Aryl phosphonate-type compounds, their reactive monomer mixture, and their use in the manufacture of ophthalmic lenses

Abstract

Provided are compounds that can act as functionalized polymerization initiators, for example, in the manufacture of ophthalmic lenses, and methods for such manufacture. These compounds have formula I: wherein R1, R2, R3, R4, R5, T, p, q, and n are as defined herein.

Description

Technical Field

[0001] Related applications

[0002] This application claims priority to U.S. Patent Application Serial No. 17 / 821,315, filed August 22, 2022; and U.S. Provisional Patent Application Serial No. 63 / 249,646, filed September 29, 2021, the entire contents of which are incorporated herein by reference.

[0003] This invention relates generally to the field of ophthalmic lenses, and more specifically to compositions and methods for imparting various properties and attributes to ophthalmic lenses formed using casting molding techniques. Prior Technology

[0004] In today's world, the use of ophthalmic lenses to correct vision is quite common. The traditional and most common method for manufacturing soft contact lenses is through casting molding, in which a polymerizable liquid is placed between two half-molds, which together form the desired shape of the lens, and the entire liquid system solidifies between the two half-molds. The lens is then removed from the mold and undergoes certain post-processing steps.

[0005] A new system and method for manufacturing contact lenses has recently been disclosed, in which an unlimited number of truly customized lenses can be easily produced in a cost-effective manner. U.S. Patent No. 8,317,505, incorporated herein by reference in its entirety, discloses a method for generating a "lens precursor form" on a single mold or optical mandrel based on individual stereo pixels by selectively projecting photochemical radiation through an optical mandrel and into a vat or bath of a photocurable reactive monomer mixture. The optical mandrel and lens precursor are then removed from the vat and inverted, such that the convex surface of the optical mandrel is upright. After a dwell period (during which uncured residual liquid from the bath remaining on the lens precursor form flows through the lens precursor form under gravity or otherwise), the residual liquid is then cured by applying fixed radiation to form the final lens. As described above, the system utilizes a single mold instead of the two and a half molds in traditional casting molding, and allows for the production of truly customized lenses by simply "re-programming" software instructions rather than changing equipment or components.

[0006] As described in '505 patent, photochemical radiation is projected through a mold and enters the reaction mixture at different locations in an array, each of which is selectively controllable, to selectively solidify the reactive mixture to a predetermined depth at any point within the array (based on "voxels"), thereby "generating" a lens from the convex side of the mold. As used herein, the term "voxel" is the same as in '505 patent and refers to a volume element, representing a value on a regular grid in three-dimensional space. A voxel can be considered a three-dimensional pixel, where each voxel is associated with a specific point in a selectively controllable array.

[0007] While '505 represents a significant advancement in lens manufacturing capabilities, further development is still needed, such as expanding the options for manufacturing customizable lenses that incorporate functional features to further enhance the lens wearer's experience. Summary of the Invention

[0008] As described in this disclosure, the invention includes novel compositions that can be used as polymerization initiators in the methods described herein and in a concurrently filed U.S. patent application entitled "OPHTHALMIC LENSES AND THEIR MANUFACTURE BY IN-MOLD MODIFICATION," which designates Michael Widman, Ghulam Maharvi, Shivkumar Mahadevan, Azaam Alli, Alex Guzman, Xin Wei, and Minghan Chen as inventors, the entire contents of which are incorporated herein by reference. Such methods utilize the techniques detailed in '505 patent to provide novel compositions and methods for spatially incorporating functional portions, geometries, and / or physical properties into ophthalmic lenses manufactured via casting molding.

[0009] This invention is particularly applicable to spatially controlling and imparting various properties to lenses manufactured via casting molding without costly procedural modifications. The compounds of this invention contain refractive index-modifying segments (including amide segments) and polymerization initiator segments. Therefore, this invention enables the use, for example, of compounds spatially incorporated into lenses to impart refractive index properties. Such properties can provide personalized patient solutions for conditions such as presbyopia.

[0010] Therefore, in one embodiment, the present invention provides a compound that can be used as a polymerization initiator in the method of manufacturing ophthalmic lenses described herein and in the applicant's concurrently filed U.S. patent application. The compound of the present invention has formula I: R1, R2, R3, R4, R5, T, p, q, and n are defined as in this paper.

[0011] In another embodiment, the present invention provides a method for forming an ophthalmic lens. The method comprises: (a) providing a mold assembly including a base surface and a front surface, the base surface and the front surface defining and surrounding a cavity therebetween, the cavity containing a reactive monomer mixture, wherein the reactive monomer mixture includes a monomer suitable for manufacturing the ophthalmic lens, a first polymerization initiator capable of being activated at a first wavelength, a first functional portion chemically linked to the first polymerization initiator, and a second polymerization initiator capable of being activated by a second activation, the second activation not substantially activating the first polymerization initiator, wherein at least one of the base surface or the front surface is light-transmitting; (b) causing the reactive monomer mixture to react with the reactive monomer. (c) Exposing one or more selective regions of the monomer mixture to a photochemical radiation source at the first wavelength to selectively polymerize a portion of the reactive monomer mixture, wherein the selectively polymerized portion is incorporated into the first functional portion; (d) exposing the reactive monomer mixture to the second activation to activate the second polymerization initiator and solidify the reactive monomer mixture; (e) removing the ophthalmic lens from the mold assembly; and (f) extracting unreacted first polymerization initiator from the ophthalmic lens, wherein the first polymerization initiator having a chemically linked first functional portion is a compound of Formula I as described herein.

[0012] In a further embodiment, the present invention provides a reactive monomer mixture for manufacturing ophthalmic lenses. The reactive monomer mixture comprises: a monomer suitable for manufacturing ophthalmic lenses; and a first polymerization initiator capable of being activated at a first wavelength. A first functional portion, which is chemically linked to the first polymerization initiator; and a second polymerization initiator, which can be activated by a second activation that does not substantially activate the first polymerization initiator, wherein the first polymerization initiator having the chemically linked first functional portion is a compound of Formula I as described herein. Simple Explanation of the Diagram

[0013] [Figure 1] Illustrates prior art equipment used for forming customized contact lenses; [Figure 2] is an enlarged view of the forming optical part of the prior art device shown in Figure 1; [Figure 3] illustrates an illustrative curing apparatus, which includes a casting mold in an exposed fixture that can be used to form lenses according to the system and method described herein. [Figure 4] shows the 500 MHz 1H-NMR spectrum of MAPO-PVP in deuterium oxide. [Figure 5] shows the SEC-MALS tomography of MAPO-PVP, PVP K30 and PVP K12. [Figure 6] shows the 500 MHz 1H-NMR spectrum of MAPO-PDMA in deuterated methanol. [Figure 7] shows the USAF 1951 test chart. [Figure 8] Image of the USAF 1951 test chart applied to a contact lens. [Figure 9] shows spherical / defocused and cylindrical projected images and the measured wavefront. Implementation

[0014] 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. All publications, patent applications, patents, and other references mentioned herein are incorporated herein by reference.

[0015] Unless otherwise indicated, a number range such as "2 to 10" or "between 2 and 10" includes the numbers that define the range (e.g., 2 and 10).

[0016] Unless otherwise indicated, ratios, percentages, parts and the like are by weight.

[0017] The phrase "number average molecular weight" refers to the number average molecular weight (Mn) of a sample; the phrase "weight average molecular weight" refers to the weight average molecular weight (Mw) of a sample; the phrase "polydispersity index" (PDI) refers to the ratio of Mw to Mn and describes the molecular weight distribution of a sample. If the type of "molecular weight" is not specified or is not obvious from the context, then it is intended to refer to the weight average molecular weight.

[0018] As used in this article, the term "about" refers to a range of + / - 10 percent of the number it modifies. For example, the phrase "about 10" would include both 9 and 11.

[0019] As used herein, the term "(meth)" indicates optional methyl substitution. Therefore, terms such as "(meth)acrylate" refer to both methacrylate and acrylate.

[0020] Where chemical structures are given, it should be understood that the substitutes disclosed as substituents on that structure can be combined in any combination. Therefore, if a structure contains substituents R* and R**, each containing three lists of potential groups, then nine combinations are revealed. The same understanding applies to combinations of properties.

[0021] The average number of repeating units in a polymer sample is called its "degree of polymerization". When using the general chemical formula of a polymer sample (such as [***] n), "n" refers to its degree of polymerization, and the formula should be interpreted as representing the number-average molecular weight of the polymer sample.

[0022] As used in this article, the term "individual" includes both humans and vertebrates.

[0023] As used herein, the term "ophthalmic device" means any device that resides in or on the eye or any part thereof (including the surface of the eye). Such devices may provide optical correction, enhance appearance, improve vision, provide therapeutic benefits (e.g., as a bandage), or deliver active ingredients (such as pharmaceutical and nutritional components), or any combination thereof. Preferred ophthalmic devices are ophthalmic lenses, including soft contact lenses, rigid contact lenses (including rigid gas-permeable lenses), hybrid contact lenses, artificial lenses, and inset and overlay lenses. Ophthalmic devices may preferably include contact lenses.

[0024] As used herein, the term "contact lens" refers to an ophthalmic device that can be placed on the cornea of ​​an individual's eye. Contact lenses can correct refractive errors to improve vision, absorb ultraviolet or visible light to provide protection or color enhancement, and may also provide cosmetic benefits, such as altering the color and pattern of the wearer's iris. Contact lenses can be made of any suitable material known in the art and can be soft lenses, rigid lenses, or hybrid lenses containing at least two dissimilar components with different physical, mechanical, or optical properties, such as modulus, water content, light transmission, or combinations thereof.

[0025] The ophthalmic devices, ophthalmic lenses, and contact lenses of the present invention may comprise polysiloxane hydrogels. These polysiloxane hydrogels generally contain at least one hydrophilic component covalently bonded to each other in a curing apparatus and at least one polysiloxane-containing component. The ophthalmic devices, ophthalmic lenses, and contact lenses of the present invention may also comprise conventional hydrogels, or combinations of conventional hydrogels and polysiloxane hydrogels.

[0026] "Macromolecule" refers to an organic compound with a number average molecular weight greater than 1500, and can be reactive or non-reactive.

[0027] As used herein, a "target macromolecule" is a desired macromolecule synthesized from reactive components including monomers, macromonomers, prepolymers, crosslinking agents, initiators, additives, diluents, and the like.

[0028] As used herein, a "monomer" is a monofunctional molecule that can undergo chain-linked growth polymerization, specifically free radical polymerization, to establish repeating units in the chemical structure of a target macromolecule. Some monomers possess bifunctional impurities that can act as crosslinking agents. A "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. A "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. A hydrophilic component may contain at least one polymerizable group. Preferably, a hydrophilic component consists of a single polymerizable group.

[0029] As used in this article, a "macromonomer" is a linear or branched macromolecule that has at least one polymerizable group that can undergo chain-linked growth polymerization and, in particular, free radical polymerization.

[0030] As used herein, the term "polymerizable" means that a compound contains at least one polymerizable group. A "polymerizable group" is a group capable of undergoing chain-linked growth polymerization (such as free radical and / or cationic polymerization), for example, a carbon-carbon double bond group polymerizable when subjected to free radical polymerization initiation conditions. Non-limiting examples of polymerizable groups include (meth)acrylates, styrene, vinyl ethers, (meth)acrylamide, N-vinyl lactone, N-vinylamide, O-vinylaminocarbamate, O-vinyl carbonate, and other vinyl groups. Preferably, the polymerizable group comprises (meth)acrylates, (meth)acrylamide, and mixtures thereof. More preferably, the polymerizable group comprises (meth)acrylates, (meth)acrylamide, N-vinyl lactone, N-vinylamide, styrene functional groups, or mixtures of any of the foregoing. The polymerizable group may be unsubstituted or substituted. For example, the nitrogen atom in (meth)acrylamide can be bonded to hydrogen, or the hydrogen can be replaced by alkyl or cycloalkyl groups (which themselves can be further substituted). Compared to "polymerizable," the term "non-polymerizable" means that the compound does not contain such radical polymerizable groups.

[0031] The foregoing examples include substituted or unsubstituted C1-6 alkyl (meth)acrylates, C1-6 alkyl (meth)acrylamide, C2-12 alkenyl, C2-12 alkenylphenyl, C2-12 alkenylnaphthyl, C2-6 alkenylphenyl, and C1-6 alkyl, wherein suitable substituents on the C1-6 alkyl group include ethers, hydroxyl groups, carboxyl groups, halogens, and combinations thereof.

[0032] Any type of free radical polymerization can be used, including but not limited to total polymerization, solution polymerization, suspension polymerization, and emulsion polymerization, as well as any controlled free radical polymerization method, such as stable free radical polymerization, nitroxy-mediated living polymerization, atom transfer radical polymerization, reversible addition-fragmentation chain transfer polymerization, organotellurium-mediated living radical polymerization, and the like.

[0033] In radical polymerization, in the absence of chain transfer reactions, the propagating chain can be terminated by radical coupling or disproportionation. In coupling, two propagating chains simply merge to form a single bond, and the resulting polymer has end groups composed of initiator fragments. In disproportionation, a propagating chain radical extracts a proton from another propagating chain adjacent to it, thereby forming a terminal double bond. Chain transfer reactions can occur with any component in the reaction mixture, such as chain transfer to monomers, chain transfer to branching polymers, chain transfer to initiators, and chain transfer to any intentionally added chain transfer agent to reduce and control molecular weight. In most chain transfer reactions, the propagating chain extracts a proton from another molecule, thereby terminating chain growth and simultaneously generating another radical. The term "chain terminating group" refers to a chemical group that ends chain growth and becomes an end group of the final polymer. In most cases, the chain-terminating group is a proton, but others are known or thought to occur, such as chain transfer to a peroxide initiator, where the chain-terminating group depends on the peroxide, for example, in the case of benzoyl peroxide, the chain-terminating group is a benzoate.

