Grafted ophthalmic devices containing inactivation regions, and processes for their preparation and use.

Abstract

An ophthalmic device is disclosed, the ophthalmic device comprising: (a) a step of providing a reactive composition, the reactive composition comprising (i) a polymerization initiator capable of forming two or more free radical groups upon first activation, wherein at least one of the free radical groups is further activatable by subsequent activation, (ii) one or more ethylenically unsaturated compounds, and (iii) a crosslinking agent; (b) a step of subjecting the reactive composition to a first activation step such that the reactive composition polymerizes thereto form a crosslinked substrate network containing covalently bonded activatable free radical initiators; and (c) inactivating at least a portion of the covalently bonded activatable free radical initiators in one or more selected regions of the crosslinked substrate network. An ophthalmic device manufactured by a process comprising: (d) a step of ensuring that the crosslinked substrate network contains retained covalently activatable free radical initiators outside one or more selected regions and optionally within one or more selected regions; (b) a step of contacting the crosslinked substrate network with a grafting composition containing one or more ethylenically unsaturated compounds, wherein the contact is carried out under conditions such that the grafting composition penetrates into the crosslinked substrate network; and (e) a step of activating the retained covalently activatable free radical initiators so that the grafting composition polymerizes with the crosslinked substrate network, thereby forming a grafted polymer network outside the selected regions and optionally partially within the selected regions.

Description

[Technical Field]

[0001] (Cross-reference of related applications) This application claims priority to U.S. Patent Application No. 18 / 426,780, filed on 30 January 2024, and U.S. Provisional Patent Application No. 63 / 492,499, filed on 28 March 2023, both of which are incorporated herein by reference.

[0002] (Field of invention) The present invention relates to ophthalmic devices such as contact lenses containing a grafted polymer network, and to processes for preparing and using ophthalmic devices. [Background technology]

[0003] The development of polymer materials prepared from individual components that contribute to desired properties is an ongoing goal in many product areas. For example, polymer materials exhibiting oxygen permeability and hydrophilicity are desirable for numerous applications in the medical device field, such as ophthalmic devices.

[0004] A common challenge in forming polymer materials that attempt to combine properties is that the individual components from which the final material is made often do not mix easily with each other. For example, in the field of contact lenses, silicone hydrogels have been found to provide lenses with significantly increased oxygen permeability, and therefore can reduce corneal edema and hypervascularity that may be associated with conventional hydrogel lenses. Silicone hydrogels have generally been prepared by polymerizing a mixture containing at least one silicone-containing monomer or silicone-containing reactive macromer and at least one hydrophilic monomer. However, since the silicone and hydrophilic components are often miscible, silicone hydrogel lenses can be difficult to manufacture.

[0005] In addition to the overall compatibility of the reactants, in some applications, it is desirable to form products from different materials, and that these materials be localized to specific areas rather than dispersed throughout. For example, in the field of ophthalmic devices, processes that allow for localized modifications of devices (such as contact lenses) can enable manufacturers to produce products with customized lens powers or other desirable properties. [Overview of the project] [Means for solving the problem]

[0006] The present invention relates to novel polymer compositions derived from a wide variety of monomers and polymers of such components, including cases where the monomers and polymers of such components are generally incompatible. The present invention further relates to a process for selectively modifying the material composition of a substrate. Such polymer compositions are used in a variety of applications, such as in ophthalmic devices such as contact lenses, intraocular lenses, punctal plugs, and intraocular implants.

[0007] Therefore, in one embodiment, the present invention is an ophthalmic device, (a) A step of providing a reactive composition, the reactive composition comprising (i) a polymerization initiator capable of forming two or more free radical groups upon first activation, wherein at least one of the free radical groups is further activatable by subsequent activation, (ii) one or more ethylenically unsaturated compounds, and (iii) a crosslinking agent. (b) A step of subjecting the reactive composition to a first activation step, wherein the reactive composition polymerizes thereto to form a crosslinked substrate network containing covalently bonded activatable free radical initiators, (c) A step of inactivating at least a portion of the covalently bonded activatable free radical initiator in one or more selected regions of the crosslinked substrate network so that the crosslinked substrate network contains retained covalently bonded activatable free radical initiator outside of one or more selected regions and optionally within one or more selected regions, (d) A step of contacting a crosslinked substrate network with a grafting composition containing one or more ethylenically unsaturated compounds, wherein the contact is carried out under conditions such that the grafting composition penetrates into the crosslinked substrate network. (e) The step of activating a retained covalently bonded, activatable free radical initiator so that the grafted composition polymerizes with the crosslinked substrate network, thereby forming a grafted polymer network outside the selected region and optionally partially within the selected region.

[0008] In another embodiment, the present invention is: (a) A crosslinked substrate network wherein at least a portion of a covalently bonded activatable free radical initiator is inactivated in one or more selected regions of the crosslinked substrate network, and the crosslinked substrate network contains the retained covalently bonded activatable free radical initiator outside of one or more selected regions and optionally within one or more selected regions; (b) The present invention provides an ophthalmic device comprising a grafted composition containing one or more ethylenically unsaturated compounds, wherein the grafted composition is localized in a crosslinked substrate network that holds covalently activatable free radical initiators, and the reaction product of a composition comprising the grafted composition.

[0009] In a further embodiment, the present invention provides a process for manufacturing an ophthalmic device, the process is (a) A step of providing a reactive composition, the reactive composition comprising (i) a polymerization initiator capable of forming two or more free radical groups upon first activation, wherein at least one of the free radical groups is further activatable by subsequent activation, (ii) one or more ethylenically unsaturated compounds, and (iii) a crosslinking agent. (b) A step of subjecting the reactive composition to a first activation step, wherein the reactive composition polymerizes thereto to form a crosslinked substrate network containing covalently bonded activatable free radical initiators, (c) A step of inactivating at least a portion of the covalently bonded activatable free radical initiator in one or more selected regions of the crosslinked substrate network so that the crosslinked substrate network contains retained covalently bonded activatable free radical initiator outside of one or more selected regions and optionally within one or more selected regions, (d) A step of contacting a crosslinked substrate network with a grafting composition containing one or more ethylenically unsaturated compounds, wherein the contact is carried out under conditions such that the grafting composition penetrates into the crosslinked substrate network. (e) The step of activating a retained covalently bonded, activatable free radical initiator so that the grafted composition polymerizes with the crosslinked substrate network, thereby forming a grafted polymer network outside the selected region and optionally partially within the selected region.

[0010] In a further embodiment, the present invention provides a process for manufacturing an ophthalmic device, the process is (a) (i) a thermal initiator, (ii) one or more ethylenically unsaturated compounds, (iii) a crosslinking agent; (iv) at least one reactive component having at least one pendant group selected from the group consisting of monoacylphosphine oxide, bisacylphosphine oxide, and combinations thereof, and (v) at least one reactive component selected from the group consisting of monoacylphosphine oxide compounds having a refractive index moiety or a light-absorbing moiety, bisacylphosphine oxide compounds having a refractive index moiety or a light-absorbing moiety, and combinations thereof, (b) A step of forming a precursor crosslinked substrate network by thermal polymerization of a reactive composition, wherein a monoacylphosphine oxide compound having a refractive index portion or a light-absorbing portion and a bisacylphosphine oxide compound having a refractive index portion or a light-absorbing portion are spatially dispersed within the precursor crosslinked substrate network, and the reactive composition is not completely polymerized. (c) A step of irradiating a precursor crosslinked substrate network in a pre-selected region, thereby initiating free radical polymerization from dispersed monoacylphosphine oxide compounds having refractive index portions or light-absorbing portions and bisacylphosphine oxide compounds having refractive index portions or light-absorbing portions, thereby incorporating the refractive index portions or light-absorbing portions into the precursor crosslinked substrate network in the pre-selected region, (d) A step of subjecting the reactive composition to thermal polymerization so that the reactive composition is completely polymerized therein to form a crosslinked substrate network having covalently bonded monoacylphosphine oxide groups or bisacylphosphine oxide groups, and optionally (e) A step of extracting unreacted monoacylphosphine oxide compounds having refractive index or light-absorbing portions and bisacylphosphine oxide compounds having refractive index or light-absorbing portions with a solvent, (f) A step of deactivating at least a portion of the covalently bonded monoacylphosphine oxide groups or bisacylphosphine oxide groups in one or more selected regions of the crosslinked substrate network so that the crosslinked substrate network includes covalently bonded monoacylphosphine oxide groups or bisacylphosphine oxide groups held outside the one or more selected regions and optionally within the one or more selected regions, (g) A step of contacting a crosslinked substrate network with a grafting composition containing one or more ethylenically unsaturated compounds, wherein the contact is carried out under conditions such that the grafting composition penetrates into the crosslinked substrate network. (h) The steps include activating the retained covalent monoacylphosphine oxide groups or bisacylphosphine oxide groups so that the grafted composition polymerizes with the crosslinked substrate network, thereby forming a grafted polymer network outside the selected region and optionally partially within the selected region, wherein steps (a) to (h) are carried out under conditions that maintain the reactivity of the precursor crosslinked substrate network and the covalent monoacylphosphine oxide groups or bisacylphosphine oxide groups in the crosslinked substrate network until the covalent monoacylphosphine oxide groups or bisacylphosphine oxide groups are intentionally irradiated or activated. [Brief explanation of the drawing]

[0011] [Figure 1] This document describes a voxel-based lithography apparatus that can be used to implement several embodiments of the present invention. [Figure 2] This document illustrates the design of mold jigs according to various embodiments of the present invention. [Figure 3] The projection images of the inactivation and grafting steps used in Example 1 are shown. [Figure 4] Micrographs of the inactivated and grafted contact lenses from Example 1 are shown. [Figure 5] An example of carrying out the method according to the present invention is shown. [Modes for carrying out the invention]

[0012] Unless otherwise specified, all scientific and technical terms used herein have the same meanings as those generally understood by those skilled in the art in the field to which this invention pertains. All publications, patent applications, patents, and other references referenced herein are incorporated herein by reference.

[0013] Unless otherwise stated, a range of numbers, such as "2-10 (from 2 to 10)" or "2-10 (between 2 and 10)," includes the numbers that define the range (e.g., 2 and 10).

[0014] Unless otherwise stated, ratios, percentages, and parts are expressed by weight.

[0015] The term "number-average molecular weight" refers to the number-average molecular weight (M) of a sample. n ) refers to the weight-average molecular weight (M) of the sample. w ) refers to the term "Multivariance Index" (PDI). w to M n This refers to the ratio obtained by dividing by a certain factor, and represents the molecular weight distribution of the sample. If the type of "molecular weight" is not specified or is not clear from the context, it is intended to mean the number-average molecular weight.

[0016] As used herein, the term “about” means a range of ±10 percent of the number it modifies. For example, the phrase “about 10” would include both 9 and 11.

[0017] As used herein, the term "(meth)" means an optional methyl substitution. Therefore, terms such as "(meth)acrylate" mean both methacrylate and acrylate.

[0018] Regardless of where the chemical structure is described, it should be understood that any combination of disclosed alternative options for substituents in the structure may be used. Therefore, if a structure has substituent R * and R ** If it contains and each of these contains a list of three possible groups, then nine combinations are disclosed. The same applies to combinations of properties.

[0019] The average number of repeating units in a polymer sample is known as the "degree of polymerization". The general chemical formula of a polymer sample is, for example, [ *** ] n When used, "n" represents the degree of polymerization of the sample, and the formula must be interpreted as representing the number-average molecular weight of the polymer sample.

[0020] In this specification, the term "individual" includes humans and vertebrates.

[0021] As used herein, the term “ophthalmic device” means any device located inside or on the eye, including on the surface of the eye, or on any part of the eye. These devices can provide optical correction, cosmetic enhancement, visual enhancement, therapeutic effects (e.g., as a bandage), or the supply of active ingredients such as pharmaceutical and nutritional supplements, or any combination thereof. Examples of ophthalmic devices include, but are not limited to, lenses, optics, and ocular implants (including, but not limited to, punctal plugs). Examples of “lenses” include soft contact lenses, hard contact lenses, hybrid contact lenses, intraocular lenses, and inlays and overlays. Ophthalmic devices may preferably include contact lenses.

[0022] As used herein, the term “contact lens” means an ophthalmic device that can be placed on the cornea of ​​an individual’s eye. Contact lenses may provide corrective, cosmetic, or therapeutic benefits, including wound healing, delivery of drugs or nutritional supplements, diagnostic evaluation or monitoring, ultraviolet protection, reduction of visible light or glare, or a combination thereof. Contact lenses may be any suitable material known in the art and may be soft lenses, hard lenses, or hybrid lenses comprising at least two distinct parts having different physical, mechanical, or optical properties, such as modulus of elasticity, water content, light transmission, or a combination thereof.

[0023] The ophthalmic device and contact lens of the present invention may be composed of a silicone hydrogel. These silicone hydrogels typically contain at least one hydrophilic monomer and at least one silicone-containing component covalently bonded to each other in a curing device. The ophthalmic device and contact lens of the present invention may also be composed of a conventional hydrogel, or a combination of a conventional hydrogel and a silicone hydrogel.

[0024] A "polymer" is an organic compound having a number-average molecular weight exceeding 1500 daltons, and may be reactive or non-reactive.

[0025] As used herein, “target macromolecule” refers to a macromolecule of interest synthesized from a reactive composition containing monomers, macromers, prepolymers, crosslinking agents, initiators, additives, diluents, etc.

[0026] As used herein, “monomer” refers to a monofunctional molecule capable of undergoing chain growth polymerization, particularly free radical polymerization, to create repeating units within the chemical structure of a target macromolecule. Some monomers have difunctional impurities that can act as crosslinking agents. “Hydrophilic monomer” is also a monomer that, when mixed with deionized water at a concentration of 5% by weight at 25°C, yields a clear single-phase solution. “Hydrophilic component” is a monomer, macromer, prepolymer, initiator, crosslinking agent, additive, or polymer that, when mixed with deionized water at a concentration of 5% by weight at 25°C, yields a clear single-phase solution.

[0027] As used herein, "macromonomer" or "macromer" is a linear or branched macromolecule having at least one polymerizable group that can undergo chain growth polymerization, specifically free radical polymerization.

[0028] 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-growth polymerization, such as a carbon-carbon double bond group that can polymerize when subjected to free radical and / or cationic polymerization, for example, under radical polymerization initiation conditions. Non-limiting examples of polymerizable groups include (meth)acrylate, styrene, vinyl ether, (meth)acrylamide, N-vinyl lactam, N-vinyl amide, O-vinyl carbamate, O-vinyl carbonate, and other vinyl groups. Preferably, the polymerizable group includes (meth)acrylate, (meth)acrylamide, and mixtures thereof. Preferably, the polymerizable group includes (meth)acrylate, (meth)acrylamide, N-vinyl lactam, N-vinyl amide, styryl 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 may be bonded to hydrogen, or hydrogen may be substituted by alkyl or cycloalkyl (which may itself be further substituted). In contrast to "polymerizable", the term "non-polymerizable" means that a compound does not contain such free radical polymerizable groups.

[0029] Examples as described above include substituted or unsubstituted C 1~6 alkyl (meth)acrylate, C 1~6 alkyl (meth)acrylamide, C 2~12 alkenyl, C 2~12 alkenylphenyl, C 2~12 alkenylnaphthyl, C 2~6 alkenylphenyl C 1~6 alkyl are included, and suitable substituents on the C 1~6 alkyl include ether, hydroxyl, carboxyl, halogen, and combinations thereof.

[0030] Any type of free radical polymerization, including bulk, solution, suspension, and emulsion, as well as any controlled radical polymerization method, such as stable free radical polymerization, nitrogen oxide-mediated living polymerization, atom transfer radical polymerization, reversible addition-cleavage chain transfer polymerization, and organotellurium-mediated living radical polymerization, may be used.

[0031] An "ethylenically unsaturated compound" is a monomer, macromer, or prepolymer containing at least one polymerizable group. Preferably, the ethylenically unsaturated compound may consist of one polymerizable group.

[0032] As used herein, “silicone-containing component” or “silicone component” typically refers to monomers, macromers, prepolymers, crosslinking agents, initiators, additives, or polymers in a reactive composition having at least one silicon-oxygen bond, in the form of siloxy groups, siloxane groups, carbosiloxane groups, or mixtures thereof. Examples of silicone-containing components useful in the present invention include U.S. Patent Nos. 3,808,178, 4,120,570, 4,136,250, 4,153,641, 4,740,533, 5,034,461, 5,070,215, 5,244,981, 5,314,960, 5,331,067, 5,371,147, 5,760,100, 5,849,811, and 5,960. No. 2,548, No. 5,965,631, No. 5,998,498, No. 6,367,929, No. 6,822,016, No. 6,943,203, No. 6,951,894, No. 7,052,131, No. No. 7,247,692, No. 7,396,890, No. 7,461,937, No. 7,468,398, No. 7,538,146, No. 7,553,880, No. 7,572,841, No. 7,666,921 , No. 7,691,916, No. 7,786,185, No. 7,825,170, No. 7,915,323, No. 7,994,356, No. 8,022,158, No. 8,163,206, No. 8,273, No. 802, No. 8,399,538, No. 8,415,404, No. 8,420,711, No. 8,450,387, No. 8,487,058, No. 8,568,626, No. 8,937,110, No. 8,9 These can be found in Patent Nos. 37,111, 8,940,812, 8,980,972, 9,056,878, 9,125,808, 9,140,825, 9,156,934, 9,170,349, 9,217,813, 9,244,196, 9,244,197, 9,260,544, 9,297,928, 9,297,929, and European Patent No. 080539. These patents are incorporated herein by reference in their entirety.

[0033] A "polymer" is a target macromolecule composed of repeating units of monomers and macromers used during polymerization.

[0034] A "homopolymer" is a polymer made from one monomer, a "copolymer" is a polymer made from two or more monomers, and a "terpolymer" is a polymer made from three monomers. A "block copolymer" consists of blocks or segments that are different in composition. A diblock copolymer has two blocks. A triblock copolymer has three blocks. A "comb-shaped or graft copolymer" is made from at least one macromer.

[0035] A "repeating unit" is the smallest atomic group within a polymer that corresponds to the polymerization of a particular monomer or macromer.

[0036] An "initiator" is a molecule that can decompose into a free radical group that can react with a monomer to initiate a free radical polymerization reaction. Thermal initiators decompose at a specific rate depending on the temperature and are typically azo compounds such as 1,1'-azobisisobutyronitrile and 4,4'-azobis(4-cyanovaleric acid), peroxides such as benzoyl peroxide, tert-butyl peroxide, tert-butyl hydroperoxide, tert-butyl peroxybenzoate, dicumyl peroxide, and lauroyl peroxide, peracids such as peracetic acid and potassium persulfate, and various redox systems. Photoinitiators decompose by photochemical processes and are typically benzyl, benzoin, acetophenone, benzophenone, camphorquinone, and derivatives of mixtures thereof, as well as various monoacyl and bisacylphosphine oxides, and combinations thereof.

[0037] A "free radical group" is a molecule that has unpaired electrons and can react with a polymerizable group to initiate a free radical polymerization reaction.

[0038] A "cross-linking agent" (or crosslinker) is a bifunctional or polyfunctional monomer capable of creating branching points and polymer networks by undergoing free radical polymerization at two or more locations on the molecule. The two or more polymerizable functional groups present in the cross-linking agent may be the same or different, and can be independently selected from, for example, vinyl groups (including allyl), (meth)acrylate groups, and (meth)acrylamide groups. Common examples include ethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, methylenebisacrylamide, and triallyl cyanurate.

[0039] A "prepolymer" is a reaction product of a monomer (or macromer) that contains residual polymerizable groups that can be further reacted to form a polymer.

[0040] A "polymer network" is a type of polymer that is a form of crosslinked macromolecules. Generally, polymer networks may swell but are insoluble in solvents. For example, the crosslinked substrate network of the present invention is a material that can swell without dissolving.

[0041] A "hydrogel" is typically a polymer network that swells in water or an aqueous solution while absorbing at least 10 weight percent of water (at 25°C). A "silicone hydrogel" is a hydrogel made from at least one silicone-containing component along with at least one hydrophilic component. The hydrophilic component may also contain a non-reactive polymer.

[0042] "Conventional hydrogels" refer to polymer networks manufactured from monomers that do not contain any siloxy, siloxane, or carbosiloxane groups. Conventional hydrogels are prepared from reactive compositions mainly containing hydrophilic monomers such as 2-hydroxyethyl methacrylate ("HEMA"), N-vinylpyrrolidone ("NVP"), N,N-dimethylacrylamide ("DMA"), or vinyl acetate.

[0043] As used herein, the term “reactive composition” means a composition containing one or more reactive components (and optionally non-reactive components) that, when mixed together and subjected to polymerization conditions, form a polymer composition. Where one or more components are present, the reactive composition may also be referred to herein as a “reactive mixture” or “reactive monomer mixture” (or RMM). A reactive composition comprises reactive components such as monomers, macromers, prepolymers, crosslinking agents, and initiators, as well as optional additives such as wetting agents, release agents, dyes, UV-VIS absorbers, light-absorbing compounds, pigments, dyes, and phototautomorphic compounds (any of which may be reactive or non-reactive, but preferably can be retained in the resulting polymer composition, as well as in pharmaceutical and nutritional supplements), and optional diluents. It will be understood that a wide range of additives may be added depending on the final product to be prepared and its intended use. The concentrations of the components of a reactive composition are expressed as weight percentages of all components in the reactive composition, with the exception of diluents. When a diluent is used, the concentration is expressed as a weight percentage based on the total amount of all components in the reaction composition and the amount of the diluent.

[0044] "Reactive components" are components of a reactive composition that become part of the chemical structure of the resulting material by covalent bonding, hydrogen bonding, electrostatic interaction, formation of interpenetrating polymer networks, or any other method. Examples, but not limited to, include silicone reactive components (e.g., the silicone-containing components listed below) and hydrophilic reactive components (e.g., the hydrophilic monomers listed below).

[0045] As used herein, the term “silicone hydrogel contact lens” means a contact lens containing at least one silicone hydrogel. Silicone hydrogel contact lenses generally have increased oxygen permeability compared to conventional hydrogels. Silicone hydrogel contact lenses utilize both their water and polymer components to deliver oxygen to the eye.

[0046] "DMD" refers to a digital micromirror device, which may be a bistable spatial light modulator consisting of an array of movable micromirrors functionally implemented throughout a CMOS SRAM. Each mirror may be independently controlled by loading data into a memory cell beneath the mirror to guide reflected light, spatially mapping pixels of video data to pixels on a display. The data electrostatically controls the tilt angle of the mirror in a binary system where the mirror state is either +X degrees (on) or -X degrees (off). Light reflected by the on-mirror can then pass through a projection lens and travel onto the screen. Light can be off-reflected to produce a darkfield, defining the black level floor of the image. The image may be generated by grayscale modulation between on-level and off-level at a speed fast enough to be integrated by the observer. A DMD (Digital Micromirror Device) may include a DLP projection system.

[0047] "DMD script" refers to a control protocol for a spatial light modulator, and further, to control signals for any system component, such as a light source or filter wheel, which may include a sequence of commands at any given time.

[0048] The term "polyfunctional" refers to a component having two or more polymerizable groups. The term "monofunctional" refers to a component having one polymerizable group.

[0049] The term "halogen" refers to fluorine, chlorine, bromine, and iodine.

[0050] As used herein, the term “alkyl” refers to an unsubstituted or substituted linear or branched alkyl group containing the indicated number of carbon atoms. If no number is indicated, an alkyl group (optionally including any substituents on the alkyl) may contain 1 to 16 carbon atoms. Preferably, an 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, iso-, sec- and tert-butyl, pentyl, hexyl, heptyl, and 3-ethylbutyl. Examples of substituents on alkyl groups include hydroxy, amino, amide, oxa, carboxy, alkylcarboxy, carbonyl, alkoxy, amide, carbamate, carbonate, halogen, phenyl, benzyl, and one, two, or three groups independently selected from combinations thereof. "Alkylene" refers to a divalent alkyl group, such as -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH2CH(CH3)CH2-, and -CH2CH2CH2CH2-.

