Monofunctional silicone monomers and silicone hydrogels formed therefrom

Abstract

The monofunctional silicone monomer has the formula I: [Chemical Formula I] JPEG2026514359000075.jpg26110 is represented by the structure of wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , x and y are as defined herein. The ophthalmic device having optical transparency is a polymerization product of a monomer mixture comprising (a) one or more of the monofunctional silicone monomers represented by the structure of formula I, and (b) one or more ophthalmic device-forming hydrophilic comonomers.

Description

[Technical Field]

[0001] Claim of priority This application claims priority to U.S. Provisional Patent Application No. 63 / 453,850, “Monofunctional Silicone Monomers and Silicone Hydrogels Formed Therefrom,” filed on 22 March 2023, the entirety of which is incorporated herein by reference. [Background technology]

[0002] In the field of biomedical devices such as contact lenses, various physical and chemical properties such as optical clarity, oxygen permeability, wettability, material strength, and stability are just some of the factors that must be carefully balanced to provide usable contact lenses. For example, good oxygen permeability is an important property for any contact lens material, as the cornea receives its oxygen supply only from contact with the atmosphere. Wettability is also important, as if the lens is not sufficiently wet, it will not remain lubricated and will not be comfortable to wear in the eye. Therefore, an optimal contact lens will have at least good oxygen permeability and good tear film wettability.

[0003] Hydrogels are a desirable class of materials for many biomedical applications, including contact lenses and intraocular lenses. Hydrogels are hydrated crosslinked polymer systems that contain water in equilibrium. Silicone hydrogels are a known class of hydrogels characterized by containing a silicone-containing substance. Typically, a silicone-containing monomer is copolymerized with a hydrophilic monomer by free radical polymerization, with either the silicone-containing monomer or the hydrophilic monomer acting as a crosslinker (a crosslinker is defined as a monomer having multiple polymerizable functional groups), or a separate crosslinker may be used. The advantage of silicone hydrogels over non-silicone hydrogels is that, due to the inclusion of a silicone-containing monomer, silicone hydrogels generally have higher oxygen permeability.

Summary of the Invention

[0004] According to an exemplary embodiment, the monofunctional silicone monomer has the formula I:

Chemical formula

[0005] According to another exemplary embodiment, an ophthalmic device which is a polymerization product of a monomer mixture, wherein the monomer mixture comprises

[0006] (a) one or more monofunctional silicone monomers represented by the formula I:

Chemical formula

[0007] (b) An ophthalmic device comprising one or more ophthalmic device-forming hydrophilic comonomers.

[0008] In yet another exemplary embodiment, an ophthalmic device is a polymerization product of a monomer mixture, wherein the monomer mixture is

[0009] (a) Formula I: [ka] One or more monofunctional silicone monomers represented by the structure shown. (In the formula, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 (where x and y are as defined herein),

[0010] (b) One or more ophthalmic device-forming hydrophilic comonomers, and

[0011] (c) An ophthalmic device comprising one or more non-functionalized comfort polymers.

[0012] According to yet another exemplary embodiment, a method for fabricating an ophthalmic device is:

[0013] (a) Curing a monomer mixture in a mold, wherein the monomer mixture is

[0014] (i) One or more monofunctional silicone monomers represented by the structure of formula I: [ka] (In the formula, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7(where x and y are as defined herein), and

[0015] (ii) A device containing one or more ophthalmic device-forming hydrophilic comonomers, which is cured,

[0016] (b) dry demolding of an ophthalmic device from a mold. [Modes for carrying out the invention]

[0017] The various exemplary embodiments described herein relate to the use of silicone monomers and silicone hydrogels with improved optical transparency in the formation of ophthalmic devices. Silicone hydrogels (SiHy), such as contact lenses made from hydrated crosslinked polymer materials containing silicone and a certain amount of water in equilibrium within the polymer matrix of the lens, are becoming increasingly popular because their high oxygen permeability minimizes adverse effects on corneal health. However, incorporating silicone into contact lens materials can have undesirable effects on the hydrophilicity and wettability of the silicone hydrogel. This is because silicone is hydrophobic and has a strong tendency to migrate to the lens surface exposed to air. Therefore, contact lens manufacturers have made considerable efforts to develop SiHy contact lenses with hydrophilic and wettable surfaces.

[0018] One method for modifying the hydrophilicity and wettability of SiHy contact lenses is to add hydrophilic monomers to the monomer mixture used to form the SiHy contact lenses. However, it has been discovered that adding monofunctional silicone monomers to a monomer mixture containing one or more ophthalmic device-forming hydrophilic monomers can cause phase separation of the monomer mixture during polymerization.

[0019] Another approach involves incorporating monomeric wetting / comfort agents, such as non-functionalized comfort polymers, e.g., high molecular weight hydrophilic polymers (e.g., polyvinylpyrrolidone (PVP)), into monomer mixtures to form interpenetrating network structures in lens preparation for producing naturally wettable SiHy contact lenses (i.e., wettable SiHy lenses without post-molding surface treatment). However, not all silicone-containing monomers are compatible with high molecular weight hydrophilic polymers. For example, while it may be possible to incorporate high molecular weight hydrophilic polymers as internal wetting / comfort agents into silicone hydrogel lenses, such polymers may be difficult to solubilize in reaction mixtures containing silicone-containing monomers and hydrophilic monomers such as vinyl lactams. Generally, it is desirable to use a larger amount of internal wetting / comfort agent such as PVP, thereby ensuring that the lens has a wettable and lubricating surface. However, when a monomer mixture is prepared containing a silicone monomer represented by the structure of formula I in which y is greater than 5, along with at least 6% by weight of a non-functionalized comfort polymer such as PVP based on the total weight of the monomer mixture, the reaction mixture becomes turbid during polymerization, resulting in an optically opaque lens.

[0020] The exemplary embodiments described herein overcome the above-mentioned drawbacks by using one or more monofunctional silicone monomers represented by the structure of Formula I to form ophthalmic devices such as SiHy contact lenses with improved properties such as hydrophilicity, wettability, and optical transparency. One or more monofunctional silicone monomers represented by the structure of Formula I are compatible with ophthalmic device-forming hydrophilic monomers in a monomer mixture. Furthermore, when one or more monofunctional silicone monomers represented by the structure of Formula I are present in a monomer mixture containing a non-functionalized comfort polymer in an amount of at least 6% by weight based on the total weight of the monomer mixture, they also help to solubilize non-functionalized comfort polymers such as PVP, thereby forming ophthalmic devices such as silicone hydrogels having a wettable and smooth surface and improved optical transparency.

[0021] As used herein, the term "SiHy" is understood to mean silicone hydrogel.

[0022] As used herein, the terms "hydrogel" or "hydrogel material" refer to a crosslinked polymer material having a three-dimensional polymer network structure (i.e., a polymer matrix), which is insoluble in water but, upon complete hydration, can retain at least 10 weight percent of water in its polymer matrix.

[0023] As used herein, “silicone hydrogel” or “SiHy” interchangeably refers to a hydrogel containing silicone. Silicone hydrogels (SiHy) are typically obtained by copolymerization of a polymerizable composition comprising at least one silicone-containing vinyl monomer, or at least one silicone-containing vinyl macromer, or at least one silicone-containing prepolymer having an ethylenically unsaturated group.

[0024] As used herein, the term "(meth)" represents any methyl substituent. Therefore, terms such as "(meth)acrylate" represent either methacrylate or acrylate, and "(meth)acrylamide" represents either methacrylamide or acrylamide.

[0025] In a non-limiting exemplary embodiment, the monofunctional silicone monomer used to form the ophthalmic device described herein is represented by the structure of formula I: [ka] In the formula, R 1 , R 2 , R 3 and R 4 R is independently hydrogen, alkyl group, haloalkyl group, cycloalkyl group, heterocycloalkyl group, alkenyl group, haloalkenyl group, aryl group and heteroaryl group, 5 , R 6 and R7 x is independently a linear or branched alkyl group, x is 1 to 6, and y is 3 to 5.

[0026] In one embodiment, R 1 , R 2 , R 3 and R 4 Hydrogen, C1~C 12 Alkyl alkyl groups, C1-C 12 Haloalkyl groups, C3-C 12 Cycloalkyl groups, C3-C 12 Heterocycloalkyl groups, C2-C 12 Alkenyl group, C2~C 12 Haloalkenyl group, C6~C 12 Aromatic groups and C6~C 12 It is a heteroaromatic group, R 5 , R 6 and R 7 These are independently linear or branched C1-C 12 It is an alkyl group, where x is between 1 and 6, and y is between 3 and 5.

[0027] In one embodiment, R 1 , R 2 , R 3 and R 4 R is independently a hydrogen atom and a C1-C6 alkyl group. 5 , R 6 and R 7 x is independently a linear or branched C1-C6 alkyl group, x is 1-6, and y is 3-5.

[0028] In one embodiment, R 1 , R 2 , R 3 and R 4 R is independently a C1-C3 alkyl group, 5 and R 6 R is independently a C1-C3 alkyl group, 7 x is a linear or branched C3-C6 alkyl group, x is 2-4, and y is 3-5.

[0029] Typical examples of alkyl groups used herein include, for example, linear or branched alkyl chain radicals containing 1 to about 30 carbon atoms, 1 to about 12 carbon atoms, or 1 to about 6 carbon atoms and hydrogen atoms, which may or may not be unsaturated with respect to other parts of the molecule (e.g., methyl, ethyl, n-propyl, 1-methylethyl (isopropyl), n-butyl, n-pentyl, methylene, ethylene, etc.). These may optionally contain one or more heteroatoms (e.g., O and N) or one or more halogen atoms (e.g., fluorine, chlorine, bromine, and iodine) to form haloalkyl groups.

[0030] Typical examples of cycloalkyl groups used herein include, for example, substituted or unsubstituted non-aromatic monocyclic or polycyclic ring systems containing about 3 to about 30 carbon atoms, or 3 to about 12 carbon atoms, or 3 to about 6 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, perhydronaphthyl, adamantyl and norbornyl groups, bridging ring groups or spirobicyclo groups (e.g., spiro-(4,4)-non-2-yl). These optionally contain one or more heteroatoms (e.g., O and N) to form heterocycloalkyl groups.

[0031] Typical examples of cycloalkylalkyl groups used herein include, for example, substituted or unsubstituted cyclic ring-containing radicals containing about 4 to about 30 carbon atoms, or 3 to about 6 carbon atoms, which directly bond to an alkyl group and then bond to the main structure of the monomer from any carbon of the alkyl group to form a stable structure. Examples include cyclopropylmethyl, cyclobutylethyl, and cyclopentylethyl. The cyclic ring may optionally contain one or more heteroatoms (e.g., O and N) to form a heterocycloalkylalkyl group.

[0032] Typical examples of cycloalkenyl groups used herein include, for example, substituted or unsubstituted cyclic ring-containing radicals containing about 3 to about 30 carbon atoms, or 3 to about 6 carbon atoms, and having at least one carbon-carbon double bond, such as cyclopropenyl, cyclobutenyl, and cyclopentenyl. The cyclic ring may optionally contain one or more heteroatoms (e.g., O and N) to form a heterocycloalkylalkyl group.

[0033] Typical examples of aryl groups used herein include, for example, substituted or unsubstituted monoaromatic or polyaromatic radicals containing about 6 to about 30 carbon atoms, or about 6 to about 12 carbon atoms, such as phenyl, naphthyl, tetrahydronaphthyl, indenyl, and biphenyl. These may optionally contain one or more heteroatoms (e.g., O and N) to form a heteroaryl group.