[0034] As used herein, "silicone-containing component" or "silicone component" refers to a monomer, macromonomer, prepolymer, crosslinking agent, initiator, additive, or polymer having at least one silicon-oxygen bond in a reactive composition. The at least one silicon-oxygen bond is generally in the form of a siloxy group, a siloxane group, a carbosiloxane group, or a mixture thereof. Examples of polysiloxane-containing components that can be used in this invention can be found in U.S. Patents 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 5,849,811. 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, 7,666, 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, 8,937,110, 8, The following patents are cited: Nos. 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 hereby incorporated by reference. The polysiloxane-containing component may contain at least one polymerizable group. The polysiloxane-containing component may preferably consist of one or two polymerizable groups.

[0035] "Polymer" refers to a target macromolecule that includes the repeating units of monomers and macromonomers used during polymerization.

[0036] A homopolymer is a polymer made from a single monomer; a copolymer is a polymer made from two or more monomers; a trimer is a polymer made from three monomers. A block copolymer is composed of blocks or segments of different compositions. A diblock copolymer has two blocks. A triblock copolymer has three blocks. A comb or graft copolymer is made from at least one macromolecular monomer.

[0037] A "repeating unit" is the smallest group of atoms in a polymer that is a polymer of a specific monomer or a macromonomer.

[0038] An "initiator" is a molecule that can decompose into free radicals that can react with monomers to initiate free radical polymerization. Thermal initiators decompose at a rate dependent on temperature; common examples include: azo compounds such as azobisisobutyronitrile and 4,4'-azobis(4-cyanopentanoic acid); peroxides such as benzoyl peroxide, tributyl peroxide, tributyl hydroperoxide, tributyl peroxybenzoate, diisopropylphenyl peroxide, and lauryl peroxide; peracids such as peracetic acid and potassium persulfate; and various redox systems. Photoinitiators decompose through a photochemical process; common examples include phenylethylene glycol, benzoin, acetophenone, diphenyl ketone, camphorquinone, and derivatives thereof, as well as various mono- and di-phosphine oxides and combinations thereof.

[0039] A "free radical group" is a molecule that has unpaired valence electrons that can react with polymerizable groups to initiate free radical polymerization.

[0040] A "cross-linking agent / crosslinker" is a bifunctional or polyfunctional monomer that can undergo free radical polymerization at two or more positions on its molecule to establish branch points and polymeric networks. The two or more polymerizable functional groups on the cross-linking agent can be the same or different, for example, independently selected from vinyl (including allyl), (meth)acrylate, and (meth)acrylamide groups. Common examples are ethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, methylenebisacrylamide, triallyl cyanurate, and similar compounds.

[0041] "Prepolymer" is the reaction product of monomers (or macromonomers) that contains residual polymerizable groups that can undergo further reactions to form polymers.

[0042] "Polymeric network" refers to a type of polymer that exists in the form of cross-linked macromolecules. Typically, polymeric networks can expand but are insoluble in solvents. For example, the cross-linked matrix network of this invention is a material that can expand but does not dissolve.

[0043] A hydrogel is a polymeric network that expands in water or an aqueous solution, typically absorbing at least 10% by weight of water (at 25°C). A silicone hydrogel is a hydrogel made of at least one silicone component and at least one hydrophilic component. The hydrophilic component may also include a non-reactive polymer.

[0044] "Conventional hydrogel" refers to a polymeric network made of monomers that do not contain any silica-oxygenated, siloxane-based, or carbosiloxane-based groups. Conventional hydrogels are prepared from reactive components that mainly contain hydrophilic monomers, such as 2-hydroxyethyl methacrylate ("HEMA"), N-vinylpyrrolidone ("NVP"), N,N-dimethylacrylamide ("DMA"), or vinyl acetate.

[0045] As used herein, the term "reactive composition" refers to a composition containing one or more reactive components (and optionally non-reactive components) mixed together (when more than one is present) and forming a polymer composition when subjected to polymerization conditions. If more than one component is present, the reactive composition may also be referred to herein as a "reactive mixture" or "reactive monomer mixture" (or RMM). A reactive composition includes: reactive components, such as monomers, macromonomers, prepolymers, crosslinking agents, and initiators; and optional additives, such as wetting agents, releasing agents, dyes, light-absorbing compounds (such as UV-VIS absorbers), pigments, dyes, and photochromic compounds (any of which may be reactive or non-reactive, but preferably retainable in the resulting polymer composition and pharmaceutical and nutrient compounds), and any diluents. It should be understood that a wide range of additives may be added based on the final product produced and its intended use. The concentration of a reactive component is expressed as a weight percentage of all components in the reactive component (excluding diluent). When a diluent is used, the concentration is expressed as a weight percentage based on the amount of all components in the reactive component and the amount of diluent.

[0046] "Reactive component" refers to a component in a reactive composition that becomes part of the chemical structure of the resulting material through covalent bonding, hydrogen bonding, electrostatic interaction, the formation of an interpenetrating polymer network, or any other means. Examples include, but are not limited to, polysiloxane reactive components (such as the polysiloxane-containing components described below) and hydrophilic reactive components (such as the hydrophilic monomers described below).

[0047] As used herein, the term "silicone hydrogel contact lens" refers to a contact lens containing at least one type of polysilicone hydrogel. Compared to conventional hydrogels, polysilicone hydrogel contact lenses typically offer increased oxygen permeability. Polysilicone hydrogel contact lenses utilize both their water and polymer inclusions to deliver oxygen to the eye.

[0048] A "DMD" stands for Digital Micromirror Device, which can be a bistable spatial light modulator composed of a movable array of micromirrors functionally mounted on a CMOS SRAM. Data is loaded into memory cells located beneath each mirror, allowing independent control of each mirror to guide reflected light and spatially map video data pixels onto the display. The data electrostatically controls the tilt angle of the mirrors in a binary manner, with the mirror state being +X degrees (on) or -X degrees (off). Light reflected from the on mirror then passes through a projection lens and is projected onto the screen. The light is reflected away to establish a dark field and define the black-level floor of the image. The image is established by adjusting the grayscale between the on and off levels at a rate fast enough for the observer to integrate. A DMD may include a digital light processing (DLP) projection system.

[0049] "DMD script" refers to the control protocol and image file used in spatial light conditioners, and also refers to the control signals of any system component, such as a light source or filter wheel, any of which may include a sequence of commands in time.

[0050] The term "multi-functional" refers to a component having two or more polymerizable groups. The term "mono-functional" refers to a component having one polymerizable group.

[0051] The terms "halogen" or "halo" refer to fluorine, chlorine, bromine, and iodine.

[0052] As used herein, the term "alkyl" means an unsubstituted or substituted straight-chain or branched alkyl group containing an indicated number of carbon atoms. If no number is indicated, the alkyl group (optionally including any substituent thereon) may contain 1 to 16 carbon atoms. Preferably, the alkyl group contains 1 to 10 carbon atoms, alternatively 1 to 7 carbon atoms, or alternatively 1 to 4 carbon atoms. Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, secondary butyl, tertiary butyl, pentyl, hexyl, heptyl, 3-ethylbutyl, and the like. Examples of substituents on the alkyl group include 1, 2, or 3 groups, which are independently selected from hydroxyl, amino, amide, oxa, carboxyl, alkylcarboxyl, carbonyl, alkoxy, amide, carbamate, carbonate, halogen, phenyl, benzyl, and combinations thereof. "alkylene" refers to divalent alkyl groups, such as -CH 2-, -CH 2CH 2-, -CH 2CH 2CH 2-, -CH 2CH(CH 3)CH 2-, and -CH 2CH 2CH 2CH 2-.

[0053] "Haloalkyl" means an alkyl group as defined above that has been substituted with one or more halogen atoms, wherein each halogen is independently F, Cl, Br, or I. F is preferred. Haloalkyl groups preferably contain 1 to 6 carbons, more preferably 1 to 4 carbons, and even more preferably 1 to 2 carbons. "Haloalkyl" includes perhaloalkyl, such as -CF3- or -CF2CF3-. "Haloalkylene" means a divalent haloalkyl, such as -CH2CF2-.

[0054] "Cycloalkyl" refers to an unsubstituted or substituted cyclic hydrocarbon containing an indicated number of cyclic carbon atoms. If the number is not indicated, the cycloalkyl may contain 3 to 12 cyclic carbon atoms. Preferably, it is a C3-C8 cycloalkyl, more preferably a C4-C7 cycloalkyl, and even more preferably a C5-C6 cycloalkyl. Examples of cycloalkyl include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. Examples of substituents on the cycloalkyl group include 1, 2, or 3 groups, which are independently selected from alkyl, hydroxyl, amino, amide, oxa, carbonyl, alkoxy, amide, carbamate, carbonate, halogroup, phenyl, benzyl, and combinations thereof. "Cycloalkylene" means a divalent cycloalkyl, such as 1,2-cyclohexyl, 1,3-cyclohexyl, or 1,4-cyclohexyl.

[0055] "Heterocycloalkyl" refers to a cycloalkyl ring or ring system as defined above, in which at least one ring carbon has been heteroatom-substituted, the heteroatom system being selected from nitrogen, oxygen, and sulfur. The heterocycloalkyl ring may optionally be fused to or otherwise attached to other heterocycloalkyl rings and / or non-aromatic hydrocarbon rings and / or benzene rings. Preferably, the heterocycloalkyl ring has 5 to 7 members. More preferably, it has 5 or 6 members. "Heterocycloalkylene" refers to a divalent heterocycloalkyl ring.

[0056] "Aryl" refers to an unsubstituted or substituted aromatic ring system containing at least one aromatic ring. The aryl group contains an indicated number of ring carbon atoms. If no number is indicated, the 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 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, amide, carbamate, carbonate, halogroup, phenyl, benzyl, and combinations thereof. "Arylene" means a divalent aryl group, such as 1,2-arylphenyl, 1,3-arylphenyl, or 1,4-arylphenyl.

[0057] "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. The heteroaryl ring may be fused or otherwise attached to one or more heteroaryl rings, aromatic or non-aromatic hydrocarbon rings, or heterocyclic alkyl rings. Examples of heteroaryls include pyridyl, furanyl, and thiophene. "Heteroarylene" refers to a divalent heteroaryl.

[0058] "Alkoxy" refers to an alkyl group attached to a molecule-loving moiety via an oxygen bridge. Examples of alkoxy groups include methoxy, ethoxy, propoxy, and isopropoxy. "Aryloxy" refers to an aryl group attached to a molecule-loving moiety via an oxygen bridge. Examples include phenoxy. "Cyclic alkoxy" refers to a cycloalkyl group attached to a molecule-loving moiety via an oxygen bridge.

[0059] "Alkylamine" refers to an alkyl group attached to the parent molecule via a -NH bridge. Alkylamines specifically refer to divalent alkylamine groups, such as -CH₂CH₂NH⁻.

[0060] "Siloxanyl" refers to a structure having at least one Si-O-Si bond. Therefore, for example, siloxanyl means a group having at least one Si-O-Si group (i.e., a siloxanyl group), and a siloxanyl compound means a compound having at least one Si-O-Si group. "Siloxanyl" encompasses monomers (e.g., Si-O-Si) and oligomeric / polymeric structures (e.g., -[Si-O]n-, where n is 2 or greater). Each silicon atom in a siloxanyl group is replaced with an independently selected RA group (where RA is as defined in options (b) to (i) of formula A) to complete its valence.

[0061] "Silyl" refers to the structure of formula R 3Si-, and "siloxy" refers to the structure of formula R 3Si-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.

[0062] "alkyleneoxy" refers to a group of the general formula -(alkylene-O)p- or -(O-alkylene)p-, 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 may be optionally substituted by one or more groups, which are independently selected from hydroxyl, halogen (e.g., fluoro), amino, amide, ether, carbonyl, carboxyl, and combinations thereof. If p is greater than 1, the alkylene groups may be the same or different, and the alkyleneoxy group may be block or random. When the alkyleneoxy group forms a terminal group in a molecule, the terminal of the alkyleneoxy group may be, for example, a hydroxyl or an alkoxy group (e.g., HO-[CH 2CH 2O] p- or CH 3O-[CH 2CH 2O] p-). Examples of poly(ethoxy) compounds include poly(ethoxy), poly(propoxy), poly(butoxy), and poly(ethoxy-co-propoxy).

[0063] "Oxaalkylene" refers to an alkylene group as defined above in which one or more non-adjacent CH2 groups have been substituted with oxygen atoms, such as -CH2CH2OCH(CH3)CH2-. "Thiaalkylene" refers to an alkylene group as defined above in which one or more non-adjacent CH2 groups have been substituted with sulfur atoms, such as -CH2CH2SCH(CH3)CH2-.

[0064] The term "linking group" refers to the portion of a polymerizable group that is bonded to a parent molecule. A linking group can be any part that does not unintentionally interfere with the polymerization of the compound to which it belongs. For example, a linking group can be a bond, or it can contain one or more alkyl groups, haloalkyl groups, amides, amines, alkylamines, carbamates, carboxylic esters (-CO 2-), aryl groups, heteroaryl groups, cycloalkyl groups, heterocycloalkyl groups, alkoxy groups, oxaalkyl groups, thiaalkyl groups, haloalkoxy groups (alkoxy groups substituted with one or more halogen groups, such as -OCF 2-, -OCF 2CF 2-, -OCF 2CH 2-), siloxyalkyl groups, alkylsiloxyalkyl groups, or combinations thereof. The linking group may optionally be substituted with one or more substituents. Suitable substituents may include substituents independently selected from the following: alkyl, halogen (e.g., fluoro), hydroxyl, HO-endalkoxy, MeO-endalkoxy, siloxyalkyl, siloxy, siloxy-endalkoxy-, siloxy-endalkyl-endalkoxy- (wherein more than one endalkoxy group may be present, and each methylene group in the endalkyl and endalkoxy groups may be optionally substituted with a hydroxyl group), ether, amine, carbonyl, carbamate, and combinations thereof. The linking group may also be substituted with a polymerizable group (such as (meth)acrylate).