[0051] "Haloalkyl" refers to an alkyl group defined by being substituted with one or more halogen atoms, where each halogen is independently F, Cl, Br, or I. The preferred halogen is F. Preferred haloalkyl groups contain 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, and even more preferably 1 to 2 carbon atoms. "Haloalkyl" includes perhaloalkyl groups such as -CF3- or -CF2CF3-. "Haloalkylene" refers to a divalent haloalkyl group such as -CH2CF2-.

[0052] "Cycloalkyl" refers to an unsubstituted or substituted cyclic hydrocarbon containing the indicated number of ring carbon atoms. If no number is indicated, the cycloalkyl may contain 3 to 12 ring 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 cycloalkyls include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. Examples of substituents on a cycloalkyl include alkyl, hydroxy, amino, amide, oxa, carbonyl, alkoxy, amide, carbamate, carbonate, halo, phenyl, benzyl, and one, two, or three groups independently selected from combinations thereof. "Cycloalkylene" means a divalent cycloalkyl group such as 1,2-cyclohexylene, 1,3-cyclohexylene, or 1,4-cyclohexylene.

[0053] "Hypercycloalkyl" refers to the cycloalkyl ring or ring system defined above, in which at least one ring carbon is substituted with a heteroatom selected from nitrogen, oxygen, and sulfur. The heterocycloalkyl ring is optionally condensed or otherwise bonded to other heterocycloalkyl rings and / or non-aromatic hydrocarbon rings and / or phenyl rings. Preferred heterocycloalkyl groups have 5 to 7 members. More preferred heterocycloalkyl groups have 5 or 6 members. Heterocycloalkylene means a divalent heterocycloalkyl group.

[0054] "Aryl" refers to an unsubstituted or substituted aromatic hydrocarbon ring system containing at least one aromatic ring. The aryl group contains the indicated number of ring carbon atoms. If no number is indicated, the aryl may contain 6 to 14 ring carbon atoms. The aromatic ring may optionally be condensed to or otherwise bonded to other aromatic or non-aromatic hydrocarbon rings. Examples of aryl groups include phenyl, naphthyl, and biphenyl. A preferred example of an aryl group is phenyl. Examples of substituents on an aryl include alkyl, hydroxy, amino, amide, oxa, carboxy, alkylcarboxy, carbonyl, alkoxy, amide, carbamate, carbonate, halo, phenyl, benzyl, and one, two, or three groups independently selected from combinations thereof. "Arylene" means a divalent aryl group, e.g., 1,2-phenylene, 1,3-phenylene, or 1,4-phenylene.

[0055] "Heteroaryl" refers to an aryl ring or ring system in which at least one ring carbon atom is substituted with a heteroatom selected from nitrogen, oxygen, and sulfur, as defined above. A heteroaryl ring may be condensed or otherwise bonded to one or more heteroaryl rings, aromatic or non-aromatic hydrocarbon rings, or heterocycloalkyl rings. Examples of heteroaryl groups include pyridyl, furyl, and thienyl. "Heteroarylene" means a divalent heteroaryl group.

[0056] "Alkoxy" refers to an alkyl group bonded to the parent molecule via an oxygen crosslink. Examples of alkoxy groups include methoxy, ethoxy, propoxy, and isopropoxy. "Aryloxy" refers to an aryl group bonded to the parent molecule via an oxygen crosslink. An example is phenoxy. "Cyclic alkoxy" refers to a cycloalkyl group bonded to the parent molecule via an oxygen crosslink.

[0057] "Alkylamine" refers to an alkyl group bonded to the parent molecule via an -NH crosslink. Alkyleneamine refers to a divalent alkylamine group such as -CH2CH2NH-.

[0058] "Siloxanil" refers to a structure having at least one Si-O-Si bond. Therefore, for example, a siloxanil group means a group having at least one Si-O-Si group (i.e., a siloxane group), and a siloxanil compound means a compound having at least one Si-O-Si group. "Siloxanil" refers to monomers (e.g., Si-O-Si) as well as oligomer / polymer structures (e.g., -[Si-O] n - encompasses a structure in which n is 2 or greater. Each silicon atom in the siloxanyl group is independently selected to complete their valence. A Group(R A This is substituted by (as defined by options (b) to (i) of equation A).

[0059] "Silyl" refers to the structure of formula R3Si-, and "siloxy" refers to the structure of formula R3Si-O-, where each R in silyl or siloxy is independently selected from trimethylsiloxy, C1-C8 alkyl (preferably C1-C3 alkyl, more preferably ethyl or methyl), and C3-C8 cycloalkyl.

[0060] "Alkylene oxy" refers to a group of the general formula -(alkylene-O-)p- or -(O-alkylene)p-, where alkylene is as defined above, and p is 1-200, or 1-100, or 1-50, or 1-25, or 1-20, or 1-10, and each alkylene is independently and optionally substituted with one or more groups independently selected from hydroxyl, halo (e.g., fluoro), amino, amide, ether, carbonyl, carboxyl, and combinations thereof. When p is greater than 1, each alkylene may be the same or different, and the alkylene oxy may be in block or random configuration. When the alkylene oxy forms a terminal group in the molecule, the terminal of the alkylene oxy may be, for example, hydroxyl or alkoxy (e.g., HO-[CH2CH2O] p -or CH3O-[CH2CH2O] p -) is possible. Examples of alkylene oxy include polymethylene oxy, polyethylene oxy, polypropylene oxy, polybutylene oxy, and poly(ethylene oxy-co-propylene oxy).

[0061] "Oxaalkylene" refers to the alkylene groups defined above, such as -CH2CH2OCH(CH3)CH2-, in which one or more non-adjacent CH2 groups are substituted by oxygen atoms. "Thialkylene" refers to the alkylene groups defined above, such as -CH2CH2SCH(CH3)CH2-, in which one or more non-adjacent CH2 groups are substituted by sulfur atoms.

[0062] The term "linking group" refers to the portion that links a polymerizable group to the parent molecule. A linking group may be any portion that does not unnecessarily interfere with the polymerization of the compound to which it is a part. For example, a linking group may be a bond or may include one or more alkylenes, haloalkylenes, amides, amines, alkyleneamines, carbamates, carboxylates (-CO2-), arylenes, heteroarylenes, cycloalkylenes, heterocycloalkylenes, alkylene oxys, oxaalkylenes, thiaalkylenes, haloalkylene oxys (alkylene oxys substituted with one or more halo groups, e.g., -OCF2-, -OCF2CF2-, -OCF2CH2-), siloxanils, alkylenesiloxanils, or combinations thereof. A linking group may be optionally substituted with one or more substituents. Suitable substituents include alkyl, halo (e.g., fluoro), hydroxyl, HO-alkyleneoxy, MeO-alkyleneoxy, siloxanyl, siloxy, siloxy-alkyleneoxy, siloxy-alkylene-alkyleneoxy (one or more alkyleneoxy groups may be present, and each methylene group in the alkylene and alkyleneoxy is independently and optionally substituted by a hydroxyl group), ether, amine, carbonyl, carbamate, and combinations thereof, which can be independently selected. The linking group may also be substituted by polymerizable groups such as (meth)acrylate.

[0063] Preferred linking groups include C1-C8 alkylenes (preferably C2-C6 alkylenes) and C1-C8 oxaalkylenes (preferably C2-C6 oxaalkylenes), each of which is optionally substituted with one or two groups independently selected from hydroxyl and siloxy. Other preferred linking groups include carboxylates, amides, C1-C8 alkylene carboxylate-C1-C8 alkylenes, or C1-C8 alkyleneamide-C1-C8 alkylenes.

[0064] When the linking group consists of a combination of the above-described parts (e.g., alkylene and cycloalkylene), the parts may be in any order. For example, in formula A below, if L is indicated as -alkylene-cycloalkylene-, then Rg-L may be either Rg-alkylene-cycloalkylene- or Rg-cycloalkylene-alkylene-. Notwithstanding this, the order listed represents the preferred order in which the parts appear in the compound, starting from the terminal polymerizable group (Rg or Pg) to which the linking group is attached. For example, in formula A, if L is indicated as alkylene-cycloalkylene, then Pg-L is preferably Pg-alkylene-cycloalkylene-.

[0065] As described above, in one embodiment, the present invention provides an ophthalmic device, the ophthalmic device comprising: (a) a step of providing a reactive composition, the reactive composition comprising (i) a polymerization initiator capable of forming two or more free radical groups upon first activation, wherein at least one of the free radical groups is further activatable by subsequent activation, (ii) one or more ethylenically unsaturated compounds, and (iii) a crosslinking agent; (b) a step of subjecting the reactive composition to a first activation step, wherein the reactive composition polymerizes thereto to form a crosslinked substrate network containing covalently bonded activatable free radical initiators; and (c) at least a portion of the covalently bonded activatable free radical initiators in one or more selected regions of the crosslinked substrate network. An ophthalmic device manufactured by a process comprising: (d) deactivating the crosslinked substrate network so that it contains retained covalently bonded, activatable free radical initiators outside one or more selected regions and optionally within one or more selected regions; (d) contacting the crosslinked substrate network with a grafting composition containing one or more ethylenically unsaturated compounds, the contact being carried out under conditions such that the grafting composition penetrates into the crosslinked substrate network; and (d) activating the retained covalently bonded, activatable free radical initiators so that the grafting composition polymerizes with the crosslinked substrate network, thereby forming a grafted polymer network outside the selected regions and optionally partially within the selected regions.

[0066] In another aspect, the present invention provides an ophthalmic device comprising a reaction product of a composition comprising: (a) a crosslinked substrate network in which at least a portion of covalently bonded activatable free radical initiators are inactivated in one or more selective regions of the crosslinked substrate network, as a result the crosslinked substrate network contains covalently bonded activatable free radical initiators retained outside one or more selective regions and optionally within one or more selective regions; and (b) a grafted composition containing one or more ethylenically unsaturated compounds, localized in the crosslinked substrate network in which the covalently bonded activatable free radical initiators are retained.

[0067] The polymerization initiator may be any composition having the ability to generate free radical groups in two or more separate activation steps. Regarding the type of polymerization initiator used or the activation mechanism, there are no specific requirements in the present invention, as long as the first and second activations can be performed sequentially. Therefore, suitable polymerization initiators can be activated, for example, by heat, visible light, ultraviolet light, electron beam irradiation, gamma ray irradiation, or a combination thereof. Examples of polymerization initiators used in the present invention include, but are not limited to, bisacylphosphine oxides ("BAPO"), bis(acyl)phosphine oxides (e.g., bis(mesitoyl)phosphinic acid), azo compounds, peroxides, α-hydroxyketones, α-alkoxyketones, 1,2-diketones, germanium compounds (such as bis(4-methoxybenzoyl)diethylgermanium), or combinations thereof. More specifically, polymerization initiators include bisacylphosphine oxide, bisacylphosphane oxide, diazo compounds, diperoxide compounds, azobis(monoacylphosphine oxide), azobis(monoacylphosphane oxide), peroxybis(monoacylphosphine oxide), peroxybis(monoacylphosphane oxide), azobis(α-hydroxyketone), peroxybis(α-hydroxyketone), azobis(1,2-diketone), peroxybis(1,2-diketone), germanium compounds, tert-butyl7-methyl-7-(tert-butylazo)peroxyoctanoate, or combinations thereof.

[0068] A BAPO reaction initiator is preferred. Examples of preferred BAPO reaction initiators, but are not limited to those with the chemical structure of formula I:

[0069] [ka] (In the formula, Ar 1 and Ar 2The substituents are independently substituted or unsubstituted aryl groups, usually substituted phenyl groups, and the substituents are linear, branched, or cyclic alkyl groups (e.g., methyl groups), linear, branched, or cyclic alkoxy groups (e.g., methoxy groups), and halogen atoms, preferably Ar 1 and Ar 2 They have the same chemical structure, R 1 is a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms, or R 1 Examples include compounds having a phenyl group, hydroxyl group, or alkoxy group having 1 to 10 carbon atoms.

[0070] It should be noted that polymerization initiators activatable by different types of energy can be used in the initial and subsequent activations. For example, materials undergoing a first thermal activation and a second irradiation activation are within the scope of the present invention. Examples of such mixed-activation materials include compounds of formulas II, III, IV, and V:

[0071] [ka] (In the formula, Ar 1 and Ar 2 The substituents are independently substituted or unsubstituted aryl groups, usually substituted phenyl groups, and the substituents are linear, branched, or cyclic alkyl groups (e.g., methyl groups), linear, branched, or cyclic alkoxy groups (e.g., methoxy groups), and halogen atoms, preferably Ar 1 and Ar 2 They have the same chemical structure, R 1 R is a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms, 2 R is a bifunctional methylene linking group which may further contain ether, ketone, or ester groups along a methylene chain having 1 to 10 carbon atoms, 3 Examples include a hydrogen atom, a hydroxyl group, or a linear, branched, or cyclic alkoxy group having 1 to 10 carbon atoms. A further example is tert-butyl 7-methyl-7-(tert-butylazo)peroxyoctanoate.

[0072] Furthermore, diazo compounds, diperoxy compounds, or azoperoxy compounds exhibiting two different decomposition temperatures can be used in the present invention.

[0073] Preferably, the polymerization initiator is a photopolymerization initiator, preferably a bisacylphosphine oxide. Bisacylphosphine oxides are preferred because they can undergo continuous activation at different wavelengths and are therefore easy to use. At longer wavelengths, bisacylphosphine oxides can form two free radical groups, one of which is a monoacylphosphine oxide. The monoacylphosphine oxide (MAPO) can then undergo a second activation at shorter wavelengths. A particularly preferred bisacylphosphine oxide is bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, for which the longer wavelength is usually above 420 nm (e.g., above 435 nm) and the shorter wavelength is usually below 420 nm. It may be preferable to use an LED or equivalent light with a bandwidth relatively narrow, like that of a radiation source, to enable the initial irradiation while protecting some or most of the MAPO groups in the crosslinked substrate network.

[0074] Other exemplary bisacylphosphine oxide compounds that can be used include bis-(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-2,4,4-trimethylpentylphosphine oxide, or bis(2,4,6-trimethylbenzoyl)phosphine acid, or salts thereof.

[0075] In the present invention, a reactive composition containing a polymerization initiator, one or more ethylenically unsaturated compounds, and a crosslinking agent is subjected to a first activation step under conditions that induce initial activation of the polymerization initiator. For example, if the polymerization initiator is BAPO, the reactive composition can be irradiated at 435 nm or higher using a suitable light source. The reactive composition consequently polymerizes to form a crosslinked substrate network. The crosslinked substrate network contains residues of the polymerization initiator as covalently activatable free radical initiators.

[0076] The activation and polymerization of the reactive composition can be carried out using techniques known to those skilled in the art. For example, the reactive components of the reactive composition can be mixed in a container. Diluents may be used to facilitate mixing. After filtering, degassing, and heating the mixture to a desired temperature, it may be irradiated under conditions that induce the initial activation of the polymerization initiator and the resulting formation of a crosslinked substrate network. The polymerization vessel may be a mold, for example, if it is desired that the product have a specific shape. For example, the reactive composition can be placed in the cavity of a mold pair (e.g., front and rear molds) and polymerized. Preferably, the crosslinked substrate network for use in the ophthalmic device of the present invention is a conventional hydrogel or a silicone hydrogel. Silicone hydrogels are more preferred.

[0077] Alternatively, the crosslinked substrate network is formed by thermal polymerization of a reactive composition comprising at least one reactive component selected from the group consisting of at least one ethylenically unsaturated compound, a monoacylphosphine oxide compound, a bisacylphosphine oxide compound, and combinations thereof, and a thermal crosslinking agent. Examples of thermal initiators include, but are not limited to, azo compounds such as azobisisobutyronitrile and 4,4'-azobis(4-cyanovaleric acid), peroxides such as benzoyl peroxide, tert-butyl peroxide, tert-butyl hydroperoxide, tert-butyl peroxybenzoate, dicumyl peroxide, and lauroyl peroxide, peracids such as peracetic acid and potassium persulfate, and various redox systems. A preferred thermal initiator is azobisisobutyronitrile. The thermal polymerization reaction is typically carried out at a temperature of 50°C to 150°C, preferably 50°C to 125°C, and most preferably 60°C to 100°C.

[0078] One type of monoacylphosphine oxide compound is a monoacylphosphine oxide monomer (MAPO-M) containing a polymerizable group and a monoacylphosphosine oxide group. MAPO-M can have many different chemical structures. For example, formula MAPO-M1;Rg-L-PO(R)(COAr 1 ), formula MAPO-M2;Rg-L-CO-POAr 1 Ar 2 Examples include: In the formula, Rg is a polymerizable group, L is a linking group (including direct bonds), and Ar 1 and Ar 2 Each of these is independently an aryl group which may have substituents. The formation of a crosslinked substrate network by thermal polymerization of a reactive composition containing the MAPO-M component generates a crosslinked substrate network having monoacylphosphine oxide groups as covalently bonded, activatable free radical initiators. As disclosed in Biomacromolecules 2001, 2, 1271-1278, an example of such a monoacylphosphine oxide monomer is (diphenylphosphosyl)-(4-vinylphenyl)-methanone (DPPM), which has the following chemical structure.

[0079] [ka]

[0080] One type of bisacylphosphine oxide compound is a bisacylphosphine oxide monomer (BAPO-M) containing a polymerizable group and a bisacylphosphosine oxide group. An example BAPO-M is the formula BAPO-M1;Rg-L-PO(COAr 1 )(COAr 2 It can be expressed as ), where Rg is a polymerizable group, L is a linking group (including direct bonds), and Ar 1 and Ar 2This is independently an aryl group which may have substituents. The thermal polymerization of a reactive composition containing the BAPO-M component forms a crosslinked substrate network, generating a crosslinked substrate network having a bisacylphosphine oxide group as a covalently bonded, activatable free radical initiator. An example of BAPO-M is ethyl 2-(bis[246-trimethylbenzoyl]-phosphoryl) methacrylate. One advantage of using MAPO-M in a reactive composition to form a covalently bonded, activatable free radical initiator in a crosslinked substrate network is the control of the concentration of monoacylphosphine oxide groups for subsequent inactivation and grafting. Inclusion of BAPO-M in a reactive composition allows for many more possible combinations of grafting and inactivation. For illustrative purposes only and not to be construed as limiting the entire range of options in any way, ophthalmic devices may be manufactured using the following process: (1) grafting a first grafting composition onto a first select region of a BAPO-M crosslinked substrate network by irradiating it with light of a wavelength that does not activate the MAPO groups formed thereon, for example, 435 nanometer light; (2) inactivating the resulting MAPO groups and any residual BAPO groups by irradiating a second select region with 405 nanometer light; and (3) grafting a second grafting composition onto a third select region of the MAPO crosslinked substrate network, which may or may not overlap with the first or second select region, depending on the level of inactivation and the location of the select regions used in each step.

[0081] As another example, and not to be interpreted as limiting the entire range of options in any way, an ophthalmic device may be manufactured using a process that includes: (1) converting BAPO groups to MAPO groups by irradiating a first selected region of a thermosetting BAPO-M crosslinked substrate network with light of a wavelength that does not activate the formed MAPO groups, for example, 435 nanometers; (2) inactivating both MAPO groups and BAPO groups in a second selected region by irradiating the second selected region with light of 405 nanometers, for example, the second selected region may optionally overlap with the first selected region; (3) grafting a first grafting composition onto an uninactivated (BAPO-containing) region by irradiating with light of 435 nanometers, for example; and (4) grafting a second grafting composition onto a first selected (MAPO-containing) region by irradiating with light of 405 nanometers, for example. No grafting occurs in the second selected region. If the first grafting composition contains a reactive dye (D1) and the second grafting composition contains another reactive dye (D2), a wide range of apodization patterns can be created on an ophthalmic device by changing the irradiation intensity profile in any or all of the steps (1) to (4) described above, and by changing the relative amounts of D1 and D2 in the grafting composition. If the ophthalmic device is a contact lens, the apodization pattern can be formed within the optical zone to enhance the optics of the ophthalmic lens, or in the periphery to modify the appearance of the iris. The crosslinked substrate network can be extracted and / or hydrated before or during the grafting steps (3) and (4) described above.

[0082] Another type of monoacylphosphine oxide compound is a monoacylphosphine oxide compound having a refractive index (MAPO-RI) moiety or a light-absorbing (MAPO-LA) moiety, as disclosed in U.S. Patent Application No. 17 / 821311, which is incorporated entirely herein by reference. Similarly, another type of bisacylphosphine oxide compound is a bisacylphosphine oxide compound having a refractive index (BAPO-RI) moiety or a light-absorbing (BAPO-LA) moiety, as disclosed in U.S. Patent Application No. 17 / 821311, which is incorporated entirely herein by reference.These MAPO-RI, MAPO-LA, BAPO-RI, and BAPO-LA compounds are described as follows: (a) a step of thermally polymerizing a reactive composition comprising at least one ethylenically unsaturated compound, a monoacylphosphine oxide monomer (MAPO-M), a bisacylphosphine oxide monomer (MAPO-M), or a combination thereof, and a thermal crosslinking agent to form a precursor crosslinked substrate network, wherein the monoacylphosphine oxide compound having a refractive index portion or a light-absorbing portion and the bisacylphosphine oxide compound having a refractive index portion or a light-absorbing portion are spatially dispersed within the precursor crosslinked substrate network, and the reactive composition is not completely polymerized; and (b) a step of irradiating the precursor crosslinked substrate network in a pre-selected region, thereby dispersing the dispersed monoacylphosphine oxide compound having a refractive index portion or a light-absorbing portion and The process comprises (a) a step of starting free radical polymerization from a bisacylphosphine oxide compound having a refractive index portion or a light-absorbing portion, thereby incorporating the refractive index portion or light-absorbing portion into a precursor crosslinked substrate network; (c) a step of thermal polymerization until the reactive composition is completely polymerized; and optionally (d) a step of extracting the unreacted monoacylphosphine oxide compound having a refractive index portion or a light-absorbing portion and the bisacylphosphine oxide compound having a refractive index portion or a light-absorbing portion with a solvent, wherein steps (a) to (d) can be incorporated into the crosslinked substrate network by a combination of thermal polymerization and photochemical reaction, carried out under conditions that maintain the reactivity of repeating units derived from the precursor crosslinked substrate network and the crosslinked substrate network, which are composed of a reactive component having at least one pendant group selected from the group consisting of monoacylphosphine oxide, bisacylphosphine oxide, and combinations thereof.

[0083] The integration of MAPO-RI, MAPO-LA, BAPO-RI, and BAPO-LA compounds into a precursor crosslinked substrate network after partial thermal curing, and subsequently into the crosslinked substrate network during complete thermal curing, can be designed to affect the overall change in optical path length, with or without simultaneous changes in the absorption spectrum in a pre-selected region of the crosslinked substrate network. MAPO-RI, MAPO-LA, BAPO-RI, and BAPO-LA compounds are spatially dispersed in the precursor crosslinked substrate network after partial thermal curing, with respect to concentrations based on curing kinetics including solubility, gelation, and phase morphology. Upon irradiation, MAPO-RI, MAPO-LA, BAPO-RI, and BAPO-LA compounds copolymerize with reactive composition components in a pre-selected recovered material. In this way, the entire optical system of the lens can be deterministically modified. The optical path length (OPL) is calculated by the following equation:

[0084]

number

[0085] The functional portion may be, for example, a refractive index portion, a light-absorbing portion, or a combination thereof. The light-absorbing portion may be used to provide various functions to an ophthalmic lens, including, for example, cosmetic features or absorption of light of specific wavelengths (e.g., absorption of high-energy visible (HEV) light and / or other wavelengths). The functional portion may provide one or more functions. For example, the light-absorbing portion may also modify the refractive index of the lens in a desired manner. Thus, the incorporated portion may achieve multiple effects.

