C4 alkyl groups; or methyl, ethoxy, hydroxyethyl and hydroxymethyl; R 43 Selected from H, straight-chain or branched substituted or unsubstituted C1 to C4 alkyl groups; or methyl, ethoxy, hydroxyethyl and hydroxymethyl; wherein R 40 and R 41 The total number of carbon atoms in the [element name] is 8 or less, including 7, 6, 5, 4, 3 or less; and R [element name] is [element name]. 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 can be 6 or less, or 4 or less. 42 and R 43 The total number of carbon atoms in the alkyl group can be 6 or less. As used herein, substituted alkyl groups include alkyl groups substituted with amine, amide, ether, hydroxyl, carbonyl, or carboxyl groups or combinations thereof.

[0310] R 40 and R 41 It can be independently selected from H, substituted or unsubstituted C1 to C2 alkyl groups. X can be a direct bond, and R 40 and R 41 It can be independently selected from H, substituted or unsubstituted C1 to C2 alkyl groups. R 42 and R 43 It can be independently selected from H, substituted or unsubstituted C1 to C2 alkyl groups, methyl, ethoxy, hydroxyethyl and hydroxymethyl.

[0311] 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% (including at least 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 repeating units derived from: N-vinyl-N-methylacetamide, N-vinylacetamide, N-vinyl-N-methylpropionamide, N-vinyl-N-methyl-2-methylpropionamide, N-vinyl-2-methylpropionamide, N-vinyl-N,N′-dimethylurea, N,N-dimethylacrylamide, methacrylamide, and acyclic amides of formulas G2 and G3.

[0312]

[0313] Examples of suitable cyclic amides that can be used to form cyclic polyamides include α-lactams, β-lactams, γ-lactams, δ-lactams, and ε-lactams. Examples of suitable cyclic polyamides include polymers and copolymers containing repeating units of formula G4.

[0314]

[0315] Where R 45 It is a hydrogen atom or a methyl group; where f is a number from 1 to 10; where X is a direct bond, -(CO)- or -(CONHR)-. 46 )-, where R 46 It is a C1 to 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).

[0316] The cyclic polyamide of the present invention may contain 50 mol% or more of repeating units of formula G4, or the cyclic polyamide may contain at least 50 mol% (including at least 70 mol% and at least 80 mol%) of repeating units of formula G4.

[0317] Polyamides can also be copolymers comprising repeating units of both cyclic and acyclic amides. Additional repeating units can 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) can be used as comonomers to form 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, 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-[(ethoxy)carbonyl]-β-alanine (VINAL, CAS#148969-96-4), 3-acrylamidopropionic acid (ACA1), 5-acrylamidovalerate (ACA2), 3-acrylamido-3-methylbutyric acid (AMBA), 2-(methacryloyloxy)ethyltrimethylammonium chloride (Q salt or METAC), 2-acrylamido-2-methylpropanesulfonic acid (AMPS), N-(2-carboxyethyl)-N,N-dimethyl-3-[(1-oxo-2-propen-1-yl)amino]-1-propaneammonium inner salt (CBT, carboxybetaine; CAS 79704-35-1), N,N-dimethyl-N-[3-[(1-oxo-2-propen-1-yl)amino]propyl]-3-sulfo-1-propaneammonium inner salt (SBT, sulfobetaine, CAS 79704-35-1). 80293-60-3), 4-hydroxy-N,N,N-trimethyl-9-oxo-4-oxide 3,5-dioxa-8-aza-4-phospha-undec-10-ene-1-ammonium inner salt (9CI) (PBT, betaine, CAS) 163674-35-9), 2-methacryloyloxyethyl phosphocholine, 3-(dimethyl(4-vinylbenzyl)ammonium)propane-1-sulfonate (DMVBAPS), 3-((3-acrylamidopropyl)dimethylammonium)propane-1-sulfonate (AMPDAPS), 3-((3-methacrylamidopropyl)dimethylammonium)propane-1-sulfonate (MAMPDAPS), 3-((3-(acryloyloxy)propyl)dimethylammonium)propane-1-sulfonate (APDAPS), methacryloyloxy)propyl)dimethylammonium)propane-1-sulfonate (MAPDAPS).

[0318] The reactive monomer mixture may comprise both acyclic polyamides and cyclic polyamides, or copolymers thereof. The acyclic polyamide may be any of the acyclic polyamides described herein or copolymers thereof, and the cyclic polyamide may be any of the cyclic polyamides described herein or copolymers thereof. The polyamide may be selected from polyvinylpyrrolidone (PVP), polyvinylmethylacetamide (PVMA), polydimethylacrylamide (PDMA), polyvinylacetamide (PNVA), poly(hydroxyethyl(meth)acrylamide), polyacrylamide, and copolymers and mixtures thereof. The polyamide may be PVP (e.g., PVP K90) and PVMA (e.g., M... having about 570 kDa). w A mixture of ).

[0319] In all cases, based on the total weight of the reactive components in the reactive monomer mixture, the total amount of all polyamides in the reactive mixture can range from 1 wt% to about 35 wt%, including the range from about 1 wt% to about 15 wt% and the range from about 5 wt% to about 15 wt%.

[0320] Unwilling to be bound by theory, when used with silicone hydrogels, the polyamide acts as an internal wetting agent. The polyamide of the present invention can be non-polymerizable and, in this case, incorporated into the silicone hydrogel as a semi-interpenetrating network. The polyamide is trapped or physically retained within the silicone hydrogel. Alternatively, the polyamide of the present invention is polymerizable, for example, as a polyamide macromonomer or prepolymer, and in this case, covalently introduced into the silicone hydrogel. Mixtures of polymerizable and non-polymerizable polyamides can also be used.

[0321] When polyamides are incorporated into a mixture of reactive monomers, their weight-average molecular weights can be at least 100,000 Daltons; greater than about 150,000 Daltons; about 150,000 Daltons to about 2,000,000 Daltons; or about 300,000 Daltons to about 1,800,000 Daltons. Higher molecular weight polyamides may be used if they are compatible with the reactive monomer mixture.

[0322] Crosslinking agent

[0323] It is generally desirable to add one or more crosslinking agents (also known as crosslinking monomers, multifunctional macromonomers, and prepolymers) to reactive mixtures. Crosslinking agents can be selected from bifunctional, trifunctional, tetrafunctional, and mixtures thereof, including silicone-containing and silicone-free crosslinking agents. Silicone-free crosslinking agents include ethylene glycol dimethacrylate (EGDMA), tetraethylene glycol dimethacrylate (TEGDMA), trimethylolpropane trimethacrylate (TMPTMA), triallyl cyanurate (TAC), glyceryl trimethacrylate, oxyethyl vinyl methacrylate (HEMAVc), allyl methacrylate, methylenebisacrylamide (MBA), and polyethylene glycol dimethacrylate (wherein the polyethylene glycol has a molecular weight of up to about 5000 Daltons). Crosslinking agents are used in reactive mixtures in conventional amounts (e.g., about 0.000415 mol to about 0.0156 mol per 100 g of reactive formulation). Alternatively, if the hydrophilic monomer and / or the organosilicon-containing component is multifunctional due to molecular design or impurities, it is optional to add a crosslinking agent to the reactive mixture. Examples of hydrophilic monomers and macromonomers that can act as crosslinking agents and (when present) do not require the addition of additional crosslinking agents to the reactive mixture include (meth)acrylate and (meth)acrylamide-terminated polyethers. Other crosslinking agents will be known to those skilled in the art and can be used to prepare the organosilicon hydrogels of the present invention.

[0324] It may be desirable to select one or more crosslinking agents with similar reactivity to other reactive components in the formulation. In some cases, it may be desirable to select a mixture of crosslinking agents with different reactivity to control some physical, mechanical, or biological properties of the resulting silicone hydrogel. The structure and morphology of the silicone hydrogel can also be affected by one or more diluents used and the curing conditions.