[0034] In exemplary embodiments, a monofunctional silicone monomer represented by the structure of formula I disclosed herein can be prepared according to the following reaction scheme I. [ka]

[0035] As described above, the monofunctional silicone monomer represented by the structure of Formula I disclosed herein is useful for forming ophthalmic devices with improved optical transparency. As used herein, the term “ophthalmic device” refers to devices placed inside and on the eye. These devices can provide optical correction, wound healing, drug delivery, diagnostic function, or improved appearance or effect on appearance, or a combination of these properties. Suitable ophthalmic devices include, for example, ophthalmic lenses (soft contact lenses (e.g., soft hydrogel lenses and soft non-hydrogel lenses), hard contact lenses (e.g., rigid gas-permeable lens materials), intraocular lenses, overlay lenses, ophthalmic inserts, and optical inserts). As will be understood by those skilled in the art, a lens is considered “soft” if it can be folded without breaking.

[0036] According to one or more additional non-limiting exemplary embodiments, which may be combined with one or more of the preceding paragraphs, an ophthalmic device is:

[0037] (a) Formula I: [ka] One or more monofunctional silicone monomers represented by the structure shown. (In the formula, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 (where x and y are as defined herein), and

[0038] (b) A polymerization product of a monomer mixture containing one or more ophthalmic device-forming hydrophilic comonomers.

[0039] One or more monofunctional silicone monomers represented by the structure of formula I disclosed herein may be present in the monomer mixture in an amount ranging from about 1% by weight to about 40% by weight, based on the total weight of the monomer mixture. In some embodiments, one or more silicone monomers represented by the structure of formula I disclosed herein may be present in the monomer mixture in an amount ranging from about 1% by weight to about 35% by weight, based on the total weight of the monomer mixture. In another exemplary embodiment, one or more silicone monomers represented by the structure of formula I disclosed herein may be present in the monomer mixture in an amount ranging from about 5% by weight to about 40% by weight, based on the total weight of the monomer mixture. In another exemplary embodiment, one or more silicone monomers represented by the structure of formula I disclosed herein may be present in the monomer mixture in an amount ranging from about 5% by weight to about 20% by weight, based on the total weight of the monomer mixture.

[0040] Suitable hydrophilic comonomers for ophthalmic device formation as component (b) include, for example, unsaturated carboxylic acids, acrylamides, vinyl lactams, hydroxyl-containing (meth)acrylates, hydrophilic vinyl carbonates, hydrophilic vinyl carbamates, hydrophilic oxazolones, and poly(alkene glycols) functionalized with polymerizable groups, as well as mixtures thereof. Typical examples of unsaturated carboxylic acids include, but are not limited to, methacrylic acid and acrylic acid, as well as mixtures thereof. Typical examples of acrylamides include, but are not limited to, alkylamides such as N,N-dimethylacrylamide and N,N-dimethylmethacrylamide, as well as mixtures thereof. Typical examples of cyclic lactams include, but are not limited to, N-vinyl-2-pyrrolidone, N-vinylcaprolactam, and N-vinyl-2-piperidone, as well as mixtures thereof. Typical examples of hydroxyl-containing (meth)acrylates include, but are not limited to, 2-hydroxyethyl methacrylate (HEMA) and glycerol methacrylate, as well as mixtures thereof. Additional ophthalmic device-forming hydrophilic comonomers include, for example, 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. 4,910,277. Other suitable ophthalmic device-forming hydrophilic comonomers will be apparent to those skilled in the art. Mixtures of the aforementioned ophthalmic device-forming hydrophilic comonomers may also be used in the monomer mixtures herein.

[0041] In one or more additional non-limiting exemplary embodiments, which may be combined with one or more of the preceding paragraphs, one or more ophthalmic device-forming hydrophilic comonomers may be present in the monomer mixture in an amount ranging from about 10% to about 80% by weight, based on the total weight of the monomer mixture. In another exemplary embodiment, one or more ophthalmic device-forming hydrophilic comonomers may be present in the monomer mixture in an amount ranging from about 20% to about 80% by weight, based on the total weight of the monomer mixture. In yet another exemplary embodiment, one or more ophthalmic device-forming hydrophilic comonomers may be present in the monomer mixture in an amount ranging from about 10% to about 50% by weight, based on the total weight of the monomer mixture.

[0042] In non-limiting exemplary embodiments, which may be combined with one or more of the preceding paragraphs, the monomer mixture may further contain one or more unfunctionalized comfort polymers. In non-limiting exemplary embodiments, examples of one or more unfunctionalized comfort polymers include polyvinylpyrrolidone (PVP) polymers. PVP is a linear homopolymer or essentially linear homopolymer in which at least 90% of the repeating units are derived from 1-vinyl-2-pyrrolidone monomers, and the remainder of the aforementioned monomer composition may include neutral monomers (e.g., vinyl or acrylate). Other synonyms for PVP include povidone, polyvidone, 1-vinyl-2-pyrrolidinone, and 1-ethenyl-2-pyrrolidone. In exemplary embodiments, the weight-average molecular weight of the aforementioned PVP is at least about 10,000, and may be, for example, about 10,000 to about 250,000, or about 30,000 to about 100,000. The weight-average molecular weight of PVP can be measured by gel permeation chromatography. Such materials are sold by various sources, for example, by ISP Technologies, Inc. under the trademark PLASDONE® K-29 / 32, and by BASF under the trademark KOLLIDON® (e.g., KOLLIDON® K-30 or K-90).

[0043] In one or more additional non-limiting exemplary embodiments, which may be combined with one or more of the preceding paragraphs, one or more non-functionalized comfort polymers may be present in the monomer mixture in an amount of at least 6% by weight, based on the total weight of the monomer mixture. In one embodiment, one or more non-functionalized comfort polymers may be present in the monomer mixture in an amount ranging from 6% by weight to about 10% by weight, based on the total weight of the monomer mixture.

[0044] In non-limiting exemplary embodiments, which may be combined with one or more of the preceding paragraphs, the monomer mixture may further contain one or more functionalized comfort polymers. Examples of one or more functionalized comfort polymers in non-limiting exemplary embodiments include functionalized poloxamers, functionalized poloxamines, and mixtures thereof. Functionalized poloxamers are derived from poloxamer block copolymers. Certain types of poloxamer block copolymers are available under the trademark Pluronic (BASF Wyandotte Corp., Wyandotte, Mich.). Poloxamers include Pluronic and reverse Pluronic. Pluronic is a series of ABA block copolymers consisting of poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) blocks, generally represented by the following structure: HO(C2H4O) a (C3H6O) b (C2H4O) a H In the equation, a is independently at least 1, and b is at least 1.

[0045] Reverse Pluronic is a series of BAB block copolymers, each composed of a poly(propylene oxide)-poly(ethylene oxide)-poly(propylene oxide) block, and is generally represented by the following structure: HO(C3H6O) b (C2H4O) a (C3H6O) b H In the formula, a is at least 1, and b is independently at least 1. Poly(ethylene oxide) (PEO) blocks are hydrophilic, while poly(propylene oxide) (PPO) blocks are inherently hydrophobic. Each series of poloxamers has a different ratio of PEO to PPO, which ultimately determines the hydrophilic-lipophilic balance (HLB) of the material. That is, the HLB value depends on the values ​​of a and b, where a represents the number of hydrophilic poly(ethylene oxide) units (PEO) present in the molecule, and b represents the number of hydrophobic poly(propylene oxide) units (PPO) present in the molecule. In one embodiment, the HLB of a poloxamer is in the range of about 5 to about 24. In another embodiment, the HLB of a poloxamer is in the range of about 1 to about 5.

[0046] Poloxamers and inverse poloxamers have terminal hydroxyl groups, which can be terminally functionalized to form functionalized poloxamers. An example of a terminally functionalized poloxamer discussed herein is poloxamerized methacrylate (e.g., Pluronic® F127 dimethacrylate) disclosed in U.S. Patent Application Publication 2003 / 0044468 and U.S. Patent No. 9,309,357, the contents of which are incorporated herein by reference. Another example is the glycidyl-terminated copolymer of polyethylene glycol and polypropylene glycol disclosed in U.S. Patent No. 6,517,933, the contents of which are incorporated herein by reference.

[0047] Poloxamers are functionalized to impart desired reactivity to the molecular ends. Functionality can be altered and determined based on the intended use of the functionalized PEO and PPO-containing block copolymer. That is, the PEO and PPO-containing block copolymer is reacted to impart terminal functionality complementary to the intended device-forming monomer mixture. As used herein, the term block copolymer is understood to mean a poloxamer having two or more blocks in its polymer backbone. In non-limiting exemplary embodiments, functionalized poloxamers are poloxamerge (meth)acrylates, reverse poloxamerge (meth)acrylates, and mixtures thereof.

[0048] While poloxamers and reverse poloxamers are considered bifunctional molecules (based on terminal hydroxyl groups), poloxamine is a tetrafunctional form; that is, the molecule is a tetrafunctional block copolymer, terminally encapsulated with primary hydroxyl groups and linked by a central diamine. Certain types of poloxamine block copolymers are available under the BASF Tetronic trademark. Poloxamine includes Tetronic and reverse Tetronic. Poloxamine has the following general structure: [ka] In the equation, a is independently at least 1, and b is independently at least 1.

[0049] Poloxamines can be functionalized to impart desired reactivity to the molecular ends. Functionality can be altered and determined based on the intended use of the functionalized PEO and PPO-containing block copolymer. That is, the PEO and PPO-containing block copolymer is reacted to impart terminal functionality complementary to the intended ophthalmic device-forming monomer mixture. As used herein, the term block copolymer is understood to mean poloxamine having two or more blocks in their polymeric backbone.

[0050] In an exemplary embodiment, one or more functionalized comfort polymers are present in the monomer mixture in an amount ranging from about 1% to about 10% by weight, based on the total weight of the monomer mixture. In another exemplary embodiment, one or more functionalized comfort polymers are present in the monomer mixture in an amount ranging from about 2% to about 7% by weight, based on the total weight of the monomer mixture.

[0051] In non-limiting exemplary embodiments, which may be combined with one or more of the preceding paragraphs, the monomer mixture may further contain one or more ophthalmic device-forming silicone comonomers in addition to one or more monofunctional silicone monomers represented by the structure of formula I. For example, typical ophthalmic device-forming silicone comonomers used for forming silicone hydrogels are well known in the art, and numerous examples are described in U.S. Patents 4,136,250, 4,153,641, 4,740,533, 5,034,461, 5,070,215, 5,260,000, 5,310,779, and 5,358,995. Specific examples of materials suitable for use herein include those disclosed in U.S. Patents No. 5,310,779, 5,387,662, 5,449,729, 5,512,205, 5,610,252, 5,616,757, 5,708,094, 5,710,302, 5,714,557 and 5,908,906, the contents of which are incorporated herein by reference.