[0065] Preferred linking groups include C1-C8 alkyl (preferably C2-C6 alkyl) and C1-C8 oxaalkyl (preferably C2-C6 oxaalkyl), each optionally substituted with one or two independently selected groups chosen from hydroxyl and silical. Preferred linking groups also include carboxylic esters, amides, C1-C8 alkyl-carboxylic ester-C1-C8 alkyl, or C1-C8 alkyl-amide-C1-C8 alkyl.

[0066] When the linking group comprises a combination of the portions described above (e.g., alkyl and cycloalkyl groups), these portions can be present in any order. For example, if in formula E below, L (linking group) is indicated as -alkyl-cycloalkyl-, then Rg-L can be Rg-alkyl-cycloalkyl- or Rg-cycloalkyl-alkyl-. Nevertheless, the order listed indicates the preferred order in which these portions appear in the compound starting from the terminal polymerizable group (Rg) to which the linking group is attached. For example, if both linking groups L and L2 are indicated as alkyl-cycloalkyl, then Rg-L is preferably Rg-alkyl-cycloalkyl-, and -L2-Rg is preferably -cycloalkyl-alkyl-Rg.

[0067] As mentioned above, in one embodiment, the present invention provides compounds that can be used to manufacture ophthalmic lenses. These compounds have formula I: R1 is independently H or methyl in each occurrence; R2 and R3 are independently H or -X'-N(R6)(R7) in each occurrence, provided that at least one R2 or R3 is -X'-N(R6)(R7), wherein X' is independently bonded or -(CO)- in each occurrence, R6 is independently H, C1-C6 alkyl, or C1-C6 alkyl carbonyl in each occurrence, and R7 is independently H, C1-C6 alkyl, or C1-C6 alkyl carbonyl in each occurrence, or R6 and R 7, when present, forms a heterocyclic alkyl ring with its equally bonded nitrogen atom, wherein the ring carbon atom is optionally substituted with a heteroatom selected from nitrogen, oxygen, and sulfur, wherein each alkyl and alkyl carbonyl group is independently and optionally substituted with hydroxyl, amino, amide, oxy, carboxyl, alkyl carboxyl, carbonyl, alkyl carbonyl, alkoxy, amide, carbamate, carbonate, halogen, phenyl, or benzyl, and each heterocyclic alkyl group is independently and optionally substituted with alkyl, hydroxyl, amino, amide, oxy, carboxyl, alkyl carboxyl, carbonyl, alkyl carbonyl, alkoxy, amide, carbamate, carbonate, halogen, phenyl, or benzyl; R4 and R5, when present, are independently alkyl, cycloalkyl, alkoxy, or halogen in each occurrence; T is a chain-terminating group; n is 10 to 4000; and p and q are independently 0, 1, 2, 3, 4, or 5.

[0068] Compounds of Formula I may include compounds of Formula I-1, which are compounds of Formula I under the following conditions: wherein one of R2 and R3 is H each time it appears.

[0069] Compounds of Formula I and Formula I-1 may include compounds of Formula I-2, which are compounds of Formula I or Formula I-1 under the following conditions: where q is 0.

[0070] Compounds of Formula I, I-1, and I-2 may include compounds of Formula I-3, which are compounds of Formula I, I-1, or I-2 under the following conditions: wherein p is 3, and R4 is independently C1-C3 alkyl each time it appears.

[0071] Compounds of Formula I, I-1, I-2, and I-3 may include compounds of Formula I-4, which are compounds of Formula I, I-1, I-2, or I-3 under the following conditions: wherein R6 and R7 together with their equally bonded nitrogen atoms form a heterocyclic alkyl ring optionally substituted with alkyl, hydroxyl, amino, amide, oxy, carboxyl, alkylcarboxyl, carbonyl, alkylcarbonyl, alkoxy, amide, carbamate, carbonate, or halogen.

[0072] Compounds of formula I, I-1, I-2, I-3, and I-4 may include compounds of formula I-5, which are compounds of formula I, I-1, I-2, I-3, or I-4 under the following conditions: wherein R6 and R7 together with their equally bonded nitrogen atoms form an imidazolidinyl, piperazinyl, pyrrolidinyl, or piperidinyl group optionally substituted with an alkyl or side-oxy group.

[0073] 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 under the following conditions: wherein R6 and R7 together with their equally bonded nitrogen atoms form 2-pyrrolidone.

[0074] Compounds of formula I, I-1, I-2, and I-3 may include compounds of formula I-7, which are compounds of formula I, I-1, I-2, or I-3 with the following condition: wherein R6 and R7 are independently H, C1-C6 alkyl, or C1-C6 alkyl carbonyl, wherein the alkyl and alkyl carbonyl are optionally substituted with hydroxyl groups.

[0075] Compounds of formula I, I-1, I-2, I-3, and I-7 may include compounds of formula I-8, which are compounds of formula I, I-1, I-2, I-3, or I-7 under the following conditions: wherein R6 and R7 are independently H or C1-C4 alkyl groups, wherein the alkyl group may optionally be substituted with a hydroxyl group.

[0076] Compounds of formula I, I-1, I-2, I-3, and I-7 may include compounds of formula I-9, which are compounds of formula I, I-1, I-2, I-3, or I-7 under the following conditions: wherein both R6 and R7 are H.

[0077] Compounds of formula I, I-1, I-2, I-3, and I-7 may include compounds of formula I-10, which are compounds of formula I, I-1, I-2, I-3, or I-7 with the following conditions: wherein R6 is H and R7 is C1-C3 alkyl or C1-C3 alkyl carbonyl, wherein the alkyl group may optionally be substituted with a hydroxyl group.

[0078] Compounds of formula I, I-1, I-2, I-3, and I-7 may include compounds of formula I-11, which are compounds of formula I, I-1, I-2, I-3, or I-7 under the following conditions, wherein R6 and R7 are C1-C3 alkyl groups that are optionally substituted with hydroxyl groups.

[0079] Compounds of formula I, I-1, I-2, I-3, and I-7 may include compounds of formula I-12, which are compounds of formula I, I-1, I-2, I-3, or I-7 with the following conditions: R6 is a C1-C3 alkyl group optionally substituted with a hydroxyl group, and R7 is a C1-C3 alkyl carbonyl group.

[0080] 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 under the following conditions: wherein X' is -(CO)-.

[0081] 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-14, 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 with the following conditions: wherein X' is a direct bond.

[0082] 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, I-12, I-13, and I-14 may include compounds of formula I-15, 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, I-12, I-13, or I-14 that have the following condition: wherein n is in the range of about 100, or about 200, or about 300 and at most about 3800, or at most about 3700, or at most about 3500. More preferably, n is in the range of about 300 to about 3700.

[0083] Compounds of illustrative formula I are shown in Table A. Table A ; ; ; ; ; ;or .

[0084] Compounds of Formula I can be readily prepared by those skilled in the art using methods described in the literature. Exemplary synthetic systems are shown in the following examples.

[0085] The compound of Formula I can be used as a functionalized photoinitiator for manufacturing ophthalmic lenses. Such a manufacturing method may include: (a) providing a mold assembly including a base surface and a front surface defining and surrounding a cavity therebetween, the cavity containing a reactive monomer mixture comprising a monomer suitable for manufacturing the ophthalmic lens, a first polymerization initiator activatable at a first wavelength, a first functional portion chemically linked to the first polymerization initiator, and a second polymerization initiator activatable by a second activation that does not substantially activate the first polymerization initiator, wherein at least one of the base surface or the front surface is light-transmitting; (b) exposing one or more selective regions of the reactive monomer mixture to the first wavelength. (c) Exposing the reactive monomer mixture to the second activation to activate the second polymerization initiator and solidify the reactive monomer mixture; (d) removing the ophthalmic lens from the mold assembly; and (e) extracting unreacted first polymerization initiator (having a chemically linked first functional portion) from the ophthalmic lens, wherein the first polymerization initiator having the chemically linked first functional portion is a compound of formula I (which may be a compound according to any of the above formulas I-1 to I-15, or may be a compound shown in Table A).

[0086] According to this method, a reactive monomer mixture is formed into an ophthalmic lens, such as a soft contact lens, by applying the mixture into a mold assembly and subsequently curing the mixture. The mold assembly includes a base surface (which is a semi-mold that contacts the rear surface of the lens) and a front surface (which contacts the front surface). When the front surface and the base surface are placed together, they define and surround a cavity between them, which, according to the invention, contains the reactive monomer mixture.

[0087] The mold components (front surface and base surface) constituting the mold assembly used in this invention can be made of various materials, including disposable or reusable materials. For example, the mold can be a thermoplastic optical mold made of any suitable material, including but not limited to polyethylene, polypropylene, other polyolefins including homopolymers, copolymers, and trimers, polystyrene, polystyrene copolymers, polyesters (such as poly(ethylene terephthalate) and poly(butylene terephthalate)), polyamide, poly(vinyl alcohol) and its derivatives, hydrogenated styrene-butadiene block copolymers (such as Tuftec), cyclic olefin polymers (such as Zeonor and Topas resins), and combinations thereof. The mold can be selected to be transparent or nearly transparent to the wavelength that will activate the first polymerization initiator, thus allowing irradiation through the front surface, the base surface, or both the front surface and the base surface. The materials between the front surface and the base surface can be the same or different. A preferred material for the front surface of the mold assembly is a 90:10 mixture of a cyclic olefin polymer and a hydrogenated styrene-butadiene block copolymer. (w / w) blends. A preferred material for the base surface of the mold assembly is a 90:10 (w / w) blend of cyclic olefin polymers and polypropylene. Other exemplary materials include blends of Zeonor and Tuftec for either or both of the base and fore-curve surfaces. The thickness of the base or fore-curve mold can vary, but is generally between 100 and 1500 micrometers, preferably between 600 and 800 micrometers, as measured at the center of the optical zone of the target lens mold design. Other mold materials that can be used include reusable molds composed of, for example, glass, quartz, or ceramics (such as alumina). BK270 and RB 270 are examples of materials suitable for transmission semi-mold molding. They can be molded or polished to achieve acceptable optical profile and surface roughness properties. Furthermore, coatings can be applied to such reusable molds to aid in the release of the cured lens. These mold coatings are generally based on polysiloxane or silane and can be partially or fully fluorinated.

[0088] The reactive monomer mixture contains a first polymerization initiator having a first functional portion (i.e., a compound of formula I) chemically linked thereto. The first polymerization initiator can be activated at a first wavelength (the wavelength for activating the first polymerization initiator can be within a range of wavelengths). As discussed above, when activated by the first wavelength, the polymerization initiator decomposes into free radicals, which can react with the monomers in the reactive monomer mixture to initiate a free radical polymerization reaction. Once polymerization is initiated by the initiator, monomer units are added to allow the polymer chain to grow, thus becoming part of the covalently linked polymer. Therefore, the first functional portion chemically linked to the initiator also becomes part of the polymer. The result is the incorporation of a functional portion into the lens. Furthermore, because the process of this invention employs a selective polymerization method, it is possible to position the functional portion at specific locations on the ophthalmic lens. This selective positioning of functional characteristics allows for the manufacture of lenses incorporating modified refractive index characteristics.

[0089] The first polymerization initiator (the compound of Formula I) can absorb and be activated by light of various wavelengths, such as ultraviolet (UV) wavelengths and / or visible light wavelengths. Preferably, the first polymerization initiator can absorb light in the visible range of the electromagnetic spectrum (about 380 nm to about 780 nm). More preferably, the first polymerization initiator is activated at wavelengths including 200 to 600 nm, or 300 to 500 nm, or 350 to 450 nm, or 380 to 450 nm.

[0090] The reactive monomer mixture contains a first functional portion chemically linked to a first polymerization initiator. As described above, this method allows for the incorporation of the first functional portion at selective sites within the ophthalmic lens. A wide variety of functional portions can be incorporated. Thus, the first wavelength, its intensity, and pattern can be selectively chosen to interact with the spectral absorbance of the monomer mixture, enabling the desired two-dimensional or three-dimensional incorporation of the first functional portion via the Beer's law effect, as described in detail in U.S. Patent No. 8,317,505, the entire contents of which are incorporated herein by reference.

[0091] The first functional component can be designed to influence the overall change in optical path length, having or not having an accompanying change in the absorption spectrum in the region of the hydrated lens formed by the first polymerization initiator. In this way, the overall optics of the lens can be modified in a defined manner. Optical path length (OPL) is calculated by the following formula: OPL = ,in The refractive index varies with the distance traveled through (multiple) media, where the optical path travels between points a and b (see Field Guide to Geometrical Optics, John E. Greivenkamp, ​​Editor, University of Arizona, SPIE Field Guides, Volume FG01, SPIE Press, Bellingham WA, USA, 2004). For homogeneous media, the OPL is simply the refractive index multiplied by the distance traveled (n multiplied by s). Theoretically, the OPL can be modified by incorporating a first functional moiety, by changing the refractive index of a region, by changing the distance light travels through that region, for example, by changing the expansion properties of the region based on modifications to composition and / or crosslinking density, which in turn affect the thickness profile of the optical zone of the lens, or by any combination of factors that change the OPL in the region. In this application, the term "refractive index moiety" is defined as the first functional moiety, which partially alters the OPL by changing the refractive index of the region generated by activating the first polymerization initiator. The composition of the reactive monomer mixture will determine the effect of expansion and / or crosslinking density on the OPL of the region generated by activating the first polymerization initiator.

[0092] The compound of Formula I incorporates the first functional part, which can act as the refractive index part. The first functional part can be a amide-based refractive index part. Relative to the main lens, the refractive index part changes the OPL of the lens in the incorporated region. The change in refractive properties across the lens can be used to impart images or other visual features to the lens, or to impart features that affect visual function, such as for the purpose of producing bifocal or multifocal lenses.

[0093] The compound of Formula I can be used as a first polymerization initiator (containing a chemically linked first functional part) and may be present in the reactive monomer mixture of the above method in an effective amount, for example, from 0.01 weight percent to 20 weight percent, based on all components of the reactive monomer mixture excluding the diluent.