[0325] Multifunctional organosilicon-containing components (including macromonomers, crosslinking agents, and prepolymers) may also be included to further increase modulus and maintain tensile strength. Organosilicon-containing crosslinking agents can be used alone or in combination with other crosslinking agents. Examples of organosilicon-containing components that can act as crosslinking agents and (when present) do not require the addition of crosslinking monomers to the reactive mixture include α,ω-bis(methacryloyloxypropyl)polydimethylsiloxane. Another example is bis-3-acryloyloxy-2-hydroxypropoxypropyl)polydimethylsiloxane (ac-PDMS).

[0326] Crosslinking agents having a rigid chemical structure and polymerizable groups that undergo free radical polymerization can also be used. Non-limiting examples of suitable rigid structures include crosslinking agents comprising phenyl and benzyl rings, such as 1,4-phenylene diacrylate, 1,4-phenylene dimethacrylate, 2,2-bis(4-methacryloyloxyphenyl)-propane, 2,2-bis[4-(2-acryloyloxyethoxy)phenyl]propane, 2,2-bis[4-(2-hydroxy-3-methacryloyloxypropoxy)-phenyl]propane, and 4-vinylbenzyl methacrylate, and combinations thereof. Based on the total weight of all reactive components, the rigid crosslinking agent can be included in an amount between about 0.5 and about 15, or 2 to 10, or 3 to 7. By adjusting the components in the reactive mixture, the physical and mechanical properties of the silicone hydrogel of the present invention can be optimized for specific applications.

[0327] Non-limiting examples of organosilicon crosslinking agents also include the aforementioned multifunctional organosilicon-containing components, such as compounds of formula E (and its sub-formulas) and the multifunctional compounds shown in Table 3.

[0328] Other components

[0329] Reactive mixtures may contain additional components, such as, but not limited to, diluents, initiators, UV absorbers, visible light absorbers, photochromic compounds, pharmaceuticals, nutritional preparations, antimicrobial substances, toners, pigments, copolymerizable dyes, non-polymerizable dyes, release agents, and combinations thereof.

[0330] The categories of diluents suitable for reactive silicone hydrogel 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.

[0331] Generally, reactive components are mixed in a diluent to form a reactive mixture. Suitable diluents are known in the art. Diluents suitable for silicone hydrogels are disclosed in WO03 / 022321 and US6020445, the disclosures of which are incorporated herein by reference. Categories of diluents suitable for reactive mixtures of silicone hydrogels 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. Primary and tertiary alcohols can be used. Preferred categories include alcohols having 5 to 20 carbon atoms and carboxylic acids having 10 to 20 carbon atoms. Specific diluents that can 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-pentanol, tert-butanol, 2-butanol, 1-butanol, 2-methyl-2-pentanol, 2-propanol, 1-propanol, ethanol, 2-ethyl-1-butanol, (3-acetoxy-2-hydroxypropoxy)propylbis(trimethylsiloxy)methylsilane, 1-tert-butoxy-2-propanol, 3,3-dimethyl-2-butanol, tert-butoxyethanol, 2-octyl-1-dodecanol, decanoic acid, octanoic acid, dodecanoic acid, 2-(diisopropylamino)ethanol, mixtures thereof, etc. Examples of amide diluents include N,N-dimethylpropionamide and dimethylacetamide.

[0332] 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, tert-pentanol, 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, and mixtures thereof.

[0333] 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, tert-pentanol, tert-butanol, 2-butanol, 1-butanol, 2-methyl-2-pentanol, 2-ethyl-1-butanol, 3,3-dimethyl-2-butanol, 2-octyl-1-dodecanol, and mixtures thereof.

[0334] If a diluent is present, there are generally no particular restrictions on the amount of diluent present. When a diluent is used, it may be present in an amount ranging from about 2% to about 70% by weight (including from about 5% to about 50% by weight and from about 15% to about 40% by weight) based on the total weight of the reactive mixture (including reactive and non-reactive formulations). Mixtures of diluents may be used.

[0335] Polymerization initiators can be used in reactive mixtures. Polymerization initiators may include at least one of lauroyl peroxide, benzoyl peroxide, isopropyl percarbonate, azobisisobutyronitrile, etc., which generate free radicals at moderately high temperatures; and photoinitiator systems such as aromatic α-hydroxy ketones, alkoxyoxobenzoin, acetophenone, acylphosphine oxides, diacylphosphine oxides, and tertiary amine-diketones, mixtures thereof, etc. Exemplary examples of photoinitiators are 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1-one, bis(2,6-dimethoxybenzoyl)-2,4-4-trimethylpentylphosphine oxide (DMBAPO), bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (Irgacure 819), 2,4,6-trimethylbenzyl diphenylphosphine oxide and 2,4,6-trimethylbenzoyl diphenylphosphine oxide, benzoin methyl ester, and compositions of camphorquinone and ethyl 4-(N,N-dimethylamino)benzoate.

[0336] Commercially available visible light initiator systems (from IGM Resins BV, The Netherlands) include 819、 1700 1800 819、 1850 and TPO initiators. Commercially available UV photoinitiators (from IGM Resins BV) include... 1173 and 2959. These and other photoinitiators that can be used are disclosed in Volume III, Photoinitiators for Free Radical Cationic & Anionic Photopolymerization, 2nd ed., by J. V. Rivicello & K. Dietliker; edited by G. Bradley; John Wiley and Sons; New York; 1998. The initiator is used in the reactive mixture in an effective amount for initiating the photopolymerization of the reactive mixture (e.g., about 0.1 parts by weight to about 2 parts by weight per 100 parts of the reactive monomer mixture). The polymerization of the reactive mixture can be initiated by heat or visible light or ultraviolet light or other methods of appropriate selection, depending on the polymerization initiator used. Alternatively, initiation can be carried out using an electron beam without a photoinitiator. However, when a photoinitiator is used, the preferred initiator is a diacylphosphine oxide, such as bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (… 819) or a combination of 1-hydroxycyclohexylphenyl ketone and bis(2,6-dimethoxybenzoyl)-2,4-4-trimethylpentylphosphine oxide (DMBAPO).

[0337] The reactive mixture used to manufacture the ophthalmic device of the present invention may contain, in addition to high-energy light-absorbing compounds, any of the polymerizable compounds and optional components described above.

[0338] Preferred reactive mixtures may include: high-energy light-absorbing compounds, such as compounds of formula I; and hydrophilic components.

[0339] Preferred reactive mixtures may comprise: 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.

[0340] Preferred reactive mixtures may include: high-energy light-absorbing compounds, such as compounds of formula I; hydrophilic components; and components containing organosilicon.

[0341] Preferred reactive mixtures may include: high-energy light-absorbing compounds, such as compounds of formula I; hydrophilic components; and components containing organosilicon, including compounds of formula D (or its sub-formulas, such as D-1, D-2, etc.).

[0342] Preferred reactive mixtures may include: high-energy light-absorbing compounds, such as compounds of formula I; hydrophilic components selected from DMA, NVP, HEMA, VMA, NVA, and mixtures thereof; silicone-containing components, including compounds of formula D (or its sub-formulas, such as D-1, D-2, etc.); and internal wetting agents.

[0343] Preferred reactive mixtures may comprise: a high-energy light-absorbing compound, such as a compound of formula I; a hydrophilic component selected from DMA, HEMA, and mixtures thereof; an organosilicon-containing component selected from 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 organosilicon-containing component, a mixture of SiMAA and mPDMS is preferred.

[0344] Preferred reactive mixtures may comprise: high-energy light-absorbing compounds, such as compounds of formula I; hydrophilic components, including mixtures of DMA and HEMA; and silicone-containing components, including mixtures of OH-mPDMS having 2 to 20 repeating units (preferably mixtures of 4 and 15 repeating units). Preferably, the reactive mixture further comprises a silicone-containing crosslinking agent, such as ac-PDMS. Even more preferably, the reactive mixture contains a wetting agent (preferably DMA, PVP, PVMA, or mixtures thereof).