[0052] In exemplary embodiments, which may be combined with one or more of the preceding paragraphs, one or more ophthalmic device-forming silicone comonomers may include one or more non-bulky organosilicon-containing monomers as representative types of ophthalmic device-forming silicone comonomers. As used herein, “organosilicon-containing monomer” contains at least one [siloxanil] or at least one [silylalkylsiloxanil] repeating unit in the monomer, macromer, or prepolymer. In exemplary embodiments, an example of a non-bulky organosilicon-containing monomer is represented by the structure of formula IIa: [Chemical formula]

[0053] In the formula, L is an ethylenically unsaturated polymerizable group, V is a linker group or a bond, and R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 are independently hydrogen, an alkyl group, a haloalkyl group, a cycloalkyl group, a heterocycloalkyl group, an alkenyl group, a haloalkenyl group or an aryl group, and R 10 and R 11 are independently hydrogen or an alkyl group (at least one of R 10 and R 11 is hydrogen), y is 2 to 7, and n is 1 to 100 or 1 to 20.

[0054] Ethylenically unsaturated polymerizable groups are well known to those skilled in the art. Suitable ethylenically unsaturated polymerizable groups include, for example, (meth)acrylate, vinyl carbonate, O-vinyl carbamate, N-vinyl carbamate and (meth)acrylamide.

[0055] The linker group is any divalent radical or moiety, and examples include a substituted or unsubstituted C1-C 12 alkyl group, an alkyl ether group, an alkenyl group, an alkenyl ether group, a haloalkyl group, a substituted or unsubstituted siloxane group, and a monomer capable of propagating ring opening.

[0056] In one embodiment, V is (meth)acrylate, L is a C1-C 12 alkylene group, and R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R9 These are independently C1~C 12 It is an alkyl group, R 10 and R 11 H or C1~C 12 It is an alkyl group, where y is between 2 and 7, and n is between 3 and 8.

[0057] In one embodiment, V is a (meth)acrylate, L is a C1-C6 alkyl group, and R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 R is independently a C1-C6 alkyl group, 10 and R 11 is independently H or a C1-C6 alkyl group, y is 2-7, and n is 1-20.

[0058] Non-bulky organosilicon-containing monomers represented by the structure of formula IIa are known in the art; see, for example, U.S. Patents 7,915,323, 7,994,356, 8,420,711, 8,827,447 and 9,039,174, the contents of which are incorporated herein by reference.

[0059] In exemplary embodiments, which may be combined with one or more of the preceding paragraphs, one or more non-bulky organosilicon-containing monomers may include compounds represented by the structure of formula IIb: [ka]

[0060] In the formula, R 12 is H or methyl, and X is O or NR 16 And here, R 16 R is selected from C1-C4 alkyl groups which may be further substituted with H or one or more hydroxyl groups, and in some embodiments it is H or methyl, 13is a divalent alkyl group (which may be further functionalized with a group selected from the group consisting of ether groups, hydroxyl groups, carbamate groups and combinations thereof; in another embodiment, it is a C1-C6 alkylene group which may be substituted with ether groups, hydroxyl groups and combinations thereof; and in yet another embodiment, it is a C1 or C3-C4 alkylene group which may be substituted with ether groups, hydroxyl groups and combinations thereof), and each R 14 R is independently a C1-C4 alkyl group which may be substituted with phenyl, fluorine, a hydroxyl group, or an ether (in another embodiment, each R 14 R is independently selected from ethyl and methyl groups, and in yet another embodiment, each R 14 (is methyl), R 15 is a C1-C4 alkyl group, a is 2-50, and in some embodiments it is 5-15.

[0061] Non-bulky organosilicon-containing monomers represented by the structure of formula IIb are known in the art; see, for example, U.S. Patents 8,703,891, 8,937,110, 8,937,111, 9,156,934 and 9,244,197, the contents of which are incorporated herein by reference.

[0062] In exemplary embodiments, which may be combined with one or more of the preceding paragraphs, one or more ophthalmic device-forming silicone comonomers may include one or more bulky silicone-containing monomers as representative types of ophthalmic device-forming silicone comonomers. In one embodiment, suitable bulky silicone-containing monomers include, for example, bulky polysiloxanyl alkyl (meth)acrylic monomers, bulky polysiloxanyl alkyl carbamate monomers, and mixtures thereof. A typical example of a bulky silicone-containing monomer is a bulky polysiloxanyl alkyl (meth)acrylic monomer, which is represented by the structure of formula III: [ka]

[0063] In the formula, X is -O- or -NR 19 - represents (where each R 19 (is hydrogen or a C1-C4 alkyl group), R 17 R independently represents hydrogen or methyl, and each R 18 represents independently a lower alkyl radical (e.g., a C1-C6 group), a phenyl radical, or a group represented by the following structure: [ka]

[0064] (In the formula, each R 18’ (where is independently a lower alkyl radical or a phenyl radical, and h is 1 to 10) or a bulky silicone-containing monomer represented by the structure of formula IV: [ka]

[0065] In the formula, X is -NR 19 - represents (where R 19 (is hydrogen or C1-C4 alkyl), R 17 represents hydrogen or methyl, and each R 18 The following groups independently represent lower alkyl radicals, phenyl radicals, or groups represented by the following structures: [ka]

[0066] (In the formula, each R18’ Each of these independently represents a lower alkyl radical or a phenyl radical, and h is between 1 and 10.

[0067] Typical examples of bulky silicone-containing monomers include 3-methacryloyloxypropyltris(trimethylsiloxy)silane or tris(trimethylsiloxy)silylpropyl methacrylate (sometimes called TRIS), tris(trimethylsiloxy)silylpropyl vinylcarbamate (sometimes called TRIS-VC), pentamethyldisiloxanylmethyl methacrylate, phenyltetramethyldisiloxanyl ethyl acetate, methyldi(trimethylsiloxy)methacryloxymethylsilane, and (3-methacryloxy-2-hydroxypropoxy)propylbis(trimethylsiloxy)methylsilane (sometimes called Sigma), as well as mixtures thereof. In one embodiment, the bulky silicone-containing monomer is a tris(trialkylsiloxy)silylalkyl methacrylate-containing monomer (for example, a tris(trimethylsiloxy)silylpropyl methacrylate-containing monomer).

[0068] Such bulky monomers may be copolymerized with silicone macromonomers, which are poly(organosiloxanes) capped with unsaturated groups at two or more ends of the molecule. U.S. Patent No. 4,153,641 discloses various unsaturated groups, such as acryloxy or methacryloxy groups.

[0069] In exemplary embodiments, which may be combined with one or more of the preceding paragraphs, one or more ophthalmic device-forming silicone comonomers may include one or more silicone-containing vinyl carbonate or vinyl carbamate monomers as representative types of ophthalmic device-forming silicone comonomers. Suitable silicone-containing vinyl carbonate or vinyl carbamate monomers include, for example, 1,3-bis[4-vinyloxycarbonyloxy)butan-1-yl]tetramethyldisiloxane, 3-(trimethylsilyl)propyl vinyl carbonate, 3-(vinyloxycarbonylthio)propyl-[tris(trimethylsiloxy)silane], 3-[tris(trimethylsiloxy)silyl]propyl vinyl carbamate, 3-[tris(trimethylsiloxy)silyl]propyl allyl carbamate, 3-[tris(trimethylsiloxy)silyl]propyl vinyl carbonate, t-butyldimethylsiloxyethyl vinyl carbonate, trimethylsilylethyl vinyl carbonate, and trimethylsilylmethyl vinyl carbonate, as well as mixtures thereof.

[0070] In exemplary embodiments, which may be combined with one or more of the preceding paragraphs, one or more ophthalmic device-forming silicone comonomers may include one or more polyurethane-polysiloxane macromonomers (sometimes called prepolymers) as representative types of ophthalmic device-forming silicone comonomers, which may have hard-soft-hard blocks similar to conventional urethane elastomers. These may be end-capped with hydrophilic monomers such as HEMA. Examples of such silicone urethanes are disclosed in various publications, including Lai, Yu-Chin, “The Role of Bulky Polysiloxanylalkyl Methacryates in Polyurethane-Polysiloxane Hydrogels,” Journal of Applied Polymer Science, Vol. 60, 1193-1199 (1996). PCT Publication Application WO96 / 31792 discloses examples of such monomers, the disclosure of which is incorporated herein by reference in whole. Further examples of silicone urethane monomers are represented by formulas V and VI: [ka] [ka] During the ceremony, D independently represents an alkyl divalent group, alkylcycloalkyl divalent group, cycloalkyl divalent group, aryl divalent group, or alkylaryl divalent group having 6 to approximately 30 carbon atoms. G independently represents an alkyl divalent group, cycloalkyl divalent group, alkylcycloalkyl divalent group, aryl divalent group, or alkylaryl divalent group having 1 to about 40 carbon atoms, and may contain ether bonds, thio bonds, or amine bonds in the main chain. * represents a urethane or ureid bond. a is at least 1, A independently represents a divalent polymeric radical of formula VII: [ka] In the formula, each R s ' independently represents an alkyl group or fluorine-substituted alkyl group having 1 to about 10 carbon atoms (which may contain ether bonds between carbon atoms), m' is at least 1, and p is a number that provides a partial molecular weight of about 400 to about 10,000. Each of E and E' independently represents a polymerizable unsaturated organic radical represented by formula VIII. [ka] In the formula, R 3 is hydrogen or methyl, R 4 is hydrogen, an alkyl radical having 1 to 6 carbon atoms, or -CO-YR 6 It is a radical (where Y is -O-, -S-, or -NH-), R 5 It is a divalent alkylene radical having 1 to approximately 10 carbon atoms. R 6 It is an alkyl radical having 1 to approximately 12 carbon atoms. X represents -CO- or -OCO-, Z represents -O- or -NH-, Ar represents an aromatic group having approximately 6 to 30 carbon atoms. w is between 0 and 6, x is 0 or 1, y is 0 or 1, and z is 0 or 1.

[0071] In exemplary embodiments which may be combined with one or more of the preceding paragraphs, one or more ophthalmic device-forming silicone comonomers may include, as representative types of ophthalmic device-forming silicone comonomers, one or more silicone-containing urethane monomers represented by formula IX: [ka] In the formula, m is at least 1, preferably 3 or 4; a is at least 1, preferably 1; p is a number that provides a partial molecular weight of about 400 to about 10,000, preferably at least 30; R 7 is the divalent group of diisocyanate after the removal of the isocyanate group (for example, the divalent group of isophorone diisocyanate), and each E'' is a group represented as follows: [ka]

[0072] In another embodiment, the silicone hydrogel material comprises about 5 to about 50 weight percent, or about 10 to about 25 weight percent, of one or more silicone macromonomers (in bulk, i.e., in the copolymerized monomer mixture), about 5 to about 75 weight percent, or about 30 to about 60 weight percent, of one or more polysiloxanyl alkyl (meth)acrylic monomers, and about 10 to about 50 weight percent, or about 20 to about 40 weight percent, of hydrophilic monomers. Generally, the silicone macromonomers are poly(organosiloxanes) capped with unsaturated groups at two or more ends of the molecule. In addition to the end groups of the structures described above, U.S. Patent No. 4,153,641 discloses additional unsaturated groups, including acryloxy or methacryloxy. Fumarate-containing materials, such as those disclosed in U.S. Patents No. 5,310,779, 5,449,729, and 5,512,205, are also useful substrates according to the non-limiting embodiments described herein. The silane macromonomer may be a silicone-containing vinyl carbonate or vinyl carbamate, or a polyurethane-polysiloxane having one or more hard-soft-hard blocks and end-capped with a hydrophilic monomer.