[0086] Light-absorbing portions can be used to provide lenses with common or custom apodization features to improve the wearer's vision. Examples of light-absorbing portions include, for example, static dyes, photochromic dyes, thermochromic dyes, leuco dyes, and combinations thereof. More specific examples include, but are not limited to, azo dyes; anthraquinone dyes; nitro dyes; phthalocyanine dyes; quinoneimine dyes; quinoline dyes; carbonyl dyes; triarylmethane dyes; methine dyes; naphthopyran; spiro(indoline)quinopyran and spiro(indoline)pyran; oxazines such as spiro(indoline)naphthoxazine, spiro(indoline)pyridobenzoxazine, spiro(benzoindoline)pyridabenzoxazine, spiro(benzoindoline)naphthoxazine and spiro(indoline)benzoxazine; mercury ditisonates; flugides; flugimids; acridine dyes; arylmethane dyes; indamines; xanthenes; acridones; or combinations thereof.

[0087] The functional portion may be a refractive index portion. The refractive index portion alters the OPL of the lens relative to the bulk lens in the region in which it is incorporated. Variations in refractive properties across the lens can be used, for example, to impart an image or other visual feature to the lens, or to impart a feature that affects visual function, for the purpose of producing a bifocal or multifocal lens. A preferred class of refractive index portions are polyamides. Exemplary polyamides include, but are not limited to, polyvinylpyrrolidone (PVP), polyvinylmethylacetamide (PVMA), polydimethylacrylamide (PDMA), polyvinylacetamide (PNVA), poly(hydroxyethyl(meth)acrylamide), polyacrylamide, and two or more copolymers thereof.

[0088] The following are some example chemical structures of MAPO-RI, MAPO-LA, BAPO-RI, and BAPO-LA compounds.

[0089] [ka] In the formula, n is an integer in the range of 10 to 4000, and T is a chain termination group.

[0090] [ka] In the formula, n is an integer in the range of 10 to 4000, and T is a chain termination group.

[0091] [ka] In the formula, x and y are integers in the range of 10 to 4000, and T is a chain termination group.

[0092] [ka] In the formula, m is an integer in the range of 10 to 3000, n is an integer in the range of 1 to 100, and each T is independently a chain termination group or initiator fragment.

[0093] [ka] In the formula, m is an integer in the range of 10 to 3000, and T is a chain termination group.

[0094] [ka] In the formula, a is an integer in the range of 1 to 100, b is an integer in the range of 1 to 100, c is an integer in the range of 1 to 250, T is independently a chain termination group or initiator fragment, and Q is derived from a hydrophilic monomer such as N,N-dimethylacrylamide, N-vinylpyrrolidone, 2-hydroxyethyl methacrylate, N-vinyl-N-methylacetamide, or N-vinylacetamide.

[0095] MAPO-RI, MAPO-LA, BAPO-RI, and BAPO-LA compounds can be used in the reactive composition in effective amounts, for example, 0.01% to 20% by weight, based on the total components in the reactive monomer mixture excluding the diluent.

[0096] According to the present invention, after the crosslinked substrate network is formed, a portion of the covalently bonded activatable free radical initiator is inactivated in one or more selective regions, and so after inactivation, the crosslinked substrate network contains the retained covalently bonded activatable free radical initiator outside one or more selective regions and optionally within one or more selective regions, depending on the level of inactivation.

[0097] Deactivation can be achieved by a variety of means, including but not limited to oxidation, reduction, and radical coupling reactions, insofar as the covalently bonded free radical initiator is converted into other chemical moieties that cannot initiate free radical polymerization. A preferred method for deactivating a crosslinked substrate network containing monoacylphosphine oxide or bisacylphosphine oxide as a covalently bonded free radical initiator involves irradiating a selected area in an oxygen-gas atmosphere, for example, in air, thereby oxidizing the monoacylphosphine oxide or bisacylphosphine oxide to other functional groups.

[0098] Ultraviolet (UV) or visible light may be used in the deactivation process depending on the composition of the crosslinked substrate network and the desired characteristics imparted by deactivation in selected regions. A preferred wavelength range for UV light is 300 to 400 nanometers, and a more preferred wavelength range for UV light is 350 to 400 nanometers. A preferred wavelength range for visible light is 400 to 500 nanometers, and a more preferred wavelength range for visible light is 400 to 450 nanometers. A preferred light source includes a narrowband light-emitting diode.

[0099] The inactivation of a crosslinked substrate network can be spatially altered by irradiation in an oxygen atmosphere using a voxel-based lithography photoforming apparatus, described later in this application, which includes a chemical beam light source and a digital micromirror (DMD) that spatially projects a predetermined DMD script onto the crosslinked substrate network. This allows for spatial variation of the inactivation level within the crosslinked substrate network. The DMD script controls the location and level of inactivation by controlling the amount of light energy delivered to specific locations within the crosslinked substrate network.

[0100] There are several methods by which inactivation can be performed. For example, inactivation may be performed as described above on a crosslinked substrate network enclosed within a mold assembly consisting of a front mold and a rear mold, the front and rear molds defining and enclosing a cavity in the shape of an ophthalmic device between them.

[0101] The deactivation may be performed on a crosslinked substrate network bonded to either the front or rear mold of the mold assembly, preferably bonded to the front mold in the conclave-up position as shown in Figure 5.

[0102] Inactivation may be carried out on an unextracted, unhydrated crosslinked substrate network, or on an extracted and / or hydrated crosslinked substrate network.

[0103] Inactivation can be performed from multiple directions, for example, from the top and bottom of the crosslinked substrate network, using one or more chemical beam light sources, one or more DMDs, and one or more DMD scripts of any choice.

[0104] When a crosslinked substrate network contains an ultraviolet absorber and ultraviolet light is used to inactivate a selected region, the intensity of the ultraviolet light is attenuated internally by absorption, depending on its path length or depth within the crosslinked substrate network. Under these conditions, inactivation is more effective on or near the surface of the crosslinked substrate network (due to less absorption), thereby enabling a means of modifying the surface or surface layer by inactivation. In this way, using bilateral inactivation configurations such as from the top and bottom of the crosslinked substrate network, the retained covalent free radical initiator is concentrated in the bulk of the crosslinked substrate network rather than in the surface layer, thereby enabling subsequent grafting only in the bulk and preventing, or at least substantially preventing, grafting on the surface of the grafted polymer network.

[0105] When a crosslinked substrate network contains a visible light absorber and visible light is used to inactivate a selected region, the intensity of the visible light may be attenuated internally within the crosslinked substrate network by absorption, depending on its path length or depth. Under these conditions, inactivation may be more effective on or near the surface of the crosslinked substrate network (due to less absorption), thereby enabling a means to modify the surface or surface layer by inactivation. Thus, using bilateral inactivation configurations such as from the top and bottom of the crosslinked substrate network, the retained covalent free radical initiator may be concentrated in the bulk of the crosslinked substrate network rather than in the surface region, thereby enabling subsequent grafting in the bulk only and preventing, or at least substantially preventing, grafting on the surface of the grafted polymer network.

[0106] According to the present invention, after deactivating at least a portion of the covalently bonded activatable free radical initiators in one or more selected regions of the crosslinked substrate network such that the crosslinked substrate network contains covalently bonded activatable free radical initiators held outside one or more selected regions and optionally within one or more selected regions, the crosslinked substrate network formed as described above is brought into contact with a grafting composition. The grafting composition contains one or more ethylenically unsaturated compounds. The crosslinked substrate network is a swellable material and therefore absorbs at least some of the grafting composition for the subsequent grafting reaction. Absorption into the crosslinked substrate network can be carried out in various ways. For example, the crosslinked substrate network may be placed in the grafting composition and swollen. Alternatively, the crosslinked substrate network may be first swollen in a solvent and then combined with the grafting composition, for example, by suspending the pre-swollen crosslinked substrate network in the grafting composition, so that the reactive components are distributed throughout the crosslinked substrate network by prior molecular diffusion and fluid exchange in the suspension. Alternatively, the crosslinked substrate network may first be extracted with a solvent (either or both an organic solvent and / or an aqueous organic solvent), and if necessary, subsequently hydrated and equilibrated in an aqueous buffer or deionized water, and then combined with the grafting composition as described above. Any organic solvent or aqueous organic solvent can be used. There is no particular minimum amount of the grafting composition that must be absorbed by the crosslinked substrate network, as long as some is present (more than 0% by weight of reactive components). In some embodiments, it may be preferable that the crosslinked substrate network is swellable at 25°C by at least 0.0001% by weight, or at least 0.01% by weight, or at least 0.1% by weight, or at least 5% by weight, or at least 10% by weight, or at least 25% by weight in the grafting composition, compared to its dry weight.

[0107] Following contact between the crosslinked substrate network and the grafted composition, at least some of the activatable free radical initiators of the crosslinked substrate network are activated. For example, if the polymerization initiator used in step (a) of this process is a bisacylphosphine oxide, the retained covalently activatable free radical initiator (in this case, monoacylphosphine oxide) can be activated by irradiation at 420 nanometers or less using a suitable light source outside one or more selective regions and optionally within one or more selective regions. According to the present invention, activation can occur anywhere on the crosslinked substrate network, except for selective regions where all of the monoacylphosphine oxide is inactivated. The grafted composition is then polymerized in the activated portions of the crosslinked substrate network having the retained monoacylphosphine oxide. Thus, the product is an ophthalmic device having local regions or volumes containing the grafted polymer network and selective regions that do not contain the grafted polymer network or whose amount varies depending on the level of inactivation, and therefore the concentration of covalently activating monoacylphosphine oxide. Any ungrafted compositions, along with any by-products or by-product polymers, can be removed from the network, for example, by solvent extraction.

[0108] Grafting outside of select regions of a crosslinked substrate network, and within one or more select regions with optional partial inactivation, allows manufacturers to alter the chemical composition of the device in those volume elements. As a result, new ophthalmic devices with desired mechanical, physical, or optical properties can be prepared. In a non-limiting example, in the contact lens field, the process of the present invention can enable custom light absorption profiles within an optical zone, including both clear (inactivated) and colored (grafted to varying degrees) sections or patterns within the optical zone. These custom light absorption profiles can be achieved by completely inactivating several select regions, such as the center of the optical zone, partially inactivating other select regions of the optical zone, then grafting a colored composition into all regions holding covalently activatable free radical initiators, followed by standard extraction, hydration, and sterilization procedures. Other examples of contact lenses include the formation of patterns, including cosmetic designs, reference markers, and barcodes, on the peripheral portion of the contact lens using a similar process, namely, creating a clear pattern, reference marker, or barcode in an inactivation process, and then grafting a colored composition sufficient to make the pattern, reference marker, or barcode visible to a third-party observer or optical scanner. The pattern, reference marker, and barcode can consist of dots, lines, shapes, symbols, letters, numbers, etc., with variable size and spacing and color intensity, thereby enabling a high level of information storage. Such patterns, reference markers, and barcodes can be used to track lenses during manufacturing, product monitoring, or clinical trials, can be used as inversion markers to ensure that the contact lens wearer's position does not invert the lens before insertion into the eye, and can be used as diagnostic tools to better fit the patient with the best prescription lens.

[0109] Using various techniques, the process of the present invention can be carried out, comprising the following steps: (a) a step of providing a reactive composition, the reactive composition comprising (i) a polymerization initiator capable of forming two or more free radical groups upon first activation, wherein at least one of the free radical groups is further activatable by subsequent activation, (ii) one or more ethylenically unsaturated compounds, and (iii) a crosslinking agent; (b) a step of subjecting the reactive composition to a first activation step, wherein the reactive composition polymerizes thereto to form a crosslinked substrate network containing covalently bonded activatable free radical initiators; and (c) a step of in one or more selected regions of the crosslinked substrate network, covalently bonded activatable free radicals (d) a step of inactivating at least a portion of the dikal initiator so that the crosslinked substrate network contains retained covalently bonded activatable free radical initiators outside one or more select regions and optionally within one or more select regions; (d) a step of contacting the crosslinked substrate network with a grafting composition containing one or more ethylenically unsaturated compounds, wherein the contact is carried out under conditions such that the grafting composition penetrates into the crosslinked substrate network; (d) a step of activating the retained covalently bonded activatable free radical initiators so that the grafting composition polymerizes with the crosslinked substrate network, thereby forming a grafted polymer network outside the select regions and optionally partially within the select regions.

[0110] Various techniques can be used to deactivate at least a portion of the covalently bonded activatable free radical initiators in one or more selected regions of the crosslinked substrate network so that the crosslinked substrate network contains covalently bonded activatable free radical initiators retained outside and optionally within one or more selected regions. The same techniques may be used to activate the retained covalently bonded activatable free radical initiators, resulting in the grafted composition polymerizing with the crosslinked substrate network outside the deactivated selected regions and optionally within the partially deactivated selected regions. Preferred techniques include, for example, voxel-based lithography commonly described in U.S. Patent Application Publication No. 2015 / 0146159, U.S. Patent No. 9075186, and U.S. Patent No. 8317505, each of which is incorporated herein by reference in whole. Further references include U.S. Patents 7,905,594, 8,157,373, 8,240,849, 8313,828, 8318,055, 8795,558, 9180,633, 9180,634, 9417,464, 9610,742, 9857,607, 10961,341, 11021,558, and 11034,789, each of which is incorporated herein by reference in its entirety. An exemplary voxel-based lithography apparatus that may be used in the present invention is shown in Figure 1.

[0111] Referring to Figure 1, a voxel-based lithography optical forming apparatus 100 may include a forming optical instrument 130 having a chemical beam 110, a spatial grating 111, and a forming optical surface 140. In some exemplary embodiments of the forming apparatus 100, radiation or light can strike the surface 140 of the forming optical instrument 130 substantially perpendicularly. The forming optical instrument 130 may be held in place via a retaining ring 121 or other fastening device that can maintain the correct orientation of the optical system relative to the forming optical instrument 130. Other paths that light can take in voxel units across the surface 140 of the optical instrument may be obvious and are within the scope of the present invention.

[0112] In exemplary embodiments where the relative orientation of the reservoir 150 and forming optics 130 with respect to the light beam may be important, the reservoir 150 may be empty or may contain a liquid 145 such as a grafting composition, and additional mechanisms for their interconnection positions may be included, such as a forming optics retaining member 170 having associated interconnection structures 180 and 122. The alignment between the retaining member 170 and the interconnection structures 180 and 122 can also provide positional control of the reservoir 150's center to the forming optics surface 140. In some exemplary embodiments with a separation ring 151, positional control may be enhanced, and the separation ring 151 can also control the volume of material added to the reservoir 150.

[0113] The reservoir 150 may be enclosed in a containment vessel 190 capable of removing atmospheric gases such as oxygen. Removal can be enhanced by flowing an inert gas such as nitrogen through a tube or channel 160 provided in the containment vessel 190. In other exemplary embodiments, the oxygen level can be controlled by controlling the dilution of oxygen in the gas flowing through the channel 160 contained in the containment vessel 190.

[0114] The forming optical device 130 can consist of various optically transparent materials, and a light beam, such as a chemical ray, can pass through the forming optical device 130 and collide with the target. For example, the forming optical device 130 may include fused silica or a transparent polymer material.

[0115] In some exemplary embodiments, the crosslinked substrate network may first be formed in a mold as described above. The crosslinked substrate network may then be positioned (not shown) on the surface 140 of the forming optical instrument and in contact with the grafting composition 145 contained in a reservoir 150. Alternatively, the crosslinked substrate network may be formed, for example, in a mold as described above and in contact with the grafting composition outside the voxel-based lithography optical forming apparatus. The crosslinked substrate network containing the grafting composition may then be positioned (not shown) on the surface 140 of the forming optical instrument. In this embodiment, the reservoir 150 may be empty or may contain, for example, a solvent, water, or additional grafting composition.

[0116] A chemical beam 110, which can be controlled and varied across the spatial grid 111, may be applied to a crosslinked lens substrate (including a grafting composition) at a wavelength appropriate for activating covalently bonded, activatable free radical initiators in the substrate. The chemical beam 110 may be controlled to collide with selective locations on the crosslinked substrate network, resulting in localized activation of the covalently bonded initiators, which leads to grafting only at those locations. Various techniques can be used to control the chemical beam to collide only with desired locations on the crosslinked substrate network. For example, a digital micromirror device (DMD) and a DMD script can be used, along with various related components, as described in U.S. Patent No. 9,075,186. A chemical beam irradiation source used in any of the deactivation and activation steps (polymerization or grafting) of the process of the present invention as herein may include multiple selectively controllable beams of chemical beam controlled by a digital micromirror device according to a predetermined script. The illumination source for chemical beam irradiation may include at least one light-emitting diode, and a predetermined DMD script can direct the chemical beam irradiation to one or more surfaces of the crosslinked substrate network.

[0117] As previously described herein, ultraviolet or visible light may be used in any deactivation step and any activation step (polymerization or grafting) of any of the processes of the present invention as described herein. The preferred wavelength range for ultraviolet light is 300 to 400 nanometers, and the more preferred wavelength range for ultraviolet light is 350 to 400 nanometers. The preferred wavelength range for visible light is 400 to 500 nanometers, and the more preferred wavelength range for visible light is 400 to 450 nanometers. Preferred light sources include narrow-band light-emitting diodes. Voxel-based lithograph optical forming apparatuses can be configured in different ways, but one preferred setup for fabricating ophthalmic lenses is to use a mold-in-fixture as shown in Figure 2. The mold-in-fixture has a transparent front mold base (201) made of a preferred plastic such as poly(methyl methacrylate) designed to hold a front mold (202) to which a crosslinked substrate network lens (204) is bonded in an upward concave position, thereby allowing the grafting composition to be distributed therein. The front mold base is also designed to be mounted on a voxel-based lithograph photoforming apparatus for chemical beam irradiation using a predetermined DMD script. The target image plane of the apparatus may be adjusted to be centered on or near the front mold (202). The mold fixture further includes magnetic spacers for holding the front mold in place. These magnetic spacers may also be designed to hold a complete contact lens mold assembly, which consists of a front mold and a rear mold, the front and rear molds defining and sealing a cavity in the shape of a contact lens between them, and an optional (not shown in Figure 2) transparent rear mold base having an opaque or light-absorbing top surface to control the amount of external light. The ladder configuration provides a mold assembly having a precursor crosslinked substrate network lens containing MAPO-M, MAPO-RI, MAPO-LA, BAPO-M, BAPO-RI, and BAPO-LA compounds, which are conveniently irradiated in a pre-selected region before completing thermal polymerization, thereby forming a crosslinked substrate network lens ready for grafting.

[0118] While the voxel-based lithography described above is a preferred technique for selective activation of crosslinked substrate networks, other techniques may also be utilized. For example, selective activation can be achieved by simply masking regions of the crosslinked substrate network that are not to be activated from activation light. The unmasked regions of the substrate may then be activated and grafted. Unreacted material may be removed, for example, by extraction.

[0119] Additional optional grafting steps may be added. Such additional grafting may be, for example, via the bulk of the grafted crosslinked substrate network, or may be more concentrated on the surface than in the core, or may be localized as selected regions of the grafted crosslinked substrate network. For example, after the localized grafting described above, the grafted crosslinked substrate network may be in contact with a second grafting composition containing one or more ethylenically unsaturated compounds. Such a second composition may be grafted onto the grafted crosslinked substrate network if the grafted crosslinked substrate network contains residual covalently bonded, activatable free radical initiators.

[0120] It should be noted that a free radical initiator covalently bonded to a crosslinked substrate network forms two free radical groups upon activation, and one of these free radical groups does not necessarily have to be covalently bonded to the substrate. Consequently, some of the reactive components in the grafted composition can polymerize via the unbonded free radical groups to form polymers that are not covalently bonded to the network. Such polymers are referred to herein as “by-product polymers.” These by-product polymers can be covalently bonded to the grafted polymer network by including a crosslinking agent in the grafted composition. The composition may contain at least some of the by-product polymers that are not covalently bonded to the grafted polymer network. To achieve this, polymerization of the grafted composition is carried out in the substantially absent presence of the crosslinking agent. “Substantially absent presence of the crosslinking agent” means that any crosslinking agent used in the grafted composition is present in substoichiometric amounts. In some embodiments, the crosslinking agent is not present in the grafted composition.

[0121] The reactive compositions and grafted compositions of the present invention contain an ethylenically unsaturated compound as a reactive component. The ethylenically unsaturated compound undergoes polymerization to form the polymer compositions described herein. As can be understood, a variety of ethylenically unsaturated compounds can be used in the present invention.

[0122] The ethylenically unsaturated compounds may be the same or different between the reactive composition and the grafted composition, but in some embodiments, it is preferable that at least some of the ethylenically unsaturated compounds in each composition are different. By using different materials in the reactive composition than those in the grafted composition, it becomes possible to design ophthalmic devices that combine desired properties of materials that may not be easily mismatched. This is one of the advantages of the present invention.

[0123] The ethylenically unsaturated compounds to be included in the reactive composition and / or grafted composition may include independently selected silicone-containing components.

[0124] The silicone-containing component may comprise one or more compounds selected from monomers or macromers, each compound independently comprising at least one polymerizable group, at least one siloxane group, and one or more linking groups connecting polymerizable groups to siloxane groups. The silicone-containing component may also comprise 1 to 220 siloxane repeating units, such as the groups defined below. The silicone-containing component may also comprise at least one fluorine atom.

[0125] The silicone-containing component may comprise one or more polymerizable groups defined above, one or more optionally repeating siloxane units, and one or more linking groups connecting the polymerizable groups to the siloxane units. The silicone-containing component may independently comprise one or more polymerizable groups which are (meth)acrylate, styryl, vinyl ether, (meth)acrylamide, N-vinyl lactam, N-vinylamide, O-vinyl carbamate, O-vinyl carbonate, vinyl group, or a mixture thereof, one or more optionally repeating siloxane units, and one or more linking groups connecting the polymerizable groups to the siloxane units.

[0126] The silicone-containing component may independently include one or more polymerizable groups which are (meth)acrylate, (meth)acrylamide, N-vinyl lactam, N-vinylamide, styryl, or a mixture thereof; one or more optionally repeating siloxane units; and one or more linking groups which connect the polymerizable groups to the siloxane units.

[0127] The silicone-containing component may independently include one or more polymerizable groups which are (meth)acrylate, (meth)acrylamide, or a mixture thereof; one or more optionally repeating siloxane units; and one or more linking groups which connect the polymerizable groups to the siloxane units.

[0128] The silicone-containing component may include one or more polymerizable compounds of formula A:

[0129] [ka] Here, at least one R A is, formula R g -L- is the base, and in the formula, R g L is a polymerizable group, L is a linking group, and the remaining R A Each of them operates independently. (a)R g -L-, (b) C1-C11 are optionally substituted with one or more hydroxyl, amino, amide, oxa, carboxy, alkylcarboxy, carbonyl, alkoxy, amide, carbamate, carbonate, halo, phenyl, benzyl, or a combination thereof. 16 Alkyl, (c) C3-C3 cells optionally substituted with one or more alkyl, hydroxy, amino, amide, oxa, carbonyl, alkoxy, amide, carbamate, carbonate, halo, phenyl, benzyl, or a combination thereof. 12 Cycloalkyl, (d) C6-C6 cells optionally substituted with one or more alkyl, hydroxy, amino, amide, oxa, carboxy, alkylcarboxy, carbonyl, alkoxy, amide, carbamate, carbonate, halo, phenyl, benzyl, or a combination thereof. 14 Aryl group, (e) Hello, (f) Alkoxy, cyclic alkoxy, or aryloxy, (g) Siloxy, (h) For example, alkylene oxyalkyl or alkoxyalkylene, such as polyethylene oxyalkyl, polypropylene oxyalkyl, or poly(ethylene oxy-co-propylene oxyalkyl), (i) A monovalent siloxane chain comprising 1 to 100 siloxane repeating units that are optionally substituted with alkyl, alkoxy, hydroxy, amino, oxa, carboxy, alkylcarboxy, alkoxy, amide, carbamate, halo, or a combination thereof, n is 0-500, or 0-200, or 0-100, or 0-20, and when n is not 0, it is understood that n is a distribution with a mode equivalent to the indicated value. When n is 2 or greater, the SiO units are the same or different R A Substituents may be supported, and different R A If substituents are present, the n groups may be in a random or block configuration.