[0345] Preferred reactive mixtures may comprise: a high-energy light-absorbing compound, such as a compound of formula I; at least one polyamide (e.g., acyclic polyamide, cyclic polyamide, or mixtures thereof) between about 1% and about 15% by weight; at least one first monofunctional hydroxyl-substituted poly(disubstituted siloxane) having 4 to 8 siloxane repeating 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) having 10 to 200, or 10 The first monofunctional hydroxyl-substituted poly(disubstituted siloxane) having 100, 10 to 50, or 10 to 20 siloxane repeating units (e.g., OH-mPDMS, where n is 10 to 200, 10 to 100, 10 to 50, or 10 to 20, preferably n is 15); about 5% to about 35% by weight of at least one hydrophilic monomer; and optionally a polyfunctional hydroxyl-substituted poly(disubstituted siloxane) having 10 to 200 or 10 to 100 siloxane repeating units (e.g., ac-PDMS). Preferably, the first monofunctional hydroxyl-substituted poly(disubstituted siloxane) and the second hydroxyl-substituted poly(disubstituted siloxane) are present at a concentration such that the weight percentage ratio of the first monofunctional hydroxyl-substituted poly(disubstituted siloxane) to the weight percentage of the second hydroxyl-substituted poly(disubstituted siloxane) is 0.4 to 1.3 or 0.4 to 1.0.

[0346] The aforementioned reactive mixture may contain optional components, such as, but not limited to, one or more initiators, internal wetting agents, crosslinking agents, other UV or HEV absorbers, and diluents.

[0347] Compounds of Formula I, when copolymerized with other reactive components, provide polymeric products containing chromophores. Such chromophores can provide the product with the desired light absorption properties as described above. For example, as described in detail above, ophthalmic devices (such as contact lenses) containing chromophores can block unwanted high-energy light. Therefore, the present invention covers ophthalmic devices that are polymeric products of reactive mixtures (comprising, for example, a hydrophilic component and an organosilicon-containing compound), wherein the polymeric product contains one or more chromophores of Formula IV as covalently bonded substituents:

[0348]

[0349] Where m and n are independently 0, 1, 2, 3, or 4; X is O, S, NR, SO, or SO2; R is independently H, C1-C6 alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, or a linker group to the polymerization product each time it appears; when R is present... 1 and R 2 At that time, R 1 and R 2Each time it appears, it is independently C1-C6 alkyl, C1-C6 alkoxy, C1-C6 alkylthio, C3-C7 cycloalkyl, aryl, halogen, hydroxyl, amino, NR 3 R 4 Or benzyl, wherein R 3 and R 4 Independently H or C1-C6 alkyl, or two adjacent R 1 Or R 2 The groups, together with the carbon atoms they are attached to, combine to form cycloalkyl or aryl rings; R 5 It is a linker group to the polymerization product; and EWG is an electron-withdrawing group (preferably cyano).

[0350] In Formula IV, X is preferably O or S. In Formula IV, the linking group to the polymerization product preferably comprises a polymerizable group and one or more residues of the following groups: alkylene group, cycloalkylene group, heterocycloalkylene group, aryl group, heteroarylene group, oxaalkylene group, alkylene-amide-alkylene group, or alkylene-amine-alkylene group. Preferred polymerizable groups include styryl, vinyl carbonate, vinyl ether, vinyl carbamate, N-vinyl lactam, N-vinylamide, (meth)acrylate, or (meth)acrylamide.

[0351] In addition to the chromophore of formula IV, the preferred polymerization product may also contain one or more covalently linked UV-absorbing chromophores. Preferred UV-absorbing chromophores include residues of benzophenone, benzotriazole, triazine, substituted acrylonitrile, salicylic acid derivatives, benzoic acid derivatives, cinnamic acid derivatives, chalcone derivatives, diphenyl ethyl ketone derivatives, crotonic acid derivatives, or mixtures thereof.

[0352] The curing of hydrogels and the manufacturing of lenses

[0353] Reactive mixtures can be formed by any of the methods known in the art, such as vibration or agitation, and by known methods used to form articles or apparatus of polymers. Reactive components are mixed together with or without a diluent to form a reactive mixture.

[0354] For example, an ophthalmic device can be prepared by mixing a reactive component and optionally one or more diluents with a polymerization initiator, curing it under appropriate conditions to form a product, which can then be shaped into a suitable form by machining, cutting, etc. Alternatively, the reactive mixture can be placed in a mold and subsequently cured into a suitable article.

[0355] A method for manufacturing molded ophthalmic devices such as silicone hydrogel contact lenses may include: preparing a reactive monomer mixture; transferring the reactive monomer mixture onto a first mold; placing a second mold on top of 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.

[0356] The reactive mixture can be cured via any known process (including spin casting and static casting) used for molding the reactive mixture during the production of contact lenses. Spin casting is disclosed in U.S. Patent Nos. 3,408,429 and 3,660,545, and static casting is disclosed in U.S. Patent Nos. 4,113,224 and 4,197,266. The contact lenses of the present invention can be formed by directly molding silicone hydrogels, a method that is both economical and allows for precise control over the final shape of the hydrated lens. In this method, the reactive mixture is placed in a mold having the final desired shape of the silicone hydrogel, and the reactive mixture is subjected to conditions that cause the monomers to polymerize, thereby producing a polymer having the general shape of the final desired product.

[0357] After curing, the lens can be extracted to remove unreacted components and detach the lens from the lens mold. Extraction can be performed using conventional extraction solutions (such as organic solvents like alcohols) or aqueous solutions.

[0358] The aqueous solution is a solution containing water. The aqueous solution of the present invention may contain at least about 20% by weight of water, or at least about 50% by weight of water, or at least about 70% by weight of water, or at least about 95% by weight of water. The aqueous solution may also contain additional water-soluble formulations, such as inorganic salts or release agents, wetting agents, slip agents, pharmaceutical and nutritional formulations, combinations thereof, etc. A release agent is a compound or mixture of compounds that, when mixed with water, reduces the time required to remove the contact lens from the mold compared to using an aqueous solution without a release agent. The aqueous solution may not require special treatment, such as purification, recycling, or special disposal processes.

[0359] Extraction can be achieved, for example, by immersing the lens in an aqueous solution or exposing it to a flowing aqueous solution. Extraction may also include, for example, one or more of the following: heating the aqueous solution; stirring the aqueous solution; increasing the content of a release agent in the aqueous solution to a level sufficient to detach the lens; mechanically or ultrasonically stirring the lens; and incorporating at least one filtration or extraction agent into the aqueous solution until it reaches a level sufficient to promote adequate removal of unreacted components from the lens. The above operations can be performed in batches or continuously, with heating, stirring, or both, or without any of these steps.

[0360] Physical agitation may be desired to facilitate extraction and demolding. For example, the lens mold component with the lens attached can be vibrated or moved back and forth in an aqueous solution. Other methods may include ultrasound through an aqueous solution.

[0361] Lenses can be sterilized by known methods (including but not limited to autoclaving).

[0362] As described 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 for lenses of various thicknesses using methods such as those described in the examples. By way of example, the preferred center thickness for measuring the transmission spectrum in a soft contact lens can be 80 to 100 micrometers, or 90 to 100 micrometers, or 90 to 95 micrometers. Typically, measurements can be taken at the center of the lens using an instrument slit width of, for example, 4 nm. Various concentrations of one or more polymerizable high-energy light-absorbing compounds can be used to achieve the aforementioned transmission properties. For example, the concentration can range from at least 1% or at least 2% and at most 10% or at most 5% based on the weight percentage of all components (excluding diluents) in the reactive mixture. Typical concentrations can range from 3% to 5%.

[0363] The silicone hydrogel ophthalmic device (e.g., contact lens) according to the invention preferably exhibits the following characteristics. All values ​​are preceded by "about", and the device may have any combination of the listed characteristics. The characteristics can be determined by methods known to those skilled in the art, such as those described in U.S. pre-grant publication US20180037690, which is incorporated herein by reference.

[0364] Water concentration %: at least 20% or at least 25% and at most 80% or at most 70%

[0365] Haze: 30% or lower, or 10% or lower

[0366] Kruss dynamic contact angle (°): 100° or less, or 50° or less

[0367] Tensile modulus (psi): 120 or lower, or 80 to 120

[0368] Oxygen permeability (Dk, Baler): at least 80, or at least 100, or at least 150, or at least 200

[0369] Elongation at break: at least 100

[0370] For ionic silica hydrogels, the following properties are also preferred (in addition to those mentioned above):

[0371] Lysozyme absorption rate (μg / lens): at least 100, or at least 150, or at least 500, or at least 700

[0372] Polyquaternium 1 (PQ1) intake (%): 15 or less, or 10 or less, or 5 or less

[0373] Some embodiments of the present invention will now be described in detail in the following examples.