[0073] In exemplary embodiments, which may be combined with one or more of the preceding paragraphs, one or more ophthalmic device-forming silicone comonomers may include one or more monomers of formula X as representative types of ophthalmic device-forming silicone comonomers: [ka] In the formula, X is a ring-opening agent residue, L is the same or different linker group or bond, V is an ethylenically unsaturated polymerizable group, R1, R2, R3, R4, R5, R6 are independently hydrogen, alkyl group, haloalkyl group, cycloalkyl group, heterocycloalkyl group, alkenyl group, haloalkenyl group or aromatic group, R7 and R8 are independently hydrogen or alkyl group (where at least one of R7 or R8 is hydrogen), y is 2 to 7, and n is 1 to 100.

[0074] Ring-opening agents are well known in the literature. Non-limiting examples of anionic ring-opening agents include alkyllithium, alkoxides, and trialkylsiloxylithium (the alkyl group may or may not contain a halo atom).

[0075] The linker group is any divalent radical or moiety, including substituted or unsubstituted alkyl groups, alkyl ether groups, alkenyl groups, alkenyl ether groups, haloalkyl groups, substituted or unsubstituted siloxane groups, and monomers capable of propagating ring opening.

[0076] Ethylene-unsaturated polymerizable groups are well known to those skilled in the art. Non-limiting examples of ethylenically unsaturated polymerizable groups include acrylates, methacrylates, vinyl carbonates, O-vinylcarbamates, N-vinylcarbamates, acrylamides, and methacrylamides.

[0077] In exemplary embodiments which may be combined with one or more of the preceding paragraphs, one or more ophthalmic device-forming silicone comonomers may include one or more monomers of formula XI as representative types of ophthalmic device-forming silicone comonomers: [ka] In the formula, L is the same or different linker group or bond, V is the same or different ethylenically unsaturated polymerizable group, R1, R2, R3, R4, R5, R6 and R9 are independently hydrogen, alkyl group, haloalkyl group, cycloalkyl group, heterocycloalkyl group, alkenyl group, haloalkenyl group or aromatic group, R7 and R8 are independently hydrogen or alkyl group (where at least one of R7 or R8 is hydrogen), y is 2 to 7, and n is 1 to 100.

[0078] In exemplary embodiments which may be combined with one or more of the preceding paragraphs, one or more ophthalmic device-forming silicone comonomers may include one or more monomers of formulas XII and XIII as representative types of ophthalmic device-forming silicone comonomers: [ka] In the formula, R9, R 10 and R 11 n is independently hydrogen, alkyl, haloalkyl, or other substituted alkyl, and n is as defined above, 1 The range is 0 to 10, [ka] In the formula, n is between 1 and 100, or between 2 and 80, or between 3 and 20, or between 5 and 15.

[0079] In exemplary embodiments, which may be combined with one or more of the preceding paragraphs, one or more ophthalmic device-forming silicone comonomers may include one or more monomers of formulas XIV to XVIII as representative types of ophthalmic device-forming silicone comonomers: [ka] [ka] [ka] [ka] and [ka]

[0080] In exemplary embodiments which may be combined with one or more of the preceding paragraphs, one or more ophthalmic device-forming silicone comonomers may include one or more monomers of formulas XIX to XXI as representative types of ophthalmic device-forming silicone comonomers: [ka] [ka] and [ka]

[0081] In the formula, R9, R 10 and R 11 n and n are independently hydrogen, alkyl groups, haloalkyl groups, or other substituted alkyl groups. 1 This is defined as described above.

[0082] In exemplary embodiments which may be combined with one or more of the preceding paragraphs, one or more ophthalmic device-forming silicone comonomers may include one or more monomers of formulas XXII to XXIV as representative types of ophthalmic device-forming silicone comonomers: [ka] [ka] and [ka]

[0083] In the formula, n is as defined above, X - It is a counterion that provides an overall neutral charge.

[0084] Counterions that can provide an overall neutral charge are well known to those skilled in the art, and examples include halide ions.

[0085] In exemplary embodiments, which may be combined with one or more of the preceding paragraphs, one or more ophthalmic device-forming silicone comonomers may include one or more monomers of formula XXV as representative types of ophthalmic device-forming silicone comonomers: [ka]

[0086] Another type of typical ophthalmic device-forming silicone comonomer is, for example, fluorinated monomers. Such monomers are used to form fluorosilicone hydrogels and to reduce deposit accumulation on contact lenses made therefrom, as disclosed, for example, in U.S. Patents 4,954,587, 5,010,141, and 5,079,319. Furthermore, the use of silicone-containing monomers having specific fluorinated side groups (i.e., -(CF2)-H) has been found to improve compatibility between hydrophilic monomer units and silicone-containing monomer units. See, for example, U.S. Patents 5,321,108 and 5,387,662.

[0087] The silicone materials described above are merely examples, and other materials can also be used as substrates, which are disclosed in various publications and are continuously being developed for use in contact lenses and other ophthalmic devices. For example, ophthalmic devices can be formed from at least one cationic monomer, such as a cationic silicone-containing monomer or a cationic fluorinated silicone-containing monomer.

[0088] In one or more additional non-limiting exemplary embodiments, which may be combined with one or more of the above-described embodiments, one or more ophthalmic device-forming silicone comonomers may be present in the monomer mixture in an amount ranging from about 5% to about 50% by weight, based on the total weight of the monomer mixture. In another exemplary embodiment, one or more ophthalmic device-forming silicone comonomers may be present in the monomer mixture in an amount ranging from about 10% to about 30% by weight, based on the total weight of the monomer mixture.

[0089] In non-limiting exemplary embodiments, which may be combined with one or more of the preceding paragraphs, the monomer mixture may further contain one or more crosslinking agents. Crosslinking agents suitable for use herein are known to those skilled in the art. For example, in non-limiting exemplary embodiments, a suitable one or more crosslinking agents include one or more crosslinking agents containing at least two ethylenically unsaturated reactive end groups. In one embodiment, the ethylenically unsaturated reactive end group is a (meth)acrylate-containing reactive end group. In another embodiment, the ethylenically unsaturated reactive end group is a non-(meth)acrylate-containing reactive end group. In one embodiment, the ethylenically unsaturated reactive end group is a combination of one or more (meth)acrylate-containing reactive end groups and one or more non-(meth)acrylate-containing reactive end groups.

[0090] In exemplary embodiments, useful crosslinking agents containing at least two ethylenically unsaturated reactive end groups include, for example, one or more di-, tri-, or tetra(meth)acrylate-containing crosslinking agents. In exemplary embodiments, useful crosslinking agents containing one or more di-, tri-, or tetra(meth)acrylates include, for example, alkane polyol di-, tri-, or tetra(meth)acrylate crosslinking agents (e.g., one or more alkylene glycol di(meth)acrylate crosslinking agents, one or more alkylene glycol tri(meth)acrylate crosslinking agents, one or more alkylene glycol tetra(meth)acrylate crosslinking agents, one or more alkanediol di(meth)acrylate crosslinking agents, alkanediol tri(meth)acrylate crosslinking agents, alkanediol tetra(meth)acrylate crosslinking agents, one or more alkanetriol di(meth)acrylate crosslinking agents, alkanetriol tri(meth)acrylate crosslinking agents, alkanetriol tetra(meth)acrylate crosslinking agents, one or more alkanetetraol di(meth)acrylate crosslinking agents, alkanetetraol tri(meth)acrylate crosslinking agents, alkanetetraol tetra(meth)acrylate crosslinking agents, etc.) and mixtures thereof.

[0091] In exemplary embodiments, examples of one or more alkylene glycol di(meth)acrylate crosslinking agents include tetraethylene glycol dimethacrylate, ethylene glycol di(meth)acrylate having about 10 or fewer ethylene glycol repeating units, and butylene glycol di(meth)acrylate. In one embodiment, examples of one or more alkanediol di(meth)acrylate crosslinking agents include butanediol di(meth)acrylate crosslinking agent and hexanediol di(meth)acrylate. In one embodiment, one or more alkanetriol tri(meth)acrylate crosslinking agents are trimethylolpropane trimethacrylate crosslinking agents. In one embodiment, one or more alkanetetraol tetra(meth)acrylate crosslinking agents are pentaerythritol tetramethacrylate crosslinking agents.

[0092] In non-limiting exemplary embodiments, suitable crosslinking agents include, for example, ethylene glycol diacrylate, diethylene glycol diacrylate, allyl acrylate, 1,3-propanediol diacrylate, 2,3-propanediol diacrylate, 1,6-hexanediol diacrylate, 1,4-butanediol diacrylate, triethylene glycol diacrylate, cyclohexane-1,1-diyldimethanol diacrylate, 1,4-cyclohexanediol diacrylate, 1,3-adamantanediool diacrylate, 1,3-adamantanediolyl diacrylate, 2,2-diethyl-1,3-propanediol diacrylate, 2,2-diisobutyl-1,3-propanediol diacrylate, 1,3-cyclohexanedimethyl diacrylate, 1,4-cyclohexanedimethyl diacrylate, neopentyl glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, and their corresponding methacrylates.

[0093] In non-limiting exemplary embodiments, suitable crosslinking agents include, for example, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, 1,3-propanediol diacrylate, 1,3-propanediol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, poly(ethylene glycol) diacrylate (Mn=700 daltons), poly(ethylene glycol) dimethacrylate (Mn=700 daltons), and poly(ethylene glycol) dimethacrylate (Mn=1000 daltons).

[0094] In one embodiment, one or more crosslinking agents containing at least two ethylenically unsaturated reactive end groups include at least one allyl-containing reactive end group and at least one (meth)acrylate-containing reactive end group. In an exemplary embodiment, one or more crosslinking agents may be allyl methacrylate.

[0095] In non-limiting exemplary embodiments, which may be combined with one or more of the preceding paragraphs, one or more crosslinking agents may be present in the monomer mixture in an amount sufficient to form an ophthalmic device. In non-limiting exemplary embodiments, which may be combined with one or more of the preceding paragraphs, one or more crosslinking agents may be present in the monomer mixture in an amount of about 0.1 to about 3.0% by weight, based on the total weight of the monomer mixture. In non-limiting exemplary embodiments, which may be combined with one or more of the preceding paragraphs, one or more crosslinking agents may be present in the monomer mixture in an amount of about 0.2 to about 1.0% by weight, based on the total weight of the monomer mixture.

[0096] In one or more additional non-limiting exemplary embodiments, which may be combined with one or more of the above-described embodiments, the monomer mixture may further contain one or more additional ophthalmic device-forming comonomers. In exemplary embodiments, one or more additional ophthalmic device-forming comonomers may include, for example, both ethylenically unsaturated groups (which enable the monomer to copolymerize with the ophthalmic device-forming hydrophilic comonomer) and epoxide groups (which do not react with the ophthalmic device-forming hydrophilic comonomer but remain to react with the copolymer). Suitable additional ophthalmic device-forming comonomers include, for example, glycidyl methacrylate, glycidyl acrylate, glycidyl vinyl carbonate, glycidyl vinyl carbamate, and 4-vinyl-1-cyclohexene-1,2-epoxide.

[0097] In a non-limiting exemplary embodiment, one or more additional ophthalmic device-forming comonomers may be present in the monomer mixture in an amount ranging from about 1% to about 20% by weight, based on the total weight of the monomer mixture. In another exemplary embodiment, one or more additional ophthalmic device-forming comonomers may be present in the monomer mixture in an amount ranging from about 3% to about 10% by weight, based on the total weight of the monomer mixture.