[0130] In equation A, there are three R's A Each of these may contain polymerizable groups, or alternatively, two R A However, each may contain a polymerizable group, or alternatively, one R A However, it may also contain polymerizable groups.

[0131] Examples of silicone-containing components suitable for use in the present invention include, but are not limited to, the compounds listed in Table B. When the compounds in Table B contain polysiloxane groups, the number of SiO repeating units in such compounds is preferably 3 to 100, more preferably 3 to 40, or even more preferably 3 to 20, unless otherwise specified.

[0132] [Table 1-1]

[0133] [Table 1-2]

[0134] Table C lists non-limiting examples of additional suitable silicone-containing components. Unless otherwise stated, where applicable, j2 is preferably 1 to 100, more preferably 3 to 40, or even more preferably 3 to 15. In compounds containing j1 and j2, the sum of j1 and j2 is preferably 2 to 100, more preferably 3 to 40, or even more preferably 3 to 15.

[0135] [Table 2-1]

[0136] [Table 2-2]

[0137] A mixture of multiple components containing silicone may be used. Examples of suitable mixtures include, but are not limited to, a mixture of mono-(2-hydroxy-3-methacrylateoxypropyloxy)-propyl-terminated mono-n-butyl-terminated polydimethylsiloxane (OH-mPDMS) having different molecular weights, such as a mixture of OH-mPDMS containing 4 and 15 SiO repeating units; a mixture of OH-mPDMS having different molecular weights (e.g., containing 4 and 15 repeating SiO repeating units) with a silicone-based crosslinking agent such as bis-3-acrylooxy-2-hydroxypropyloxypropyl polydimethylsiloxane (ac-PDMS); and a mixture of 2-hydroxy-3-[3-methyl-3,3-di(trimethylsiloxy)silylpropoxy]-propyl methacrylate (SiMAA) with a mono-methacrylateoxypropyl-terminated mono-n-butyl-terminated polydimethylsiloxane (mPDMS), such as mPDMS1000.

[0138] The silicone-containing component used in this invention may have an average molecular weight of approximately 400 to approximately 4000 daltons.

[0139] Silicone-containing components(s) may be present in amounts of up to approximately 95% by weight, or approximately 10 to approximately 80% by weight, or approximately 20 to approximately 70% by weight, based on all the reactive components of the formulation (excluding diluents).

[0140] The ethylenically unsaturated compounds to be included in the reactive composition and / or grafted composition may include independently selected hydrophilic components. Examples of hydrophilic components include those that, when combined with the remaining reactive components, can impart at least about 20% or at least about 25% water content to the resulting composition. Suitable hydrophilic components include hydrophilic monomers, prepolymers, and polymers. Preferably, the hydrophilic component has at least one polymerizable group and at least one hydrophilic functional group. Examples of polymerizable groups include acrylic, methacrylic, acrylamide, methacrylamide, fumaric acid, maleic acid, styryl, isopropenylphenyl, O-vinyl carbonate, O-vinylcarbamate, allyl, O-vinylacetyl, and double bonds of N-vinyllactam and N-vinylamide.

[0141] The terms "vinyl-type" or "vinyl-containing" monomers refer to monomers that have a vinyl group (-CH=CH2) and are generally highly reactive. Such hydrophilic vinyl-containing monomers are known to polymerize relatively easily.

[0142] "Acrylic" monomers or "acrylic-containing" monomers are monomers that contain an acrylic group (CH2=CRCOX), where R is H or CH3 and X is O or N. These monomers are also known to polymerize easily and include N,N-dimethylacrylamide (DMA), 2-hydroxyethyl methacrylamide, polyethylene glycol monomethacrylate, methacrylic acid, acrylic acid, and mixtures thereof.

[0143] Hydrophilic monomers having at least one hydroxyl group (hydroxyalkyl monomer) may be used. The hydroxyalkyl group may be selected from C2-C4 mono- or dihydroxysubstituted alkyl groups and poly(ethylene glycol) having 1-10 repeating units, or from 2-hydroxyethyl, 2,3-dihydroxypropyl, or 2-hydroxypropyl, and combinations thereof.

[0144] Examples of hydroxyalkyl monomers include 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2,3-dihydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 1-hydroxypropyl 2-(meth)acrylate, 2-hydroxy-2-methylpropyl (meth)acrylate, 3-hydroxy-2,2-dimethylpropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxyethyl (meth)acrylamide, N-(2-hydroxypropyl)(meth)acrylamide, N,N-bis(2-hydroxyethyl)(meth)acrylamide, N,N-(2-hydroxypropyl)(meth)acrylamide, N-(3-hydroxypropyl)(meth)acrylamide, 2,3-dihydroxypropyl (meth)acrylamide, glycerol (meth)acrylate, polyethylene glycol monomethacrylate, and mixtures thereof.

[0145] The hydroxyalkyl monomer may also be selected from the group consisting of 2-hydroxyethyl methacrylate, glycerol methacrylate, 2-hydroxypropyl methacrylate, hydroxybutyl methacrylate, 3-hydroxy-2,2-dimethylpropyl methacrylate, and mixtures thereof.

[0146] The hydroxyalkyl monomer may include 2-hydroxyethyl methacrylate, 3-hydroxy-2,2-dimethylpropyl methacrylate, hydroxybutyl methacrylate, or glycerol methacrylate.

[0147] When more than approximately 3% by weight of hydrophilic polymer is desired, hydroxyl-containing (meth)acrylamide is generally excessively hydrophilic and therefore cannot be included in the compatibilization of hydroxyalkyl monomers. Hydroxyl-containing (meth)acrylate may be included in the reactive composition, and a smaller amount of hydroxyalkyl monomer may be selected to provide the final lens with a haze value of less than approximately 50% or less than approximately 30%.

[0148] It will be understood that the amount of hydroxyl components varies depending on a number of factors, including the number of hydroxyl groups in the hydroxyalkyl monomer, the amount of hydrophilic functional groups in the silicone-containing components, molecular weight, and presence. Hydrophilic hydroxyl components may be present in the reactive composition in amounts of about 15% or less, about 10% or less by weight, about 3-15% by weight, or about 5-15% by weight.

[0149] Hydrophilic vinyl-containing monomers that can be incorporated into polymer compositions include monomers such as hydrophilic N-vinyl lactam and N-vinylamide monomers, which include N-vinylpyrrolidone (NVP), N-vinyl-2-piperidone, N-vinyl-2-caprolactam, N-vinyl-3-methyl-2-caprolactam, N-vinyl-3-methyl-2-piperidone, N-vinyl-4-methyl-2-piperidone, N-vinyl-4-methyl-2-caprolactam, N-vinyl-3-ethyl-2-pyrrolidone, N-vinyl-4,5-dimethyl-2-pyrrolidone, N-vinylacetamide (NVA), N-vinyl-N-methylacetamide (VMA), N-vinyl-N-ethylacetamide, N-vinyl-N-ethylformamide, N-vinylformamide, N-vinyl-N-methylpropionamide, N-vinyl-N-methyl-2-methylpropionamide, and N-vinyl-2-methylpropionamide. Pionamide, 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 Examples include don, 1-isopropyl-3-methylene-2-pyrrolidone, 1-isopropyl-5-methylene-2-pyrrolidone, N-vinyl-N-ethylacetamide, N-vinyl-N-ethylformamide, N-vinylformamide, N-vinylisopropylamide, N-vinylcaprolactam, N-carboxyvinyl-β-alanine (VINAL), N-carboxyvinyl-α-alanine, N-vinylimidazole, and mixtures thereof.

[0150] Examples of hydrophilic O-vinylcarbamate and O-vinyl carbonate monomers that can be used in the present invention include N-2-hydroxyethyl vinylcarbamate and N-carboxy-β-alanine N-vinyl ester. Further examples of hydrophilic vinyl carbonate monomers or vinylcarbamate monomers are disclosed in U.S. Patent No. 5,070,215, and hydrophilic oxazolone monomers are disclosed in U.S. Patent No. 4,910,277.

[0151] Examples of vinyl carbamates and carbonates that can be used include N-2-hydroxyethyl vinyl carbamate, N-carboxy-β-alanine N-vinyl ester, other hydrophilic vinyl monomers (including vinyl imidazole, ethylene glycol vinyl ether (EGVE), di(ethylene glycol) vinyl ether (DEGVE), allyl alcohol, 2-ethyl oxazoline, vinyl acetate, acrylonitrile), and mixtures thereof.

[0152] (Meth)acrylamide monomers can also be used as hydrophilic monomers. Examples include NN-dimethylacrylamide, acrylamide, N,N-bis(2-hydroxyethyl)acrylamide, acrylonitrile, N-isopropylacrylamide, N,N-dimethylaminopropyl(meth)acrylamide, and any of the hydroxyl-functionalized (meth)acrylamides listed above.

[0153] Hydrophilic monomers that may be incorporated into the polymers disclosed herein may be selected from N,N-dimethylacrylamide (DMA), 2-hydroxyethylacrylamide, 2-hydroxyethylmethacrylamide, N-hydroxypropylmethacrylamide, bishydroxyethylacrylamide, 2,3-dihydroxypropyl(meth)acrylamide, N-vinylpyrrolidone (NVP), N-vinyl-N-methylacetamide, N-vinylmethacetamide (VMA), and polyethylene glycol monomethacrylate.

[0154] The hydrophilic monomer may be selected from DMA, NVP, VMA, NVA, and mixtures thereof.

[0155] The hydrophilic monomers may be macromers of ethylene oxide and propylene oxide, linear or branched poly(ethylene) glycols, poly(propylene glycols), or statistically random or block copolymers. These polyether macromers have one polymerizable group. Non-limiting examples of such polymerizable groups include acrylates, methacrylates, styrenes, vinyl ethers, acrylamides, methacrylamides, and other vinyl compounds. These polyether macromers may include acrylates, methacrylates, acrylamides, methacrylamides, and mixtures thereof. Other suitable hydrophilic monomers will become apparent to those skilled in the art.

[0156] Hydrophilic monomers may also include charged monomers, but are not limited to, acrylic acid, methacrylic acid, 3-acrylamidopropionic acid (ACA1), 4-acrylamidobutyric acid, 5-acrylamidopetanonic acid (ACA2), 3-acrylamido-3-methylbutyric acid (AMBA), N-vinyloxycarbonyl-α-alanine, N-vinyloxycarbonyl-β-alanine (VINAL), 2-vinyl-4,4-dimethyl-2-oxazolin-5-one (VDMO), reactive sulfonates (e.g., sodium-2-(acrylamido)-2-methylpropanesulfonate (AMPS), potassium 3-sulfopropyl(meth)acrylate, sodium 3-sulfopropyl(meth)acrylate, disodium bis-3-sulfopropylitaconate, dipotassium bis-3-sulfopropylitaconate, sodium vinylsulfonate, vinylsulfonate, styrenesulfonate, sulfoethyl methacrylate, and combinations thereof).

[0157] Hydrophilic monomers can be selected from N,N-dimethylacrylamide (DMA), N-vinylpyrrolidone (NVP), 2-hydroxyethyl methacrylate (HEMA), N-vinylmetacetoamide (VMA), and N-vinyl N-methylacetamide (NVA), N-hydroxypropyl methacrylamide, mono-glycerol methacrylate, 2-hydroxyethylacrylamide, 2-hydroxyethyl methacrylamide, bishydroxyethylacrylamide, 2,3-dihydroxypropyl(meth)acrylamide, and mixtures thereof.

[0158] The hydrophilic monomer can be selected from DMA, NVP, HEMA, VMA, NVA, and mixtures thereof.

[0159] Hydrophilic monomers (including hydroxylalkyl monomers) may be present in amounts of approximately 1 to approximately 60% by weight, approximately 5 to approximately 50% by weight, or approximately 5 to approximately 40% by weight, up to a maximum of approximately 60% by weight, based on the weight of all reactive components.

[0160] Other hydrophilic monomers that may be used include polyoxyethylene polyols in which one or more terminal hydroxyl groups are replaced by polymerizable groups. An example is polyethylene glycol in which one or more terminal hydroxyl groups are replaced by polymerizable groups. An example is polyethylene glycol that reacts with 1 molar equivalent or more of end-capping groups such as isocyanatoethyl methacrylate ("IEM"), methacrylic anhydride, methacryloyl chloride, and vinyl benzoyl chloride to produce a polyethylene polyol having one or more terminally polymerizable olefin groups bonded to the polyethylene polyol by a bonding moiety such as a carbamate or ester group.

[0161] Further examples include hydrophilic vinyl carbonate or vinyl carbamate monomers disclosed in U.S. Patent No. 5,070,215, and hydrophilic oxazolone monomers disclosed in U.S. Patent No. 4,190,277. Other suitable hydrophilic monomers will become apparent to those skilled in the art.

[0162] Hydrophilic monomers that can be incorporated into the polymer compositions disclosed herein include hydrophilic monomers such as N,N-dimethylacrylamide (DMA), 2-hydroxyethyl acrylate, glycerol methacrylate, 2-hydroxyethyl methacrylamide, N-vinylpyrrolidone (NVP), N-vinyl methacrylamide, HEMA, and poly(ethylene glycol) methyl ether methacrylate (mPEG).

[0163] Examples of hydrophilic monomers include DMA, NVP, HEMA, and mixtures thereof.

[0164] The reactive composition and / or grafted composition may contain one or more independently selected ethylenically unsaturated zwitterionic compounds, such as ethylenically unsaturated betaine. Preferably, the zwitterionic compound is present in the grafted composition. Examples of suitable compounds include N-(2-carboxyethyl)-N,N-dimethyl-3-[(1-oxo-2-propen-1-yl)amino]-1-propaneaminium intramolecular salt (CAS 79704-35-1, also known as 3-acrylamide-N-(2-carboxyethyl)-N,N-dimethylpropane-1-aminium or CBT); 3-methacrylamide-N-(2-carboxyethyl)-N,N-dimethylpropane-1-aminium; N,N-dimethyl-N-[3-[(1-oxo-2-propen-1-yl)amino]propyl]3-sulfo-1-propaneaminium intramolecular salt (CAS 80293-60-3, also known as 3-((3-acrylamidepropyl)dimethylammoniopropane-1-sulfonate or SBT); 3-((3-methacrylamidepropyl)dimethylammonio)propane-1-sulfonate 3,5-Dioxa-8-aza-4-phosphaundeca-10-ene-1-aminium 4-hydroxy-N,N,N-trimethyl-9-oxo intramolecular salt 4-oxide (CAS 163674-35-9, "PBT"); 2-(acrylamideethoxy)-(2-(trimethylammonio)ethyl)phosphate; 2-(methacrylamideethoxy)-(2-(trimethylammonio)ethyl)phosphate; 4-hydroxy -N,N,N,10-tetramethyl-9-oxo-3,5,8-trioxa-4-phosphaunde-10-ene-1-aminium intramolecular salt 4 oxide (CAS 67881-98-5, also known as 2-(methacryloyloxy)ethyl(2-trimethylammonio)ethyl) phosphate or MPC); or 2-(acryloyloxy)ethyl(2-(trimethylammonio)ethyl phosphate.

[0165] The reactive composition and / or grafted composition may contain one or more independently selected ethylenically unsaturated quaternary ammonium salts. Preferably, the quaternary ammonium salt is present in the grafted composition. Examples of suitable compounds include 2-(methacryloyloxy)ethyltrimethylammonium chloride; 2-(acryloyloxy)ethyltrimethylammonium chloride; 3-methacrylamide-N,N,N-trimethylpropane-1-aminium chloride; or 3-acrylamide-N,N,N-trimethylpropane-1-aminium chloride.

[0166] The reactive composition and / or grafted composition may contain one or more independently selected ethylenically unsaturated pharmacochemical components. Preferably, the pharmacochemical compound is present in the grafted composition. Examples of suitable compounds include cyclosporine or salicylate monomers.

[0167] The reactive composition and / or grafted composition may contain one or more independently selected ethylenically unsaturated peptides. Preferably, the peptides are present in the grafted composition. Exemplary compounds include, for example, those in which the amino terminus of the peptide can be acylated with known co-reagents and catalysts using acylating agents such as (meth)acryloyl chloride, (meth)acryl anhydride, isopropenyl α,α-dimethylbenzyl isocyanate, and 2-isocyanatoethyl methacrylate to form monomers suitable for incorporation into the reactive compositions of the present invention.

[0168] The reactive composition of the present invention contains a crosslinking agent. The crosslinking agent may be optionally present in the grafted composition. Various crosslinking agents may be used, including silicone-containing and silicone-free crosslinking agents, and mixtures thereof. Examples of suitable crosslinking agents include ethylene glycol dimethacrylate (EGDMA), diethylene glycol dimethacrylate, trimethylolpropane trimethacrylate (TMPTMA), tetraethylene glycol dimethacrylate (TEGDMA), triallyl cyanurate (TAC), glycerol trimethacrylate, 1,3-propanediol dimethacrylate, 2,3-propanediol dimethacrylate, 1,6-hexanediol dimethacrylate, 1,4-butanediol dimethacrylate, methacryloxyethyl vinylcarbonate (HEMAVc), aryl methacrylate, methylene bisacrylamide (MBA), and polyethylene glycol dimethacrylate (where the polyethylene glycol preferably has a molecular weight of up to 5,000 daltons). The crosslinking agent is used in typical amounts known to those skilled in the art, for example, about 0.000415 to about 0.0156 moles per 100g of the reactive component in the reaction composition.

[0169] It should be noted that when an ethylenically unsaturated compound (e.g., a hydrophilic monomer or a silicone-containing monomer) acts as a crosslinking agent, for example, because it is bifunctional or polyfunctional, the addition of another crosslinking agent to the reaction composition is optional. In this case, the ethylenically unsaturated compound is also considered a crosslinking agent. Examples of hydrophilic monomers that can act as crosslinking agents and, if present, do not require the addition of an additional crosslinking agent to the reaction composition include the polyoxyethylene polyols described above, which contain two or more terminal methacrylate moieties. Examples of silicone-containing monomers that can act as crosslinking agents and, if present, do not require the addition of a crosslinking monomer to the reaction composition include α,ω-bismethacrylateoxypropyl polydimethylsiloxane. Furthermore, any of the polyfunctional silicone-containing components disclosed above can be used as a crosslinking agent.

[0170] Either or both of the reactive composition and the grafting composition may contain additional components, but are not limited to, UV absorbers, phototautomorphic compounds, pharmaceutical compounds, and nutritional supplements, antimicrobial compounds, reactive colorants, pigments, copolymerizable and nonpolymerizable dyes, release agents, and combinations thereof. Other components that may be present in the first and / or grafting composition include wetting agents such as those disclosed in U.S. Patent No. 6,367,929, International Publication Nos. 03 / 22321 and 03 / 22322, and compatibility agents such as those disclosed in U.S. Patent Application Publication Nos. 2003 / 162862 and 2003 / 125498. A preferred UV absorber is 2-(2'-hydroxy-5-methacrylyloxyethylphenyl)-2H-benzotriazole, commonly known as Norbloc. The total amount of additives may be up to about 20% by weight. The reactive composition may contain up to approximately 18% by weight of a wetting agent, or approximately 5 to approximately 18% by weight of a wetting agent.

[0171] As used herein, the wetting agent is a hydrophilic polymer having a weight-average molecular weight of over 5,000 Daltons, between 150,000 and 2,000,000 Daltons, between 300,000 and 1,800,000 Daltons, or between 500,000 and 1,500,000 Daltons.

[0172] The amount of any wetting agent that can be added to the reactive composition and / or grafted composition of the present invention may vary depending on the other components used and the desired properties of the resulting product. When present, the internal wetting agent in the reactive composition may be present in amounts of about 1% to about 20% by weight, about 2% to about 15% by weight, or about 2% to about 12% by weight, based on the total weight of all the reactive components. Preferably, the wetting agent is present in the reactive composition when used.

[0173] Examples of wetting agents include, but are not limited to, homopolymers, statistical random copolymers, diblock copolymers, triblock copolymers, segmented block copolymers, graft copolymers, and mixtures thereof. Non-limited examples of internal wetting agents are copolymers prepared by free radical polymerization of suitable monomers, including polyamides, polyesters, polylactones, polyimides, polylactams, polyethers, polyacid homopolymers, and acrylates, methacrylates, styrenes, vinyl ethers, acrylamides, methacrylamides, N-vinyl lactams, N-vinylamides, O-vinyl carbamates, O-vinyl carbonates, and other vinyl compounds. Wetting agents may be produced from any hydrophilic monomer, including those listed herein.

[0174] The wetting agent may include an acyclic polyamide containing a pendant acyclic amide group and capable of association with a hydroxyl group. The cyclic polyamide contains a cyclic amide group and is also capable of association with a hydroxyl group.

[0175] Suitable examples of acyclic polyamides include formula XXIX or formula XXX:

[0176] [ka] (In the formula, X is a direct bond, -(CO)- or -(CO)-NHR) e - and R 26 and R 27 is either H or a methyl group, and R e R is a C1-C3 alkyl group, a H is selected from linear or branched substituted or unsubstituted C1-C4 alkyl groups, R b R is selected from H, linear or branched substituted or unsubstituted C1-C4 alkyl groups, amino groups having up to 2 carbon atoms, amide groups having up to 4 carbon atoms, and alkoxy groups having up to 2 carbon groups. c R is selected from H, linear or branched substituted or unsubstituted C1-C4 alkyl groups, or methyl, ethoxy, hydroxyethyl and hydroxymethyl. d R is selected from H, linear or branched substituted or unsubstituted C1-C4 alkyl groups, or methyl, ethoxy, hydroxyethyl, and hydroxymethyl. a and R b The total number of carbon atoms is 8 or less, including 7, 6, 5, 4, 3, or less, and R c and R d Examples include polymers and copolymers containing repeating units of the form R (the total number of carbon atoms is 8 or less, including 7, 6, 5, 4, 3, or less). a and R b The total number of carbon atoms may be 6 or less, or 4 or less. c and R d The total number of carbon atoms may be six or less. As used herein, substituted alkyl groups include alkyl groups substituted with amine groups, amide groups, ether groups, hydroxyl groups, carbonyl groups, carboxyl groups, or combinations thereof.

[0177] R a and R bX can be independently selected from H, substituted or unsubstituted C1-C2 alkyl groups. X may be directly bonded, and R a and R b This can be independently selected from H, substituted or unsubstituted C1-C2 alkyl groups.

[0178] R c and R d This can be independently selected from H, substituted or unsubstituted C1-C2 alkyl groups, methyl, ethoxy, hydroxyethyl, and hydroxymethyl.

[0179] The acyclic polyamide of the present invention may contain a majority of repeating units of formula XXIX or formula XXX, or the acyclic polyamide may contain at least 50 mol% of repeating units of formula XXIX or formula XXX, with at least about 70 mol% and at least 80 mol%.

[0180] Specific examples of repeating units of formulas XXIX and XXX include 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 repeating units derived from acyclic amides of formulas XXXI and XXXII.

[0181] [ka]

[0182] Suitable cyclic amides that can be used to form cyclic polyamides include α-lactams, β-lactams, γ-lactams, δ-lactams, and ε-lactams. A suitable example of a cyclic polyamide is formula XXXIII:

[0183] [ka] (In the formula, f is a number from 1 to 10, and X is a direct bond, -(CO)-, or -(CO)-NH-R) e - and R e R is a C1-C3 alkyl group, 28 Examples include polymers and copolymers containing repeating units of (where is a hydrogen atom or a methyl group). In formula XXXIII, f may be 8 or less, including 7, 6, 5, 4, 3, 2, or 1. In formula XXXIII, f may be 6 or less, including 5, 4, 3, 2, or 1, or it may be 2 to 8, including 2, 3, 4, 5, 6, 7, or 8, or it may be 2 or 3.

[0184] When X is directly bonded, f can be 2. In such cases, the cyclic polyamide can be polyvinylpyrrolidone (PVP).

[0185] A cyclic polyamide may contain 50 mol% or more of repeating units of formula XXXIII, or a cyclic polyamide may contain at least about 50 moles of repeating units of formula XXXIII, comprising at least about 70 mol% and at least about 80 mol%.