[0374] Example

[0375] Test methods

[0376] Measure the UV-Vis spectra of compounds in solution on a Perkin Elmer Lambda 45 or Agilent Cary 6000i UV / VIS scanning spectrometer. Allow the instrument to thermally equilibrate for at least 30 minutes before use. For the Perkin Elmer instrument, use a scan range of 200 nm to 800 nm; a scan rate of 960 nm / min; a slit width of 4 nm; and select transmittance or absorbance mode, along with baseline correction. For the Cary instrument, use a scan range of 200 nm to 800 nm; a scan rate of 600 nm / min; a slit width of 2 nm; and select transmittance or absorbance mode, along with baseline correction. Perform baseline correction before analyzing the sample using the automatic zeroing function.

[0377] Using a wetting solution, the UV-Vis spectra of contact lenses partially formed from the claimed composition were measured on a Perkin Elmer Lambda 45 UV / VIS or Agilent Cary 6000i UV / VIS scanning spectrometer. The instrument was thermally equilibrated for at least thirty minutes before use. For the Perkin Elmer instrument, the scan range was 200 nm to 800 nm; the scan speed was 960 nm / min; the slit width was 4 nm; the mode was set to transmittance; and baseline correction was selected. Baseline correction was performed using cuvettes comprising a plastic two-piece lens holder and the same solvent. These two-piece contact lens holders were designed to hold the sample in the quartz cuvette at the point through which the incident beam passed. The reference cuvette also included a two-piece holder. To ensure a constant sample thickness, all lenses were made using the same mold. The center thickness of the contact lenses was measured using an electronic thickness gauge. The reported center thickness and percentage of transmittance were obtained by averaging the data from three individual lenses.

[0378] It is important to ensure that the outer surface of the cuvette is completely clean and dry, and that there are no air bubbles inside the cuvette. Measurement repeatability can be improved by keeping the reference cuvette and its lens holder constant, and by using the same sample cuvette and its lens holder for all samples, thus ensuring that both cuvettes are correctly inserted into the instrument.

[0379] The following abbreviations will be used throughout the embodiments and figures, and have the following meanings:

[0380] BC: Back surface or base surface plastic mold

[0381] FC: Front Curved Surface Plastic Mold

[0382] DMA: N,N-dimethylacrylamide (Jarchem)

[0383] HEMA: 2-Hydroxyethyl Methacrylate (Bimax)

[0384] PVP: Poly(N-vinylpyrrolidone) (ISP Ashland)

[0385] PDMA: Polydimethylacrylamide

[0386] PVMA: Polyvinylmethylacetamide

[0387] EGDMA: Ethylene dimethacrylate (Esstech)

[0388] TEGDMA: Tetraethylene dimethacrylate (Esstech)

[0389] Irgacure 819: Bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (BASF or Ciba Specialty Chemicals)

[0390] Irgacure 1870: Blend of bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide with 1-hydroxy-cyclohexyl-phenyl-one (BASF or Ciba Specialty Chemicals)

[0391] mPDMS: Mono-n-butyl-terminated monomethacryloyloxypropyl-terminated polydimethylsiloxane (M n =800-1000 Daltons (Gelest)

[0392] HO-mPDMS: Mono-n-butyl-terminated mono(2-hydroxy-3-methacryloyloxypropoxy)-propyl-terminated polydimethylsiloxane (M n =400-1500 Daltons (Ortec or DSM-Polymer Technology Group)

[0393] ac-PDMS: Bis-3-acryloyloxy-2-hydroxypropoxypropyl polydimethylsiloxane (Tegomer V-Si 2250 from Evonik)

[0394] Blue HEMA: 1-Amino-4-[3-(4-(2-methacryloyloxy-ethoxy)-6-chlorotriazine-2-ylamino)-4-sulfophenylamino]anthraquinone-2-sulfonic acid, as described in U.S. Patent 5,944,853.

[0395] Da: Dalton or g / molar

[0396] kDa: A unit of atomic mass equal to 1,000 Daltons.

[0397] SiMAA: 2-Acrylic acid, 2-methyl-2-hydroxy-3-[3-[1,3,3,3-tetramethyl-1-[(trimethylsilyl)oxy]disiloxyl]propoxy]propyl ester (Toray) or 3-(3-(1,1,1,3,5,5,5-heptamethyltrisiloxane-3-yl)propoxy)-2-hydroxypropyl methacrylate

[0398] RB247: 1,4-bis[2-methacryloyloxyethylamino]-9,10-anthraquinone

[0399] BHT: Butylhydroxytoluene

[0400] D3O: 3,7-Dimethyl-3-octanol (Vigon)

[0401] DIW: Deionized Water

[0402] MeOH: Methanol

[0403] IPA: Isopropyl alcohol

[0404] HCl: hydrochloric acid

[0405] CH2Cl2 or DCM: Methylene chloride or dichloromethane

[0406] SOCl2: thionyl chloride

[0407] mCPBA: m-chloroperbenzoic acid

[0408] EtOAc: Ethyl acetate

[0409] NH2CH2CH2OH: Ethanolamine or 2-aminoethanol

[0410] Norbloc: 2-(2′-hydroxy-5-methacryloyloxyethylphenyl)-2H-benzotriazole (Janssen)

[0411] PP: Polypropylene, a homopolymer of propylene.

[0412] TT: Tuftec, which stands for hydrogenated styrene-butadiene block copolymer (Asahi Kasei Chemicals).

[0413] Z: Zeonor, which is a polycyclic olefin thermoplastic polymer (Nippon Zeon Co Ltd).

[0414] TL03 lighting: Phillips TLK 40W / 03 bulb

[0415] LED: Light Emitting Diode

[0416] 1 N NMR: Proton nuclear magnetic resonance spectrum

[0417] UV-VIS: Ultraviolet-Visible Spectrum

[0418] L: Rise

[0419] mL: milliliters

[0420] Equiv. or eq.: equivalent

[0421] kg: kilogram

[0422] g: grams

[0423] mol: mole

[0424] mmol: millimole

[0425] min: minutes

[0426] nm: nanometer

[0427] TLC: Thin-layer chromatography

[0428] Borate buffer wetting solution: Dissolve 18.52 g (300 mmol) of boric acid, 3.7 g (9.7 mmol) of sodium borate decahydrate and 28 g (197 mmol) of sodium sulfate in enough deionized water to fill a 2-liter volumetric flask.

[0429] Example 1 - Synthesis of 2-(2-cyanoacetamido)ethyl methacrylate (A) and methacrylate as shown in Scheme 2 Ethyl ester of 2-(2-cyano-2-(9H-thioxanth-9-ylidene)acetamido) (B)

[0430]

[0431] In a nitrogen atmosphere, methyl cyanoacetate (40 g, 0.4037 mol) and 25 mL dichloromethane were stirred in a 500 mL three-necked round-bottom flask equipped with a reflux condenser. 2-Aminoethanol (23.8 g, 0.3897 mol, approximately 0.97 eq.) was added to the solution via a feeding funnel, after which the temperature was raised and methylene chloride began to reflux. After the exothermic reaction ceased, external heat was applied to continue the gentle reflux for a total of two hours. Ethanolamine was then not observed by thin-layer chromatography.

[0432] The reaction can also be carried out at room temperature and is completed within a few hours.

[0433] The mixture was cooled to room temperature, and all methylene chloride was evaporated under reduced pressure. The remaining oil was washed three times with 50 mL of ethyl acetate to remove unreacted starting material and nonpolar impurities. The remaining ethyl acetate was then removed under reduced pressure, and the resulting oil was used for acylation without any further purification.