[0098] In non-limiting exemplary embodiments, which may be combined with one or more of the preceding paragraphs, the monomer mixture may further contain a reactive (polymerizable) ultraviolet (UV) absorber and / or a reactive blue light absorber. A preferred reactive UV absorber may be any known reactive UV absorber. In non-limiting exemplary embodiments, preferred reactive UV absorbers include, for example, 2-(2'-hydroxy-3'-methallyl-5'-methylphenyl)benzotriazole (commercially available from Polysciences, Inc., Warrington, Pa. as o-Methallyl Tinuvin P ("oMTP")), 3-(2H-benzo[d][1,2,3]triazole-2-yl)-4-hydroxyphenylethyl methacrylate, and 2-(3-(tert-butyl)-4-hydroxy-5-(5-methoxy-2H-benzo[d][1,2,3]triazole-2-yl)phenoxy)ethyl methacrylate.

[0099] In one exemplary embodiment, suitable UV absorbers include, for example, one or more compounds of the following formula: [ka] [ka] (2-propenoic acid, 2-methyl, 2-(4-benzoyl-3-hydroxyphenoxy)-1-[(4-benzoyl-3-hydroxyphenoxy)methyl ester), [ka] [ka] [ka] and [ka] These compounds are merely illustrative and not intended to be limiting. Any known or subsequently developed UV-blocking agent is intended for use herein.

[0100] In exemplary embodiments, the UV absorber may be present in the monomer mixture in an amount ranging from about 0.1% to about 5% by weight, based on the total weight of the monomer mixture. In another exemplary embodiment, the UV absorber may be present in the monomer mixture in an amount ranging from about 1.5% to about 2.5% by weight, based on the total weight of the monomer mixture. In yet another non-limiting exemplary embodiment, the UV absorber may be present in the monomer mixture in an amount ranging from about 1.5% to about 2% by weight, based on the total weight of the monomer mixture.

[0101] Many reactive blue light absorbing compounds are known. Preferred reactive blue light absorbing compounds are described in U.S. Patents 5,470,932, 8,207,244, and 8,329,775, the contents of which are incorporated herein by reference. In one embodiment, the blue light absorbing dye is N-2-[3-(2'-methylphenylazo)-4-hydroxyphenyl]ethyl methacrylamide. In exemplary embodiments, the blue light absorber may be present in the monomer mixture in an amount ranging from about 0.005 to about 1% by weight, based on the total weight of the monomer mixture. In another exemplary embodiment, the blue light absorber may be present in the monomer mixture in an amount ranging from about 0.01 to about 1% by weight, based on the total weight of the monomer mixture.

[0102] In non-limiting exemplary embodiments, which may be combined with one or more of the preceding paragraphs, the monomer mixture may further contain a diluent. Suitable diluents include, for example, at least one borate ester of C1-C8 monohydric alcohols, water-soluble or partially water-soluble monohydric alcohols, and mixtures thereof. In one embodiment, the diluent includes, for example, at least one borate ester of C1-C5 monohydric alcohols. Suitable borate esters of C1-C8 monohydric alcohols include, for example, trimethyl borate, triethyl borate, tri-n-propyl borate, triisopropyl borate, tri-n-butyl borate, and tri-tert-butyl borate. Suitable water-soluble or partially water-soluble monohydric alcohols include, for example, monohydric alcohols having 1 to 5 carbon atoms, such as methanol, ethanol, isopropyl alcohol, 1-propanol, t-butyl alcohol, 2-butyl alcohol, 2-methyl-1-propanol, t-amyl alcohol, and other C5 isomers.

[0103] In non-limiting exemplary embodiments, which may be combined with one or more of the preceding paragraphs, the monomer mixture contains about 5% to about 50% by weight of diluent, based on the total weight of the monomer mixture. In one embodiment, the monomer mixture contains about 15% to about 30% by weight of diluent, based on the total weight of the monomer mixture.

[0104] The monomer mixture may further contain various additives, such as antioxidants, colorants, lubricants, internal wetting agents, and reinforcing agents, as well as other components well known in the art, as may be necessary and within limits that do not impair the purpose and effect of the exemplary embodiments.

[0105] In a non-limiting exemplary embodiment, which may be combined with one or more of the preceding paragraphs, the ophthalmic device disclosed herein may be a high-water-content silicone ophthalmic device, such as a silicone hydrogel having an equilibrium water content of at least about 35% by weight. In another exemplary embodiment, the high-water-content silicone ophthalmic device disclosed herein may have an equilibrium water content of at least about 50% by weight. In another exemplary embodiment, the high-water-content silicone ophthalmic device disclosed herein may have an equilibrium water content of at least about 60% by weight. In another exemplary embodiment, the high-water-content silicone ophthalmic device disclosed herein may have an equilibrium water content of at least about 70% by weight. In another exemplary embodiment, the ophthalmic device disclosed herein may be a high-water-content silicone ophthalmic device having an equilibrium water content of about 35% by weight to about 80% by weight.

[0106] An exemplary embodiment of an ophthalmic device (e.g., a contact lens or intraocular lens) can be prepared by polymerizing the aforementioned monomer mixture to form a product, which is then shaped into a suitable form by, for example, turning, injection molding, compression molding, or cutting. For example, when manufacturing a contact lens, the initial mixture may be polymerized in a tube to obtain a rod-shaped article, which is then cut into a button shape. The button can then be turned into a contact lens.

[0107] Alternatively, ophthalmic devices such as contact lenses may be cast directly from a mixture in a mold, such as a polypropylene mold, by methods such as rotary casting and static casting. Rotary casting is disclosed in U.S. Patents 3,408,429 and 3,660,545, and static casting is disclosed in U.S. Patents 4,113,224, 4,197,266 and 5,271,875. Rotary casting involves placing the mixture to be polymerized into a mold and rotating the mold in a controlled manner while exposing the mixture to a radiation source such as ultraviolet light. Static casting involves placing a monomer mixture between two mold sections (one mold section having a shape that forms the front surface of the lens and the other mold section having a shape that forms the rear surface of the lens), and curing the mixture within the mold assembly, for example, by radical polymerization of the mixture to form the lens. Examples of radical reaction techniques for curing lens materials include thermal radiation, infrared radiation, electron beam radiation, gamma ray radiation, and ultraviolet (UV) radiation, or a combination of such techniques may be used. U.S. Patent No. 5,271,875 describes a static casting method that enables the formation of a finished lens within a mold cavity defined by a rear mold and a front mold. As an additional method, U.S. Patent No. 4,555,732 discloses a process in which an excess monomer mixture is cured by rotary casting in a mold to form a molded article having a front lens surface and a relatively large thickness, and then the rear surface of the cured rotary-cast article is turned to obtain a contact lens having a desired thickness and rear lens surface.

[0108] Coincidence can be promoted by exposing the mixture to heat (thermosetting) and / or radiation such as ultraviolet rays, visible light, or high-energy radiation. A polymerization initiator may be contained in the mixture to facilitate the polymerization process. Representative examples of radical thermal polymerization initiators include organic peroxides such as acetyl peroxide, lauroyl peroxide, decanoyl peroxide, stearoyl peroxide, benzoyl peroxide, t-butyl peroxy pivalate, and peroxydicarbonate. Representative examples of diazo initiators include VAZO 64 and VAZO 67. Representative UV initiators are known in the art and include benzoin methyl ether, benzoin ethyl ether, Darocur® 1173, 1164, 2273, 1116, 2959, 3331 (EM Industries), and Irgacure® 651 and 184 (Ciba-Geigy). Representative visible light initiators include IRGACURE 819 and other phosphine oxide type initiators. Generally, the initiator is used in the monomer mixture at a concentration of about 0.01 to about 5% by weight of the total mixture.

[0109] Polymerization is generally carried out in a reaction medium such as a solution or dispersion using a solvent such as water or an alkanol containing 1 to 4 carbon atoms such as methanol, ethanol, 2-propanol. Alternatively, any mixture of the above solvents may be used.

[0110] Generally, the polymerization is carried out for about 15 minutes to about 72 hours and, for example, in an inert atmosphere of nitrogen or argon. If desired, the resulting polymerization product may be dried under reduced pressure (e.g., for about 5 to about 72 hours) before use or left in an aqueous solution.

[0111] Upon polymerization of the mixture, a polymer is obtained which, upon hydration, preferably forms a hydrogel. When manufacturing a hydrogel lens, the mixture may at least contain the aforementioned diluent which is ultimately replaced by water when the polymerization product is hydrated to form a hydrogel. Generally, the water content of the hydrogel is as described above, i.e., at least about 50% by weight. The amount of diluent used should be less than about 50% by weight, and in most cases, the diluent content is less than about 30% by weight. However, in a specific polymer system, the actual limit is determined by the solubility of the various monomers in the diluent. In order to produce an optically transparent copolymer, it is important that no phase separation occurs between the comonomer and the diluent or between the diluent and the final copolymer that results in visual opacity.

[0112] Furthermore, the maximum amount of diluent that can be used depends on the amount of swelling the diluent imparts to the final polymer. Excessive swelling can cause or may cause the copolymer to disintegrate when the diluent is replaced by water during hydration. Suitable diluents include, but are not limited to, ethylene glycol, glycerin, liquid poly(ethylene glycol), alcohols, alcohol / water mixtures, ethylene oxide / propylene oxide block copolymers, low molecular weight linear poly(2-hydroxyethyl methacrylate), glycol esters of lactic acid, formamide, ketones, dialkyl sulfoxides, butyl carbitol, and borate salts discussed herein, and mixtures thereof.

[0113] IfIf If optionally, it may be desirable to remove residual diluent from the lens prior to the edge finishing operation, which can be achieved by evaporation at near atmospheric pressure or under reduced pressure. Higher temperatures may be used to shorten the time required to evaporate the diluent. The time, temperature, and pressure conditions of the solvent removal process vary depending on factors such as the volatility of the diluent and the specific monomer components and can be readily determined by one skilled in the art. If desired, the mixture used to manufacture the hydrogel lens may further contain wetting agents known in the prior art for manufacturing hydrogel materials.

[0114] In the case of intraocular lenses, the monomer mixture to be polymerized may further contain monomers to increase the refractive index of the resulting polymerization product. Examples of such monomers include aromatic (meth)acrylates such as phenyl(meth)acrylate, 2-phenylethyl(meth)acrylate, 2-phenoxyethyl methacrylate, and benzyl(meth)acrylate.

[0115] The ophthalmic devices, such as contact lenses, obtained herein may be subjected to any machining operations. For example, any machining process may include buffing or polishing of the lens edge and / or surface. Generally, such machining processes can be carried out before or after demolding the product from the mold (for example, dry demolding by lifting the lens from the mold using vacuum tweezers, and then transferring the lens to a second set of vacuum tweezers using mechanical tweezers and smoothing the surface or edge against a rotating surface). The lens may then be inverted and the other side of the lens may be machined.

[0116] Next, the lens may be transferred to an individual lens package containing buffered saline solution. This saline solution may be added to the package either before or after the lens transfer. Suitable package designs and materials are known in the art. The plastic package is releasably sealed with a film. Suitable sealing films are known in the art and include foils, polymer films, and mixtures thereof. To ensure a sterile product, the sealed package containing the lens is then sterilized. Suitable sterilization means and conditions are known in the art and include, for example, autoclaving.

[0117] As will be readily apparent to those skilled in the art, other processes may be included in the molding and packaging processes described above. Such other processes include, for example, coating the formed lenses, surface treatment of the lenses during formation (e.g., by mold transfer), inspection of the lenses, disposal of defective lenses, cleaning of the mold halves, reuse of the mold halves, and combinations thereof.