[0094] The reactive monomer mixture of this method contains a second polymerization initiator. The second polymerization initiator can be activated by a second activation that does not substantially activate (e.g., less than 50 mol%, preferably less than 20 mol%, more preferably less than 5 mol%, and further preferably less than 1 mol%) the first polymerization initiator. For example, the second polymerization initiator can be activated by photonic or thermal energy that does not substantially activate the first initiator. Preferably, the second polymerization initiator is a thermal initiator. Examples of thermal initiators include, but are not limited to: azo compounds, such as azobisisobutyronitrile and 4,4'-azobis(4-cyanopentanoic acid); peroxides, such as benzoyl peroxide, tert-butyl peroxide, tert-butyl hydroperoxide, tert-butyl peroxybenzoate, diisopropylphenyl peroxide, and lauryl peroxide; peracids, such as peracetic acid and potassium persulfate; and various redox systems. A preferred thermal initiator is azobisisobutyronitrile (AIBN). Optionally, the second polymerization initiator may contain a chemically linked second functional portion, which may be the same as or different from the first functional portion. An effective amount of the second polymerization initiator is used in the reactive monomer mixture to initiate the polymerization of the reactive monomer mixture, for example, about 0.1 to about 2 parts by weight per 100 parts of the reactive monomer mixture.

[0095] According to this method, one or more selective regions of a reactive monomer mixture (in the cavity of a mold assembly) are exposed to a photochemical radiation source at a first wavelength, thereby selectively activating a first polymerization initiator (a compound of formula I) and thus selectively polymerizing a portion of the reactive monomer mixture. Advantageously, because the first polymerization initiator has a first functional portion chemically linked thereto, the selectively polymerized portion of the reactive monomer mixture is incorporated into the first functional portion.

[0096] Various techniques can be used to selectively activate the first polymerization initiator. Preferred techniques are based on stereolithography, generally as described, for example, in US20150146159, US9075186, and US8317505, the entire contents of which are incorporated herein by reference. Additional references include US7905594, US8157373, US8240849, US8313828, US8318055, US8795558, US9180633, US9180634, US9417464, US9610742, and US9857607, the entire contents of which are incorporated herein by reference.

[0097] Figure 1 illustrates an exemplary prior art device described in US8317505 (“505 Patent”), which can be used to selectively control individual beam arrays of photochemical radiation to cure or partially cure reactive monomer mixtures, such as mixtures used to form ophthalmic lenses. The light system is generated by a photochemical radiation source or light source 120 and appears as light in a defined wavelength band, but with some spatial variation in intensity and direction. Element 130 is a spatial intensity controller or collimator that focuses, diffuses, and in some embodiments collimates the light to produce a beam 140 with highly uniform intensity and preferably centered at a predetermined wavelength. Furthermore, in some embodiments, beam 140 is projected onto a digital micromirror device (DMD) 110 including a selectively controllable array of mirrors, which divides the beam into intensity pixel elements, each of which can be assigned a digital on or off value. In practice, the mirrors at each pixel reflect the light in one of two paths. The “on” path (object 150) is the path that causes photons to travel toward the reactive chemical medium. In the "OFF" path, light is reflected along different paths, which lie between the paths depicted as objects 116 and 117. This "OFF" path guides photons onto a light stopper 115, which is carefully designed to absorb and trap any photons directed toward it. Referring back to the "ON" path 150, the light depicted in this path actually comprises many different pixel values, which have been set to "ON" and guided spatially along appropriate individual paths corresponding to their pixel positions. The time-averaged intensity of each pixel element along its individual path 150 can be represented as a spatial intensity distribution 160, which traverses a spatial grid defined by DMD 110. Alternatively, with constant intensity projected onto each mirror, object 160 can represent a spatial-temporal exposure distribution. The computer program that selectively controls the mirror array (on / off time) is referred to herein as an "instruction file".

[0098] The '505 patent describes a beam of light that is vertically projected onto a light-transmitting forming optic 180 and enters the volume of a reactive monomer mixture 302 (FIG. 2), wherein the selectively controllable beam of photochemical radiation passes through the forming optic based on a three-dimensional pixel according to a command file, causing selective curing of the reactive monomers in the tank.

[0099] The method described herein can utilize the apparatus of Figures 1 and 2, but replaces the forming optical element (male mold) with a conventional two-part casting mold (such as the exemplary casting mold shown in Figure 3). As shown in Figure 3, the curing apparatus 200 includes a first half-mold 201 and a second half-mold 202, which together form the shape of the cured contact lens to be formed, at least one of which is translucent, and a reactive monomer mixture 204 fills the entire space therebetween. The first half-mold and the second half-mold are fixed in place within the curing apparatus 200, which includes a first portion 210a and a second portion 210b, at least a portion (i.e., 210b in Figure 3) is similarly translucent. A selectively controllable photochemical radiation source 205 (such as the one described above) is directed to selectively project onto the translucent half-mold and the exposed clamp portion, as illustrated. The apparatus may further include a light absorber 212, which is designed to capture stray light after it has passed through the translucent clamp portion, the half-mold, and the reactive monomer mixture. In an alternative, the relative mold and / or fixture portion may be opaque or otherwise light-absorbing, such as if the mold or fixture portion contains a carbon black-filled thermoplastic (such as styrene or polymethyl methacrylate (PMMA)).

[0100] The method described herein can be used to spatially incorporate (two-dimensional or three-dimensional) functional parts, geometries, or physical properties into an ophthalmic lens formed between two half-molds. As discussed above, this can be achieved by incorporating a first polymerization initiator, connected to a first functional part activated by a first predetermined wavelength or wavelength range, and a second polymerization initiator, connected or not connected to a second functional part, into a reactive monomer mixture. The second polymerization initiator can be activated by a second activation that does not substantially activate the first initiator. The second activation can be, for example, by applying photonic energy and / or thermal energy. Therefore, the curing apparatus can selectively apply photonic energy and / or thermal energy to selectively and differentially cure and / or otherwise selectively activate functional chemistry.

[0101] For example, according to the predetermined digital instruction file as described above, the reactive monomer mixture can be first exposed to light of a first wavelength or wavelength range via photochemical radiation source 205. The light of the first wavelength will activate the first polymerization initiator, thereby causing free radical polymerization. The desired degree and depth of polymerization at each point in the photochemical radiation beam array are defined by the pre-programmed instruction file and wavelength of the photochemical radiation, because it can interact slightly or heavily with the spectral absorption of the reactive monomer mixture in a manner that conforms to Beer's Law. The first functional portion attached to the first polymerization initiator is incorporated into the polymer chain of the selectively polymerized reactive monomer mixture. After exposure to photochemical radiation, the mold assembly can be exposed again to a second energy, preferably thermal energy, that does not substantially activate the first photoinitiator. To achieve this, the mold assembly shown in Figure 3 can be simply placed in a heat-controlled environment (such as an oven) until the reactive monomer mixture cures, for example, at approximately 90 degrees Celsius for approximately two to three hours.

[0102] As an alternative, after exposure to the first photochemical radiation, the semi-mold and exposure fixture assembly are placed in a heated device for approximately 20 minutes to allow the reactive monomer mixture to fully gel, preventing unwanted relative movement of the BC mold relative to the FC mold. At this point, the BC mold is removed from the heated device, and the exposure fixture is removed from the semi-mold. The semi-mold is then immediately returned to the heated device for the final curing time. If necessary, this allows for reuse of the exposure fixture during the remainder of the final lens curing step. The formed lens object can then be removed from the semi-molds 202 and 203 and subjected to an extraction process to remove unreacted first polymerization initiator. The extraction process for removing unreacted first polymerization initiator can be complete or incomplete. In some cases, removing all unreacted first polymerization initiator is not necessary to achieve the desired characteristics or optical effects. In other cases, the extraction process removes only a portion of the unreacted first initiator, allowing for optional irradiation steps using a lower concentration of the first polymerization initiator. Alternatively, the extraction process may remove substantially all of the unreacted first initiator. After removing the unreacted first polymerization initiator, standard post-processing steps of lens extraction and lens hydration to remove other reactive monomer components can be performed to form the final ophthalmic lens. In some cases, the standard post-processing steps of lens extraction and hydration using an aqueous alcohol solution, water, and a buffer can also extract the unreacted first polymerization initiator, thereby combining two or more extraction steps into a single operation. The resulting lens will possess various spatially incorporated properties, as determined by the different curing methods applied to the individual portions. The first wavelength, its intensity, and pattern are selectively chosen to interact with the spectral absorbance of the reactive monomer mixture, thereby achieving the desired two-dimensional or three-dimensional incorporation via the Beer's Law effect, as described in detail in '505 patent.

[0103] The method described herein allows for the incorporation of functional chemicals into lenses, which can alter the refractive properties within the lens. Changes in refractive properties can be used to impart images or other visual features to the lens, or to impart features that affect visual function, such as for the purpose of producing bifocal or multifocal lenses.

[0104] While the lithography based on stereoscopic pixels described above is a preferred technique for selectively activating the first polymerization initiator (the compound of Formula I), other techniques can also be used. For example, selective activation can be provided by masking regions of the reactive monomer mixture that do not require polymerization with a first wavelength of light. The unmasked regions of the reactive monomer mixture can then undergo activation and selective polymerization. The photomask can be binary in nature, but more preferably grayscale. The specifications and fabrication of such photomasks are known to those skilled in the art of grayscale lithography.

[0105] Preferably, the reactive monomer mixture has sufficient viscosity so that the polymerized portion does not diffuse undesirably immediately during or after the first selective polymerization described above. Various options are available to provide such viscosity. For example, a reactive monomer mixture containing a viscous component (such as a macromonomer or prepolymer) can be used. Diluents can also be excluded, or at least used in low concentrations, to avoid significantly reducing the viscosity of the reactive monomer mixture.

[0106] A preferred method is to perform restricted pre-curing of the reactive monomer mixture by brief activation with a second polymerization initiator before or simultaneously with the first activation. Thus, for example, if the second polymerization initiator is a thermal initiator, the reactive monomer mixture in the mold assembly can be heated to briefly activate the thermal initiator, thereby initiating some polymerization of the reactive monomer mixture. Once the desired viscosity is reached, initiation and polymerization can be stopped. For example, if the thermal initiator is AIBN, such pre-curing can be achieved by heating the reactive monomer mixture to a temperature, for example, in the range of 40 to 150 degrees Celsius, for about 0.1 to 120 minutes. Preferably, the pre-curing step is performed before the selective activation of the first polymerization initiator.

[0107] According to this method, complete curing of the reactive monomer mixture occurs after selective polymerization. This complete curing employs a second polymerization initiator present in the reactive monomer mixture. Specifically, the second polymerization initiator is activated to initiate the polymerization of the remaining reactive components in the reactive monomer mixture.

[0108] As mentioned above, the reactive monomer mixture of this method contains monomers suitable for manufacturing the desired ophthalmic lens. For example, the reactive monomer mixture may contain one or more of the following: hydrophilic components, hydrophobic components, polysiloxane-containing components, wetting agents (such as polyamide), crosslinking agents, and other components (such as diluents and initiators). hydrophilic components

[0109] Examples of suitable families of hydrophilic monomers that may be present in mixtures of reactive monomers include (meth)acrylates, styrene, vinyl ethers, (meth)acrylamide, N-vinyl lactam, N-vinylamide, N-vinyl amide, N-vinyl urea, O-vinylaminocarbamate, O-vinyl carbonate, other hydrophilic vinyl compounds, and mixtures thereof.

[0110] 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) (Meth)acrylamide, N-(2-hydroxybutyl)(meth)acrylamide, N-(3-hydroxybutyl)(meth)acrylamide, N-(4-hydroxybutyl)(meth)acrylamide, 2-aminoethyl (meth)acrylate, 3-aminopropyl (meth)acrylate, 2-aminopropyl (meth)acrylate, N-2-aminoethyl (meth)acrylamide, N-3-aminopropyl (meth)acrylamide, N-2-aminopropyl (meth)acrylamide, N,N-bis-2-aminoethyl (meth)acrylamide, N,N-bis-3-aminopropyl (meth)acrylamide, N,N-bis-2-aminopropyl (meth)acrylamide, glyceryl methacrylate, polyethylene glycol monomethacrylate, (meth)acrylic acid, vinyl acetate, acrylonitrile, and mixtures thereof.

[0111] 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-[(vinyloxy)carbonyl]-β-alanine (VINAL), 3-acrylaminopropionic acid (ACA1), 5-acrylaminovalerate (ACA2), 3-acrylamino-3-methylbutyric acid (AMBA), 2-(methacrylamino)ethyltrimethylammonium chloride (Q salt or METAC), 2-acrylamino-2-methylpropanesulfonic acid (AMPS), 1-propanenium, N-( 2-Carboxyethyl)-N,N-dimethyl-3-[(1-sideoxy-2-propen-1-yl)amino]-, inner salt (CBT), 1-propanemonium,N,N-dimethyl-N-[3-[(1-sideoxy-2-propen-1-yl)amino]propyl]-3-sulfonic acid-, inner salt (SBT), 3,5-di(8-azo-4-phosphine-undecyl-10-en-1-ammonium),4-hydroxy-N,N,N-trimethyl-9-sideoxy-, inner salt,4-oxide (9CI) (PBT), 2-methacryloxyethylphosphoniccholine, 3-(dimethyl(4-vinylbenzyl)ammonium)propane-1-sulfonate (DMVBAPS), 3-((3-propenylaminopropyl)dimethylammonium)propane-1-sulfonate (AMPDAPS), 3-((3-methacrylaminopropyl)dimethylammonium)propane-1-sulfonate (MAMPDAPS), 3-((3-(propenyloxy)propyl)dimethylammonium)propane-1-sulfonate (APDAPS), and methacryloxy)propyl)dimethylammonium)propane-1-sulfonate (MAPDAPS).