[0434] In a three-necked round-bottom flask equipped with a reflux condenser, a feeding funnel, and a magnetic stir bar, crude N-2-hydroxyethylacetamide derivative was dissolved in 150 mL of dichloromethane containing 40 g of pyridine (approximately 0.5 mol). The flask was immersed in an ice bath and cooled to approximately 0 °C. Methacrylamide chloride (45.76 g, approximately 0.44 mol) was added dropwise through the feeding funnel, and the resulting reaction mixture was warmed to room temperature while continuously stirring. 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 diluted HCl aqueous solution. 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 mg of BHT was added as an inhibitor to the combined organic fractions, and ethyl acetate was removed by rotary evaporation under reduced pressure. During solvent removal, the crude product crystallized from the solution. When approximately 100 mL of ethyl acetate remained in the flask, 250 mL of hexane was added, and the crude product was separated by vacuum filtration using a sintered 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 give 53 g (approximately 70% yield) of 2-(2-cyanoacetamido)ethyl methacrylate (A). 1 ¹H 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, ethylene), 6.11 (1H, bs, ethylene), 6.52 (1H, bs, NH).

[0435] Under a nitrogen atmosphere, a mixture of 9H-thioxanth-9-one (2.12 g, 0.01 mol) and thionyl chloride (5 mL, 8.2 g, approx. 0.07 mol) was refluxed in a 50 mL round-bottom flask with constant stirring. After two hours, the red solution was evaporated to dryness to ensure that all unreacted thionyl chloride was removed from the system. 2-(2-cyanoacetamido)ethyl methacrylate (A) (2.3 g, 0.0117 mol, approx. 1.17 eq.) and 15 mL of dichloromethane were added, and the resulting reaction mixture was heated to reflux under nitrogen. The reaction was monitored by thin-layer chromatography. After two hours, no change was observed in the chromatogram, so the reactive mixture was cooled to room temperature. 2-(2-cyano-2-(9H-thioxanthoxy-9-ylidene)acetamido)ethyl methacrylate (B) was isolated as yellow crystals (3.2 g, yield 82%) after passing through a short silica gel column (CH2Cl2, followed by 8 wt% EtOAc in CH2Cl2). The UV-VIS transmission spectrum of a 0.2 mM methanol solution of compound B was obtained in [the following section is missing from the original text]. Figure 1 As shown in the image. 1 ¹H NMR (500MHz, CDCl₃) δ 1.84 (3H, s, CH₃), 3.47 (2H, m, CH₂NH), 4.01 (2H, t, CH₂OC=O), 5.55 (1H, m, ethylene), 5.91 (1H, bs, NH), 5.98 (1H, bs, ethylene), 7.24 (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).

[0436] Example 2 - Synthesis of 2-(2-cyano-2-(9H-xanthon-9-ylidene)acetamide of methacrylic acid as shown in Scheme 3 Ethyl ester (C)

[0437]

[0438] Under a nitrogen atmosphere, a mixture of 9H-xanthon-9-one (5.0 g, 0.0255 mol) and thionyl chloride (10 mL, 16.4 g, approx. 0.138 mol) was refluxed in a 50 mL round-bottom flask with constant stirring. After three hours, the red solution was evaporated to dryness to ensure that all unreacted thionyl chloride was removed from the system. 2-(2-cyanoacetamido)ethyl methacrylate (A) (6.0 g, 0.0306 mol, approx. 1.2 eq.) and 20 mL of dichloromethane were added, and the resulting reaction mixture was heated to reflux under nitrogen. The reaction was monitored by thin-layer chromatography. After 2.5 hours, the mixture was cooled to room temperature, and 2-(2-cyano-2-(9H-xanthon-9-ylidene)acetamido)ethyl methacrylate (C) was purified by passing it through a short silica gel column (CH2Cl2 with ethyl acetate in CH2Cl2). The grayish-white precipitate formed during rotary evaporation was washed with hexane and dried overnight in a vacuum oven at 40°C. The UV-VIS transmission spectrum of compound (C) in 0.2 mM methanol solution was... Figure 1 As shown in the image. 1 ¹H NMR (500MHz, CDCl₃) δ 1.85 (3H, s, CH₃), 3.60 (2H, dd, CH₂NH), 4.2 (2H, t, CH₂OC=O), 5.53 (1H, t, ethylene), 5.99 (1H, bs, ethylene), 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).

[0439] Example 3 - Synthesis of 2-(2-cyano-2-(10-methylacridin-9(10H)-methacrylic acid) as shown in Scheme 4 Acetamidoethyl ester (D) (Hypothetical example)

[0440]

[0441] Under a nitrogen atmosphere, a mixture of 10-methylacridin-9(10H)-one (2.09 g, 0.01 mol) and thionyl chloride (5 mL, 8.2 g, approx. 0.07 mol) was refluxed in a 50 mL round-bottom flask with constant stirring. After two hours, the solution was evaporated to dryness, ensuring that all unreacted thionyl chloride was removed from the system. 2-(2-cyanoacetamido)ethyl methacrylate (A) (2.3 g, 0.0117 mol, approx. 1.17 eq.) and 15 mL of dichloromethane were added, and the resulting reaction mixture was heated to reflux under nitrogen. The reaction was monitored by thin-layer chromatography. When no change was observed in the chromatogram, the reactive mixture was cooled to room temperature. 2-(2-cyano-2-(10-methylacridin-9(10H)-ylidene)acetamido)ethyl methacrylate (D) can be separated by known methods, for example, after passing through a short silica gel column.

[0442] Example 4 - Synthesis of 2-(2-cyano-2-(10,10-trioxo-9H-thioxanthyl-9-)methacrylic acid as shown in Scheme 5 (Subunit) Acetamido) Ethyl ester (E)

[0443]

[0444] 2.32 g of m-chloroperbenzoic acid (75% purity, about 2 eq., mCPBA) was added to a cold solution of 2-(2-cyano-2-(9H-thioxanthoxy-9-ylidene)acetamido)ethyl methacrylate (B) (2.0 g, 5.2 mmol) in dichloromethane. The mixture was cold-stirred for one hour and then warmed to room temperature. As the reaction proceeded, the solution lost its yellow color, and a white solid crystallized or precipitated from the solution. The eluent was evaporated under reduced pressure. The residue was redissolved in ethyl acetate and extracted with a diluted alkaline solution followed by a diluted salt solution. The organic layer was separated, and the solvent was removed by rotary evaporation under reduced pressure. The residue was washed with hexane over a sintered glass funnel and dried under vacuum. The UV-VIS transmission spectrum of a 0.2 mM methanol solution of compound E was obtained. Figure 1 As shown in the image. 1 ¹H 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, ethylene), 5.95 (1H, m, ethylene), 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).

[0445] Example 5 - Synthesis of 2-(2-cyanoacetamido)ethyl methacrylate (F) and N-(2-(2-) Cyano-2-(9H-thioxanth-9-ylidene)acetamido)ethyl)methacrylamide (G)

[0446]

[0447] In a nitrogen atmosphere, methyl cyanoacetate (22 g, 0.22 mol) and 250 mL dichloromethane were stirred in a 500 mL three-necked round-bottom flask equipped with a reflux condenser. The solution was cooled in a water bath, and 1,2-aminoethane (12 g, 0.2 mol, approximately 0.9 eq.) was added to the mixture. As the reaction proceeded, the mixture became increasingly heterogeneous, and the product precipitated from the solution. After stirring at room temperature for four hours, the evaporation was evaporated under reduced pressure, and the residue was washed with ethyl acetate on a sintered glass funnel and dried at 50 °C for further use. 1 H NMR (500MHz, D2O) δ2.74 (2H, t, CH2NH2), 3.29 (2H, t, CH2NH), 3.38 (2H, s, CH2CN).

[0448] 12.7 g (0.1 mol) of 2-aminoethylcyanoacetamide and 12.0 g of sodium carbonate were stirred in 150 mL of methanol and cooled in an ice bath. Methacrylamide chloride (11.5 g, 1.1 eq.) was added dropwise to the suspension while maintaining the reaction temperature below 30 °C. After the reaction was complete, all volatiles were evaporated under reduced pressure, the product was redissolved in acetonitrile, and the solution was filtered to remove all present salts. The acetonitrile was evaporated under reduced pressure, and the resulting solid was washed with ethyl acetate over a sintered glass funnel to give the desired 2-(2-cyanoacetamido)ethylmethacrylamide (F). 1 ¹H 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, ethylene), 5.63 (1H, m, ethylene).