[0118] The following examples are provided to enable those skilled in the art to carry out the invention and are merely illustrative. The examples should not be read as limiting the scope of the invention as defined in the claims.

[0119] In the examples, the following abbreviations are used.

[0120] HEMA: 2-hydroxyethyl methacrylate.

[0121] NVP: N-vinyl-2-pyrrolidone.

[0122] DMA: N,N-dimethylacrylamide.

[0123] EGDMA: Ethylene glycol dimethacrylate.

[0124] AMA: Allyl methacrylate.

[0125] TRIS: Tris(trimethylsiloxy)silylpropyl methacrylate.

[0126] TRIS MA: Tris(trimethoxysilylpropyl) methacrylate.

[0127] SIGMA: (3-methacryloxy-2-hydroxypropoxy)propylbis(trimethylsiloxy)methylsilane.

[0128] PVP: Polyvinylpyrrolidone with a weight-average molecular weight of 1,300,000 Da.

[0129] Capmul PG-8: Propylene glycol monocaprylate.

[0130] UV416: 2-(4-benzoyl-3-hydroxyphenoxy)ethyl acrylate.

[0131] Vazo(trademark)64: Azobisisobutyronitrile (AIBN).

[0132] IMVT: 1,4-bis(4-(2-methacryloxyethyl)phenylamino)anthraquinone.

[0133] M1EDS6: A compound having the following structure and available from Gelest:

Chemical formula

[0134] MCR-M11: A compound having the following structure:

Chemical formula

[0139] SKD-131-069-92: A compound available from Momentive with the following structure: [ka]

[0140] Various polymerization products were formed as described below and their characteristics were evaluated using the following standard test procedures.

[0141] Oxygen permeability (also known as Dk) is determined by the following procedure. Other methods and / or instruments may be used, as long as the obtained oxygen permeability values ​​are equivalent to those of the method described. The oxygen permeability of silicone hydrogels is measured by polarography (ANSI Z80.20-1998) using an O2 Permeometer Model 201T instrument (Createch, Albany, California, USA) equipped with a probe having a circular gold cathode at the center of the probe end and a silver anode insulated from the cathode. Measurements are performed only on pre-examined, pinhole-free, flat silicone hydrogel film samples with three different central thicknesses ranging from 150 to 600 microns. The central thickness of the film sample may be measured using a Rehder ET-1 electronic thickness gauge. Generally, the film sample has a disc shape. Measurements are performed by immersing the film sample and probe in a bath containing circulating phosphate-buffered saline (PBS) equilibrated at 35°C ± 0.2°C. Before immersing the probe and film sample in the PBS bath, center the film sample on a cathode moistened with equilibrated PBS, ensuring that there are no air bubbles or excess PBS between the cathode and the film sample. Then, secure the film sample to the probe with the mounting cap, ensuring that the cathode portion of the probe is in contact only with the film sample. In the case of silicone hydrogel films, it is often useful to use a Teflon polymer film (e.g., a disc shape) between the probe cathode and the film sample. In this case, first place the Teflon film on the moistened cathode, then place the film sample on the Teflon film, ensuring that there are no air bubbles or excess PBS under the Teflon film or film sample. After collecting the measurement data, only data with a correlation coefficient (R2) of 0.97 or higher should be entered into the calculation of the Dk value. At least two Dk measurements should be obtained for each thickness, satisfying the R2 value.

[0142] Using known regression analysis, oxygen permeability (Dk) is calculated from film samples of at least three different thicknesses. Film samples hydrated with solutions other than PBS are first immersed in purified water for at least 24 hours to equilibrate, and then immersed in PHB for at least 12 hours to equilibrate. Instruments are cleaned regularly and calibrated regularly using RGP standards. Upper and lower limits are established by calculating + / - 8.8% of the repository values ​​established by William J. Benjamin et al., "The Oxygen Permeability of Reference Materials, Optom Vis Sci 7(12s):95(1997)" (the disclosure thereof is incorporated herein by reference in its entirety).

[0143] Moisture content (%): Two sets of six hydration lenses or film are dipped on a piece of filter paper to remove excess water and then weighed (wet weight). Next, the sample is placed in a jar containing a desiccant and heated in a microwave oven for 10 minutes. Then, the sample is left to stand for 30 minutes to equilibrate at room temperature and weighed again (dry weight). Moisture content (%) is calculated from the wet and dry weights.

[0144] Contact Angle (CBCA): Captured bubble contact angle data was collected using a First Ten Angstroms FTA-1000 prop shape analyzer. All samples were rinsed with HPLC-grade water before analysis to remove any packaging solution components from the sample surface. Before data acquisition, the surface tension of the water used in all experiments was measured using the drop-drop method. A surface tension value of 70–72 dynes / cm was expected for the water to be suitable for use. All lens samples were placed in a curved sample holder and immersed in a quartz cell filled with HPLC-grade water. For each sample, the advancing and receding captured bubble contact angles were collected. The advancing contact angle is defined as the angle measured in water as the bubble recedes from the lens surface (water advances across the entire surface). All captured bubble data was collected using a high-speed digital camera focused on the sample / bubble interface. This contact angle was calculated using the digital frame immediately preceding the movement of the contact line at the sample / bubble interface. This receding contact angle is defined as the angle measured in water as bubbles spread across the sample surface (water recedes from the surface).

[0145] Modulus of elasticity (g / mm²) 2 The elongation (%) and elongation (%) were measured using an Instron (Model 4502) instrument with the film sample immersed in borate-buffered saline, according to ASTM 1708. The preferred size of the film sample is 22 mm in gauge length and 4.75 mm in width, and the sample further has ends that form a dogbone shape for gripping the sample with the clamp of the Instron instrument, and a thickness of 100 ± 50 microns.

[0146] Tensile strength (g / mm 2 ) was measured using ASTM test method D1708a.

[0147] Transparency / Turbidity – Transparency / turbidity is measured by placing the lens in a wet cell and comparing it to a set of standards to evaluate the clearest and most turbid parts of the lens. The evaluation is assigned a value from 1 to 5, with a rating of 5 indicating a clear lens and a rating of 1 indicating a turbid lens.

[0148] Example 1 Preparation of silicone monomers having the following structure: [ka] This follows a typical reaction scheme. [ka]

[0149] In an oven-dried 2 L two-necked round-bottom flask equipped with a magnetic stirrer and condenser, 2,2,4,4,6,6,8,8-octamethyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane (29.6 g, 0.1 mol) and anhydrous cyclohexane (150 mL) were added under a nitrogen atmosphere with stirring. Butyllithium (6.4 g, 0.1 mol) was added to the above reaction mixture, followed by cyclohexane (25 mL). After stirring for 1 hour, tetrahydrofuran (THF) (70 mL, distilled over sodium / benzophenone) was added, and the reaction mixture was continued to stir for a further 16 hours. Next, N-(3-(chlorodimethylsilyl)propyl)acrylamide (20.5 g, 0.1 mol) was added, and the mixture was stirred for a further 24 hours. Next, the reaction mixture was filtered, silica gel (3.5 g, dried at 160°C for 3 hours) was added, and the reaction mixture was stirred for a further 4 hours. The reaction mixture was filtered through a layer of Celite (20 g), and butylated hydroxytoluene (BHT) (5 mg) was added to the filtrate. Next, the filtrate was concentrated under reduced pressure (40°C / 0.3 mmHg). Heptane (200 mL) was added to the concentrate with stirring, and the mixture was washed with DI water (100 mL), sodium bicarbonate aqueous solution (2 × 100 mL, prepared by dissolving 10 g of sodium bicarbonate in 200 mL of DI water), brine (100 mL), and finally DI water (100 mL). Heptane (50 mL) was added, and the mixture was dried on MgSO4 (15 g) for 20 hours. The MgSO4 was filtered off, and the solvent was removed using a rotary evaporator. The crude product was stirred on activated basic alumina (30 g) for 24 hours, and then filtered on a thin layer of Celite. By removing the residual solvent at 25°C and 0.2 mmHg for 30 minutes, the desired product was obtained as a clear oily substance in the form of 40 g.

[0150] Example 2 and Comparative Examples A and B A monomer mixture was prepared by mixing the following components listed in Table 1 in terms of their weight. [Table 1]

[0151] The obtained monomer mixture was introduced into a polypropylene mold assembly and cast into a contact lens. Next, the mold assembly and monomer mixture were heat-cured for approximately 3 hours to form the contact lens. The resulting contact lens was then demolded from the mold assembly.

[0152] The monomer mixture in Example 2 was homogeneous, resulting in a contact lens with optical transparency. The monomer mixtures in Comparative Examples A and B separated during polymerization, resulting in non-uniform lenses.

[0153] Example 3 and Comparative Examples C and D A monomer mixture was prepared by mixing the following components listed in Table 2 in terms of their weight. [Table 2]

[0154] The obtained monomer mixture was introduced into a polypropylene mold assembly and cast into a contact lens. Next, the mold assembly and monomer mixture were heat-cured for approximately 3 hours to form a contact lens. The resulting contact lens was then demolded from the mold assembly.

[0155] The monomer mixture in Example 3 was homogeneous, and a contact lens with optical transparency was obtained. The monomer mixtures in Comparative Examples C and D underwent phase separation during polymerization, resulting in phase-separated lenses that lacked transparency.

[0156] Example 4 and Comparative Example E A monomer mixture was prepared by mixing the following components listed in Table 3 in terms of their weight. [Table 3]

[0157] The obtained monomer mixture was introduced into a polypropylene mold assembly and cast into a contact lens. Next, the mold assembly and monomer mixture were heat-cured for approximately 3 hours to form a contact lens. The resulting contact lens was then demolded from the mold assembly.

[0158] The monomer mixture in Example 4 was homogeneous, and a contact lens with optical transparency was obtained. The monomer mixture in Comparative Example E was heterogeneous during polymerization, and a cloudy mixture lacking transparency was obtained.

[0159] Example 5 and Comparative Example F A monomer mixture was prepared by mixing the following components listed in Table 4 in terms of their weight. [Table 4]

[0160] The obtained monomer mixture was introduced into a polypropylene mold assembly and cast into a contact lens. Next, the mold assembly and monomer mixture were heat-cured for approximately 3 hours to form a contact lens. The resulting contact lens was then demolded from the mold assembly.

[0161] The monomer mixture in Example 5 was homogeneous, and a contact lens with optical transparency was obtained. The monomer mixture in Comparative Example F was heterogeneous during polymerization, and a cloudy mixture lacking transparency was obtained.

[0162] According to one aspect of this disclosure, a monofunctional silicone monomer is represented by the structure of formula I: [ka]

[0163] In the formula, R 1 , R 2 , R 3 and R 4R is independently hydrogen, alkyl group, haloalkyl group, cycloalkyl group, heterocycloalkyl group, alkenyl group, haloalkenyl group, aryl group and heteroaryl group, 5 , R 6 and R 7 x is independently a linear or branched alkyl group, x is 1 to 6, and y is 3 to 5.

[0164] In a non-limiting exemplary embodiment, which may be combined with one or more of the preceding paragraphs, R 1 , R 2 , R 3 and R 4 Hydrogen, C1~C 12 Alkyl alkyl groups, C1-C 12 Haloalkyl groups, C3-C 12 Cycloalkyl groups, C3-C 12 Heterocycloalkyl groups, C2-C 12 Alkenyl group, C2~C 12 Haloalkenyl group, C6~C 12 Aromatic groups and C6~C 12 It is a heteroaromatic group, R 5 , R 6 and R 7 These are independently linear or branched C1-C 12 It is an alkyl group, where x is between 1 and 6, and y is between 3 and 5.