[0112] Non-limiting examples of hydrophilic N-vinyl lactones and N-vinyl lactone monomers include: N-vinylpyrrolidone (NVP), N-vinyl-2-piperidone, N-vinyl-2-caprolactone, N-vinyl-3-methyl-2-caprolactone, N-vinyl-3-methyl-2-piperidone, N-vinyl-4-methyl-2-piperidone, N-vinyl-4-methyl-2-caprolactone, 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-ethylmethylamine, N-vinylmethylamine, N-vinyl-N-methylpropionamide, N-vinyl-N-methyl-2-methylpropionamide, N- Vinyl-2-methylpropionic acid, 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-ethylmethylamine, N-vinylmethylamine, N-vinylisopropylacetamide, N-vinylcaprolactam, N-vinylimidazolium, and mixtures thereof.

[0113] Non-limiting examples of hydrophilic O-vinylcarbamates and O-vinyl carbonate monomers include N-2-hydroxyethyl vinylcarbamate and N-vinyl ester of N-carboxy-β-propanone. Further examples of hydrophilic vinyl carbonates or vinylcarbamate monomers are disclosed in U.S. Patent No. 5,070,215. Hydrophilic acezolinone monomers are disclosed in U.S. Patent No. 4,910,277.

[0114] Other hydrophilic vinyl compounds include ethylene glycol vinyl ether (EGVE), di(ethylene glycol) vinyl ether (DEGVE), allyl alcohol, and 2-ethylhexazolin.

[0115] The hydrophilic monomer may also be a macromonomer or prepolymer of linear or branched poly(ethylene glycol), poly(propylene glycol), or statistically random or block copolymers of ethylene oxide and propylene oxide, having polymerizable moieties such as (meth)acrylates, styrene, vinyl ethers, (meth)acrylamide, N-vinylamide, and the like. These polyether macromonomers have one polymerizable group; the prepolymer may have two or more polymerizable groups.

[0116] The present invention relates to preferred hydrophilic monomer systems 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.

[0117] 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, clarity, wettability, protein absorption, and the like. Wettability can be measured by contact angle, and the desired contact angle is less than about 100°, less than about 80°, and less than about 60°. The hydrophilic monomers can be present in amounts ranging from, for example, from about 0.1 to about 100 weight percent, alternatively from about 1 to about 80 weight percent, alternatively from about 5 to about 65 weight percent, alternatively from about 40 to about 60 weight percent, or alternatively from about 55 to about 60 weight percent, based on the total weight of the reactive components in the reactive monomer mixture. Contains polysiloxane components

[0118] The polysiloxane-containing component in the reactive monomer mixture applicable to the present invention comprises 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 polymerizable group(s) to one or more siloxane groups(s). The polysiloxane-containing component may, for example, contain 1 to 220 repeating siloxane units, such as groups as defined below. The polysiloxane-containing component may also contain at least one fluorine atom.

[0119] The polysiloxane-containing component may comprise: one or more polymerizable groups as defined above; one or more optionally repeatable siloxane units; and a polymerizable group connected to one or more linking groups of the siloxane units. The polysiloxane-containing component may comprise: one or more polymerizable groups, wherein the polymerizable groups are independently (meth)acrylate, styrene, vinyl ether, (meth)acrylamide, N-vinyl lactam, N-vinylamide, O-vinylaminocarbamate, O-vinyl carbonate, vinyl, or a mixture thereof; one or more optionally repeatable siloxane units; and a polymerizable group connected to one or more linking groups of the siloxane units.

[0120] The polysiloxane component may include: one or more polymerizable groups, wherein the polymerizable groups are independently (meth)acrylate, (meth)acrylamide, N-vinyl lactam, N-vinylamide, styrene, or a mixture thereof; one or more optionally repeatable siloxane units; and a linker group connecting the polymerizable group to one or more of the siloxane units.

[0121] The polysiloxane component may include: one or more polymerizable groups, wherein the polymerizable groups are independently (meth)acrylate, (meth)acrylamide, or a mixture thereof; one or more optionally repeatable siloxane units; and a linker group connecting the polymerizable group to one or more of the siloxane units.

[0122] The polysiloxane component may contain one or more polymerizable compounds of formula A: Formula A in: At least one RA group of the formula R gL-, wherein R g is a polymerizable group and L is a linking group, and the remaining RA groups are each independently: (a) R gL-, (b) C1-C16 alkyl, optionally substituted with one or more hydroxyl, amino, amide, oxa, carboxyl, alkylcarboxyl, carbonyl, alkoxy, amide, carbamate, carbonate, halogen, phenyl, benzyl, or combinations thereof. (c) C3-C12 cycloalkyl, optionally substituted with one or more alkyl, hydroxyl, amino, amide, oxa, carbonyl, alkoxy, amide, carbamate, carbonate, halogen, phenyl, benzyl, or combinations thereof. (d) C6-C14 aryl, optionally substituted with one or more alkyl, hydroxyl, amino, amide, oxa, carboxyl, alkylcarboxyl, carbonyl, alkoxy, amide, carbamate, carbonate, halogen, phenyl, benzyl, or combinations thereof. (e) Halogen, (f) Alkoxy, cyclic alkoxy, or aryloxy groups, (g) siloxy groups, (h) Alkyloxy-alkyl or alkoxy-alkyloxy-alkyl, such as poly(ethoxyalkyl), poly(propoxyalkyl), or poly(ethoxy-co-propoxyalkyl), or (i) A monovalent siloxane chain comprising 1 to 100 repeating siloxane units, optionally substituted with alkyl, alkoxy, hydroxy, amino, oxa, carboxyl, alkylcarboxyl, alkoxy, amide, carbamate, halogen, or combinations thereof; and The n-system is defined as 0 to 500, 0 to 200, 0 to 100, or 0 to 20, where it should be understood that when n is not 0, the n-system has a distribution equal to the mode of the specified value. When the n-system is 2 or greater, the SiO unit may have the same or different RA substituents, and if different RA substituents are present, the n groups may be in random or block configurations.

[0123] In formula A, each of the three RAs may contain a polymerizable group, or alternatively, each of the two RAs may contain a polymerizable group, or alternatively, one RA may contain a polymerizable group.

[0124] Examples of polysiloxane-containing components applicable to this invention include, but are not limited to, the compounds listed in Table B. When the compounds in Table B contain polysiloxane groups, unless otherwise indicated, 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. Table B 1 Monomethacryloxypropyl-terminated mono-n-butyl-terminated polydimethylsiloxane (mPDMS) (preferably containing 3 to 15 SiO repeating units) 2 Monoacryloxypropyl-terminated mono-n-butyl-terminated polydimethylsiloxane 3 Mono(meth)acrylic oxypropyl-terminated mono-n-methyl-terminated polydimethylsiloxane 4 Mono(meth)acryloxypropyl-terminated mono-n-butyl-terminated polydiethylsiloxane 5 Mono(meth)acrylic oxypropyl-terminated mono-n-methyl-terminated polydiethylsiloxane 6 Mono(meth)acrylamide alkyl polydialkylsiloxane 7 Mono(meth)propenyloxyalkyl-terminated monoalkyl polydiarylsiloxanes 8 3-Methylpropenyloxypropyltris(trimethylsiloxy)silane (TRIS) 9 3-Methylpropenoxypropylbis(trimethylsiloxy)methylsilane 10 3-Methylpropenoxypropylpentamethyldisiloxane 11 Mono(meth)acrylamide alkyl polydialkylsiloxane 12 Mono(meth)acrylamide alkyl polydimethylsiloxane 13 N-(2,3-dihydroxypropane)-N'-(propyltetra(dimethylsiloxy)dimethylbutylsilane)acrylamide 14 N-[3-Tris(trimethylsiloxy)silyl]-propylacrylamide (TRIS-Am) 15 2-Hydroxy-3-[3-Methyl-3,3-di(trimethylsiloxy)silylpropoxy]propyl methacrylate (SiMAA) 16 2-Hydroxy-3-methylpropenoxypropyloxypropyl-trimethylsiloxane 17 Mono(2-hydroxy-3-methacryloxypropyloxy)-propyl-terminated mono-n-butyl-terminated polydimethylsiloxane (OH-mPDMS) (containing 4 to 30, or 4 to 20, or 4 to 15 SiO repeating units) 18 19 20 twenty one twenty two twenty three twenty four

[0125] Additional non-limiting examples of suitable polysiloxane-containing components are listed in Table C. Unless otherwise indicated, j2 is preferably 1 to 100, more preferably 3 to 40, or even more preferably 3 to 15 when 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. Table C 25 26 p series 1 to 10 27 p series 5 to 10 28 29 30 1,3-Bis[4-(vinyloxycarbonyloxy)but-1-yl]tetramethyl-disiloxane 31 3-(vinyloxycarbonylthio)propyl-[trimethylsiloxy)silane] 32 3-[Tris(trimethylsiloxy)silyl]propyl allylaminocarbamate 33 3-[Tris(trimethylsiloxy)silyl]propyl vinylcarbamate 34 Trimethylsiloxy)silylstyrene (styryl-TRIS) 35 36 37 38 39 40 41 42 m ≈ 3.5 to 5.5; n ≈ 4 to 6.5; p ≈ 22 to 26 43 IEM-PDMS(Mn ≈ 3000)-IPDI-PDMS(Mn ≈ 2000)-IPDI-PDMS(Mn ≈ 3000)-IEM (see WO2016100457)

[0126] Mixtures containing polysiloxane components may be used. For example, suitable mixtures may include, but are not limited to: mixtures of mono(2-hydroxy-3-methacryloxypropyloxy)-propyl-terminated mono-n-butyl-terminated polydimethylsiloxanes (OH-mPDMS) with different molecular weights, such as mixtures of OH-mPDMS 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) together with polysiloxane-based crosslinking agents (such as bis-3-acryloxy-2-hydroxypropyloxypropyl polydimethylsiloxane (ac-PDMS)); and mixtures of 2-hydroxy-3-[3-methyl-3,3-di(trimethylsiloxy)siloxypropyloxy]-propyl methacrylate (SiMAA) and mono(methacryloxypropyl)-terminated mono-n-butyl-terminated polydimethylsiloxanes (mPDMS) (such as mPDMS 1000).

[0127] The polysiloxane-containing component used in this invention may have an average molecular weight of about 400 to about 4000 Daltons.

[0128] (Multiple) polysiloxane-containing components may be present in amounts of up to about 95% by weight, or about 10% to about 80% by weight, or about 20% to about 70% by weight, based on all reactive components of the reactive monomer mixture (excluding diluents). polyamide

[0129] The reactive monomer mixture may include at least one polyamide. As used herein, the term "polyamide" refers to a polymer and copolymer comprising repeating units containing amide groups. Polyamides may comprise cyclic amide groups, acyclic amide groups, and combinations thereof, and may be any polyamide known to those skilled in the art. Acyclic polyamides comprise acyclic amide groups and are capable of associating with hydroxyl groups. Cyclic polyamides comprise cyclic amide groups and are capable of associating with hydroxyl groups.

[0130] Suitable examples of acyclic polyamides include polymers and copolymers containing repeating units of formulas G1 and G2: Formula G1 Formula G2 Wherein X is a direct bond, -(CO)-, or –(CONHR 44)-, wherein R 44 is a C1 to C3 alkyl group; R 40 is selected from H, a straight-chain or branched substituted or unsubstituted C1 to C4 alkyl group; R 41 is selected from H, a straight-chain or branched substituted or unsubstituted C1 to C4 alkyl group, an amino group having at most two carbon atoms, an amino group having at most four carbon atoms, and an alkoxy group having at most two carbon atoms; R 42 is selected from H, a straight-chain or branched substituted or unsubstituted C1 to C4 alkyl group; or methyl, ethoxy, hydroxyethyl, and hydroxymethyl; R 43 is selected from H, a straight-chain or branched substituted or unsubstituted C1 to C4 alkyl group; or methyl, ethoxy, hydroxyethyl, and hydroxymethyl; wherein R 40 and R The total number of carbon atoms in R41 is 8 or fewer, including 7, 6, 5, 4, 3, or fewer; and the total number of carbon atoms in R42 and R43 is 8 or fewer, including 7, 6, 5, 4, 3, or fewer. The total number of carbon atoms in R40 and R41 may be 6 or fewer or 4 or fewer. The total number of carbon atoms in R42 and R43 may be 6 or fewer. As used herein, substituted alkyl groups include alkyl groups substituted with amines, amides, ethers, hydroxyl groups, carbonyl groups, or carboxyl groups, or combinations thereof.

[0131] R 40 and R 41 may be independently selected from H, substituted or unsubstituted C1 to C2 alkyl groups. X may be a direct bond, and R 40 and R 41 may be independently selected from H, substituted or unsubstituted C1 to C2 alkyl groups. R 42 and R 43 may be independently selected from H, substituted or unsubstituted C1 to C2 alkyl groups, methyl, ethoxy, hydroxyethyl, and hydroxymethyl.

[0132] The acyclic polyamides of the present invention may comprise a majority of repeating units of formula G1 or formula G2, or the acyclic polyamides may comprise at least 50 mole percent of repeating units of formula G1 or formula G2, including at least 70 mole percent and at least 80 mole percent. Specific examples of repeating units of formula G1 or formula G2 include repeating units derived from the following: 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 polyamides of formulas G5 and G3. G5 Formula G3 Examples of suitable cyclic amides for forming cyclic polyamides include α-lactamamines, β-lactamamines, γ-lactamamines, δ-lactamamines, and ε-lactamamines. Examples of suitable cyclic polyamides include polymers and copolymers containing repeating units of formula G4. Formula G4 In formula G4, R 45 represents a hydrogen atom or a methyl group; f represents a number from 1 to 10; X represents a direct bond, -(CO)-, or –(CONHR 46)-; and R 46 represents a C1 to C3 alkyl group. In formula G4, 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 G4, f can be 2 or 3. When X represents a direct bond, f can be 2. In such cases, the cyclic polyamine can be polyvinylpyrrolidone (PVP).