[0449] Under a nitrogen atmosphere, a mixture of thioxanthone (4.24 g, 0.02 mol) and 8 mL of thionyl chloride (13.12 g, approx. 0.11 mol) was gently refluxed with constant stirring. After heating for two hours, the solution was evaporated to dryness under reduced pressure to ensure the removal of all unreacted thionyl chloride. 2-(2-cyanoacetamido)ethylmethacrylamide (F) (4.2 g, approx. 1.1 eq.) and 20 mL of degassed methylene chloride were added to the flask, and the mixture was gently refluxed under nitrogen for 3 hours while monitoring the progress by TLC. The evaporation was evaporated under reduced pressure, and the organic matter was washed with ethyl acetate. A large amount of precipitate rich in the major product was observed. The suspension was filtered, and the residual solids were washed with ethyl acetate and then dried in a vacuum oven. The UV-VIS transmission spectrum of a 0.2 mM methanol solution of compound G was obtained. Figure 2 As shown in the image.1 ¹H NMR (500MHz, CDCl₃) δ 1.89 (3H, s, CH₃), 3.26 (2H, m, CH₂NH), 3.32 (2H, m, CH₂NH), 5.33 (1H, m, ethylene), 5.68 (1H, m, ethylene), 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).

[0450] Example 6 - Synthesis of N-(2-(2-cyano-2-(10-methylacridin-9(10H)-ylidene)acetamide as shown in Scheme 7 (H)-(ethyl)-methylacrylamide

[0451]

[0452] 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) over 30 minutes at -20 °C. The reaction was warmed to room temperature and stirred for 3 hours over 2 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, yield 66%, purity >95%) as a white solid.

[0453] N-(2-(2-cyanoacetamido)ethyl)methacrylamide (3): A solution of methacrylic 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 hour. The reaction was cooled to 0 °C, and compound 2 (28 g, 220 mmol, 1.0 equiv) was added in portions to the reaction mixture at 0 °C. The reaction was warmed to room temperature and stirred for 5 hours, at which point LC-MS indicated that the reaction was complete. The resulting precipitate was filtered and washed with dichloromethane (2 × 100 mL) to give compound 3 (25.1 g, yield 60%, purity >95%) as a white solid.

[0454] 9,9-Dichloro-10-methyl-9,10-dihydroacridine (5): A solution of compound 4 (10 g, 4.85 mmol, 1.0 equiv) in thionyl chloride (200 mL, 2.75 mol, 55 equiv) was stirred for 2 hours at 60 °C. 1¹H-NMR indicated that the reaction was complete. Thionyl chloride was removed under reduced pressure. The residue was azeotropically reacted with toluene (2 × 20 mL) to give crude compound 5 as a yellow solid (12.5 g), which was subsequently used.

[0455] 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 at 0 °C 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). The reaction was warmed to room temperature and stirred for 2 hours, at which point LC-MS indicated completion. The mixture was passed through a silica gel stopper (150 g) and eluted with dichloromethane (500 mL). The organic matter was concentrated under reduced pressure. The residue was purified by passing through silica gel (800 g) and eluted with ethyl acetate to give compound (H) as a yellow solid. The solid was ground with methyl tert-butyl ether (2 × 200 mL) for 2 hours. The solid was collected by filtration and ground with chloroform (50 mL) for 30 minutes to obtain pure compound (H) (11.9 g, two-step yield 60%, purity 97.5%), which was a yellow solid.

[0456] The UV-VIS transmission spectrum of a 0.2 mM methanol solution of compound H at... Figure 2 The results are shown in the figure. ¹H NMR (500 MHz, DMSO-d6) δ 1.87 (3H, m, CH3), 3.15-3.20 (4H, m, CH2NH), 3.72 (3H, s, CH3N), 5.36 (1H, s, ethylene), 5.68 (1H, m, ethylene), 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).

[0457] Example 7 - Synthesis of 2-(2-cyanoacetamido)ethylacrylamide (I) and N-(2-(2-cyanoacetamido)ethylacrylamide (I) as shown in Scheme 8. 2-(9H-xanthon-9-ylidene)acetamido)ethyl)acrylamide (J)

[0458]

[0459] 2-(2-Cyanoacetamido)ethylacrylamide (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 g sodium carbonate were stirred in 150 mL of methanol while cooling in an ice bath. Acryloyl chloride (9.9 g, 1.1 eq.) was added dropwise to the suspension, while maintaining the reaction temperature below 30 °C throughout. After the reaction was complete, all volatiles were evaporated under reduced pressure, the product was redissolved in acetonitrile, and the solution was filtered to remove all present salts. The acetonitrile was evaporated under reduced pressure, and the resulting solid was washed with ethyl acetate over a sintered glass funnel to give the desired 2-(2-cyanoacetamido)ethylacrylamide (I). 1 ¹H NMR (500MHz, CD₃OD) δ 3.22–3.31 (8H, m, NH, CH₂), 5.59 (¹H, dd, ethylene), 6.14 (2H, dd, ethylene).

[0460] Under a nitrogen atmosphere, a mixture of xanthonone (3.92 g, 0.02 mol) and 5 mL of thionyl chloride (8.2 g, approx. 0.07 mol) in 10 mL of toluene was gently refluxed with constant stirring. After heating for six hours, the solution was cooled and the volatiles were evaporated under reduced pressure to ensure the removal of all unreacted thionyl chloride from the system. 2-(2-cyanoacetamido)ethylacrylamide (I) (3.8 g, approx. 1.05 eq.) and 20 mL of methylene chloride were added to the flask, and the mixture was gently refluxed under nitrogen for 3 hours while monitoring the progress by TLC. The volatile components were evaporated under reduced pressure. The residue was washed with warm ethyl acetate and filtered through a sintered glass funnel. The filter cake was washed with additional ethyl acetate and then with water. The pale yellow solid was dried in a vacuum oven. The UV-VIS transmission spectrum of a 0.2 mM methanol solution of compound J was obtained. Figure 2 As shown in the image. 1 ¹H NMR (500MHz, DMSO-d6) δ 3.15–3.25 (4H, m, CH₂), 5.62 (¹H, dd, ethylene), 6.08–6.23 (2H, m, ethylene), 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).

[0461] Example 8 - Synthesis of 2-(2-cyanoacetoxy)ethyl methacrylate (K) and methacrylate as shown in Scheme 9 2-(2-cyano-2-(9H-thioxanth-9-ylidene)acetoxy)ethyl ester (L)

[0462]

[0463] 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. Ethyl dimethylaminopropylcarbodiimide hydrochloride (EDC) (20 g, 0.104 mol) was then added to the suspension in four batches (5 g each). As a less polar derivative formed, the mixture gradually became more homogeneous, and after the reaction was complete, the evaporation was carried out 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 evaporation of the solvent under reduced pressure. 1 ¹H 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, ethylene), 6.10 (1H, m, ethylene).

[0464] Under a nitrogen atmosphere, a mixture of thioxanthone (4.24 g, 0.02 mol) and 8 mL of thionyl chloride (13.12 g, approximately 0.11 mol) was gently refluxed with constant stirring. After heating for two hours, the solution was evaporated to dryness under reduced pressure to ensure the removal of all unreacted thionyl chloride. A solution of 2-(2-cyanoacetoxy)ethyl methacrylate (K) (4.33 g, approximately 1.1 eq.) in 20 mL of degassed methylene chloride was added to the flask, and the mixture was gently refluxed under nitrogen for 3 hours while monitoring the progress by TLC. The residue was washed with methanol to remove most of the unreacted starting thioxanthone, concentrated, and the crude product was purified by chromatography on a silica gel stopper and dried under vacuum overnight. The UV-VIS transmission spectrum of compound L in a 0.2 mM solution in dichloromethane was obtained. Figure 2 As shown in the image. 1 ¹H NMR (500MHz, CDCl₃) δ 1.92 (3H, s, CH₃), 4.36 (2H, m, CH₂), 4.44 (2H, m, CH₂), 5.59 (1H, m, ethylene), 6.10 (1H, m, ethylene), 7.24–7.62 (7H, m, Ar-H), 8.1 (1H, m, Ar-H).