[0165] In a non-limiting exemplary embodiment, which may be combined with one or more of the preceding paragraphs, R 1 , R 2 , R 3 and R 4 R is independently a hydrogen atom and a C1-C6 alkyl group. 5 , R 6 and R 7 x is independently a linear or branched C1-C6 alkyl group, x is 1-6, and y is 3-5.

[0166] In a non-limiting exemplary embodiment, which may be combined with one or more of the preceding paragraphs, R 1 , R 2 , R 3 and R 4R is independently a C1-C3 alkyl group, 5 and R 6 R is independently a C1-C3 alkyl group, 7 x is a linear or branched C3-C6 alkyl group, x is 2-4, and y is 3-5.

[0167] In a non-limiting exemplary embodiment, which may be combined with one or more of the preceding paragraphs, R 1 , R 2 , R 3 , R 4 , R 5 and R 6 is methyl, and R 7 x is a linear or branched C3-C6 alkyl group, x is 2-4, and y is 3-5.

[0168] According to another aspect of the disclosure, ophthalmic devices are

[0169] (a) Formula I: [ka] One or more monofunctional silicone monomers represented by the structure shown.

[0170] In the formula, R 1 , R 2 , R 3 and R 4 R is independently hydrogen, alkyl group, haloalkyl group, cycloalkyl group, heterocycloalkyl group, alkenyl group, haloalkenyl group, aryl group and heteroaryl group, 5 , R 6 and R 7 x is independently a linear or branched alkyl group, x is 1 to 6, y is 3 to 5, and

[0171] (b) A polymerization product of a monomer mixture containing one or more ophthalmic device-forming hydrophilic comonomers.

[0172] In a non-limiting exemplary embodiment which may be combined with one or more of the preceding paragraphs, in a monofunctional silicone monomer, R 1 , R 2 , R 3 and R 4 Hydrogen, C1~C 12 Alkyl alkyl groups, C1-C 12 Haloalkyl groups, C3-C 12 Cycloalkyl groups, C3-C 12 Heterocycloalkyl groups, C2-C 12 Alkenyl group, C2~C 12 Haloalkenyl group, C6~C 12 Aromatic groups and C6~C 12 It is a heteroaromatic group, R 5 , R 6 and R 7 These are independently linear or branched C1-C 12 It is an alkyl group, where x is between 1 and 6, and y is between 3 and 5.

[0173] In a non-limiting exemplary embodiment which may be combined with one or more of the preceding paragraphs, in a monofunctional silicone monomer, R 1 , R 2 , R 3 and R 4 R is independently a hydrogen atom and a C1-C6 alkyl group. 5 , R 6 and R 7 x is independently a linear or branched C1-C6 alkyl group, x is 1-6, and y is 3-5.

[0174] In a non-limiting exemplary embodiment which may be combined with one or more of the preceding paragraphs, in a monofunctional silicone monomer, R 1 , R 2 , R 3 and R 4 R is independently a C1-C3 alkyl group, 5 and R 6 R is independently a C1-C3 alkyl group, 7 x is a linear or branched C3-C6 alkyl group, x is 2-4, and y is 3-5.

[0175] In a non-limiting exemplary embodiment which may be combined with one or more of the preceding paragraphs, in a monofunctional silicone monomer, R 1 , R 2 , R 3 , R 4 , R 5 and R 6 is methyl, and R 7 x is a linear or branched C3-C6 alkyl group, x is 2-4, and y is 3-5.

[0176] In non-limiting exemplary embodiments, which may be combined with one or more of the preceding paragraphs, one or more ophthalmic device-forming hydrophilic comonomers are selected from the group consisting of unsaturated carboxylic acids, acrylamides, vinyl lactams, hydroxyl-containing (meth)acrylates, hydrophilic vinyl carbonates, hydrophilic vinyl carbamates, hydrophilic oxazolones, and poly(alkene glycols) functionalized with polymerizable groups.

[0177] In a non-limiting exemplary embodiment, which may be combined with one or more of the preceding paragraphs, one or more ophthalmic device-forming hydrophilic comonomers are selected from the group consisting of acrylamides, vinyl lactams, and hydroxyl group-containing (meth)acrylates.

[0178] In non-limiting exemplary embodiments, which may be combined with one or more of the preceding paragraphs, the acrylamide is one or more of N,N-dimethylacrylamide and N,N-dimethylmethacrylamide.

[0179] In a non-limiting exemplary embodiment, which may be combined with one or more of the preceding paragraphs, the cyclic lactam is one or more of N-vinyl-2-pyrrolidone, N-vinylcaprolactam, and N-vinyl-2-piperidone.

[0180] In non-limiting exemplary embodiments, which may be combined with one or more of the preceding paragraphs, the hydroxyl group-containing (meth)acrylate is one or more of 2-hydroxyethyl methacrylate (HEMA) and glycerol methacrylate.

[0181] In a non-limiting exemplary embodiment, which may be combined with one or more of the preceding paragraphs, the monomer mixture is:

[0182] Based on the total weight of the monomer mixture, one or more monofunctional silicone monomers in an amount of approximately 1% to approximately 40% by weight, and

[0183] The monomer mixture contains approximately 10% to 80% by weight of one or more ophthalmic device-forming hydrophilic comonomers.

[0184] In a non-limiting exemplary embodiment, which may be combined with one or more of the preceding paragraphs, the monomer mixture further comprises one or more non-functionalized comfort polymers.

[0185] In non-limiting exemplary embodiments, which may be combined with one or more of the preceding paragraphs, one or more unfunctionalized comfort polymers include polyvinylpyrrolidone polymers.

[0186] In non-limiting exemplary embodiments, which may be combined with one or more of the preceding paragraphs, the weight-average molecular weight of the polyvinylpyrrolidone polymer is at least about 10,000.

[0187] In non-limiting exemplary embodiments, which may be combined with one or more of the preceding paragraphs, the weight-average molecular weight of the polyvinylpyrrolidone polymer is approximately 10,000 to approximately 250,000.

[0188] In non-limiting exemplary embodiments, which may be combined with one or more of the preceding paragraphs, the weight-average molecular weight of the polyvinylpyrrolidone polymer is approximately 30,000 to approximately 100,000.

[0189] In a non-limiting exemplary embodiment, which may be combined with one or more of the preceding paragraphs, one or more non-functionalized comfort polymers are present in the monomer mixture in an amount of at least 6% by weight, based on the total weight of the monomer mixture.

[0190] In non-limiting exemplary embodiments, which may be combined with one or more of the preceding paragraphs, one or more non-functionalized comfort polymers are present in the monomer mixture in an amount ranging from 6% to about 10% by weight, based on the total weight of the monomer mixture.

[0191] In a non-limiting exemplary embodiment, which may be combined with one or more of the preceding paragraphs, the monomer mixture further comprises one or more functionalized comfort polymers.

[0192] In a non-limiting exemplary embodiment, which may be combined with one or more of the preceding paragraphs, one or more functionalized comfort polymers include one or more functionalized poloxamers and functionalized poloxamines.

[0193] In non-limiting exemplary embodiments, which may be combined with one or more of the preceding paragraphs, one or more functionalized comfort polymers include functionalized poloxamers derived from poloxamer block copolymers.

[0194] In a non-limiting exemplary embodiment, which may be combined with one or more of the preceding paragraphs, the functionalized poloxamer is one or more poloxamerge (meth)acrylates and reverse poloxamerge (meth)acrylates.

[0195] In non-limiting exemplary embodiments, which may be combined with one or more of the preceding paragraphs, one or more functionalized comfort polymers are present in the monomer mixture in an amount ranging from about 1% by weight to about 10% by weight, based on the total weight of the monomer mixture.

[0196] In a non-limiting exemplary embodiment, which may be combined with one or more of the preceding paragraphs, the monomer mixture further comprises one or more ophthalmic device-forming silicone comonomers.

[0197] In a non-limiting exemplary embodiment, which may be combined with one or more of the preceding paragraphs, one or more ophthalmic device-forming silicone comonomers include hydroxyl group-containing silicone comonomers.

[0198] In non-limiting exemplary embodiments, which may be combined with one or more of the preceding paragraphs, the hydroxyl group-containing silicone comonomer includes (3-methacryloxy-2-hydroxypropoxy)propylbis(trimethylsiloxy)methylsilane.

[0199] In non-limiting exemplary embodiments, which may be combined with one or more of the preceding paragraphs, one or more ophthalmic device-forming silicone comonomers include one or more bulky silicone comonomers.

[0200] In a non-limiting exemplary embodiment, which may be combined with one or more of the preceding paragraphs, one or more bulky silicone comonomers are of formula II: [ka]

[0201] (In the formula, X is -O- or -NR) 19 - represents (where R 19 (where R is hydrogen or a C1-C4 alkyl group), each R 17 R independently represents hydrogen or methyl, and each R 18 This independently represents a C1-C6 alkyl group, a phenyl group, or a group represented below. [ka]

[0202] (In the formula, each R 18’ (where is independently a C1-C6 alkyl radical or a phenyl radical, and h is 1-10), and comprises one or more bulky silicone-containing comonomers represented by the structure of formula III: [ka]

[0203] In the formula, X is -NR 19 - represents (where R 19(is hydrogen or a C1-C4 alkyl group), R 17 represents hydrogen or methyl, and each R 18 The group independently represents a C1-C6 alkyl group, a phenyl group, or a group represented as follows: [ka]

[0204] (In the formula, each R 18’ (where is independently a C1-C6 alkyl group or a phenyl group) and h is 1-10.

[0205] In non-limiting exemplary embodiments, which may be combined with one or more of the preceding paragraphs, one or more ophthalmic device-forming silicone comonomers are present in the monomer mixture in an amount ranging from about 5% to about 50% by weight, based on the total weight of the monomer mixture.

[0206] In a non-limiting exemplary embodiment, which may be combined with one or more of the preceding paragraphs, the monomer mixture further comprises one or more crosslinking agents, one or more reactive ultraviolet absorbers, and one or more reactive blue light absorbers.

[0207] In a non-limiting exemplary embodiment, which may be combined with one or more of the preceding paragraphs, the equilibrium water content of the ophthalmic device is approximately 35% to approximately 80% by weight.

[0208] In a non-limiting exemplary embodiment, which may be combined with one or more of the preceding paragraphs, the ophthalmic device is an optically transparent silicone hydrogel.

[0209] According to yet another aspect of this disclosure, a method for manufacturing an ophthalmic device is:

[0210] (a) Curing a monomer mixture in a mold, wherein the monomer mixture is

[0211] (i) One or more monofunctional silicone monomers represented by the structure of formula I: [ka]

[0212] (In the formula, R 1 , R 2 , R 3 and R 4 R is independently hydrogen, alkyl group, haloalkyl group, cycloalkyl group, heterocycloalkyl group, alkenyl group, haloalkenyl group, aryl group and heteroaryl group, 5 , R 6 and R 7 (where x is independently a linear or branched alkyl group, x is 1 to 6, and y is 3 to 5) and

[0213] (ii) A device containing one or more ophthalmic device-forming hydrophilic comonomers, which is cured,

[0214] (b) dry demolding of an ophthalmic device from a mold.