[0133] The cyclic polyamide of the present invention may contain 50 mole percent or more of repeating units of formula G4, or the cyclic polyamide may contain at least 50 mole percent of repeating units of formula G4, including at least 70 mole percent and at least 80 mole percent.

[0134] 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 monomer listed as a suitable hydrophilic monomer can be used as a comonomer 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 the like, and mixtures thereof. Ionic monomers may also be included. Examples of ionic monomers include (meth)acrylic acid, N-[(vinyloxy)carbonyl]-β-propanonic acid (VINAL, CAS #148969-96-4), 3-propenylaminopropionic acid (ACA1), 5-propenylaminovaleric acid (ACA2), 3-propenylamino-3-methylbutyric acid (AMBA), 2-(methacryloxy)ethyltrimethylammonium chloride (Q salt or METAC), 2-propenylamino-2-methylpropanesulfonic acid (AMPS), 1-propanium, N-(2-carboxyethyl)-N,N-dimethyl-3-[(1-sideoxy-2-propen-1-yl)amino]-, inner salt (CBT, carboxylate betaine; CAS 79704-35-1), 1-Propanammonium, N,N-dimethyl-N-[3-[(1-sideoxy-2-propen-1-yl)amino]propyl]-3-sulfonic acid-, inner salt (SBT, sulfonic acid betaine, CAS 80293-60-3), 3,5-di-8-aza-4-phosphine undecyl-10-en-1-ammonium, 4-hydroxy-N,N,N-trimethyl-9-sideoxy-, inner salt, 4-oxide (9CI) (PBT, phosphate betaine, CAS 163674-35-9), 2-methylpropenyloxyethylphosphocholine, 3-(dimethyl(4-vinylbenzyl)ammonium)propane-1-sulfonate (DMVBAPS), 3-((3-propenylaminopropyl)dimethylammonium)propane-1-sulfonate (AMPDAPS), 3-((3-methylpropenylaminopropyl)dimethylammonium)propane-1-sulfonate (MAMPDAPS), 3-((3-(propenyloxy)propyl)dimethylammonium)propane-1-sulfonate (APDAPS), methpropenyloxy)propyl)dimethylammonium)propane-1-sulfonate (MAPDAPS).

[0135] The reactive monomer mixture may comprise both acyclic polyamines and cyclic polyamines or copolymers thereof. The acyclic polyamine may be any of the acyclic polyamines or copolymers thereof described herein, and the cyclic polyamine may be any of the cyclic polyamines or copolymers thereof described herein. The polyamine may be selected from the group consisting of: polyvinylpyrrolidone (PVP), polyvinylmethyl acetamide (PVMA), polydimethylacrylamide (PDMA), polyvinylacetamide (PNVA), poly(hydroxyethyl(meth)acrylamide), polyacrylamide, and copolymers and mixtures thereof. The polyamine may be a mixture of PVP (e.g., PVP K90) and PVMA (e.g., having a Mw of about 570 kDa).

[0136] The total amount of all polyamides in the reactive monomer 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%, in all cases based on the total weight of the reactive components of the reactive monomer mixture.

[0137] Without being bound by theory, when used with polysiloxane hydrogels, polyamides act as internal wetting agents. The polyamides of this invention can be non-polymerizable, and in this case, they are incorporated into the polysiloxane hydrogel to form a semi-interpenetrating network. The polyamides are trapped or physically retained within the polysiloxane hydrogel. Alternatively, the polyamides of this invention can be polymerizable, for example, as polyamide macromonomers or prepolymers, and in this case, they are covalently incorporated into the polysiloxane hydrogel. Mixtures of polymerizable and non-polymerizable polyamides can also be used.

[0138] When polyamides are incorporated into a mixture of reactive monomers, they may have the following weight-average molecular weights: at least 100,000 Daltons; greater than about 150,000; between about 150,000 and about 2,000,000 Daltons; between about 300,000 and about 1,800,000 Daltons. If the higher molecular weight polyamide is compatible with the reactive monomer mixture, it may be used. Crosslinking agent

[0139] It is generally desirable to add one or more crosslinking agents (also known as crosslinking monomers), multifunctional macromonomers, and prepolymers to a mixture of reactive monomers. Crosslinking agents can be selected from bifunctional, trifunctional, tetrafunctional, and mixtures thereof, including polysiloxane-containing and non-polysiloxane-containing crosslinking agents. Non-polysiloxane-containing crosslinking agents include ethylene glycol dimethacrylate (EGDMA), tetraethylene glycol dimethacrylate (TEGDMA), trimethylolpropane trimethacrylate (TMPTMA), triallyl cyanurate (TAC), glycerol trimethacrylate, methacryloyloxyethyl vinyl carbonate (HEMAVc), allyl methacrylate, methylene diacrylamide (MBA), and polyethylene glycol dimethacrylate (wherein polyethylene glycol has a molecular weight of up to about 5000 Daltons). The crosslinking agent can be used in normal amounts, for example, about 0.000415 to about 0.0156 moles per 100 grams of reactive formulation in the reactive monomer mixture. Alternatively, if the hydrophilic monomer and / or the polysiloxane-containing component is multifunctional due to molecular design or impurities, it is optional to add the crosslinking agent to the reactive monomer mixture. Examples of hydrophilic monomers and macromonomers that can be used as crosslinking agents and, when present, do not require the addition of additional crosslinking agents to the reactive monomer mixture include (meth)acrylate and (meth)acrylamide-terminated polyethers. Other crosslinking agents are known to those skilled in the art and can be used to manufacture the polysiloxane hydrogel of the present invention.

[0140] Ideally, a crosslinking agent with a reactivity similar to one or more of the other reactive components in the formulation can be selected. In some cases, a mixture of crosslinking agents with different reactivity can be chosen to control certain physical, mechanical, or biological properties of the resulting polysiloxane hydrogel. The structure and morphology of the polysiloxane hydrogel can also be affected by the (various) diluents used and the curing conditions.

[0141] It may also include multifunctional polysiloxane-containing components (including macromonomers, crosslinking agents, and prepolymers) to further increase the modulus and retain tensile strength. Polysiloxane-containing crosslinking agents can be used alone or in combination with other crosslinking agents. Examples of polysiloxane-containing components that can act as crosslinking agents and, when present, do not require the addition of crosslinking monomers to the reactive monomer mixture include α,ω-dimethacryloxypropylpolydimethylsiloxane. Another example is bis-3-acryloxy-2-hydroxypropyloxypropylpolydimethylsiloxane (ac-PDMS).

[0142] Crosslinking agents having rigid chemical structures and polymerizable groups undergoing 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-epoxyphenyl diacrylate, 1,4-epoxyphenyl dimethacrylate, 2,2-bis(4-methacryloxyphenyl)propane, 2,2-bis[4-(2-propenyloxyethoxy)phenyl]propane, 2,2-bis[4-(2-hydroxy-3-methacryloxypropoxy)phenyl]propane, and 4-vinylbenzyl methacrylate, and combinations thereof. A rigid crosslinking agent may be included in amounts between about 0.5 and about 15, or 2 to 10, or 3 to 7, based on the total weight of all reactive components. The physical and mechanical properties of the polysiloxane hydrogel of the present invention can be optimized for specific applications by adjusting the components in the reactive monomer mixture.

[0143] Non-limiting examples of polysiloxane crosslinking agents also include the multifunctional polysiloxane-containing components described in Table C above. Other ingredients

[0144] Reactive monomer mixtures may contain additional components, such as, but not limited to, diluents, initiators, UV absorbers, visible light absorbers, photochromic compounds, pharmaceuticals, nutrients, antimicrobial substances, colorants, pigments, copolymerizable dyes, nonpolymerizable dyes, release agents, and combinations thereof.

[0145] The categories of diluents suitable for reactive monomer mixtures of polysiloxane 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. Diluents can be primary, secondary, and tertiary alcohols.

[0146] Typically, reactive components are mixed in a diluent to form a reactive monomer mixture. Suitable diluents are known in the art. Suitable diluents for polysiloxane hydrogels are disclosed in WO 03 / 022321 and US 6020445, the disclosures of which are incorporated herein by reference.

[0147] Suitable diluents for polysiloxane hydrogel reactive monomer 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. 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.

[0148] Specific diluents that may be used include 1-ethoxy-2-propanol, diisopropylaminoethanol, isopropanol, 3,7-dimethyl-3-octanol, 1-decanol, 1-dodecanol, 1-octanol, 1-pentanol, 2-pentanol, 1-hexanol, 2-hexanol, 2-octanol, 3-methyl-3-pentanol, tripentanol, tributanol, 2-butanol, 1-butanol, 2-methyl-2-pentanol, 2-propanol, 1-propanol, ethanol, 2-ethyl-1-butanol, (3-ethoxy-2-hydroxypropoxy)-propylbis(trimethylsiloxy)methylsilane, 1-tributoxy-2-propanol, 3,3-dimethyl-2-butanol, tributoxyethanol, 2-octyl-1-dodecanol, decanoic acid, octanoic acid, dodecanoic acid, 2-(diisopropylamino)ethanol, mixtures thereof, and the like. Examples of acetamide diluents include N,N-dimethylpropionic acid and dimethylacetamide.

[0149] 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, tripentanol, tributanol, 2-butanol, 1-butanol, 2-methyl-2-pentanol, 2-ethyl-1-butanol, ethanol, 3,3-dimethyl-2-butanol, 2-octyl-1-dodecanol, decanoic acid, octanoic acid, dodecanoic acid, mixtures thereof, and the like.

[0150] 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, tripentanol, tributanol, 2-butanol, 1-butanol, 2-methyl-2-pentanol, 2-ethyl-1-butanol, 3,3-dimethyl-2-butanol, 2-octyl-1-dodecanol, mixtures thereof, and the like.

[0151] 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 in the range of about 5 to about 50% by weight and in the range of about 15 to about 40% by weight, based on the total weight of the reactive monomer mixture (including reactive and non-reactive formulations). Mixtures of diluents may be used.

[0152] In addition to the first polymerization initiator and the second polymerization initiator, the reactive monomer mixture used to manufacture the ophthalmic lens of the present invention may contain any of the above-mentioned polymerizable compounds and optional components.

[0153] The reactive monomer mixture may include: a first polymerization initiator having a first functional portion (i.e., a compound of formula I) chemically linked thereto, a second polymerization initiator that can be activated by a second activation that does not substantially activate the first polymerization initiator, and a hydrophilic component.

[0154] The reactive monomer mixture may comprise: a first polymerization initiator having a first functional portion (i.e., a compound of formula I) chemically linked thereto; a second polymerization initiator capable of being activated by a second activation that does not substantially activate the first polymerization initiator; a hydrophilic component; 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.

[0155] The reactive monomer mixture may include: a first polymerization initiator having a first functional portion (i.e., a compound of formula I) chemically linked thereto, a second polymerization initiator that can be activated by a second activation that does not substantially activate the first polymerization initiator, and a hydrophilic component, and a polysiloxane-containing component.

[0156] The reactive monomer mixture may comprise: a first polymerization initiator having a first functional portion (i.e., a compound of formula I) chemically linked thereto; a second polymerization initiator capable of being activated by a second activation that does not substantially activate the first polymerization initiator; and a hydrophilic component selected from DMA, HEMA, and mixtures thereof; a polysiloxane component selected from 2-hydroxy-3-[3-methyl-3,3-di(trimethylsiloxy)silylpropoxy]-propyl methacrylate (SiMAA), monomethacryloxypropyl-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 components containing polysiloxane, a mixture of SiMAA and mPDMS is preferred.

[0157] The reactive monomer mixture may comprise: a first polymerization initiator having a first functional portion (i.e., a compound of formula I) chemically linked thereto; a second polymerization initiator capable of being activated by a second activation that does not substantially activate the first polymerization initiator; and a hydrophilic component comprising a mixture of DMA and HEMA; and a polysiloxane component comprising a mixture of OH-mPDMS having 2 to 20 repeating units (preferably a mixture of 4 and 15 repeating units). Preferably, the reactive monomer mixture further comprises a polysiloxane crosslinking agent, such as ac-PDMS. Also preferably, the reactive monomer mixture contains a wetting agent (preferably DMA, PVP, PVMA, or a mixture thereof).

[0158] The reactive monomer mixture may comprise: a first polymerization initiator having a first functional portion (i.e., a compound of formula I) chemically linked thereto; a second polymerization initiator capable of being activated by a second activation that does not substantially activate the first polymerization initiator; and a hydrophilic component; in about 1 and about 15 At least one polyamide (e.g., acyclic polyamide, cyclic polyamide, or mixtures thereof) between wt%; at least one first monofunctional hydroxylated poly(disubstituted siloxane) having 4 to 8 siloxane repeating units (e.g., OH-mPDMS, wherein n is 4 to 8, preferably n is 4); at least one second hydroxylated poly(disubstituted siloxane) having 10 to 200, or 10 to 100, or 10 to 50, or 10 to 20 siloxane repeating units (e.g., OH-mPDMS, wherein n is 10 to 200, or 10 to 100, or 10 to 50, or 10 to 20, preferably n is 15); about 5 to about 35 The product comprises, by weight, at least one hydrophilic monomer; and optionally, a polyfunctional hydroxylated poly(disubstituted siloxane) having 10 to 200, or 10 to 100 siloxane repeating units (e.g., ac-PDMS). Preferably, the first monofunctional hydroxylated poly(disubstituted siloxane) and the second hydroxylated poly(disubstituted siloxane) are present at a concentration providing a ratio of 0.4 to 1.3 or 0.4 to 1.0 weight percentage of the first monofunctional hydroxylated poly(disubstituted siloxane) to the second hydroxylated poly(disubstituted siloxane).

[0159] The reactive monomer mixture may include: a first polymerization initiator having a first functional portion (i.e., a compound of formula I) chemically linked thereto; a second polymerization initiator that can be activated by a second activation that does not substantially activate the first polymerization initiator; and a hydrophilic component, such as DMA; a polysiloxane component, such as compound 8 (TRIS) in Table B; and a polysiloxane macromonomer (such as compound 42 in Table C).