[0186] Specific examples of repeating units of formula XXXIII include PVP homopolymers and N-vinylpyrrolidone-derived repeating units that form vinylpyrrolidone copolymers or N-vinylpyrrolidone substituted with hydrophilic substituents such as phosphorylcholine.

[0187] Polyamides may also be copolymers containing cyclic amides, acyclic amide repeating units, or copolymers containing both cyclic and acyclic amide repeating units. Additional repeating units may be formed from monomers selected from hydroxyalkyl (meth)acrylates, alkyl (meth)acrylates, or other hydrophilic monomers and siloxane-substituted acrylates or methacrylates. Any of the monomers listed as preferred hydrophilic monomers may be used as comonomers to form additional repeating units. Specific examples of additional monomers that may be used to form polyamides include 2-hydroxyethyl methacrylate, vinyl acetate, acrylonitrile, hydroxypropyl methacrylate, 2-hydroxyethyl acrylate, methyl methacrylate and hydroxybutyl methacrylate, GMMA, PEGS, and mixtures thereof. Ionic monomers may also be included. Examples of ionic monomers include acrylic acid, methacrylic acid, 2-methacryloyloxyethyl phosphorylcholine, 3-(dimethyl(4-vinylbenzyl)ammonium)propane-1-sulfonate (DMVBAPS), 3-((3-acrylamidopropyl)dimethylammonium)propane-1-sulfonate (AMPDAPS), 3-((3-methacrylamidopropyl)dimethylammonium)propane-1-sulfonate (MAMPDAPS), 3-((3-(acryloyloxy)propyl)dimethylammonium)propane-1-sulfonate (APDAPS), and methacryloyloxy)propyl)dimethylammonium)propane-1-sulfonate (MAPDAPS).

[0188] The reactive composition may comprise both acyclic and cyclic polyamides, or copolymers thereof. Acyclic polyamides may be any of the acyclic polyamides described herein or copolymers thereof, while cyclic polyamides may be any of the cyclic polyamides described herein or copolymers thereof. Polyamides may be selected from the group consisting of polyvinylpyrrolidone (PVP), polyvinylmethylacetamide (PVMA), polydimethylacrylamide (PDMA), polyvinylacetamide (PNVA), poly(hydroxyethyl(meth)acrylamide), polyacrylamide, and copolymers and mixtures thereof.

[0189] Wetting agents may be prepared from DMA, NVP, HEMA, VMA, NVA, and combinations thereof. Wetting agents may also be reactive components, as defined herein, having polymerizable groups, for example, produced by an acylation reaction between a pendant hydroxyl group on a HEMA repeating unit of an internal wetting agent and methacryloyl chloride or methacryloyl anhydride. Other methods of functionalization will be apparent to those skilled in the art.

[0190] Such internal wetting agents are disclosed in U.S. Patents No. 6,367,929, No. 6,822,016, No. 7,052,131, No. 7,666,921, No. 7691,916, No. 7786,185, No. 8022,158, and No. 8450,387.

[0191] Generally, the reactive components in a reactive composition may be dispersed or dissolved in a diluent. Suitable diluents are known in the art or can be easily determined by those skilled in the art. For example, suitable diluents for the preparation of silicone hydrogels are disclosed in International Publication No. 03 / 022321 and U.S. Patent No. 6,020,445 (the disclosure of which is incorporated herein by reference).

[0192] Suitable diluents for silicone hydrogel reaction mixtures include alcohols having 2 to 20 carbon atoms, amides having 10 to 20 carbon atoms derived from primary amines, and carboxylic acids having 8 to 20 carbon atoms. Primary and secondary alcohols are preferred. Preferred types include alcohols having 5 to 20 carbon atoms and carboxylic acids having 10 to 20 carbon atoms.

[0193] Specific diluents that can be used include 1-ethoxy-2-propanol, diisopropylaminoethanol, isopropanol, 3,7-dimethyl-3-octanol, 1-decanol, 1-dodecanol, 1-octanol, 1-pentanol, 2-pentanol, 1-hexanol, 2-hexanol, 2-octanol, 3-methyl-3-pentanol, tert-amyl alcohol, tert-butanol, 2-butanol, 1-butanol, 2-methyl-2-pentanol. This includes ethanol, 2-propanol, 1-propanol, ethanol, 2-ethyl-1-butanol, (3-acetoxy-2-hydroxypropyloxy)propylbis(trimethylsiloxy)methylsilane, 1-tert-butoxy-2-propanol, 3,3-dimethyl-2-butanol, tert-butoxyethanol, 2-octyl-1-dodecanol, decanoic acid, octanoic acid, dodecanoic acid, 2-(diisopropylamino)ethanol, and mixtures thereof.

[0194] Preferred diluents include 3,7-dimethyl-3-octanol, 1-dodecanol, 1-decanol, 1-octanol, 1-pentanol, 1-hexanol, 2-hexanol, 2-octanol, 3-methyl-3-pentanol, 2-pentanol, t-amyl alcohol, tert-butanol, 2-butanol, 1-butanol, 2-methyl-2-pentanol, 2-ethyl-1-butanol, ethanol, 3,3-dimethyl-2-butanol, 2-octyl-1-dodecanol, decanoic acid, octanoic acid, dodecanoic acid, and mixtures thereof.

[0195] More preferred diluents include 3,7-dimethyl-3-octanol, 1-dodecanol, 1-decanol, 1-octanol, 1-pentanol, 1-hexanol, 2-hexanol, 2-octanol, 1-dodecanol, 3-methyl-3-pentanol, 1-pentanol, 2-pentanol, t-amyl alcohol, tert-butanol, 2-butanol, 1-butanol, 2-methyl-2-pentanol, 2-ethyl-1-butanol, 3,3-dimethyl-2-butanol, 2-octyl-1-dodecanol, and mixtures thereof.

[0196] Suitable diluents for non-silicone-containing reaction compositions include glycerin, ethylene glycol, ethanol, methanol, ethyl acetate, methylene chloride, polyethylene glycol, polypropylene glycol, borate esters of dihydric alcohols (but not limited to these), and combinations thereof, as disclosed in U.S. Patents No. 4,018,853, No. 4,680,336, and No. 5,039,459, as well as low number-average molecular weight polyvinylpyrrolidone (PVP).

[0197] A mixture of multiple diluents may be used. The diluent may be used in an amount up to about 55% by weight of the total components of the reactive composition. More preferably, it is used in an amount less than about 45% by weight of the total components of the reactive composition, and even more preferably, in an amount of about 15 to about 40% by weight.

[0198] In a preferred embodiment, the crosslinked substrate network of the present invention may be a silicone hydrogel (containing a covalently bonded, activatable free radical initiator such as a MAPO group), and the grafted composition may, following polymerization, provide a hydrophilic graft material (which may optionally be charged) comprising, for example, poly(N,N-dimethylacrylamide) (PDMA), polymerized polyethylene glycol monomethacrylate (e.g., having a number average molecular weight of about 300 to about 1000) (poly(mPEG)), a copolymer of 2-hydroxyethyl methacrylate and methacrylic acid, and 2-(methacryloyloxy)ethyl (2-(trimethylammonio)ethyl) phosphate (MPC). Such a grafted polymer network can exhibit improved biocompatibility and biometric properties when used in ophthalmic devices.

[0199] The crosslinked substrate network is a silicone hydrogel (containing covalently bonded, activatable free radical initiators such as MAPO groups), and the grafted composition provides a hydrophobic siloxane-containing material after polymerization. Such grafted polymer networks may exhibit modified physical, mechanical, and surface properties such as oxygen gas permeability (Dk), elastic modulus, and coefficient of friction, as well as improved handling, such as intraocular contact lens insertion and removal.

[0200] The crosslinked substrate network may be a conventional hydrogel (for example, containing a copolymer of 2-hydroxyethyl methacrylate and methacrylic acid, and containing a MAPO group), and the grafting composition provides a hydrophilic graft material (which may be optionally charged) such as a polyamide following polymerization. Examples include PDMA, polyvinylpyrrolidone (PVP), poly(N-vinyl N-methylacetamide) (PVMA), and copolymers thereof. Such grafted polymer networks can exhibit improved biocompatibility and biometric properties, for example, when used in ophthalmic devices.

[0201] The crosslinked substrate network may be a conventional hydrogel (e.g., a copolymer of 2-hydroxyethyl methacrylate and methacrylic acid and containing MAPO groups), and the grafted composition provides a hydrophobic siloxane-containing material following polymerization. Such a grafted polymer network can exhibit desired physical and mechanical properties, such as oxygen gas permeability (Dk) and elastic modulus, as well as improved biocompatibility and handleability.

[0202] Regarding ophthalmic devices such as contact lenses containing one or more silicone-containing components, the silicone-containing component is preferably present at about 95 wt% or less, or about 10 - about 80, or about 20 - about 70 wt% based on all the reactive components present, including the reactive composition and the reactive second composition. Suitable hydrophilic components may be present in an amount of about 10 - about 60 wt%, or about 15 - about 50 wt%, or about 20 - about 40 wt% based on all the reactive components present, preferably including the reactive composition and the grafted composition.

[0203] It should be noted that the process for making the polymer composition of the present invention may include any additional optional steps. For example, after step (b), an ink or dye may be added to the crosslinked substrate network. Next, the remaining steps (such as step (c)) may be carried out. This enables the ink or dye to be sandwiched within the grafted polymer network.

[0204] In ophthalmic devices such as contact lenses, the crosslinked substrate network is preferably a silicone hydrogel that well-balances the properties that make the device desirable. These properties include water content, haze, contact angle, elastic modulus, oxygen permeability, liquid uptake, lysozyme uptake, and PQ1 uptake. Examples of preferred properties are shown below. "About" is attached before all values, and the ophthalmic device can have any combination of the listed properties. Water content: at least 20%, or at least 25% Haze: 30% or less, or 10% or less Dynamic contact angle (DCA (°)): 100° or less, or 50° or less Elastic modulus (psi): 120 or less, or 80 - 120 Oxygen permeability (Dk (barrels)): at least 80, or at least 100, or at least 150, or at least 200 Elongation at break: at least 100

[0205] Regarding the ionic silicone hydrogel, (in addition to those described above) the following properties may also be preferable. Lysozyme uptake (μg / lens): at least 100, or at least 150, or at least 500, or at least 700 Polyquaternium - 1 (PQ1) uptake (%): 15 or less, or 10 or less, or 5 or less

[0206] The final ophthalmic device can be manufactured by various techniques. For example, in the case of a hydrogel contact lens, the reactive composition described above can be cured in a mold or formed by rotational molding or static molding. The method of rotational molding is disclosed in U.S. Patent Nos. 3,408,429 and 3,660,545, and the method of static molding is disclosed in U.S. Patent Nos. 4,113,224 and 4,197,266. In one embodiment, the contact lens of the present invention is formed by direct molding of the hydrogel, which is economical and enables precise control over the final shape of the hydrated contact lens. Regarding this method, the reactive composition is placed in a mold having the desired shape, and the reactive composition is passed through the conditions described above, whereby the reactive components polymerize to create a crosslinked substrate network within the final desired product having the appropriate shape.

[0207] The crosslinked substrate network formed after curing may be extracted to remove unreacted components and released from the contact lens mold. The crosslinked substrate network may then be immersed in a grafting composition (which may optionally contain a diluent) for a sufficient amount of time to allow the reactive composition to penetrate the crosslinked substrate network to the desired level. The suspension may then be irradiated as described above to form the grafted product, and the contact lens may then be extracted to remove unreacted components.

[0208] The crosslinked substrate network and contact lenses can be extracted using conventional extraction fluids (such as organic solvents, e.g., alcohol), or using aqueous solutions. The aqueous solution is a solution containing water. The aqueous solution may contain at least about 30% by weight of water, or at least about 50% by weight of water, at least about 70% by weight of water, or at least about 90% by weight of water.

[0209] Extraction can be achieved, for example, by immersing the crosslinked substrate network or contact lens in an aqueous solution, or by exposing the material to a stream of aqueous solution. Extraction may also include, for example, heating the aqueous solution, stirring the aqueous solution, increasing the concentration of the release agent in the aqueous solution to a concentration sufficient to cause the crosslinked substrate network to be released from the mold, mechanical or ultrasonic stirring, or incorporating at least one leaching agent into the aqueous solution to a concentration sufficient to facilitate the removal of unreacted components from the crosslinked substrate network or contact lens. With or without the addition of heat, vibration, or both, the aforementioned steps may be carried out in a batch process or a continuous process.

[0210] Some embodiments may also include adding physical agitation to facilitate leaching and demolding. For example, the mold portion of the crosslinked substrate network to which the crosslinked substrate network adheres may be vibrable or movable back and forth in the aqueous solution. Other embodiments may include passing ultrasonic waves through the aqueous solution.

[0211] Contact lenses can be disinfected by well-known methods, such as high-pressure steam sterilization, although these methods are not limited to those mentioned above.

[0212] Clause To ensure completeness, various aspects of this disclosure are described in the following numbered clauses.

[0213] Article 1. An ophthalmic device, a. A step of providing a reactive composition, wherein the reactive composition comprises (i) a polymerization initiator capable of forming two or more free radical groups upon first activation, wherein at least one of the free radical groups is further activatable by subsequent activation, (ii) one or more ethylenically unsaturated compounds, and (iii) a crosslinking agent. b. A step of subjecting the reactive composition to a first activation step, wherein the reactive composition polymerizes thereto to form a crosslinked substrate network containing covalently bonded activatable free radical initiators, c. A step of inactivating at least a portion of the covalently bonded activatable free radical initiator in one or more selected regions of the crosslinked substrate network so that the crosslinked substrate network contains retained covalently bonded activatable free radical initiator outside of one or more selected regions and optionally within one or more selected regions. d. A step of contacting a crosslinked substrate network with a grafting composition containing one or more ethylenically unsaturated compounds, wherein the contact is carried out under conditions such that the grafting composition penetrates into the crosslinked substrate network. e. An ophthalmic device formed by a process comprising the step of activating a retained covalently bonded, activatable free radical initiator so that the grafted composition polymerizes with a crosslinked substrate network, thereby forming a grafted polymer network outside a selected region and optionally partially within a selected region.

[0214] Clause 2. The inactivation of step (c) is the ophthalmic device described in Clause 1 that varies spatially within the ophthalmic device.

[0215] Clause 3. The inactivation step (c) is achieved by irradiation in an oxygen gas atmosphere, for the ophthalmic device described in Clause 1 or 2.

[0216] Clause 4. The inactivation step (c) is carried out using ultraviolet light having a wavelength of 300 nanometers to 400 nanometers, for the ophthalmic device described in any one of Clauses 1 to 3.

[0217] Clause 5. The grafting step (e) is carried out using visible light having a wavelength of 400 nanometers to 450 nanometers, for the ophthalmic device described in Clause 4.

[0218] Clause 6. The inactivation step (c) is carried out using visible light having a wavelength of 400 nanometers to 500 nanometers, for the ophthalmic device described in any one of Clauses 1 to 3.

[0219] Clause 7. The grafting step (e) is carried out using ultraviolet light having a wavelength of 300 nanometers to 400 nanometers, for the ophthalmic device described in Clause 6.

[0220] Clause 8. The ultraviolet light has a wavelength of 350 nanometers to 400 nanometers, for the ophthalmic device described in Clause 4 or Clause 7.

[0221] Clause 9. The visible light has a wavelength of 400 nanometers to 450 nanometers, for the ophthalmic device described in Clause 5 or Clause 6.

[0222] Clause 10. The grafting composition of step (d) contains a crosslinking agent, for the ophthalmic device described in Clause 1.

[0223] Clause 11. The grafting composition of step (d) does not contain a crosslinking agent, for the ophthalmic device described in Clause 1.

[0224] Clause 12. One or more ethylenically unsaturated compounds in step (a) are (meth)acrylate, (meth)acrylamide, styryl, vinyl, N-vinyl lactam, N-vinyl amide, O-vinyl ether, O-vinyl carbonate, O-vinyl carbamate, C 2~12 alkenyl, C 2~12 alkenylphenyl, C 2~12 alkenylnaphthyl, and C 2~6 alkenylphenyl-C 1~6 An ophthalmic device according to any one of clauses 1 to 11, comprising one or more polymerizable groups independently selected from alkyl.

[0225] Clause 13. One or more ethylenically unsaturated compounds in step (d) are (meth)acrylate, (meth)acrylamide, styryl, vinyl, N-vinyl lactam, N-vinyl amide, O-vinyl ether, O-vinyl carbonate, O-vinyl carbamate, C 2~12 alkenyl, C 2~12 alkenylphenyl, C 2~12 alkenylnaphthyl, and C 2~6 alkenylphenyl-C 1~6 An ophthalmic device according to any one of clauses 1 to 12, comprising one or more polymerizable groups independently selected from alkyl.

[0226] Clause 14. The polymerization initiator is bisacylphosphine oxide, bisacylphosphane oxide, diazo compound, diperoxide compound, azobis(monoacylphosphine oxide), azobis(monoacylphosphane oxide), peroxybis(monoacylphosphine oxide), peroxybis(monoacylphosphane oxide), azobis(α-hydroxy ketone), peroxybis(α-hydroxy ketone), azobis(1,2-diketone), peroxybis(1,2-diketone), germanium-based compound, tert-butyl 7-methyl-7-(tert-butylazo)peroxyoctanoate, or a combination thereof. An ophthalmic device according to any one of clauses 1 to 13.

[0227] Clause 15. An ophthalmic device according to any one of Clauses 1 to 14, wherein the polymerization initiator is bisacylphosphine oxide or bis(acyl)phosphine oxide.

[0228] Clause 16. An ophthalmic device according to any one of Clauses 1 to 15, wherein the hydrogel is in the form of a hydrogel, the reactive composition contains one or more silicone-containing components, and the grafting composition contains one or more hydrophilic reactive components.

[0229] Clause 17. An ophthalmic device according to any one of Clauses 1 to 15, wherein the hydrogel is in the form of a hydroactive composition containing one or more hydrophilic reactive components, and the grafting composition contains one or more silicone-containing components.

[0230] Clause 18. An ophthalmic device according to any one of Clauses 1 to 15, wherein the reactive composition, the grafted composition, or both the reactive composition and the grafted composition contains one or more additives selected from UV absorbers, phototautomorphic compounds, pharmaceutical compounds, nutritional supplements, antimicrobial compounds, reactive colorants, pigments, copolymerizable dyes, nonpolymerizable dyes, release agents, wetting agents, and other release agents.

[0231] Clause 19. The ophthalmic device according to Clause 18, wherein the UV absorber is 2-(2'-hydroxy-5-methacrylyloxyethylphenyl)-2H-benzotriazole.

[0232] Clause 20. An ophthalmic apparatus according to any one of Clauses 1 to 19, wherein the process further comprises, optionally, extracting the crosslinked substrate network with a solvent after step (c), and hydrating the extracted crosslinked substrate network with an aqueous solution.

[0233] Clause 21. An ophthalmic device according to any one of Clauses 1 to 20, wherein the process further comprises, following step (e), contacting a crosslinked substrate network with a second grafting composition containing one or more ethylenically unsaturated compounds, and activating retained covalently bonded activatable free radical initiators, such that the second grafting composition polymerizes with the crosslinked substrate network outside the selected region and optionally partially within the selected region.

[0234] Clause 22. An ophthalmic device as described in any one of Clauses 1 to 21, wherein process steps (a) and (b) are performed within a mold assembly comprising a front mold and a rear mold, the front mold and the rear mold defining and sealing a cavity in the shape of the ophthalmic device between them, and process steps (c), (d), and (e) are performed within the mold assembly after the rear mold has been removed.

[0235] Clause 23. An ophthalmic apparatus according to any one of Clauses 1 to 22, wherein the chemical source in steps (c) and (e) includes multiple selectively controllable beams of chemical irradiation controlled by a digital micromirror device according to a predetermined script.

[0236] Clause 24. The ophthalmic apparatus as described in Clause 23, wherein multiple selectively controllable beams of chemical beam, controlled by a digital micromirror device according to a prescribed script, are directed toward one or more surfaces of the ophthalmic apparatus.

[0237] Clause 25. The digital micromirror device is an ophthalmic device as described in Clause 23 or 24, comprising an illumination source including at least one light-emitting diode.

[0238] Clause 26. An ophthalmic device as described in any one of Clauses 1 to 25, which is selected from the group consisting of contact lenses, intraocular lenses, punctal plugs, and ocular implants.

[0239] Clause 27. An ophthalmic device is an ophthalmic device as described in Clause 26, which is a contact lens or an intraocular lens.

[0240] Clause 28. An ophthalmic device comprising a reaction product of a composition, wherein the composition is a. A crosslinked substrate network wherein at least a portion of a covalently bonded activatable free radical initiator is inactivated in one or more selected regions of the crosslinked substrate network, and the crosslinked substrate network contains the retained covalently bonded activatable free radical initiator outside of one or more selected regions and optionally within one or more selected regions. b. A grafted composition comprising one or more ethylenically unsaturated compounds, wherein the grafted composition is localized in a crosslinked substrate network that holds covalently bonded, activatable free radical initiators, for use in ophthalmic devices.

[0241] Clause 29. The ophthalmic device according to Clause 28, wherein the concentration of the retained covalently bonded, activatable free radical initiator is spatially varied within the crosslinked substrate network.

[0242] Clause 30. The ophthalmic device according to Clause 28 or 29, wherein the crosslinked substrate network is a reaction product of a reactive composition comprising (i) a polymerization initiator capable of forming two or more free radical groups upon first activation, wherein at least one of the free radical groups is further activatable by subsequent activation, (ii) one or more ethylenically unsaturated compounds, and (iii) a crosslinking agent.

[0243] Clause 31. The polymerization initiator is a bisacylphosphine oxide, a diazo compound, a diperoxide compound, azobis(monoacylphosphine oxide), azobis(monoacylphosphine oxide), peroxybis(monoacylphosphine oxide), peroxybis(monoacylphosphine oxide), azobis(α-hydroxyketone), peroxybis(α-hydroxyketone), azobis(30,2-diketone), peroxybis(1,2-diketone), a germanium compound, tert-butyl7-methyl-7-(tert-butylazo)peroxyoctanoate, or a combination thereof, as described in Clause 30.

[0244] Clause 32. The polymerization initiator is bisacylphosphine oxide or bis(acyl)phosphine oxide, as described in Clause 31.

[0245] Clause 33. The ophthalmic device according to Clause 28, wherein the covalently bonded activatable free radical initiator is selected from the group consisting of monoacylphosphine oxide, bisacylphosphine oxide, and combinations thereof.

[0246] Clause 34. The ophthalmic device according to Clause 28, wherein the crosslinked substrate network is formed by thermal free radical polymerization of a reactive monomer mixture comprising at least one reactive component having at least one pendant group selected from the group consisting of monoacylphosphine oxide, bisacylphosphine oxide, and combinations thereof.

[0247] Clause 35. An ophthalmic device according to Clause 34, further comprising a monoacylphosphine oxide compound having a refractive index portion, a bisacylphosphine oxide compound having a refractive index portion, or a combination thereof.

[0248] Clause 36. The ophthalmic device described in Clause 35, wherein the refractive index portion is polyamide.

[0249] Clause 37. The ophthalmic device as described in Clause 36, wherein the polyamide includes polyvinylpyrrolidone (PVP), polyvinylmethylacetamide (PVMA), polydimethylacrylamide (PDMA), polyvinylacetamide (PNVA), poly(hydroxyethyl(meth)acrylamide), polyacrylamide, two or more copolymers thereof, or two or more combinations thereof.

[0250] Clause 38. The ophthalmic device according to Clause 35, wherein the light-absorbing portion comprises a static dye, a photochromic dye, a thermochromic dye, a leuco dye, or a combination of two or more thereof.