[0465] Example 9 - Organosilicon hydrogel formulation containing compound (B)

[0466] A reactive monomer mixture was prepared, consisting of 77 wt% of the formulations listed in Table 4 and 23 wt% of diluent D3O. The reactive monomer mixture was individually filtered under pressure through a 3 μm filter using a stainless steel syringe.

[0467] Table 4

[0468]

[0469] Formulation 9A-9D was degassed at ambient temperature under vacuum (40 Torr) for 45 minutes. Then, approximately 75 μL of the reactive mixture was dispensed into the FC (concentrated ferrite) made from a 90:10 (w / w) Zeonor / TT blend at room temperature using an Eppendorf pipette in a glove box with a nitrogen atmosphere and less than approximately 0.1% to 0.2% oxygen. The BC (concentrated ferrite) made from a 90:10 (w / w) Z:TT blend was then placed onto the FC. The molds were equilibrated in the glove box for at least twelve hours prior to dispensing. The pallets comprising the eight mold components were each transferred to adjacent glove boxes maintained at 65°C, and a strength of approximately 2 mW / cm was applied at the pallet location. 2 The 435nm LED light cures the lens from top to bottom for 15 minutes.

[0470] The lenses were manually demolded, with most adhering to the FC, and detached by suspending them in approximately one liter of 70% IPA for about one hour, then soaking twice in fresh 70% IPA for 30 minutes each time; then soaking twice in fresh DIW for 15 minutes each time; and then soaking twice in a wetting solution for 30 minutes each time. The lenses were then equilibrated and stored in a borate-buffered wetting solution. Those skilled in the art will recognize that the exact lens detachment process can vary depending on the lens formulation and molding material, in terms of the concentration of the isopropanol aqueous solution, the number of washes with each solvent, and the duration of each step. The aim of the lens detachment process is to detach all lenses without defects and to transform the network swollen by the diluent into a hydrogel swollen by the wetting solution. The average center thickness of each lens group was measured: 9A = 87.7 μm, 9B = 85.3 μm, 9C = 87.3 μm, and 9D = 85.7 μm.

[0471] Figures 3 to 5 The UV-VIS spectrum of lenses made from formulations 9A-9D is shown, indicating that compound (B) or compound (B) and The combination of these can provide full or near-full absorption between 300 nm and 400 nm, with some absorption occurring in the high-energy visible region between 400 nm and 450 nm.

[0472] Example 10 - Organosilicon hydrogel formulation containing compounds (B) and (C)

[0473] A reactive monomer mixture was prepared, consisting of 77% by weight of the formulations listed in Table 5 and 23% by weight of diluent D3O. The reactive monomer mixture was individually filtered under pressure through a 3 μm filter using a stainless steel syringe.

[0474] Table 5

[0475]

[0476] Formulation 10A-10D was degassed at ambient temperature by applying a vacuum (40 Torr) for 45 minutes. Then, approximately 75 μL of the reactive mixture was dispensed into the FC (fermented concrete) made from a 90:10 (w / w) Zeonor / TT blend at room temperature using an Eppendorf pipette in a glove box with a nitrogen atmosphere and less than approximately 0.1% to 0.2% oxygen. The BC (fermented concrete) made from a 90:10 (w / w) Z:TT blend was then placed onto the FC. The molds were equilibrated in the glove box for at least twelve hours prior to dispensing. The pallets containing the eight mold components were each transferred to adjacent glove boxes maintained at 65°C, and an intensity of approximately 2 mW / em was applied at the pallet location. 2 The 435nm LED light cures the lens from top to bottom for 15 minutes.

[0477] The lenses were manually demolded, with most adhering to the FC, and detached by suspending them in approximately one liter of 70% IPA for about one hour, then soaking twice in fresh 70% IPA for 30 minutes each time; then soaking twice in fresh DIW for 15 minutes each time; and then soaking twice in a wetting solution for 30 minutes each time. The lenses were then equilibrated and stored in a borate-buffered wetting solution. Those skilled in the art will recognize that the exact lens detachment process can vary depending on the lens formulation and molding material, in terms of the concentration of the isopropanol aqueous solution, the number of washes with each solvent, and the duration of each step. The aim of the lens detachment process is to detach all lenses without defects and to transform the network swollen by the diluent into a hydrogel swollen by the wetting solution. The average center thickness of each lens group was measured: 10A = 93.7 μm, 10B = 93.7 μm, 10C = 95.3 μm, and 10D = 92.3 μm.

[0478] Figures 6 to 8 The UV-VIS spectra of lenses made from formulation 10A-10D are shown, indicating that the combination of compounds (B) and (C) provides complete or near-complete absorption between 300 nm and 400 nm, with some absorption in the high-energy visible region between 400 nm and 450 nm. These figures also show that compound (C) alone provides absorption across a wide range of wavelengths.

[0479] Example 11

[0480] Lenses were manufactured using a reactive monomer mixture containing the components listed as 9D in Table 4, along with the same curing and hydration steps, except that the oxygen concentration in the glove box was less than 0.5%. Lenses were packaged in glass vials containing PS and then placed on a windowsill with direct sunlight (11A) or on top of a cabinet without direct sunlight, under only indoor lighting (11B). Controls were stored in darkness. The UV-Vis transmission spectra of the lenses were measured after 3, 5, 9, 15, and 21 weeks of exposure, as shown in the figure. Figure 9 and Figure 10 As shown.

[0481] For lenses exposed to direct sunlight, the absorption of high-energy visible light between 400 nm and 450 nm does not change over time. During the duration of the study, the UV-VIS transmission spectrum exhibits a small variation (approximately 1%) between 450 nm and 700 nm.

[0482] For lenses exposed to indoor lighting, the absorption of high-energy visible light between 400 nm and 450 nm did not change over time. During the duration of the study, the UV-VIS transmission spectrum varied by no more than approximately 2% or 3% between 450 nm and 700 nm.

[0483] Examples 12-25 are hypothetical examples.

[0484] Example 12: (Z)-Methacrylic acid 2-(2-cyano-2-(3-hydroxyacridin-9(10H)-ylidene)acetamido) Ethyl acetate

[0485] The title compound can be synthesized from 3-hydroxyacridone (CAS registration number: 20168-55-2) using a process similar to that described above.

[0486] Example 13: Ethyl 2-(2-cyano-2-(10-methylacridin-9(10H)-ylidene)acetamido)methacrylate

[0487] The title compound can be synthesized from N-methylacridone (719-54-0) through a process similar to that described above.

[0488] Example 14: 2-(2-cyano-2-(3,6-dihydroxyacridin-9(10H)-ylidene)acetamidomethacrylic acid) Ethyl acetate

[0489] The title compound can be synthesized from 3,6-dihydroxyacridone (122105-95-7) through a process similar to that described above.

[0490] Example 15: (E)-Methacrylic acid 2-(2-(7H-benzo[c]xanthon-7-ylidene)-2-cyanoacetamido)ethyl ester

[0491] The title compound can be synthesized from benzo[C]xanthonone (63154-69-8) through a process similar to that described above.

[0492] Example 16: (Z)-Methacrylic acid 2-(2-cyano-2-(3-methoxy-9H-xanthine-9-ylidene)acetamido) Ethyl acetate

[0493] The title compound can be synthesized from 3-methoxyxanthone (3722-52-9) using a process similar to that described above.

[0494] Example 17: 2-(2-cyano-2-(3,6-dihydroxy-9H-xanthon-9-ylidene)acetamido)methacrylic acid ester

[0495] The title compound can be synthesized from 3,6-dihydroxyxanthonone (1214-24-0) through a process similar to that described above.

[0496] Example 18: (E)-Methacrylic acid 2-(2-cyano-2-(2-methyl-9H-xanthon-9-ylidene)acetamido)ethyl ester

[0497] The title compound can be synthesized from 2-methylxanthone (2680-45-1) using a process similar to that described above.

[0498] Example 19: (E)-Methacrylic acid 2-(2-cyano-2-(1-hydroxy-9H-xanthon-9-ylidene)acetamido)ethyl ester

[0499] The title compound can be synthesized from 1-hydroxyxanthonone (19-41-5) using a process similar to that described above.