[0160] The reactive monomer mixture may include: a first polymerization initiator having a first functional portion (i.e., a compound of formula I) chemically linked thereto; a second polymerization initiator that can be activated by a second activation that does not substantially activate the first polymerization initiator; and a hydrophilic component, such as DMA and / or NVP; a polysiloxane component, such as compound 14 ((TRIS-Am)) in Table B; and a polysiloxane macromonomer (such as compound 43 (IEM-PDMS-IPDI-PDMS-IPDI-PDMS-IEM)) in Table C.

[0161] The reactive monomer mixture may include: a first polymerization initiator having a first functional portion (i.e., a compound of formula I) chemically linked thereto; a second polymerization initiator that can be activated by a second activation that does not substantially activate the first polymerization initiator; and a hydrophilic component, such as VMA; and a polysiloxane macromonomer, such as compound 35 in Table C.

[0162] The reactive monomer mixture may include: a first polymerization initiator having a first functional portion (i.e., a compound of formula I) chemically linked thereto; a second polymerization initiator that can be activated by a second activation that does not substantially activate the first polymerization initiator; and a hydrophilic component, such as VMA and / or NVP; a polysiloxane component, such as compound 28 in Table C (e.g., where j2 is about 16); and a polysiloxane macromonomer (such as compound 35 in Table C).

[0163] The reactive monomer mixture may include: a first polymerization initiator having a first functional portion (i.e., a compound of formula I) chemically linked thereto; a second polymerization initiator that can be activated by a second activation that does not substantially activate the first polymerization initiator; and a hydrophilic component, such as VMA and / or NVP; a polysiloxane component, such as compound 18 in Table B (e.g., where j2 is about 4); and a polysiloxane macromonomer (such as compound 41 in Table C).

[0164] The aforementioned reactive monomer mixture may contain optional components, such as, but not limited to, internal wetting agents, crosslinking agents, other UV or HEV absorbers, and diluents. Furthermore, ophthalmic lenses manufactured from the aforementioned reactive monomer mixture may undergo further processing, including but not limited to plasma treatment, application of coatings (such as in-package coating (IPC) as described in US8480227), and the like.

[0165] The formed lens object can then be removed from the semi-mold by mechanical means, solvent expansion, or a combination thereof, followed by an extraction process to remove unreacted first polymerization initiator. The extraction process for removing unreacted first polymerization initiator can be complete or incomplete. In some cases, removing all unreacted first polymerization initiator is not necessary to achieve the desired characteristics or optical effects. In other cases, the extraction process removes only a portion of the unreacted first initiator, allowing for optional irradiation steps using a lower concentration of the first polymerization initiator. Alternatively, the extraction process can remove substantially all of the unreacted first initiator. After removing the unreacted first polymerization initiator, standard post-processing steps of lens extraction and lens hydration to remove other reactive monomer components can be performed to form the final ophthalmic lens. In some cases, standard post-processing steps of lens extraction and hydration using aqueous alcohol solutions, water, and buffers can also extract unreacted first polymerization initiator, thereby combining two or more extraction steps into a single operation.

[0166] The aqueous solution is a solution containing water. The aqueous solution of this invention contains at least about 20% by weight water, or at least about 50% by weight water, or at least about 70% by weight water, or at least about 95% by weight water. The aqueous solution may also include additional water-soluble formulations, such as inorganic salts or release agents, wetting agents, slip agents, pharmaceutical and nutritional formulations, combinations thereof, and the like. Release agents are compounds or mixtures of compounds that, when combined with water, can reduce the time required to release the contact lens from the mold compared to using an aqueous solution that does not contain a release agent. The aqueous solution may not require special treatment (e.g., purification, recycling) or special disposal procedures.

[0167] Extraction can be achieved, for example, by immersing the lens in an aqueous solution or exposing the lens to a stream of aqueous solution. Extraction may also include, for example, one or more of the following: heating the aqueous solution; stirring the aqueous solution; increasing the level of a leaching agent in the aqueous solution to a level sufficient to cause lens leaching; mechanically or ultrasonically agitating the lens; and incorporating at least one leaching or extraction agent into the aqueous solution, wherein the level of the leaching or extraction agent is sufficient to promote adequate removal of unreacted components from the lens. The foregoing can be performed in batch or continuous processes, regardless of whether heating, agitation, or both are involved.

[0168] Physical agitation may be necessary to aid in leaching and release. For example, the lens module to which the lens is attached may be vibrated or moved back and forth in the aqueous solution. Other methods may include passing the aqueous solution through an ultrasonic wave.

[0169] Lenses can be sterilized by known means, such as, but not limited to, autoclaving.

[0170] As indicated above, preferred ophthalmic lenses are contact lenses, and more preferably soft hydrogel contact lenses. Polysiloxane hydrogel ophthalmic lenses (e.g., contact lenses) prepared according to the present invention preferably exhibit the following properties. All values ​​are in the sense of "about," and the lens may have any combination of the listed properties. Properties can be determined by methods known to those skilled in the art, such methods being, for example, those described in U.S. Patent Early Publication US20180037690, which is incorporated herein by reference. Water concentration %: at least 20% or at least 25% and at most 80% or at most 70%. Haze: 30% or less, or 10% or less Forward dynamic contact angle (Wilhelmy plate method): 100° or less, or 80° or less; or 50° or less Tensile modulus (psi): 120 or less, or 80 to 120 Oxygen permeability (Dk, Barrer): at least 80, or at least 100, or at least 150, or at least 200 Elongation at break: at least 100

[0171] For ion-modified silica hydrogels, the following properties may also be preferred (in addition to those mentioned above): Lysozyme absorption (µg / lens): at least 100, or at least 150, or at least 500, or at least 700 Polyquaternary ammonium salt 1 (PQ1) absorption (%): 15 or less, or 10 or less, or 5 or less

[0172] Some embodiments of the present invention will now be described in detail in the following examples. Example

[0173] The following abbreviations will be used in all instances and diagrams and have the following meanings: DMA:N,N-Dimethylacrylamide (Jarchem) HEMA: 2-Hydroxyethyl methacrylate (Bimax) PVP K12, K30, or K90: Poly(N-vinylpyrrolidone) (ISP Ashland) TEGDMA: Tetraethylene glycol dimethacrylate (Esstech) Omnirad 819: Bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (IGM Resins) AIBN: Azobisisobutyronitrile [CAS 78-67-1] SiMAA: 2-Acrylic acid, 2-methyl-2-hydroxy-3-[3-[1,3,3,3-tetramethyl-1-[(trimethylsilyl)oxy]disiloxane]propoxy]propyl ester (Toray) or 3-(3-(1,1,1,3,5,5,5-heptamethyltrisiloxane-3-yl)propoxy)-2-hydroxypropyl methacrylate HO-mPDMS: Mono-n-butyl-terminated mono(2-hydroxy-3-methacryloxypropyloxy)-propyl-terminated polydimethylsiloxane (Mn = 1400 g / mol, n = 15) (Ortec or DSM-Polymer Technology Group) Norbloc: 2-(2'-hydroxy-5-methylpropenyloxyethylphenyl)-2H-benzotriazole (Janssen) Blue HEMA: 1-amino-4-[3-(4-(2-methacryloxyethoxy)-6-chlorotris(2-ylamino)-4-sulfonicoaniline]anthraquinone-2-sulfonic acid, as described in U.S. Patent No. 5,944,853. Boric acid buffer solution: Dissolve 18.52 g (300 mmol) boric acid, 3.7 g (9.7 mmol) sodium borate decahydrate, and 28 g (197 mmol) sodium sulfate in enough deionized water to fill a 2-liter volumetric flask. D3O: 3,7-Dimethyl-3-octanol (Vigon) HCl: hydrochloric acid IPA: 2-Propanol ACN: Acetonitrile THF: Tetrahydrofuran PEO: Polyethylene oxide DMF: Dimethylformamide DCM: Dichloromethane PP: Polypropylene, a homopolymer of propylene. TT: Tuftec, a hydrogenated styrene-butadiene block copolymer (Asahi Kasei Chemicals) Z: Zeonor, a polycyclic olefin thermoplastic polymer (Nippon Zeon Co Ltd). LED: Light Emitting Diode 1N NMR: Proton Nuclear Magnetic Resonance Spectroscopy UV-VIS: Ultraviolet-Vis Spectroscopy TLC: Thin-layer chromatography ID:inner diameter L: Liter mL: milliliters mM: millimolec M: Volume Mole Equiv. or eq.: equivalent quantity kg: kilogram g: grams mg: milligrams mol: mole mmol: millimole min: minutes mm: millimeter cm: centimeters µm: micrometer nm: nano mW: milliwatt mJ: millijoules Pascal PSI: pounds per square inch Absorption %T: Percentage of transmission APO: Mono-aminophosphine oxide DMD: Digital Micromirror Device Example Example 1 – Synthesis of mono-terminated poly(N-vinylpyrrolidone) (MAPO-PVP) with mono-acidyl phosphine oxide, as shown in Scheme A.

[0174] Under yellow light, a three-necked round-bottom flask equipped with a reflux condenser was filled with N-vinylpyrrolidone (20.0 g), ethanol (41.0 g), and Omnirad 819 (1.0 g), degassed, and heated at 65 °C under nitrogen. The reaction mixture was then irradiated for thirty minutes with a 435 nm LED lamp with an intensity of approximately 1.22 mW / cm². The reaction mixture was quenched in air and cooled to room temperature. The solvent was removed under reduced pressure, followed by precipitation in cold diethyl ether to obtain a white solid after filtration. The white solid was suspended in diethyl ether (50 mL) and stirred for 30 minutes, then filtered again. The product (“MAPO-PVP”) was then washed with diethyl ether (3 × 50 mL) and air-dried to obtain a white powder (16.0 g, 80% yield). The polymer structure is characterized by a 500 MHz 1H-NMR spectrum in deuterium oxide; see Figure 4. Molecular weight and its distribution were determined by viscosity comparison and size exclusion multiangle light scattering (SEC-MALS) for commercially available samples of PVP K12-K90. It should be noted that the product "MAPO-PVP" is a mixture of mono-acylphosphine oxide-terminated PVP and mono-acyl-terminated PVP as shown in Scheme A. The type of monoacyl group depends on the type of bisacylphosphine oxide initiator used in the copolymerization; if the initiator has two different acyl groups, then "MAPO-PVP" is a mixture of two mono-acylphosphine oxide-terminated PVPs and two mono-acyl-terminated PVPs. It is important to protect these materials from ambient light during storage. MAPO-PVP is an example of the first formula in Table A. Option A

[0175] Viscosity measurements were performed at room temperature on an Anton-Paar rheometer using a CP50-1 cone-plate, with shear rates ranging from 1 sec⁻¹ to 500 sec⁻¹, a run time of 400 seconds, and data collected every 10 seconds. Measurements were repeated and averaged. The viscosity results are shown in Table 1. The viscosity data indicate that MAPO-PVP exhibits a slightly higher viscosity than PVP K30. Table 1. Viscosity Data sample Viscosity (Pa-sec) PVP K12 0.0011176 PVP K30 0.0012584 PVP K90 0.0034210 MAPO-PVP 0.0014032

[0176] The molecular weight of the polymer was determined by using size exclusion chromatography with multi-angle light scattering (SEC-MALS) relative to the molecular weight of commercially available samples of PVP K12 and PVP K30. The SEC-MALS setup used 20% ACN (v / v) in deionized water (containing 50 mM Na₂SO₄) as the mobile phase at a flow rate of 0.3 mL / min (at 40°C), and three Tosoh Biosciences TSK-gel columns connected in series [SuperAW3000 4 µm, 6.0 mm ID × 15 cm (PEO / DMF exclusion limit = 60,000 g / mol), SuperAW4000 6 µm, 6.0 mm ID × 15 cm (PEO / DMF exclusion limit = 400,000 g / mol), and SuperAW5000 7 µm, 6.0 mm ID × 15 cm (PEO / DMF exclusion limit = 4,000,000 g / mol)]. It was equipped with an online Agilent 1200 UV / VIS diode array detector, a Wyatt Optilab rEX interferometer, and a Wyatt... A mini-DAWN Treos multi-angle laser scattering (MALS) detector (λ=658 nm) was used. Molecular weight and polydispersity data were calculated using the Wyatt ASTRA 6.1.1.17 SEC / LS software suite. Figure 5 shows the SEC-MALS chromatograms of PVP K12, PVP K30, and MAPO-PVP. Since the chromatograms of PVP K30 and MAPO-PVP are similar, it is inferred that PVP K30 and MAPO-PVP have similar molecular weight distributions.

[0177] Example 2 – Synthesis of mono-terminated poly(N,N-dimethylacrylamide) (MAPO-PDMA) with mono-acrylamide oxide: Under yellow light, a three-necked round-bottom flask equipped with a reflux condenser was filled with 11.0 g of N,N-dimethylacrylamide, 11.0 g of ethanol, and 400 mg of Omnirad 819, degassed, and heated at 75 °C under nitrogen. The reaction mixture was then irradiated for twenty minutes with a 435 nm LED lamp having an intensity of approximately 1.22 mW / cm². The reaction was then quenched in air and cooled to room temperature, followed by precipitation in cold diethyl ether to give a white solid, which was redissolved in methanol and precipitated again with diethyl ether. This precipitation procedure was repeated once more to give a white solid (65% yield). MAPO-PDMA is characterized by its 500 MHz 1H-NMR spectrum in deuterated methanol; see Figure 6.