[0251] Clause 39. The crosslinked substrate network is as follows: a. A step of thermally polymerizing a reactive composition comprising at least one ethylenically unsaturated compound, at least one reactive component selected from the group consisting of a monoacylphosphine oxide monomer (MAPO-M), a bisacylphosphine oxide monomer (MAPO-M), or a combination thereof, and a thermal crosslinking agent to form a precursor crosslinked substrate network, wherein the monoacylphosphine oxide compound having a refractive index portion or a light-absorbing portion and the bisacylphosphine oxide compound having a refractive index portion or a light-absorbing portion are spatially dispersed within the precursor crosslinked substrate network, and the reactive composition is not completely polymerized. b. A step of irradiating a precursor crosslinked substrate network in a pre-selected region, thereby initiating free radical polymerization from dispersed monoacylphosphine oxide compounds having refractive index portions or light-absorbing portions and bisacylphosphine oxide compounds having refractive index portions or light-absorbing portions, thereby incorporating the refractive index portions or light-absorbing portions into the precursor crosslinked substrate network. c. A step of thermal polymerization until the reactive composition is completely polymerized, and optionally d. A step of extracting the unreacted monoacylphosphine oxide compound having a refractive index or light-absorbing portion and the bisacylphosphine oxide compound having a refractive index or light-absorbing portion with a solvent, An ophthalmic device according to any one of Clauses 35 to 37, wherein steps (a) to (d) are performed by a combination of thermal polymerization and photopolymerization, carried out under conditions that preserve the reactivity of repeating units derived from a precursor crosslinked substrate network structure and a crosslinked substrate network structure having at least one pendant group selected from the group consisting of monoacylphosphine oxide, bisacylphosphine oxide, and combinations thereof.

[0252] Clause 40. Process step (a) is carried out at a temperature of 60°C to 100°C, for the ophthalmic apparatus as described in Clause 39.

[0253] Clause 41. The ophthalmic device according to Clause 39 or 40, wherein process step (a) is carried out using azobisisobutyronitrile as a thermal initiator.

[0254] Clause 42. The ophthalmic apparatus according to any one of Clauses 39 to 41, wherein the chemical source in step (b) includes multiple selectively controllable beams of chemical irradiation controlled by a digital micromirror device according to a predetermined script.

[0255] Clause 43. The ophthalmic device according to Clause 42, wherein the digital micromirror device includes an illumination source comprising at least one light-emitting diode.

[0256] Clause 44. An ophthalmic device as described in Clause 43, wherein the light-emitting diode emits radiation having one or more wavelengths in the range of 365 nanometers to 450 nanometers.

[0257] Clause 45. One or more ethylenically unsaturated compounds in the grafted composition and reactive composition are (meth)acrylate, (meth)acrylamide, styryl, vinyl, N-vinyl lactam, N-vinylamide, O-vinyl ether, O-vinyl carbonate, O-vinyl carbamate, C 2~12 Alkenil, C 2~12 Alkenylphenyl, C 2~12 Alkenylnaphthyl, and C 2~6Alkenylphenyl-C 1~6 An ophthalmic device according to any one of clauses 28 to 44, comprising a polymerizable group independently selected from alkyl groups.

[0258] Clause 46. An ophthalmic device according to any one of Clauses 28 to 44, wherein the crosslinked substrate network is formed from one or more silicone-containing components, and the grafted composition contains a hydrophilic reactive component.

[0259] Clause 47. An ophthalmic device according to any one of Clauses 28 to 44, wherein the crosslinked substrate network is formed from one or more hydrophilic reactive components, and the grafted composition contains one or more silicone-containing components.

[0260] Clause 48. An ophthalmic device according to any one of Clauses 28 to 44, wherein the crosslinked substrate network is formed from one or more hydrophilic reactive components, and the grafted composition contains hydrophilic reactive components.

[0261] Clause 49. An ophthalmic device according to any one of Clauses 28 to 44, wherein the crosslinked substrate network is formed from one or more silicone-containing components, and the grafted composition contains one or more silicone-containing components.

[0262] Clause 50. An ophthalmic device according to any one of Clauses 28 to 49, wherein the crosslinked substrate network, the grafted composition, or both the crosslinked substrate network and the grafted composition contain one or more additives selected from UV absorbers, phototautomorphic compounds, pharmaceutical compounds, nutritional supplements, antimicrobial compounds, colorants, pigments, dyes, release agents, and wetting agents.

[0263] Clause 51. The ophthalmic device according to Clause 50, wherein the UV absorber is 2-(2'-hydroxy-5-methacrylyloxyethylphenyl)-2H-benzotriazole.

[0264] Clause 52. An ophthalmic device as described in any one of Clauses 28 to 51, which is selected from the group consisting of contact lenses, intraocular lenses, punctal plugs, and ocular implants.

[0265] Clause 53. An ophthalmic device is a contact lens or an intraocular lens, as described in Clause 52.

[0266] Article 54. A process for manufacturing an ophthalmic device, a. A step of providing a reactive composition, wherein the reactive composition comprises (i) a polymerization initiator capable of forming two or more free radical groups upon first activation, wherein at least one of the free radical groups is further activatable by subsequent activation, (ii) one or more ethylenically unsaturated compounds, and (iii) a crosslinking agent. b. A step of subjecting the reactive composition to a first activation step, wherein the reactive composition polymerizes thereto to form a crosslinked substrate network containing covalently bonded activatable free radical initiators, c. A step of inactivating at least a portion of the covalently bonded activatable free radical initiator in one or more selected regions of the crosslinked substrate network so that the crosslinked substrate network contains retained covalently bonded activatable free radical initiator outside of one or more selected regions and optionally within one or more selected regions. d. A step of contacting a crosslinked substrate network with a grafting composition containing one or more ethylenically unsaturated compounds, wherein the contact is carried out under conditions such that the grafting composition penetrates into the crosslinked substrate network. e. A process comprising the step of activating a retained covalently bonded, activatable free radical initiator so that the grafted composition polymerizes with a crosslinked substrate network, thereby forming a grafted polymer network outside the selected region and optionally partially within the selected region.

[0267] Clause 55. The inactivation of step (c) is spatially varied within the ophthalmic device as described in Clause 54.

[0268] Clause 56. The inactivation step (c) is achieved by irradiation in an oxygen gas atmosphere, as described in Clause 54 or 55.

[0269] Clause 57. The inactivation step (c) is carried out using ultraviolet light having a wavelength of 300 nanometers to 400 nanometers, as described in any one of Clauses 54 to 56.

[0270] Clause 58. The grafting step (e) is carried out using visible light having a wavelength of 400 nanometers to 450 nanometers, as described in Clause 57.

[0271] Clause 59. The inactivation step (c) is carried out using visible light having a wavelength of 400 nanometers to 500 nanometers, as described in any one of Clauses 54 to 56.

[0272] Clause 60. The grafting step (e) is carried out using ultraviolet light having a wavelength of 300 nanometers to 400 nanometers, as described in Clause 59.

[0273] Clause 61. Ultraviolet light having a wavelength of 350 nanometers to 400 nanometers, as described in Clause 57 or Clause 60.

[0274] Clause 62. The ophthalmic device described in Clause 58 or 59, wherein the visible light has a wavelength of 400 nanometers to 450 nanometers.

[0275] Clause 63. The grafting composition of step (e) is the process described in Clause 54, comprising a crosslinking agent.

[0276] Clause 64. The grafting composition of step (e) is free of crosslinking agents, as described in Clause 54.

[0277] Clause 65. One or more ethylenically unsaturated compounds in step (a) are (meth)acrylate, (meth)acrylamide, styryl, vinyl, N-vinyl lactam, N-vinyl amide, O-vinyl ether, O-vinyl carbonate, O-vinyl carbamate, C 2~12 alkenyl, C 2~12 alkenylphenyl, C 2~12 alkenylnaphthyl, and C 2~6 alkenylphenyl-C 1~6 alkyl, and the process according to any one of Clauses 54 to 64, comprising one or more polymerizable groups independently selected therefrom.

[0278] Clause 66. One or more ethylenically unsaturated compounds in step (e) are (meth)acrylate, (meth)acrylamide, styryl, vinyl, N-vinyl lactam, N-vinyl amide, O-vinyl ether, O-vinyl carbonate, O-vinyl carbamate, C 2~12 alkenyl, C 2~12 alkenylphenyl, C 2~12 alkenylnaphthyl, and C 2~6 alkenylphenyl-C 1~6 alkyl, and the process according to any one of Clauses 54 to 65, comprising one or more polymerizable groups independently selected therefrom.

[0279] Clause 67. The polymerization initiator is bisacylphosphine oxide, bisacylphosphane oxide, diazo compound, diperoxide compound, azobis(monoacylphosphine oxide), azobis(monoacylphosphane oxide), peroxybis(monoacylphosphine oxide), peroxybis(monoacylphosphane oxide), azobis(α-hydroxy ketone), peroxybis(α-hydroxy ketone), azobis(1,2-diketone), peroxybis(1,2-diketone), germanium-based compound, tert-butyl 7-methyl-7-(tert-butylazo)peroxyoctanoate, or a combination thereof, and the process according to any one of Clauses 54 to 66.

[0280] Clause 68. The polymerization initiator is bisacylphosphine oxide or bis(acyl)phosphine oxide, in the process described in Clause 67.

[0281] Clause 69. The process according to any one of Clauses 54 to 67, wherein the hydrogel is in the form of a hydrogel, the reactive composition contains one or more silicone-containing components, and the grafted composition contains one or more hydrophilic reactive components.

[0282] Clause 70. The process according to any one of Clauses 54 to 67, wherein the hydrogel is in the form of a hydrogel, the reactive composition contains one or more hydrophilic reactive components, and the grafting composition contains one or more silicone-containing components.

[0283] Clause 71. The process according to any one of Clauses 54 to 70, wherein the reactive composition, the grafted composition, or both the reactive composition and the grafted composition contains one or more additives selected from UV absorbers, phototautomorphic compounds, pharmaceutical compounds, nutritional supplements, antimicrobial compounds, reactive colorants, pigments, copolymerizable dyes, nonpolymerizable dyes, release agents, wetting agents, and release agents.

[0284] Clause 72. The UV absorber is 2-(2'-hydroxy-5-methacrylyloxyethylphenyl)-2H-benzotriazole, in the process described in Clause 71.

[0285] Clause 73. The process according to any one of Clauses 54 to 72, further comprising, after step (e), contacting the crosslinked substrate network with a second grafting composition containing one or more ethylenically unsaturated compounds, and activating retained covalently bonded activatable free radical initiators, such that the second grafting composition polymerizes with the crosslinked substrate network outside the region of choice and optionally within the region of choice.

[0286] Clause 74. Process steps (a) and (b) are performed within a mold assembly comprising a front mold and a rear mold, the front mold and the rear mold defining and sealing a cavity in the shape of an ophthalmic device between them, and process steps (c), (d), and (e) are performed within the mold assembly after the rear mold has been removed, as described in any one of Clauses 54 to 73.

[0287] Article 75. A process for manufacturing an ophthalmic device, the process is: a. A step of providing a reactive composition containing (i) a thermal initiator, (ii) one or more ethylenically unsaturated compounds, (iii) a crosslinking agent, (iv) at least one reactive component having at least one pendant group selected from the group consisting of monoacylphosphine oxide, bisacylphosphine oxide, and combinations thereof, and (v) at least one reactive component selected from the group consisting of monoacylphosphine oxide compounds having a refractive index portion or a light-absorbing portion, bisacylphosphine oxide compounds having a refractive index portion or a light-absorbing portion, and combinations thereof. b. A step of forming a precursor crosslinked substrate network by thermal polymerization of a reactive composition, wherein a monoacylphosphine oxide compound having a refractive index portion or a light-absorbing portion and a bisacylphosphine oxide compound having a refractive index portion or a light-absorbing portion are spatially dispersed within the precursor crosslinked substrate network, and the reactive composition is not completely polymerized. c. A step of irradiating a precursor crosslinked substrate network in a pre-selected region, thereby initiating free radical polymerization from dispersed monoacylphosphine oxide compounds having refractive index portions or light-absorbing portions and bisacylphosphine oxide compounds having refractive index portions or light-absorbing portions, thereby incorporating the refractive index portions or light-absorbing portions into the precursor crosslinked substrate network in the pre-selected region. d. A step of subjecting the reactive composition to thermal polymerization so that the reactive composition is completely polymerized and forms a crosslinked substrate network having covalently bonded monoacylphosphine oxide groups or bisacylphosphine oxide groups, and optionally e. A step of extracting unreacted monoacylphosphine oxide compounds having refractive index or light-absorbing portions and bisacylphosphine oxide compounds having refractive index or light-absorbing portions with a solvent, f. A step of inactivating at least a portion of the covalently bonded monoacylphosphine oxide groups or bisacylphosphine oxide groups in one or more selected regions of the crosslinked substrate network so that the crosslinked substrate network includes covalently bonded monoacylphosphine oxide groups or bisacylphosphine oxide groups held outside one or more selected regions and optionally within one or more selected regions, g. A step of contacting a crosslinked substrate network with a grafting composition containing one or more ethylenically unsaturated compounds, wherein the contact is carried out under conditions such that the grafting composition penetrates into the crosslinked substrate network. h. The process includes activating the retained covalent monoacylphosphine oxide groups or bisacylphosphine oxide groups so that the grafted composition polymerizes with the crosslinked substrate network, thereby forming a grafted polymer network outside the selected region and optionally partially within the selected region. Here, steps (a) to (h) are carried out under conditions that maintain the reactivity of the precursor crosslinked substrate network and the covalently bonded monoacylphosphine oxide groups or bisacylphosphine oxide groups in the crosslinked substrate network until the covalently bonded monoacylphosphine oxide groups or bisacylphosphine oxide groups are intentionally irradiated or activated.

[0288] Clause 76. Process step (b) is carried out at a temperature of 60°C to 100°C, for the ophthalmic device as described in Clause 75.

[0289] Clause 77. Process step (b) is carried out using azobisisobutyronitrile as a thermal initiator, for the ophthalmic device according to Clause 75 or 76.

[0290] The process according to any one of Clauses 75 to 77, wherein the chemical source in step (c) comprises multiple selectively controllable beams of chemical irradiation controlled by a digital micromirror device in accordance with a predetermined script.

[0291] Clause 79. A digital micromirror apparatus comprising a light source including at least one light-emitting diode, the process described in Clause 78.

[0292] Clause 80. A light-emitting diode is produced by the process described in Clause 79, which produces radiation having one or more wavelengths in the range of 365 nanometers to 450 nanometers.

[0293] Clause 81. The deactivation of step (f) is a process described in any one of Clauses 75-80 that is spatially varied within the ophthalmic device.

[0294] Clause 82. The deactivation step (c) is the process described in any one of Clauses 75 to 81, which is achieved by irradiation in an oxygen gas atmosphere.

[0295] Clause 83. The deactivation step (c) is carried out using ultraviolet light having a wavelength of 300 nanometers to 400 nanometers, as described in any one of Clauses 75 to 82.

[0296] Clause 84. The grafting step (e) is carried out using visible light having a wavelength of 400 nanometers to 450 nanometers, as described in Clause 83.

[0297] Clause 85. The deactivation step (c) is carried out using visible light having a wavelength of 400 nanometers to 500 nanometers, as described in any one of Clauses 75 to 82.

[0298] Clause 86. The grafting step (e) is carried out using ultraviolet light having a wavelength of 300 nanometers to 400 nanometers, as described in Clause 85.

[0299] Clause 87. Ultraviolet light having a wavelength of 350 nanometers to 400 nanometers, as described in Clause 83 or 86.

[0300] Clause 88. Visible light having wavelengths of 400 nanometers to 450 nanometers, as described in Clause 84 or 85.

[0301] Clause 89. The grafting composition of step (g) is a process according to any one of Clauses 75 to 88, comprising a crosslinking agent.

[0302] Clause 90. The grafting composition of step (g) is free of crosslinking agents, as described in any one of Clauses 75 to 88.

[0303] Clause 91. One or more ethylenically unsaturated compounds in step (a) are (meth)acrylate, (meth)acrylamide, styryl, vinyl, N-vinyl lactam, N-vinylamide, O-vinyl ether, O-vinyl carbonate, O-vinyl carbamate, C 2~12 Alkenil, C 2~12 Alkenylphenyl, C 2~12 Alkenylnaphthyl, and C 2~6 Alkenylphenyl-C 1~6 The process according to any one of the clauses 75 to 90, comprising one or more polymerizable groups independently selected from alkyl groups.

[0304] Clause 92. One or more ethylenically unsaturated compounds in step (g) are (meth)acrylate, (meth)acrylamide, styryl, vinyl, N-vinyl lactam, N-vinylamide, O-vinyl ether, O-vinyl carbonate, O-vinyl carbamate, C 2~12 Alkenil, C 2~12 Alkenylphenyl, C 2~12 Alkenylnaphthyl, and C 2~6 Alkenylphenyl-C 1~6 The process according to any one of the clauses 75 to 91, comprising one or more polymerizable groups independently selected from alkyl groups.

[0305] Clause 93. The process according to any one of Clauses 75 to 92, wherein the hydrogel is in the form of a hydrogel, the reactive composition contains one or more silicone-containing components, and the grafting composition contains one or more hydrophilic reactive components.

[0306] Clause 94. The process according to any one of Clauses 75 to 92, wherein the hydrogel is in the form of a hydrogel, the reactive composition contains one or more hydrophilic reactive components, and the grafting composition contains one or more silicone-containing components.

[0307] Clause 95. The process according to any one of Clauses 75 to 94, wherein the reactive composition, the grafted composition, or both the reactive composition and the grafted composition contains one or more additives selected from UV absorbers, phototautomorphic compounds, pharmaceutical compounds, nutritional supplements, antimicrobial compounds, reactive colorants, pigments, copolymerizable dyes, nonpolymerizable dyes, release agents, wetting agents, and release agents.

[0308] Clause 96. The UV absorber is 2-(2'-hydroxy-5-methacrylyloxyethylphenyl)-2H-benzotriazole, in the process described in Clause 95.

[0309] The process according to any one of the clauses 75 to 96, further comprising, after step (h), a step of contacting the crosslinked substrate network with a second grafting composition containing one or more ethylenically unsaturated compounds, and activating retained covalently bonded activatable free radical initiators, so that the second grafting composition polymerizes with the crosslinked substrate network outside the region of choice and optionally within the region of choice.

[0310] Clause 98. Process steps (a) to (f), excluding optional step (e), are carried out within a mold assembly comprising a front mold and a rear mold, the front mold and the rear mold defining and sealing a cavity in the shape of an ophthalmic device between them, and process steps (g) and (h) are carried out within the mold assembly after the rear mold has been removed, as described in any one of Clauses 75 to 97.

[0311] Clause 99. The selected area is an ophthalmic device as described in Clause 1 or Clause 28, which forms a pattern.

[0312] Clause 100. The selected area is an ophthalmic device as described in Clause 1 or Clause 28, which forms a reference marker.

[0313] Clause 101. The selected area is an ophthalmic device as described in Clause 1 or Clause 28, which forms a barcode.

[0314] Article 102. Ophthalmic devices, (a) To provide a first reactive composition, the first reactive composition comprising (i) a polymerization initiator capable of forming two or more free radical groups during a first activation, wherein at least one of the free radical groups is further activatable by subsequent activation, (ii) one or more ethylenically unsaturated compounds, and (iii) a crosslinking agent, (b) A step of subjecting the first reactive composition to a first activation step, wherein the first reactive composition polymerizes therein to form a crosslinked substrate network containing covalently bonded activatable free radical initiators, (c) Contacting a crosslinked substrate network with a grafting composition containing one or more ethylenically unsaturated compounds, wherein the contact is carried out under conditions such that the grafting composition penetrates into the crosslinked substrate network. (d) Formed by a process comprising activating a covalently bonded activatable free radical initiator in a selected region of the crosslinked substrate network such that the grafted composition polymerizes with the crosslinked substrate network in one or more selected regions, Steps (a) and (b) are performed within a mold assembly consisting of a front mold and a rear mold, the front mold and the rear mold defining and enclosing a cavity in the shape of an ophthalmic device between them, and steps (c) and (d) are performed within the mold assembly after the rear mold has been removed, for an ophthalmic device.

[0315] Article 103. A process for manufacturing an ophthalmic device, the process is: (a) A step of providing a first reactive composition, the first reactive composition comprising (i) a polymerization initiator capable of forming two or more free radical groups upon first activation, wherein at least one of the free radical groups is further activateable by subsequent activation, (ii) one or more ethylenically unsaturated compounds, and (iii) a crosslinking agent. (b) A step of subjecting the first reactive composition to a first activation step, wherein the first reactive composition polymerizes therein to form a crosslinked substrate network containing covalently bonded activatable free radical initiators, (c) A step of contacting a crosslinked substrate network with a grafting composition containing one or more ethylenically unsaturated compounds, wherein the contact is carried out under conditions such that the grafting composition penetrates into the crosslinked substrate network. (d) A step of activating the covalently bonded activatable free radical initiator of the crosslinked substrate network, thereby polymerizing the grafted composition with the crosslinked substrate network, Steps (a) and (b) are performed within a mold assembly consisting of a front mold and a rear mold, the front mold and the rear mold defining and enclosing a cavity in the shape of an ophthalmic device between them, and steps (c) and (d) are performed within the mold assembly after the rear mold has been removed.

[0316] Clause 104. The grafting composition of step (c) is an ophthalmic device as described in Clause 102 or a process as described in Clause 103, comprising a crosslinking agent.

[0317] Clause 105. The grafting composition of step (c) is free of crosslinking agents, and is the ophthalmic device described in Clause 102 or the process described in Clause 103.

[0318] Clause 106. One or more ethylenically unsaturated compounds in step (a) are (meth)acrylate, (meth)acrylamide, styryl, vinyl, N-vinyl lactam, N-vinylamide, O-vinyl ether, O-vinyl carbonate, O-vinyl carbamate, C 2~12 Alkenil, C 2~12 Alkenylphenyl, C 2~12 Alkenylnaphthyl, and C 2~6 Alkenylphenyl-C 1~6 An ophthalmic device according to Clause 102, or a process according to Clause 103, comprising one or more polymerizable groups independently selected from alkyl groups.

[0319] Clause 107. One or more ethylenically unsaturated compounds in step (c) are (meth)acrylate, (meth)acrylamide, styryl, vinyl, N-vinyl lactam, N-vinylamide, O-vinyl ether, O-vinyl carbonate, O-vinyl carbamate, C 2~12 Alkenil, C 2~12 Alkenylphenyl, C 2~12 Alkenylnaphthyl, and C 2~6 Alkenylphenyl-C 1~6 An ophthalmic device according to clause 102 or 103, comprising one or more polymerizable groups independently selected from alkyl groups.

[0320] Clause 108. The polymerization initiator is a bisacylphosphine oxide, a diazo compound, a diperoxide compound, azobis(monoacylphosphine oxide), azobis(monoacylphosphine oxide), peroxybis(monoacylphosphine oxide), peroxybis(monoacylphosphine oxide), azobis(α-hydroxyketone), peroxybis(α-hydroxyketone), azobis(1,2-diketone), peroxybis(1,2-diketone), a germanium compound, tert-butyl 7-methyl-7-(tert-butylazo)peroxyoctanoate, or a combination thereof, as described in Clause 102 or 103.

[0321] Clause 109. The polymerization initiator is bisacylphosphine oxide or bis(acyl)phosphine oxide, as described in Clause 102 or 103.

[0322] Clause 110. An ophthalmic device according to Clause 102 or 103, wherein the hydrogel is in the form of a first reactive composition containing one or more silicone-containing components, and the grafting composition contains one or more hydrophilic reactive components.

[0323] Clause 111. An ophthalmic device according to Clause 102 or 103, wherein the hydrogel is in the form of a first reactive composition containing one or more hydrophilic reactive components, and the grafting composition contains one or more silicone-containing components.

[0324] Clause 112. An ophthalmic device according to Clause 102 or 103, wherein the first reactive composition, the grafting composition, or both the first reactive composition and the grafting composition contain one or more additives selected from UV absorbers, phototautomorphic compounds, pharmaceutical compounds, nutritional supplements, antimicrobial compounds, reactive colorants, pigments, copolymerizable dyes, nonpolymerizable dyes, release agents, wetting agents, and release agents.

[0325] Clause 113. An ophthalmic device as described in Clause 102 or 103, selected from the group consisting of contact lenses, intraocular lenses, punctal plugs, and ocular implants.