[0500] Example 20: (E)-Methacrylic acid 2-(2-cyano-2-(2,4-dichloro-9H-thioxanth-9-ylidene)acetamide ethyl acetate

[0501] The title compound can be synthesized from 2,4-dichlorothioxanone using a process similar to that described above.

[0502] Example 21: (E)-Methacrylate 2-(2-(2-chloro-9H-thioxanthoxy-9-ylidene)-2-cyanoacetamido)ethyl ester

[0503] The title compound can be synthesized from 2-chlorothioxanone using a process similar to that described above.

[0504] Example 22: (E)-Methacrylic acid 2-(2-cyano-2-(2-isopropyl-9H-thioxanthoxy-9-ylidene)acetamido) Ethyl ester and (E)-methacrylic acid 2-(2-cyano-2-(4-isopropyl-9H-thioxanthoxy-9-ylidene)acetamido)ethyl ester

[0505] The title compound in mixture form can be synthesized from a mixture of 2- and 4-isopropylthioxanthone using a process similar to that described above.

[0506] Examples 23-25

[0507] Contact lenses made from the silicone hydrogel formulations shown in Table 6 can be prepared using a process similar to that described in Example 6. In these examples, 77% by weight of the formulations listed in Table 6 are diluted with 23% by weight of a diluent (e.g., D3O).

[0508] Table 6

[0509]

[0510]

Claims

1. An ophthalmic device, said ophthalmic device being a reaction product of a reactive mixture, said reactive mixture comprising: High-energy light-absorbing compounds that can be polymerized; and One or more monomers, said one or more monomers being suitable for manufacturing ophthalmic devices. The ophthalmic device described herein transmits light: 45% or less of the light has wavelengths between 280 nm and 399 nm; 1% to 70% of light has wavelengths between 400 nm and 409 nm; At least 80% of the light has wavelengths between 450nm and 800nm. 10% to 95% of light has wavelengths between 410 nm and 424 nm; and At least 50% of the light has wavelengths between 425 nm and 449 nm. The polymerizable high-energy light-absorbing compound mentioned above includes compounds of formula I: Formula I in: m and n are 0; T is either O or NR; X is O, S, NR, or SO2; Y is a C1-C6 alkylene group; P g The polymerizable group is selected from (meth)acrylate groups and (meth)acrylamide groups; R is independently H or C1-C6 alkyl each time it appears; and EWG is an electron-withdrawing group, which is a cyano group.

2. The ophthalmic device according to claim 1, wherein the ophthalmic device transmits: 20% or less of the light with wavelengths between 280 nm and 399 nm; 3% to 70% of light has wavelengths between 400 nm and 409 nm; and At least 85% of the light has a wavelength between 450 nm and 800 nm.

3. The ophthalmic device according to claim 1, wherein the ophthalmic device further comprises a second polymerizable high-energy light-absorbing compound.

4. The ophthalmic device of claim 3, wherein the second polymerizable high-energy light-absorbing compound is a UV-absorbing compound.

5. The ophthalmic device according to claim 4, wherein the UV-absorbing compound comprises a compound of formula I, benzophenone, benzotriazole, triazine, substituted acrylonitrile, salicylic acid derivative, benzoic acid derivative, cinnamic acid derivative, chalcone derivative, diphenyl ethyl ketone derivative, crotonic acid derivative, or mixtures thereof.

6. The ophthalmic device according to any one of claims 1 to 5, wherein the polymerizable high-energy light-absorbing compound comprises a mixture of a compound of formula I wherein X is S and a compound of formula I wherein X is O.

7. The ophthalmic device according to any one of claims 1 to 5, 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.

8. The ophthalmic device according to any one of claims 1 to 5, wherein the ophthalmic device is a silicone hydrogel contact lens, and wherein the silicone hydrogel contact lens has a contact angle of 70° or less, a water content of at least 25%, and an oxygen permeability of at least 80 bar.

9. An ophthalmic device, said ophthalmic device being a polymerization product of a reactive mixture comprising a hydrophilic component and an organosilicon-containing compound, said polymerization product containing one or more chromophores of formula IV as covalently bonded substituents: Formula IV in m and n are 0; X is O, S, NR, or SO2; R is independently H or C1-C6 alkyl each time it appears; R 5 The linker to the polymerization product comprises polymerizable groups and C1-C6 alkylene group residues. The polymerizable group is selected from (meth)acrylate groups and (meth)acrylamide groups; and EWG is an electron-withdrawing group, specifically a cyano group. The ophthalmic device described herein transmits light: 45% or less of the light has wavelengths between 280 nm and 399 nm; 1% to 70% of light has wavelengths between 400 nm and 409 nm; At least 80% of the light has wavelengths between 450nm and 800nm. 10% to 95% of light has wavelengths between 410 nm and 424 nm; and At least 50% of the light has a wavelength between 425 nm and 449 nm.

10. The ophthalmic device according to claim 9, wherein X is O.

11. The ophthalmic device according to claim 9, wherein X is S.

12. The ophthalmic device according to any one of claims 9 to 11, wherein the polymerization product further comprises one or more UV-absorbing chromophores covalently linked to the polymerization product.

13. The ophthalmic device of claim 12, wherein the UV-absorbing chromophore is a residue of benzophenone, benzotriazole, triazine, substituted acrylonitrile, salicylic acid derivative, benzoic acid derivative, cinnamic acid derivative, chalcone derivative, diphenyl ethyl ketone derivative, crotonic acid derivative, or a mixture thereof.

14. A silicone hydrogel contact lens, said silicone hydrogel contact lens being a reaction product of a reactive mixture comprising: a polymerizable high-energy light-absorbing compound; and one or more monomers suitable for manufacturing ophthalmic devices, wherein said contact lens has a contact angle of 70° or less, a water content of at least 25%, and an oxygen permeability of at least 80 bar, and wherein said contact lens is substantially photostable. The silicone hydrogel contact lens transmits light: 45% or less of the light has wavelengths between 280 nm and 399 nm; 1% to 70% of light has wavelengths between 400 nm and 409 nm; At least 80% of the light has wavelengths between 450nm and 800nm. 10% to 95% of light has wavelengths between 410 nm and 424 nm; and At least 50% of the light has wavelengths between 425 nm and 449 nm. The polymerizable high-energy light-absorbing compound mentioned above includes compounds of formula I: Formula I in: m and n are 0; T is either O or NR; X is O, S, NR, or SO2; Y is a C1-C6 alkylene group; P g The polymerizable group is selected from (meth)acrylate groups and (meth)acrylamide groups; R is independently H or C1-C6 alkyl each time it appears; and EWG is an electron-withdrawing group, which is a cyano group.

15. A silicone hydrogel, said silicone hydrogel being formed from a reactive mixture comprising: High-energy light-absorbing compounds; At least one polyamide, ranging from 1% to 15% by weight; At least one first monofunctional hydroxyl-substituted poly(disubstituted siloxane) having 4 to 8 siloxane repeating units; At least one second hydroxyl-substituted poly(disubstituted siloxane), which is a monofunctional hydroxyl-substituted poly(disubstituted siloxane) having 10 to 200 siloxane repeating units; and At least one hydrophilic monomer, ranging from 5% to 35% by weight. The silicone hydrogel can be used to make silicone hydrogel contact lenses, and the silicone hydrogel contact lenses transmit light. 45% or less of the light has wavelengths between 280 nm and 399 nm; 1% to 70% of light has wavelengths between 400 nm and 409 nm; At least 80% of the light has wavelengths between 450nm and 800nm. 10% to 95% of light has wavelengths between 410 nm and 424 nm; and At least 50% of the light has wavelengths between 425 nm and 449 nm. The polymerizable high-energy light-absorbing compound mentioned above includes compounds of formula I: Formula I in: m and n are 0; T is either O or NR; X is O, S, NR, or SO2; Y is a C1-C6 alkylene group; P g The polymerizable group is selected from (meth)acrylate groups and (meth)acrylamide groups; R is independently H or C1-C6 alkyl each time it appears; and EWG is an electron-withdrawing group, which is a cyano group.

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