[0178] The molecular weight of the polymer was determined by using SEC-MALS (Spectroscopic Separation-Meltdown Chromatography-Multi-Angle Light Scattering). The SEC-MALS setup used methanol (containing 10 mM LiBr) as the mobile phase at a flow rate of 0.6 mL / min (at 50 °C), and three Tosoh Biosciences TSK-gel columns connected in series: SuperAW3000 4 µm, 6.0 mm ID × 15 cm (PEO / DMF exclusion limit = 60,000 g / mole), SuperAW4000 6 µm, 6.0 mm ID × 15 cm (PEO / DMF exclusion limit = 400,000 g / mole), and SuperAW5000 7 µm, 6.0 mm ID × 15 cm (PEO / DMF exclusion limit = 4,000,000 g / mole). It also featured an online Agilent 1200 UV / VIS diode array detector, a Wyatt Optilab rEX interferometer / refractometer, and a Wyatt mini-DAWN. Treos Multi-Angle Laser Scattering (MALS) detector (λ=658 nm). Absolute molecular weight was determined using a dη / dc value of 0.183 mL / g (λ=658 nm) at 30°C. Absolute molecular weight and polydispersity data were calculated using Wyatt ASTRA 6.1.1.17 SEC / LS software suite. The number-mean molecular weight was determined to be 56,500 g / mol; the weight-mean molecular weight was determined to be 96,100 g / mol; resulting in a polydispersity index [Mw / Mn] of 1.6.

[0179] Example 3 (Predicted) – Synthesis of a mono-terminated poly(N-vinylpyrrolidone-co-N,N-dimethylacrylamide) with mono-acrylamide oxide: Under yellow light, a three-necked round-bottom flask equipped with a reflux condenser was filled with N-vinylpyrrolidone (10.0 g), N,N-dimethylacrylamide (10.0 g), ethanol (41.0 g), and Omnirad 819 (1.0 g), degassed, and heated at 65°C under nitrogen. The reaction mixture was then irradiated for thirty minutes with a 435 nm LED lamp with an intensity of approximately 1.22 mW / cm². The reaction mixture was quenched in air and cooled to room temperature. The solvent was removed under reduced pressure, followed by precipitation in cold diethyl ether to obtain a white solid after filtration. The white solid was suspended in diethyl ether (50 mL) and stirred for 30 minutes, then filtered again. The product ("MAPO-poly[NVP-co-DMA]") was then washed with diethyl ether (3 × 50 mL) and air-dried to obtain a white powder. Example 4 (Optical Path Length Modification)

[0180] A reactive monomer mixture comprising the formulations listed in Table 2 was formed. The reactive monomer mixture was degassed by applying a vacuum for approximately 15 minutes. Then, approximately 100 μL of the reactive monomer mixture was applied to the Zeonor base curve mold, and subsequently, the Zeonor front curve mold was placed on top of the base curve mold. The resulting mold assembly was transferred to the irradiation fixture shown in Figure 3, and then connected to a computer-controlled light projector, in which a 365 nm LED light source with an intensity of 47.5 mW / cm² was directed to different volumes within the mold cavity and modulated by a digital light processing chip or digital micromirror device. Table 2. Formula [Components] [Weight Percentage] OH-mPDMS (n=15) 22.69% SiMAA 20.50% DMA 19.72% HEMA 5.51% Blue HEMA 0.01% PVP K90 2.24% PVP-MAPO (Example 1) 7.85% TEGDMA 1.31% Norbloc 1.46% AIBN 0.25% D3O (diluent) 18.45% [total] [100.00%]

[0181] A computer-controlled projector was programmed to illuminate or irradiate the USAF 1951 test target shown in Figure 7. The USAF 1951 test chart is a widely known image, encompassing a broad array of spatial frequencies and recognizable numbers, and is therefore a good reference for objectively measuring the overall quality of the image profile. The reactive monomer mixture in the cavity was irradiated with a computer-controlled light projector at a maximum energy of 700 mJ / cm² and an exposure time of 31.6 seconds to impart the USAF 1951 test chart image profile to the contact lens. The lens was then heated to 90°C for 2 hours and 45 minutes to thermally cure the remaining reactive monomer mixture into a contact lens. The resulting lens was released using a 70% (v / v) IPA aqueous solution (soaked for approximately one hour), extracted twice with a 70% (v / v) IPA aqueous solution for 30 minutes each time, hydrated with deionized water for 30 minutes, and then equilibrated with the packaging solution. The final optical micrograph of the hydrated lens is shown in Figure 8. Note: The precise conditions of a computer-controlled light projector typically require optimization based on the composition of the reactive monomer mixture and the projected image. This optimization usually involves altering the energy [energy = LED intensity × DMD decay × exposure time] delivered to the reactive monomer mixture in the cavity and the exposure time. Preferably, optimization uses the highest possible intensity and the shortest possible exposure time.

[0182] To improve spatial resolution, the above experiments were repeated with a pre-curing step at 90°C for 5, 10, and 15 minutes prior to light projector irradiation. The pre-curing step increases the viscosity of the reactive monomer mixture before light projector irradiation, thereby improving image quality by reducing molecular motion. Based on this data, the 10-minute pre-curing step appears to improve the quality and reproducibility of the resulting contour images. Example 2 (Optical Features)

[0183] Example 1 involves a ten-minute pre-curing repetition, but instead of projecting an image, a computer-controlled light projector irradiates a dot pattern, with individual dots exposed to different energy levels. This creates columns of different optical paths due to localized changes in volume and refractive index after the lens has been demolded, extracted, hydrated, and equilibrated as described in Example 1. In this way, a calibration curve is generated by plotting the applied energy (mJ) versus the effect of δ optical path length (wavefront measurement in the wave after conversion from the packaging solution to air) on the wavefront values ​​of untreated lenses of the same design at each column location. For energy exposures below 100 mJ, the calibration curve is reasonably linear and deterministic. This relationship allows for the predictable generation of optical characteristics, such as adding spherical or defocused or cylindrical powers to lenses manufactured in cavities designed to exhibit only a fixed spherical power. Based on this information, using an exposure time of 3.6 seconds and an energy level of 86 mJ / cm², the computer-controlled projector irradiates spherical or cylindrical power images into the lens cavity. The projected image and the two-dimensional plot of the measured delta wavefront obtained from the fully balanced lens are shown in Figure 9. By increasing the defocus, the estimated change in spherical power is about 0.7 diopters, and the estimated increase in cylindrical power is about 0.12 diopters.

[0184] The parameters of contact lenses in packaged solutions are measured using a calibrated dual interferometry method. These parameters include the equivalent spherical power (diopter or D) at multiple apertures, cylindrical power (diopter or D) at multiple apertures, diameter (mm), center thickness (mm or mm), sagittal height (mm or mm), and root mean square (RMS) optical path wavefront deviation in micrometers (µm) relative to the lens design target, and are sometimes expressed as a wavefront that eliminates spherical / cylindrical power and coma, as measured using a 6.5 mm aperture. The instrument consists of a custom-designed, dedicated interferometer for measuring wavefront parameters and a Lumetrics OptiGauge® II low coherence interferometer for measuring the dimensional parameters of sagittal height and center thickness. These two individual instruments are similar to Lumetrics Clearwave™ Plus, and the software is similar to Lumetrics OptiGauge Control Center v7.0 or later. The Clearwave™ Plus Clearwave camera is used to locate the lens edge, and then the lens center is calculated. This center is used to align a 1310 nm interferometer probe with the lens center for measuring the sagittal height and center thickness. The transmitted wavefront is also collected using a wavefront sensor (shack-Hartmann sensor). Several parameters of the transmitted wavefront from the contact lens are measured, and other parameters are calculated based on these measurements.

[0185] The collected data are used to calculate discrepancies by comparing measured values ​​from the target. These include the root mean square optical path wavefront deviation (eliminating spherical / cylindrical power and coma deviation) relative to the lens design target in µm (e.g., RMS_65 measured with a 6.5 mm aperture), the second equivalent spherical power deviation relative to the lens design target in diopter (D) (e.g., PW2EQD measured with a 5 mm aperture), the deviation relative to the lens design target diameter in mm (DMD), the deviation relative to the lens design target base curve radius in mm (calculated from the measured sagittal height and target lens diameter according to ISO 18369-3, BCD), and the deviation relative to the lens design target center thickness in mm (CTD). After subtracting the designed inner spherical power based on the mold design, these data are used to calculate the amount of increase in spherical or cylindrical power caused by modulation and localized light convergence.

[0186] 110: Digital Microscope Device / DMD 115: Light Stopper 116,117:Object 120: Photochemical radiation source or light source 130: Components 140: Beam 150: Path / Object 160: Spatial Intensity Distribution / Object 180: Translucent forming optical components 200: Curing equipment 201: Half mold 202: Semi-mold 203: Half mold 204: Reactive monomer mixture 205: Photochemical radiation source 210a: Part 1 210b: Part Two 212: Light Absorber 302: Reactive monomer mixture

[0187] none

Claims

1. A compound of formula I: wherein R1 is independently H or methyl in each occurrence; R2 and R3 are independently H or -X'-N(R6)(R7) in each occurrence, provided that at least one R2 or R3 is -X'-N(R6)(R7), wherein X' is independently bonded or -(CO)- in each occurrence, R6 is independently H, C1-C6 alkyl, or C1-C6 alkyl carbonyl in each occurrence, and R7 is independently H, C1-C6 alkyl, or C1-C6 alkyl carbonyl in each occurrence, or R6 and R 7, when present, forms a heterocyclic alkyl ring with its equally bonded nitrogen atom, wherein the ring carbon atom is optionally substituted with a heteroatom selected from nitrogen, oxygen, and sulfur, wherein each alkyl and alkyl carbonyl group is independently and optionally substituted with hydroxyl, amino, amide, oxy, carboxyl, alkyl carboxyl, carbonyl, alkyl carbonyl, alkoxy, amide, carbamate, carbonate, halogen, phenyl, or benzyl, and each heterocyclic alkyl group is independently and optionally substituted with alkyl, hydroxyl, amino, amide, oxy, carboxyl, alkyl carboxyl, carbonyl, alkyl carbonyl, alkoxy, amide, carbamate, carbonate, halogen, phenyl, or benzyl; R4 and R5, when present, are independently alkyl, cycloalkyl, alkoxy, or halogen in each occurrence; T is a chain-terminating group; n is 10 to 4000; and p and q are independently 0, 1, 2, 3, 4, or 5.

2. The compound as claimed in claim 1, wherein one of R2 and R3 is H each time it appears.

3. The compound as described in any one of claims 1 to 2, wherein q is 0.

4. The compound as claimed in any one of claims 1 to 2, wherein p is 3-ary and R4 is independently C1-C3 alkyl each time it appears.

5. The compound as claimed in any one of claims 1 to 2, wherein R6 and R7 together with their equally bonded nitrogen atoms form a heterocyclic alkyl ring optionally substituted with alkyl, hydroxyl, amino, amide, oxy, carboxyl, alkylcarboxyl, carbonyl, alkylcarbonyl, alkoxy, amide, carbamate, carbonate, or halogen.

6. The compound as claimed in any one of claims 1 to 2, wherein R6 and R7 together with their equally bonded nitrogen atoms form an imidazolidinyl, piperazinyl, pyrrolidinyl, or piperidinyl group optionally substituted with an alkyl or side-oxy group.

7. The compound as claimed in any one of claims 1 to 2, wherein R6 and R7 together with their equally bonded nitrogen atoms form a 2-pyrrolidone.

8. The compound as claimed in any one of claims 1 to 2, wherein R6 and R7 are independently H, C1-C6 alkyl, or C1-C6 alkylcarbonyl, wherein the alkyl and alkylcarbonyl groups are optionally substituted with hydroxyl groups.

9. The compound as claimed in any one of claims 1 to 2, wherein R6 and R7 are independently H or C1-C4 alkyl groups, wherein the alkyl groups are optionally substituted with hydroxyl groups.

10. The compound as claimed in any one of claims 1 to 2, wherein both R6 and R7 are H.

11. The compound as claimed in any one of claims 1 to 2, wherein R 6 is H and R 7 is C 1-C 3 alkyl or C 1-C 3 alkyl carbonyl, wherein the alkyl group is optionally substituted with a hydroxyl group.

12. The compound as claimed in any one of claims 1 to 2, wherein R6 and R7 are independently C1-C3 alkyl groups optionally substituted with hydroxyl groups.

13. The compound as claimed in any one of claims 1 to 2, wherein R6 is a C1-C3 alkyl group optionally substituted with a hydroxyl group, and R7 is a C1-C3 alkyl carbonyl group.

14. The compound as claimed in any one of claims 1 to 2, wherein X' is -(CO)-.

15. The compound as claimed in any one of claims 1 to 2, wherein X' is a direct bond.

16. The compound as described in claim 1, which is:

17. A method for forming an ophthalmic lens, the method comprising: (a) providing a mold assembly including a base surface and a front surface defining and surrounding a cavity therebetween, the cavity containing a reactive monomer mixture, wherein the reactive monomer mixture includes a monomer suitable for manufacturing the ophthalmic lens, a first polymerization initiator capable of being activated at a first wavelength, a first functional portion chemically linked to the first polymerization initiator, and a second polymerization initiator capable of being activated by a second activation, the second activation not substantially activating the first polymerization initiator, wherein at least one of the base surface or the front surface is light-transmitting; (b) exposing one or more selective regions of the reactive monomer mixture to a photochemical radiation source at the first wavelength to selectively polymerize a portion of the reactive monomer mixture, wherein the selectively polymerized portion is incorporated into the first functional portion; (c) exposing the reactive monomer mixture to the second activation to activate the second polymerization initiator and cure the reactive monomer mixture; (d) (e) Remove the ophthalmic lens from the mold assembly; and (e) extract unreacted first polymerization initiator from the ophthalmic lens, wherein the first polymerization initiator having a chemically linked first functional portion is a compound as described in any one of claims 1 to 16.

18. A reactive monomer mixture for manufacturing ophthalmic lenses, the reactive monomer mixture comprising: a monomer suitable for manufacturing the ophthalmic lens; a first polymerization initiator capable of being activated at a first wavelength; a first functional portion chemically linked to the first polymerization initiator; and a second polymerization initiator capable of being activated by a second activation that does not substantially activate the first polymerization initiator, wherein the first polymerization initiator having the chemically linked first functional portion is a compound as described in any one of claims 1 to 16.

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