[0326] Article 114. Ophthalmic devices, (a) A step of providing a crosslinked substrate network having a pendant group selected from a bisacylphosphine oxide group, a monoacylphosphine oxide group, and a combination thereof, and having an ultraviolet absorber, a visible light absorber, and a light absorber selected from a combination thereof, (b) A step of inactivating the pendant group with light having a wavelength that is partially absorbed by the light absorber, (c) A step of contacting a crosslinked substrate network with a grafted composition containing one or more ethylenically unsaturated compounds, (d) A process comprising the step of activating a pendant group with light having a wavelength that is substantially not absorbed by a light absorber, An ophthalmic device formed by a process, wherein steps (a) and (b) are optionally performed within a mold assembly consisting of a front mold and a rear mold, the front mold and the rear mold defining and sealing a cavity in the shape of an ophthalmic device between them, and steps (c) and (d) are optionally performed within the mold assembly after the rear mold has been removed, and step (b) is optionally performed from above and below the mold assembly.

[0327] Article 115. Ophthalmic devices, (a) A step of providing a thermocured crosslinked substrate network having pendant bisacylphosphine oxide groups, (b) A step of converting bisacylphosphine oxide groups to monoacylphosphine oxide groups in a first selected region of the thermocured crosslinked substrate network, (c) A step of inactivating both bisacylphosphine oxide groups and monoacylphosphine oxide groups in a second selected region of the thermocured crosslinked substrate network, (d) A step of contacting a thermocured crosslinked substrate network with a first grafting composition containing one or more ethylenically unsaturated compounds, (e) A step of activating bisacylphosphine oxide groups so that the first grafted composition polymerizes with the thermocured crosslinked substrate network, (f) Optionally, a step of extracting a first grafted composition from a thermocured crosslinked substrate network, (g) A step of contacting a thermocured crosslinked substrate network with a second grafting composition containing one or more ethylenically unsaturated compounds, (h) A process comprising the step of activating monoacylphosphine oxide groups such that a second grafted composition polymerizes with a thermocured crosslinked substrate network, Herein, steps (a), (b), and (c) are performed as necessary in a mold assembly comprising a front mold and a rear mold, the front mold and the rear mold defining and sealing a cavity between them in the shape of an ophthalmic device, and steps (d) to (h) are performed as necessary in the mold assembly after the rear mold has been removed, the ophthalmic device being formed by the process. [Examples]

[0328] The diameter (DM) of the contact lens was measured using a calibrated Van Keuren micro-optical comparator equipped with a Mitutoyo digital mechanical micrometer head. The contact lens was placed concave-side down in a crystal cell completely filled with a borate-buffered packaging solution. The cap was placed on top of the cell, taking care to prevent air from being trapped underneath. The cell was then placed on the comparator platform, and the lens image was magnified and positioned so that one end of the lens touched the center line of the screen. The first end was marked, and the lens was moved along the diameter until the second end touched the center line of the screen, after which the data button was pressed again to mark the second end. Typically, two diameter measurements are performed and the average is recorded in the data sheet.

[0329] The water content (WC) was determined by weight. The lenses were equilibrated in the packaging solution for 24 hours. Three test lenses were removed from the packaging solution using a sponge-tipped swab and placed on a blotting wipe moistened with the packaging solution. Both sides of the lens were brought into contact with the wipe. Using tweezers, the test lenses were placed on a weighing pan and weighed. Two more sets of samples were prepared and weighed. All weight measurements were performed three times, and the average of these values ​​was used in the calculation. The wet weight was defined as the combined weight of the weighing pan and wet lenses minus the weight of the weighing pan alone.

[0330] Dry weight was measured by placing the sample dish in a vacuum oven preheated to 60°C for 30 minutes. Vacuum was applied until the pressure reached at least 1 inch Hg, although lower pressures were also acceptable. The vacuum valve and pump were turned off, and the lens was dried for at least 12 hours (usually overnight). The purge valve was opened, and dry air or dry nitrogen gas was introduced. The oven was allowed to reach atmospheric pressure. The weighing dish was removed and weighed. Dry weight was defined as the total weight of the weighing dish and the dry lens minus the weight of the weighing dish alone. The moisture content of the test lens was calculated as follows: % moisture content = (wet weight - dry weight) / wet weight × 100. The mean and standard deviation of the moisture content were calculated, and the mean was reported as the percentage moisture content of the test lens.

[0331] The weight increase of the grafted lens was calculated from "average dry weight of the grafted lens - average dry weight of the base lens" and expressed as a percentage. Both the grafted lens and the base lens were equilibrated in deionized water for several hours to remove any residual salts. Typically, the weights of at least three lenses were measured for each sample, and the average value was calculated.

[0332] The refractive index (RI) of contact lenses was measured using a Leica ARIAS 500 Abbe refractometer in manual mode or a Reichert ARIAS 500 Abbe refractometer in automatic mode, at a prism gap distance of 100 micrometers. The instruments were calibrated at 20°C (±0.2°C) using deionized water. The prism assembly was opened, and the test lens was placed on the lower prism between the magnetic dots closest to the light source. If the prism was dry, a few drops of saline solution were applied to the bottom prism. The front curved portion of the lens was brought into contact with the bottom prism. The prism assembly was then closed. After adjusting the control unit so that the shadow lines appeared in the reticle field of view, the refractive index was measured. The refractive index (RI) measurements were performed on five test lenses. The average refractive index (RI) calculated from the five measurements was recorded as the refractive index, along with its standard deviation.

[0333] Oxygen permeability (Dk) was determined using the polarographic method outlined in ISO 9913-1:1996 and ISO 18369-4:2006, with the following modifications. Measurements were performed in an environment containing 2.1% oxygen, created by equipping the test chamber with nitrogen and air inlets set to an appropriate ratio of, for example, 1800 mL / min of nitrogen and 200 mL / min of air. t / Dk was calculated using the controlled oxygen concentration. Borate-buffered saline was used. Dark current was measured using a pure humidified nitrogen environment instead of using an MMA lens. The lens was not wiped before measurement. Four lenses were stacked instead of using lenses of various thicknesses (t) measured in centimeters. A curved sensor was used instead of a flat sensor, with a radius of 7.8 mm. Calculations for the 7.8 mm radius sensor and 10% (v / v) airflow were performed as follows. Dk / t=(measured current - dark current)×(2.97×10-8mL O2) / (μA-sec-cm 2 -mmHg)

[0334] Edge correction was associated with the material's Dk.

[0335] For all Dk values ​​less than 90 bars, t / Dk (edge ​​correction) = [1 + (5.88 × t)] × (t / Dk)

[0336] For Dk values ​​between 90 and 300 bars, t / Dk (edge ​​correction) = [1 + (3.56 × t)] × (t / Dk)

[0337] For Dk values ​​greater than 300 bars, t / Dk (edge ​​correction) = [1 + (3.16 × t)] × (t / Dk)

[0338] The non-edge-corrected Dk was calculated from the reciprocal of the slope obtained from the linear regression analysis of the data, where the x variable was the central thickness in centimeters and the y variable was the t / Dk value. On the other hand, the edge-corrected Dk (EC Dk) was calculated from the reciprocal of the slope obtained from the linear regression analysis of the data, where the x variable was the central thickness in centimeters and the y variable was the edge-corrected t / Dk value. The obtained Dk values ​​were reported in bars.

[0339] Lens wetting was measured using a calibrated Kruss K100 surface tensile meter at room temperature (23±4°C) and a modified Wilhelmy plate method with a surfactant-free borate-buffered saline as the probe solution. All equipment had to be clean and dry, and vibrations around the equipment had to be kept to a minimum during the test. Wetting is usually reported as the forward contact angle (Kruss DCA). The surface tensile meter was equipped with a humidity generator, and temperature and humidity gauges were placed inside the surface tensile meter chamber. Relative humidity was maintained at 70±5%. The experiment was performed by immersing lens samples of known circumference in a packaging solution of known surface tension while measuring the force on the sample due to wetting using a highly sensitive balance. The forward contact angle of the packaging solution on the lens was determined from the force data collected during sample immersion. The backward contact angle was similarly determined from the force data while the sample was being removed from the liquid. The Wilhelmy plate method is based on the following formula: Fg = γρcosθ - Equation B, where F = wetting force between the liquid and the lens (mg), and g = acceleration due to gravity (980.665 cm / s²). 2) is where γ = surface tension of the probe solution (dyne / cm), ρ = circumference of the contact lens in the liquid / lens meniscus (cm), θ = dynamic contact angle (degrees), and B = buoyancy (mg). B is zero at zero depth of immersion. Typically, the test specimen was cut from the central region of the contact lens. Each specimen was approximately 5 mm wide and 14 mm long, attached to a metal clip using plastic tweezers, pierced with a metal wire hook, and equilibrated in the packaging solution for at least 3 hours. Each sample was then circulated four times, and the results were averaged to obtain the advancing and receding contact angles of the lens. A typical measurement rate was 12 mm / min. During data acquisition and analysis, the sample remained completely immersed in the packaging solution without contact with the metal clip. The reported advancing and receding contact angles of the experimental lens were obtained by averaging the values ​​from five individual lenses.

[0340] Lens wettability was measured using the KRUSS DSA-100™ instrument with a stationary droplet technique at room temperature, and deionized water was used as the probe solution (stationary droplet). The lenses to be tested were rinsed with deionized water to remove the filling solution. Each test lens was placed on lint-free blotting paper moistened with the filling solution. Both sides of the lens were brought into contact with the blotting paper to remove surface water without drying the lens. To ensure proper planarization, the lenses were placed "dish-side down" on the convex surface of the plastic mold for the contact lens. The plastic mold and lens were placed in a droplet instrument holder to ensure proper central syringe alignment. A 3-4 microliter droplet of deionized water was formed on the tip of a syringe using DSA 100-Drop Shape Analysis software to ensure that the droplet reliably dripped away from the lens. The droplet was smoothly released onto the lens surface by moving the needle downwards. The needle was immediately retrieved after dispensing the droplet. The droplet remained in equilibrium on the lens for 5–10 seconds, and the contact angle was measured between the droplet image and the lens surface. Typically, 3–5 lenses were evaluated, and the average contact angle was reported.

[0341] The mechanical properties of the contact lenses were measured using an Instron model 1122 or 5542 tensile testing machine equipped with a load cell and pneumatic grip control. A lens with a diopter of -1 is considered to have a preferred lens geometry due to its uniform thickness profile in the center. Dogbone-shaped specimens cut from a lens with a diopter of -1.00, having a length of 0.522 inches, an ear width of 0.276 inches, and a neck width of 0.213 inches, were placed in the grip and stretched to fracture at a constant strain rate of 2 inches per minute. The center thickness of the dogbone specimens was measured using an electronic thickness gauge before testing. The initial gauge length (L) of the specimen was measured. o ) and sample length at fracture (L f The following was measured: At least five specimens of each composition were measured, and the average value was used to calculate the percentage elongation to fracture. Percent elongation = [(L f -L o ) / L o ] × 100. The modulus (M) was calculated as the slope of the initial straight portion of the stress-strain curve, and the unit of the modulus of elasticity is pounds per square inch or psi. Tensile strength (TS) was calculated from the peak load and the original cross-sectional area. Tensile strength = peak load divided by the original cross-sectional area, and the unit of tensile strength is psi. Toughness was calculated from the energy to break and the original volume of the sample. Toughness = energy to break divided by the original volume of the sample. The unit of toughness is in-lbs / in 3 Elongation to break (ETB) was also recorded as a percentage of the strain at the time of fracture.

[0342] The present invention will now be described with reference to the following embodiments. Before describing some exemplary embodiments of the present invention, it will be understood that the present invention is not limited to the details of the configuration or processing steps revealed in the following description. Other embodiments of the present invention are possible and can be practiced or carried out in various ways.

[0343] The present invention will now be described with reference to the following embodiments. Before describing some exemplary embodiments of the present invention, it will be understood that the present invention is not limited to the details of the configuration or processing steps revealed in the following description. Other embodiments of the present invention are possible and can be practiced or carried out in various ways.

[0344] The following abbreviations are used throughout the examples and have the following meanings. BC: Curved base or back plastic mold made from PP, TT, Z, or blends thereof. FC: Curved front plastic mold made from PP, TT, Z, or blends thereof. PP: Polypropylene, a homopolymer of propylene. TT: Tuftec (Asahi Kasei Chemicals), a hydrogenated styrene-butadiene block copolymer. Z: Zeonor (Nippon Zeon Co Ltd), a polycycloolefin thermoplastic polymer. RMM: Reactive Monomer Mixture LED: Light-emitting diode DMA: N,N-dimethylacrylamide (Jarchem) HEMA: 2-hydroxyethyl methacrylate (Bimax) DPPM: (diphenylphosphoryl)-(4-vinylphenyl)-methanone

[0345] [ka] PVP K90: Poly(N-vinylpyrrolidone) [CAS 9003-39-8] (Ashland) mPDMS: Mono-n-butyl-terminated monomethacrylateoxypropyl-terminated polydimethylsiloxane (M n (=800-1000 Daltons) (Gelest) SiMAA: 2-Propenic acid, 2-methyl-2-hydroxy-3-[3-[1,3,3,3-tetramethyl-1-[(trimethylsilyl)oxy]disiloxanyl]propoxy]propyl ester (Toray), or 3-(3-(1,1,1,3,5,5,5-heptamethyltrisiloxane-3-yl)propoxy)-2-hydroxypropyl methacrylate HO-mPDMS(n=4): Mono-n-butyl-terminated mono-(2-hydroxy-3-methacrylateoxypropyl)-propyl ether-terminated polydimethylsiloxane (Ortec or DSM-Polymer Technology Group)

[0346] [ka] HO-mPDMS(n=15): Mono-n-butyl-terminated mono-(2-hydroxy-3-methacrylateoxypropyloxy)-propyl-terminated polydimethylsiloxane (M n (=1400 Daltons) (Ortec or DSM-Polymer Technology Group)

[0347] [ka] TEGDMA: Tetraethylene glycol dimethacrylate (Esstech) Omnirad 403: Bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide Omnirad 1173: 2-Hydroxy-2-methyl-1-phenylpropanone (IGM Resins) Omnirad 1700: A mixture of 25 wt% Omnirad 403 and 75 wt% Omnirad 1173 (IGM Resins) Omnirad 1870: A mixture of 70 wt% Omnirad 403 and 30 wt% Omnirad 1173 (IGM Resins) Omnirad 819: Bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide [CAS 162881-26-7] (IGM Resins) AIBN: Azobisisobutyronitrile [CAS 78-67-1] Norbloc: 2-(2'-hydroxy-5-methacrylyloxyethylphenyl)-2H-benzotriazole (Janssen) RB247: 1,4-Bis[2-methacrylateoxyethylamino]-9,10-anthraquinone [CAS#109561-07-1] IMT Blue: 1-amino-4-((4-(2-bromoacrylamide)-2-sulfonatophenyl)amino)-910-dioxo-910-dihydroanthracene-2-sulfonate sodium.

[0348] [ka] DIW: Deionized water IPA: Isopropyl alcohol 3E3P:3-ethyl3-pentanol D3O: 3,7-dimethyl-3-octanol (Vigon) PS: Borate buffer package solution: 18.52 grams (300 mmol) of boric acid, 3.7 grams (9.7 mmol) of sodium borate decahydrate, and 28 grams (197 mmol) of sodium sulfate were dissolved in sufficient deionized water and filled a 2-liter volumetric flask. WC: Water content (weight%) EC Dk: Edge-corrected oxygen gas permeability (barrel) M: Modulus of elasticity (psi) TS: Tensile strength (psi) ETB: Elongation at Break (%) RI: Refractive index Droplet:Advanced contact angle (degrees) mm: millimeters cm: centimeter μm: micrometer nm: nanometer L: liter mL: milliliter μL: microliter mW: milliwatts g: grams mol: mole g / mol: grams / mol mg: milligrams μg: microgram min: minutes Da or Dalton: Grams / Mole kDa: Kilodalton

[0349] Example 1: MAPO inactivation and subsequent grafting RMM was prepared consisting of 77 wt percent of the formulations listed in Table 1 and 23 wt percent of the diluent D3O. The RMM was then filtered through a 3 μm filter using a stainless steel syringe and degassed by applying a vacuum (approximately 40 mmHg). Approximately 75 μL of the reactive mixture was introduced into a Zeonor FC using nitrogen gas atmosphere and approximately 0.5 percent oxygen gas. Next, a Zeonor BC was placed on the FC, thereby forming a lens mold assembly of minus 1 diopter. Pallets containing eight lens mold assemblies each were transported through a curing tunnel, during which the pallets were subjected to a curing rate of approximately 4.5 mW / cm² on the surface of the pallets. 2 Irradiation was performed using 435nm LED light with an intensity of 65°C for a total of 10 minutes. The light source was positioned on a pallet. The BC was mechanically removed under yellow illumination. The pallet holding the FC with the bonded lens was stored in a nitrogen atmosphere and in the dark until further use.

[0350] [Table 3]

[0351] Working under yellow light inside the glove box, the FC, with the lens still attached, was placed on the mold jig shown in Figure 2 and mounted on an optical lens forming apparatus equipped with a digital light projection unit that modulates light using a micromirror device and directs it towards the FC and the attached lens. The light source of the apparatus was 53 mW / cm². 2 The LED was 405 nanometers with an intensity of . Lens 1A on the mold jig was equilibrated under ambient conditions in air, and then irradiated with image 3A for about 30 seconds as shown in Figure 3. Another lens 1B on another mold jig was equilibrated under ambient conditions in air, and then irradiated with image 3A for about 60 seconds as shown in Figure 3. The imaged lenses and mold jigs were then placed in a glove box containing nitrogen gas atmosphere and equilibrated under these inert conditions. Once equilibrated, about 150 microliters of a degassed 2.0 wt% solution of 50:50 (v / v) 1-propanol:IMT blue was added. The DIW was distributed onto the lens attached to the FC on the mold jig. After 6 minutes (sufficient time for the dye solution to diffuse into the lens, but not long enough to affect lens adhesion to the FC), the mold fixture was irradiated for approximately 150 seconds under nitrogen using the same 405 nanometer light source with Image 3B (a 9 mm diameter spot with peripheral lettering) as shown in Figure 3, thereby grafting the dye onto the lens at locations where the retained monoacylphosphine oxide groups were present.

[0352] The lens was isolated by removing the mold jigs from the apparatus and mechanically removing the FC. The lens was then immersed in a 70% (v / v) IPA aqueous solution for 15 hours, rinsed twice with DIW and twice with PS, and then stored in PS in a vial.

[0353] Micrographs of example lenses 1A and 1B are shown in Figure 4, demonstrating that inactivation of the selected region (image 3A) was successful in both lenses, but the resolution of image 3A is dependent on the amount of inactivation energy applied and increases with increasing energy. Furthermore, the micrographs show that partially inactivated or grayscale regions can be generated by modulating the amount of inactivation energy within or across different selected regions. In any case, extensive patterns, markings, and barcodes can be fabricated using the inactivation process following dye grafting.

[0354] Example 2: Apodized lens with markings (predictive) Example 1 is repeated, except that the RMM consists of the formulation components listed in Table 2, contains no diluent, image 3A containing the numbers 123 is projected onto the peripheral ring surrounding the optical zone of the lens, and image 3B is a spot image with an intensity gradient that increases linearly from the center to the edge of the lens.

[0355] [Table 4]

[0356] Example 3: Thermo-cured crosslinked substrate network lens (predictive) Example 2 is repeated, except that the RMM is shown in Table 3 and the crosslinked substrate network lens is fabricated by thermal free radical copolymerization at a temperature of 60°C to 100°C.

[0357] [Table 5]

[0358] [Implementation Method] (1) An ophthalmic device, a) A step of providing a reactive composition, wherein the reactive composition comprises (i) a polymerization initiator capable of forming two or more free radical groups upon first activation, wherein at least one of the free radical groups is further activatable by subsequent activation, (ii) one or more ethylenically unsaturated compounds, and (iii) a crosslinking agent. b) A step of subjecting the reactive composition to a first activation step, wherein the reactive composition polymerizes thereto to form a crosslinked substrate network containing covalently bonded activatable free radical initiators, c) A step of inactivating at least a portion of the covalently bonded activatable free radical initiator in one or more selected regions of the crosslinked substrate network so that the crosslinked substrate network contains retained covalently bonded activatable free radical initiator outside of the one or more selected regions, d) A step of contacting the crosslinked substrate network with a grafting composition containing one or more ethylenically unsaturated compounds, wherein the contact is carried out under conditions such that the grafting composition penetrates into the crosslinked substrate network. e) A step of activating the retained covalently bonded activatable free radical initiator so that the grafted composition polymerizes with the crosslinked substrate network, thereby forming a grafted polymer network outside the selected region, An ophthalmic device formed by a process that includes [a specific term]. (2) The ophthalmic apparatus according to Embodiment 1, wherein the inactivation in step (c) is spatially varied within the ophthalmic apparatus. (3) The ophthalmic apparatus according to Embodiment 1 or 2, wherein the inactivation step (c) is achieved by irradiation at a wavelength capable of activating the initiator, and the initiation is performed in an atmosphere containing oxygen gas. (4) The ophthalmic device according to Embodiment 1, wherein the grafting composition in step (d) contains a crosslinking agent. (5) The ophthalmic device according to Embodiment 1, wherein the grafting composition in step (d) does not contain a crosslinking agent.

[0359] (6) The ophthalmic device according to Embodiment 1, wherein in step (c), only a portion of the covalently bonded activatable free radical initiator is inactivated in the selected region, and step (e) further comprises the step of forming a grafted network in the selected region. (7) The one or more ethylenically unsaturated compounds of step (a) are (meth)acrylate, (meth)acrylamide, styryl, vinyl, N-vinyl lactam, N-vinylamide, O-vinyl ether, O-vinyl carbonate, O-vinyl carbamate, C 2~12 Alkenil, C 2~12 Alkenylphenyl, C 2~12 Alkenylnaphthyl, and C 2~6 Alkenylphenyl-C 1~6 An ophthalmic device according to any one of embodiments 1 to 6, comprising one or more polymerizable groups independently selected from alkyl groups. (8) The one or more ethylenically unsaturated compounds of step (d) are (meth)acrylate, (meth)acrylamide, styryl, vinyl, N-vinyl lactam, N-vinylamide, O-vinyl ether, O-vinyl carbonate, O-vinyl carbamate, C 2~12 Alkenil, C 2~12 Alkenylphenyl, C 2~12 Alkenylnaphthyl, and C 2~6 Alkenylphenyl-C 1~6 An ophthalmic device according to any one of embodiments 1 to 7, comprising one or more polymerizable groups independently selected from alkyl groups. (9) The polymerization initiator is a bisacylphosphine oxide, a bisacylphosphine oxide, a diazo compound, a diperoxide compound, azobis(monoacylphosphine oxide), azobis(monoacylphosphine oxide), peroxybis(monoacylphosphine oxide), peroxybis(monoacylphosphine oxide), azobis(α-hydroxyketone), peroxybis(α-hydroxyketone), azobis(1,2-diketone), peroxybis(1,2-diketone), a germanium compound, tert-butyl 7-methyl-7-(tert-butylazo)peroxyoctanoate, or a combination thereof, as described in any of Embodiments 1 to 8. (10) The ophthalmic device according to any one of Embodiments 1 to 9, wherein the polymerization initiator is bisacylphosphine oxide or bis(acyl)phosphine oxide.

[0360] (11) An ophthalmic device according to any one of Embodiments 1 to 10, wherein the hydrogel is in the form of a hydrogel, the reactive composition contains one or more silicone-containing components, and the grafted composition contains one or more hydrophilic reactive components. (12) An ophthalmic device according to any one of Embodiments 1 to 11, wherein the reactive composition, the grafting composition, or both the reactive composition and the grafting composition contain one or more additives selected from UV absorbers, phototautomorphic compounds, pharmaceutical compounds, nutritional supplements, antimicrobial compounds, reactive colorants, pigments, copolymerizable dyes, nonpolymerizable dyes, release agents, wetting agents, and release agents. (13) An ophthalmic device according to any one of embodiments 1 to 12, further comprising the step of contacting the crosslinked substrate network with a second grafting composition containing one or more ethylenically unsaturated compounds, thereby activating retained covalently bonded activatable free radical initiators, so that the second grafting composition polymerizes with the crosslinked substrate network outside the selected region and optionally partially within the selected region. (14) The ophthalmic device according to any one of embodiments 1 to 13, wherein steps (a) and (b) are performed within a mold assembly comprising a front mold and a rear mold, the front mold and the rear mold defining and sealing a cavity in the shape of the ophthalmic device between them, and process steps (c), (d), and (e) are performed within the mold assembly after the rear mold has been removed. (15) The ophthalmic device according to any one of embodiments 1 to 14, wherein the ophthalmic device is selected from the group consisting of contact lenses, intraocular lenses, punctal plugs, and ocular implants.

[0361] (16) The ophthalmic device according to Embodiment 15, wherein the ophthalmic device is a contact lens or an intraocular lens. (17) An ophthalmic device which is a reaction product of a composition, wherein the composition is a) A crosslinked substrate network containing covalently bonded activatable free radical initiators outside of one or more selected regions and optionally partially within said one or more selected regions, b) An ophthalmic device comprising a grafting composition containing one or more ethylenically unsaturated compounds, wherein the grafting composition is localized in the crosslinked substrate network that holds covalently activatable free radical initiators. (18) The ophthalmic device according to Embodiment 17, wherein the concentration of the retained covalently bonded activatable free radical initiator varies spatially within the crosslinked substrate network. (19) The ophthalmic device according to Embodiment 17 or 18, wherein the crosslinked substrate network is a reaction product of a reactive composition comprising (i) a polymerization initiator capable of forming two or more free radical groups upon first activation, wherein at least one of the free radical groups is further activatable by subsequent activation, (ii) one or more ethylenically unsaturated compounds, and (iii) a crosslinking agent. (20) The ophthalmic device according to Embodiment 19, wherein the polymerization initiator is a bisacylphosphine oxide, a diazo compound, a diperoxide compound, azobis(monoacylphosphine oxide), azobis(monoacylphosphine oxide), peroxybis(monoacylphosphine oxide), peroxybis(monoacylphosphine oxide), azobis(α-hydroxyketone), peroxybis(α-hydroxyketone), azobis(1,2-diketone), peroxybis(1,2-diketone), a germanium compound, tert-butyl 7-methyl-7-(tert-butylazo)peroxyoctanoate, or a combination thereof.

[0362] (21) The ophthalmic device according to Embodiment 20, wherein the polymerization initiator is bisacylphosphine oxide or bis(acyl)phosphine oxide. (22) The ophthalmic device according to Embodiment 17, wherein the covalently bonded activatable free radical initiator is selected from the group consisting of monoacylphosphine oxide, bisacylphosphine oxide, and combinations thereof. (23) The ophthalmic device according to Embodiment 17, wherein the crosslinked substrate network is formed by the thermal free radical polymerization of a reactive monomer mixture comprising at least one reactive component having at least one pendant group selected from the group consisting of monoacylphosphine oxide, bisacylphosphine oxide, and combinations thereof. (24) The one or more ethylenically unsaturated compounds in the grafted composition and the reactive composition are (meth)acrylate, (meth)acrylamide, styryl, vinyl, N-vinyl lactam, N-vinylamide, O-vinyl ether, O-vinyl carbonate, O-vinyl carbamate, C 2~12 Alkenil, C 2~12 Alkenylphenyl, C 2~12 Alkenylnaphthyl, and C 2~6 Alkenylphenyl-C 1~6An ophthalmic device according to any one of embodiments 17 to 23, comprising a polymerizable group independently selected from alkyl groups. (25) The ophthalmic device according to any one of embodiments 17 to 24, wherein the crosslinked substrate network is formed from one or more silicone-containing components, and the grafted composition contains a hydrophilic reactive component.

[0363] (26) The ophthalmic device according to any one of embodiments 17 to 24, wherein the crosslinked substrate network is formed from one or more hydrophilic reactive components, and the grafted composition contains one or more silicone-containing components. (27) The ophthalmic device according to any one of embodiments 17 to 24, wherein the crosslinked substrate network is formed from one or more hydrophilic reactive components, and the grafted composition contains hydrophilic reactive components. (28) The ophthalmic device according to any one of embodiments 17 to 24, wherein the crosslinked substrate network is formed from one or more silicone-containing components, and the grafted composition contains one or more silicone-containing components. (29) An ophthalmic device according to any one of embodiments 17 to 28, wherein the crosslinked substrate network, the grafted composition, or both the crosslinked substrate network and the grafted composition contain one or more additives selected from UV absorbers, phototautomorphic compounds, pharmaceutical compounds, nutritional supplements, antimicrobial compounds, colorants, pigments, dyes, dyes, release agents, and wetting agents. (30) The ophthalmic device according to any one of embodiments 17 to 29, wherein the ophthalmic device is selected from the group consisting of contact lenses, intraocular lenses, punctal plugs, and ocular implants.

[0364] (31) The ophthalmic device according to Embodiment 30, wherein the ophthalmic device is a contact lens or an intraocular lens. (32) A process for manufacturing an ophthalmic device, a) A step of providing a reactive composition, wherein the reactive composition comprises (i) a polymerization initiator capable of forming two or more free radical groups upon first activation, wherein at least one of the free radical groups is further activatable by subsequent activation, (ii) one or more ethylenically unsaturated compounds, and (iii) a crosslinking agent. b) A step of subjecting the reactive composition to a first activation step, wherein the reactive composition polymerizes thereto to form a crosslinked substrate network containing covalently bonded activatable free radical initiators, c) A step of inactivating at least a portion of the covalently bonded activatable free radical initiator in one or more selected regions of the crosslinked substrate network so that the crosslinked substrate network contains retained covalently bonded activatable free radical initiator outside of the one or more selected regions, d) A step of contacting the crosslinked substrate network with a grafting composition containing one or more ethylenically unsaturated compounds, wherein the contact is carried out under conditions such that the grafting composition penetrates into the crosslinked substrate network. e) A step of activating the retained covalently bonded activatable free radical initiator so that the grafted composition polymerizes with the crosslinked substrate network, thereby forming a grafted polymer network outside the selected region, A process that includes this. (33) The ophthalmic apparatus according to Embodiment 32, wherein the inactivation in step (c) is spatially varied within the ophthalmic apparatus. (34) The ophthalmic apparatus according to embodiment 32 or 33, wherein the deactivation step (c) is achieved by irradiation in an oxygen gas atmosphere. (35) The process according to Embodiment 32, wherein the grafting composition in step (d) contains a crosslinking agent.

[0365] (36) The process according to Embodiment 32, wherein the grafting composition in step (d) does not contain a crosslinking agent. (37) The process according to Embodiment 32, wherein in step (c), only a portion of the covalently bonded activatable free radical initiator is inactivated in the selected region, and step (e) partially comprises forming a grafted network in the selected region. (38) The one or more ethylenically unsaturated compounds of step (a) are (meth)acrylate, (meth)acrylamide, styryl, vinyl, N-vinyl lactam, N-vinylamide, O-vinyl ether, O-vinyl carbonate, O-vinyl carbamate, C 2~12 Alkenil, C 2~12 Alkenylphenyl, C 2~12 Alkenylnaphthyl, and C 2~6 Alkenylphenyl-C 1~6 The process according to any one of embodiments 32 to 37, comprising one or more polymerizable groups independently selected from alkyl groups. (39) The one or more ethylenically unsaturated compounds of step (e) are (meth)acrylate, (meth)acrylamide, styryl, vinyl, N-vinyl lactam, N-vinylamide, O-vinyl ether, O-vinyl carbonate, O-vinyl carbamate, C 2~12 Alkenil, C 2~12 Alkenylphenyl, C 2~12 Alkenylnaphthyl, and C 2~6 Alkenylphenyl-C 1~6 The process according to any one of embodiments 32 to 38, comprising one or more polymerizable groups independently selected from alkyl groups. (40) The process according to any one of Embodiments 32 to 39, wherein the polymerization initiator is a bisacylphosphine oxide, a diazo compound, a diperoxide compound, azobis(monoacylphosphine oxide), azobis(monoacylphosphine oxide), peroxybis(monoacylphosphine oxide), peroxybis(monoacylphosphine oxide), azobis(α-hydroxyketone), peroxybis(α-hydroxyketone), azobis(1,2-diketone), peroxybis(1,2-diketone), a germanium compound, tert-butyl 7-methyl-7-(tert-butylazo)peroxyoctanoate, or a combination thereof.

[0366] (41) The process according to Embodiment 40, wherein the polymerization initiator is bisacylphosphine oxide or bis(acyl)phosphine oxide. (42) The process according to any one of embodiments 32 to 40, wherein the hydrogel is in the form of a hydrogel, the reactive composition contains one or more silicone-containing components, and the grafting composition contains one or more hydrophilic reactive components. (43) The process according to any one of embodiments 32 to 42, wherein the reactive composition, the grafting composition, or both the reactive composition and the grafting composition contain one or more additives selected from UV absorbers, phototautomorphic compounds, pharmaceutical compounds, nutritional supplements, antimicrobial compounds, reactive colorants, pigments, copolymerizable dyes, nonpolymerizable dyes, release agents, wetting agents, and release agents. (44) The process according to any one of embodiments 32 to 43, further comprising, after step (e), contacting the crosslinked substrate network with a second grafting composition containing one or more ethylenically unsaturated compounds to activate retained covalently bonded activatable free radical initiators so that the second grafting composition polymerizes with the crosslinked substrate network outside the selected region and optionally partially within the selected region. (45) The process according to any one of embodiments 32 to 44, wherein process steps (a) and (b) are performed in a mold assembly comprising a front mold and a rear mold, the front mold and the rear mold defining and sealing a cavity in the shape of the ophthalmic device between them, and process steps (c), (d), and (e) are performed in the mold assembly after the rear mold has been removed.

[0367] (46) The ophthalmic device according to Embodiment 1 or Embodiment 17, wherein the selected region forms a pattern. (47) The ophthalmic device according to Embodiment 1 or Embodiment 17, wherein the selected region forms a reference marker. (48) The ophthalmic device according to Embodiment 1 or Embodiment 17, wherein the selected area forms a barcode.

Claims

1. An ophthalmic device, a) A step of providing a reactive composition, wherein the reactive composition comprises (i) a polymerization initiator capable of forming two or more free radical groups upon first activation, wherein at least one of the free radical groups is further activatable by subsequent activation, (ii) one or more ethylenically unsaturated compounds, and (iii) a crosslinking agent. b) A step of subjecting the reactive composition to a first activation step, wherein the reactive composition polymerizes thereto to form a crosslinked substrate network containing covalently bonded activatable free radical initiators, c) A step of inactivating at least a portion of the covalently bonded activatable free radical initiator in one or more selected regions of the crosslinked substrate network so that the crosslinked substrate network contains retained covalently bonded activatable free radical initiator outside of the one or more selected regions, d) A step of contacting the crosslinked substrate network with a grafting composition containing one or more ethylenically unsaturated compounds, wherein the contact is carried out under conditions such that the grafting composition penetrates into the crosslinked substrate network. e) A step of activating the retained covalently bonded activatable free radical initiator so that the grafted composition polymerizes with the crosslinked substrate network, thereby forming a grafted polymer network outside the selected region, An ophthalmic device formed by a process that includes [a specific term].

2. The ophthalmic apparatus according to claim 1, wherein the inactivation in step (c) is spatially varied within the ophthalmic apparatus.

3. The ophthalmic apparatus according to claim 1 or 2, wherein the inactivation step (c) is achieved by irradiation at a wavelength capable of activating the initiator, and the initiation is performed in an atmosphere containing oxygen gas.

4. The ophthalmic device according to claim 1, wherein the grafting composition in step (d) contains a crosslinking agent.

5. The ophthalmic device according to claim 1, wherein the grafting composition in step (d) does not contain a crosslinking agent.

6. The ophthalmic device according to claim 1, wherein in step (c), only a portion of the covalently bonded activatable free radical initiator is inactivated in the selected region, and step (e) partially comprises forming a grafted network within the selected region.

7. The one or more ethylenically unsaturated compounds in step (a) are (meth)acrylate, (meth)acrylamide, styryl, vinyl, N-vinyl lactam, N-vinylamide, O-vinyl ether, O-vinyl carbonate, O-vinylcarbamate, C ２～１２ Alkenil, C ２～１２ Alkenylphenyl, C ２～１２ Alkenylnaphthyl, and C ２～６ Alkenylphenyl-C １～６ The ophthalmic device according to claim 1, comprising one or more polymerizable groups independently selected from alkyl groups.

8. The one or more ethylenically unsaturated compounds in step (d) are (meth)acrylate, (meth)acrylamide, styryl, vinyl, N-vinyl lactam, N-vinyl amide, O-vinyl ether, O-vinyl carbonate, O-vinyl carbamate, C ２～１２ alkenyl, C ２～１２ alkenyl phenyl, C ２～１２ alkenyl naphthyl, and C ２～６ alkenyl phenyl-C １～６ The ophthalmic device according to claim 1, comprising one or more polymerizable groups independently selected from alkyl.

9. The polymerization initiator is a bisacylphosphine oxide, a bisacylphosphine oxide, a diazo compound, a diperoxide compound, azobis(monoacylphosphine oxide), azobis(monoacylphosphine oxide), peroxybis(monoacylphosphine oxide), peroxybis(monoacylphosphine oxide), azobis(α-hydroxyketone), peroxybis(α-hydroxyketone), azobis(1,2-diketone), peroxybis(1,2-diketone), a germanium compound, tert-butyl7-methyl-7-(tert-butylazo)peroxyoctanoate, or a combination thereof, as described in claim 1.

10. The ophthalmic device according to claim 1, wherein the polymerization initiator is bisacylphosphine oxide or bis(acyl)phosphine oxide.

11. The ophthalmic device according to claim 1, wherein the hydrogel is in the form of a hydrogel, the reactive composition contains one or more silicone-containing components, and the grafted composition contains one or more hydrophilic reactive components.

12. The ophthalmic device according to claim 1, wherein the reactive composition, the grafting composition, or both the reactive composition and the grafting composition contain one or more additives selected from UV absorbers, phototautomorphic compounds, pharmaceutical compounds, nutritional supplements, antimicrobial compounds, reactive colorants, pigments, copolymerizable dyes, nonpolymerizable dyes, release agents, wetting agents, and release agents.

13. The ophthalmic apparatus according to claim 1, further comprising the step of contacting the crosslinked substrate network with a second grafting composition containing one or more ethylenically unsaturated compounds, thereby activating retained covalently bonded activatable free radical initiators, so that the second grafting composition polymerizes with the crosslinked substrate network outside the selected region and optionally partially within the selected region.

14. The ophthalmic device according to claim 1, wherein steps (a) and (b) are performed within a mold assembly comprising a front mold and a rear mold, the front mold and the rear mold defining and sealing a cavity in the shape of the ophthalmic device between them, and process steps (c), (d), and (e) are performed within the mold assembly after the rear mold has been removed.

15. The ophthalmic device according to claim 1, wherein the ophthalmic device is selected from the group consisting of contact lenses, intraocular lenses, punctal plugs, and ocular implants.

16. The ophthalmic device according to claim 15, wherein the ophthalmic device is a contact lens or an intraocular lens.

17. An ophthalmic device which is a reaction product of a composition, wherein the composition is a) A crosslinked substrate network containing covalently bonded activatable free radical initiators outside of one or more select regions and optionally partially within the one or more select regions, b) An ophthalmic device comprising a grafting composition containing one or more ethylenically unsaturated compounds, wherein the grafting composition is localized in the crosslinked substrate network that holds covalently activatable free radical initiators.

18. The ophthalmic device according to claim 17, wherein the concentration of the retained covalently bonded, activatable free radical initiator varies spatially within the crosslinked substrate network.

19. The ophthalmic device according to claim 17 or 18, wherein the crosslinking substrate network is a reaction product of a reactive composition comprising (i) a polymerization initiator capable of forming two or more free radical groups upon first activation, wherein at least one of the free radical groups can be further activated by subsequent activation, (ii) one or more ethylenically unsaturated compounds, and (iii) a crosslinking agent.

20. The polymerization initiator is a bisacylphosphine oxide, a bisacylphosphine oxide, a diazo compound, a diperoxide compound, azobis(monoacylphosphine oxide), azobis(monoacylphosphine oxide), peroxybis(monoacylphosphine oxide), peroxybis(monoacylphosphine oxide), azobis(α-hydroxyketone), peroxybis(α-hydroxyketone), azobis(1,2-diketone), peroxybis(1,2-diketone), a germanium compound, tert-butyl7-methyl-7-(tert-butylazo)peroxyoctanoate, or a combination thereof, as described in claim 19.

21. The ophthalmic device according to claim 20, wherein the polymerization initiator is bisacylphosphine oxide or bis(acyl)phosphine oxide.

22. The ophthalmic device according to claim 17, wherein the covalently bonded activatable free radical initiator is selected from the group consisting of monoacylphosphine oxide, bisacylphosphine oxide, and combinations thereof.

23. The ophthalmic device according to claim 17, wherein the crosslinked substrate network is formed by the thermal free radical polymerization of a reactive monomer mixture comprising at least one reactive component having at least one pendant group selected from the group consisting of monoacylphosphine oxide, bisacylphosphine oxide, and combinations thereof.

24. The one or more ethylenically unsaturated compounds in the grafted composition and the reactive composition are (meth)acrylate, (meth)acrylamide, styryl, vinyl, N-vinyl lactam, N-vinylamide, O-vinyl ether, O-vinyl carbonate, O-vinylcarbamate, C ２～１２ Alkenil, C ２～１２ Alkenylphenyl, C ２～１２ Alkenylnaphthyl, and C ２～６ Alkenylphenyl-C １～６ The ophthalmic device according to claim 17, comprising a polymerizable group independently selected from alkyl groups.

25. The ophthalmic device according to claim 17, wherein the crosslinked substrate network is formed from one or more silicone-containing components, and the grafted composition contains a hydrophilic reactive component.

26. The ophthalmic device according to claim 17, wherein the crosslinked substrate network is formed from one or more hydrophilic reactive components, and the grafted composition contains one or more silicone-containing components.

27. The ophthalmic device according to claim 17, wherein the crosslinked substrate network is formed from one or more hydrophilic reactive components, and the grafted composition contains hydrophilic reactive components.

28. The ophthalmic device according to claim 17, wherein the crosslinked substrate network is formed from one or more silicone-containing components, and the grafted composition contains one or more silicone-containing components.

29. The ophthalmic device according to claim 17, wherein the crosslinked substrate network, the grafting composition, or both the crosslinked substrate network and the grafting composition contain one or more additives selected from UV absorbers, phototautomorphic compounds, pharmaceutical compounds, nutritional supplements, antimicrobial compounds, colorants, pigments, dyes, release agents, and wetting agents.

30. The ophthalmic device according to claim 17, wherein the ophthalmic device is selected from the group consisting of contact lenses, intraocular lenses, punctal plugs, and ocular implants.

31. The ophthalmic device according to claim 30, wherein the ophthalmic device is a contact lens or an intraocular lens.

32. A process for manufacturing ophthalmic devices, a) A step of providing a reactive composition, wherein the reactive composition comprises (i) a polymerization initiator capable of forming two or more free radical groups upon first activation, wherein at least one of the free radical groups is further activatable by subsequent activation, (ii) one or more ethylenically unsaturated compounds, and (iii) a crosslinking agent. b) A step of subjecting the reactive composition to a first activation step, wherein the reactive composition polymerizes thereto to form a crosslinked substrate network containing covalently bonded activatable free radical initiators, c) A step of inactivating at least a portion of the covalently bonded activatable free radical initiator in one or more selected regions of the crosslinked substrate network so that the crosslinked substrate network contains retained covalently bonded activatable free radical initiator outside of the one or more selected regions, d) A step of contacting the crosslinked substrate network with a grafting composition containing one or more ethylenically unsaturated compounds, wherein the contact is carried out under conditions such that the grafting composition penetrates into the crosslinked substrate network. e) A step of activating the retained covalently bonded activatable free radical initiator so that the grafted composition polymerizes with the crosslinked substrate network, thereby forming a grafted polymer network outside the selected region, A process that includes this.

33. The ophthalmic apparatus according to claim 32, wherein the inactivation in step (c) is spatially varied within the ophthalmic apparatus.

34. The ophthalmic apparatus according to claim 32 or 33, wherein the inactivation step (c) is achieved by irradiation in an oxygen gas atmosphere.

35. The process according to claim 32, wherein the grafting composition in step (d) contains a crosslinking agent.

36. The process according to claim 32, wherein the grafting composition in step (d) does not contain a crosslinking agent.

37. The process according to claim 32, wherein in step (c), only a portion of the covalently bonded activatable free radical initiator is inactivated in the selected region, and step (e) partially comprises forming a grafted network within the selected region.

38. The one or more ethylenically unsaturated compounds in step (a) are (meth)acrylate, (meth)acrylamide, styryl, vinyl, N-vinyl lactam, N-vinylamide, O-vinyl ether, O-vinyl carbonate, O-vinylcarbamate, C ２～１２ Alkenil, C ２～１２ Alkenylphenyl, C ２～１２ Alkenylnaphthyl, and C ２～６ Alkenylphenyl-C １～６ The process according to claim 32, comprising one or more polymerizable groups independently selected from alkyl groups.

39. The one or more ethylenically unsaturated compounds in step (e) are (meth)acrylate, (meth)acrylamide, styryl, vinyl, N-vinyl lactam, N-vinylamide, O-vinyl ether, O-vinyl carbonate, O-vinylcarbamate, C ２～１２ Alkenil, C ２～１２ Alkenylphenyl, C ２～１２ Alkenylnaphthyl, and C ２～６ Alkenylphenyl-C １～６ The process according to claim 32, comprising one or more polymerizable groups independently selected from alkyl groups.

40. The process according to claim 32, wherein the polymerization initiator is a bisacylphosphine oxide, a bisacylphosphine oxide, a diazo compound, a diperoxide compound, azobis(monoacylphosphine oxide), azobis(monoacylphosphine oxide), peroxybis(monoacylphosphine oxide), peroxybis(monoacylphosphine oxide), azobis(α-hydroxyketone), peroxybis(α-hydroxyketone), azobis(1,2-diketone), peroxybis(1,2-diketone), a germanium compound, tert-butyl7-methyl-7-(tert-butylazo)peroxyoctanoate, or a combination thereof.

41. The process according to claim 40, wherein the polymerization initiator is bisacylphosphine oxide or bis(acyl)phosphine oxide.

42. The process according to claim 32, wherein the hydrogel is in the form of a hydrogel, the reactive composition contains one or more silicone-containing components, and the grafting composition contains one or more hydrophilic reactive components.

43. The process according to claim 32, wherein the reactive composition, the grafting composition, or both the reactive composition and the grafting composition contain one or more additives selected from UV absorbers, phototautomorphic compounds, pharmaceutical compounds, nutritional supplements, antimicrobial compounds, reactive colorants, pigments, copolymerizable dyes, nonpolymerizable dyes, release agents, wetting agents, and release agents.

44. The process according to claim 32, further comprising, after step (e), contacting the crosslinked substrate network with a second grafting composition containing one or more ethylenically unsaturated compounds to activate retained covalently bonded activatable free radical initiators so that the second grafting composition polymerizes with the crosslinked substrate network outside the selected region and optionally partially within the selected region.

45. The process according to claim 32, wherein process steps (a) and (b) are performed in a mold assembly comprising a front mold and a rear mold, the front mold and the rear mold defining and sealing a cavity in the shape of the ophthalmic device between them, and process steps (c), (d), and (e) are performed in the mold assembly after the rear mold has been removed.

46. The ophthalmic apparatus according to claim 1 or claim 17, wherein the selected region forms a pattern.

47. The ophthalmic apparatus according to claim 1 or claim 17, wherein the selected region forms a reference marker.

48. The ophthalmic apparatus according to claim 1 or claim 17, wherein the selected area forms a barcode.

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