[0215] In a non-limiting exemplary embodiment which may be combined with one or more of the preceding paragraphs, in a monofunctional silicone monomer, R 1 , R 2 , R 3 and R 4 Hydrogen, C1~C 12 Alkyl alkyl groups, C1-C 12 Haloalkyl groups, C3-C 12 Cycloalkyl groups, C3-C 12 Heterocycloalkyl groups, C2-C 12 Alkenyl group, C2~C 12 Haloalkenyl group, C6~C 12 Aromatic groups and C6~C 12 It is a heteroaromatic group, R 5 , R 6 and R 7 These are independently linear or branched C1-C 12 It is an alkyl group, where x is between 1 and 6, and y is between 3 and 5.

[0216] In a non-limiting exemplary embodiment which may be combined with one or more of the preceding paragraphs, in a monofunctional silicone monomer, R 1 , R 2 , R 3 and R 4 R is independently a hydrogen atom and a C1-C6 alkyl group. 5 , R 6 and R 7 x is independently a linear or branched C1-C6 alkyl group, x is 1-6, and y is 3-5.

[0217] In a non-limiting exemplary embodiment which may be combined with one or more of the preceding paragraphs, in a monofunctional silicone monomer, R 1 , R 2 , R 3 and R 4 R is independently a C1-C3 alkyl group, 5 and R 6 R is independently a C1-C3 alkyl group, 7 x is a linear or branched C3-C6 alkyl group, x is 2-4, and y is 3-5.

[0218] In a non-limiting exemplary embodiment which may be combined with one or more of the preceding paragraphs, in a monofunctional silicone monomer, R 1 , R 2 , R 3 , R 4 , R 5 and R 6 is methyl, and R 7 x is a linear or branched C3-C6 alkyl group, x is 2-4, and y is 3-5.

[0219] In non-limiting exemplary embodiments, which may be combined with one or more of the preceding paragraphs, one or more ophthalmic device-forming hydrophilic comonomers are selected from the group consisting of unsaturated carboxylic acids, acrylamides, vinyl lactams, hydroxyl-containing (meth)acrylates, hydrophilic vinyl carbonates, hydrophilic vinyl carbamates, hydrophilic oxazolones, and poly(alkene glycols) functionalized with polymerizable groups.

[0220] In non-limiting exemplary embodiments, which may be combined with one or more of the preceding paragraphs, one or more ophthalmic device-forming hydrophilic comonomers are selected from the group consisting of acrylamide, vinyl lactams, and hydroxyl-containing (meth)acrylates.

[0221] In non-limiting exemplary embodiments, which may be combined with one or more of the preceding paragraphs, the acrylamide is one or more of N,N-dimethylacrylamide and N,N-dimethylmethacrylamide.

[0222] In a non-limiting exemplary embodiment, which may be combined with one or more of the preceding paragraphs, the cyclic lactam is one or more of N-vinyl-2-pyrrolidone, N-vinylcaprolactam, and N-vinyl-2-piperidone.

[0223] In non-limiting exemplary embodiments, which may be combined with one or more of the preceding paragraphs, the hydroxyl group-containing (meth)acrylate is one or more of 2-hydroxyethyl methacrylate (HEMA) and glycerol methacrylate.

[0224] In a non-limiting exemplary embodiment, which may be combined with one or more of the preceding paragraphs, the monomer mixture is:

[0225] Based on the total weight of the monomer mixture, one or more monofunctional silicone monomers in an amount of approximately 1% to approximately 40% by weight, and

[0226] The monomer mixture contains approximately 10% to 80% by weight of one or more ophthalmic device-forming hydrophilic comonomers.

[0227] In a non-limiting exemplary embodiment, which may be combined with one or more of the preceding paragraphs, the monomer mixture further comprises one or more non-functionalized comfort polymers.

[0228] In non-limiting exemplary embodiments, which may be combined with one or more of the preceding paragraphs, one or more unfunctionalized comfort polymers include polyvinylpyrrolidone polymers.

[0229] In non-limiting exemplary embodiments, which may be combined with one or more of the preceding paragraphs, the weight-average molecular weight of the polyvinylpyrrolidone polymer is at least about 10,000.

[0230] In non-limiting exemplary embodiments, which may be combined with one or more of the preceding paragraphs, the weight-average molecular weight of the polyvinylpyrrolidone polymer is approximately 10,000 to approximately 250,000.

[0231] In non-limiting exemplary embodiments, which may be combined with one or more of the preceding paragraphs, the weight-average molecular weight of the polyvinylpyrrolidone polymer is approximately 30,000 to approximately 100,000.

[0232] In a non-limiting exemplary embodiment, which may be combined with one or more of the preceding paragraphs, one or more non-functionalized comfort polymers are present in the monomer mixture in an amount of at least 6% by weight, based on the total weight of the monomer mixture.

[0233] In non-limiting exemplary embodiments, which may be combined with one or more of the preceding paragraphs, one or more non-functionalized comfort polymers are present in the monomer mixture in an amount ranging from 6% to about 10% by weight, based on the total weight of the monomer mixture.

[0234] In a non-limiting exemplary embodiment, which may be combined with one or more of the preceding paragraphs, the monomer mixture further comprises one or more functionalized comfort polymers.

[0235] In a non-limiting exemplary embodiment, which may be combined with one or more of the preceding paragraphs, one or more functionalized comfort polymers include one or more functionalized poloxamers and functionalized poloxamines.

[0236] In non-limiting exemplary embodiments, which may be combined with one or more of the preceding paragraphs, one or more functionalized comfort polymers include functionalized poloxamers derived from poloxamer block copolymers.

[0237] In a non-limiting exemplary embodiment, which may be combined with one or more of the preceding paragraphs, the functionalized poloxamer is one or more poloxamerge (meth)acrylates and reverse poloxamerge (meth)acrylates.

[0238] In non-limiting exemplary embodiments, which may be combined with one or more of the preceding paragraphs, one or more functionalized comfort polymers are present in the monomer mixture in an amount ranging from about 1% by weight to about 10% by weight, based on the total weight of the monomer mixture.

[0239] In a non-limiting exemplary embodiment, which may be combined with one or more of the preceding paragraphs, the monomer mixture further comprises one or more ophthalmic device-forming silicone comonomers.

[0240] In a non-limiting exemplary embodiment, which may be combined with one or more of the preceding paragraphs, one or more ophthalmic device-forming silicone comonomers include hydroxyl group-containing silicone comonomers.

[0241] In non-limiting exemplary embodiments, which may be combined with one or more of the preceding paragraphs, the hydroxyl group-containing silicone comonomer includes (3-methacryloxy-2-hydroxypropoxy)propylbis(trimethylsiloxy)methylsilane.

[0242] In non-limiting exemplary embodiments, which may be combined with one or more of the preceding paragraphs, one or more ophthalmic device-forming silicone comonomers include one or more bulky silicone comonomers.

[0243] In a non-limiting exemplary embodiment, which may be combined with one or more of the preceding paragraphs, one or more bulky silicone comonomers are of formula II: [ka]

[0244] (In the formula, X is -O- or -NR) 19 - represents (where R 19 (where R is hydrogen or a C1-C4 alkyl group), each R 17 R independently represents hydrogen or methyl, and each R 18 The group independently represents a C1-C6 alkyl group, a phenyl group, or a group represented as follows: [ka]

[0245] (In the formula, each R 18’ (where is independently a C1-C6 alkyl radical or a phenyl radical) and h is 1-10, or comprises one or more bulky silicone-containing comonomers represented by the structure of formula III: [ka]

[0246] In the formula, X is -NR 19 - represents (where R 19 (is hydrogen or a C1-C4 alkyl group), R 17 represents hydrogen or methyl, and each R 18 The group independently represents a C1-C6 alkyl group, a phenyl group, or a group represented as follows: [ka]

[0247] (In the formula, each R 18’ (where represents a C1-C6 alkyl group or a phenyl group independently), and h is 1-10.

[0248] In a non-limiting exemplary embodiment, which may be combined with one or more of the preceding paragraphs, one or more ophthalmic device-forming silicone comonomers are present in the monomer mixture in an amount ranging from about 5% to about 50% by weight, based on the total weight of the monomer mixture.

[0249] In a non-limiting exemplary embodiment, which may be combined with one or more of the preceding paragraphs, the monomer mixture further comprises one or more crosslinking agents, one or more reactive ultraviolet absorbers, and one or more reactive blue light absorbers.

[0250] In a non-limiting exemplary embodiment, which may be combined with one or more of the preceding paragraphs, the equilibrium water content of the ophthalmic device is approximately 35% to approximately 80% by weight.

[0251] In a non-limiting exemplary embodiment, which may be combined with one or more of the preceding paragraphs, the ophthalmic device is an optically transparent silicone hydrogel.

[0252] The various features disclosed herein are described in the context of a single embodiment for the sake of brevity, but may be provided separately or in any suitable partial combination. All combinations of embodiments are specifically encompassed by the exemplary embodiments disclosed herein as if every possible combination were disclosed individually and explicitly. Furthermore, all partial combinations enumerated in embodiments describing such variables are also specifically encompassed in the compositions of the present invention and are disclosed herein as if every possible such partial combination were disclosed individually and explicitly herein.

[0253] It will be understood that various modifications are possible to the embodiments disclosed herein. Therefore, the above description should be interpreted not as limiting, but merely as an example of preferred embodiments. For example, the functions described and implemented above as the best mode for carrying out the invention are for illustrative purposes only. Those skilled in the art can implement other configurations and methods without departing from the scope and spirit of the invention. Furthermore, those skilled in the art will be able to conceive of other modifications within the scope and spirit of the features and advantages appended herein.

Claims

1. Formula I: [Chemistry I] A monofunctional silicone monomer represented by the structure, In the formula, R １ , R ２ , R ３ and R ４ R is independently hydrogen, alkyl group, haloalkyl group, cycloalkyl group, heterocycloalkyl group, alkenyl group, haloalkenyl group, aryl group and heteroaryl group, ５ , R ６ and R ７ A monofunctional silicone monomer in which x is independently a linear or branched alkyl group, x is 1 to 6, and y is 3 to 5.

2. R １ 、 R ２ 、 R ３ and R ４ are independently hydrogen, C １ -C １２ alkyl group, C １ -C １２ haloalkyl group, C ３ -C １２ cycloalkyl group, C ３ -C １２ heterocycloalkyl group, C ２ -C １２ alkenyl group, C ２ -C １２ haloalkenyl group, C ６ -C １２ aromatic group and C ６ -C １２ heteroaromatic group, and R ５ 、 R ６ and R ７ are independently straight-chain or branched C １ -C １２ alkyl group, x is 1 to 6, y is 3 to 5, the monofunctional silicone monomer according to claim 1.

3. R １ , R ２ , R ３ and R ４ Hydrogen and C are independent of each other. １ ~C ６ It is an alkyl group, R ５ , R ６ and R ７ C is independently a linear or branched chain １ ~C ６ The monofunctional silicone monomer according to claim 1, wherein it is an alkyl group, x is 1 to 6, and y is 3 to 5.

4. R １ , R ２ , R ３ and R ４ C is independent １ ~C ３ It is an alkyl group, R ５ and R ６ C is independent １ ~C ３ It is an alkyl group, R ７ C is a straight-chain or branched-chain C ３ ~C ６ The monofunctional silicone monomer according to claim 1, wherein it is an alkyl group, x is 2 to 4, and y is 3 to 5.

5. R １ , R ２ , R ３ , R ４ , R ５ and R ６ is methyl, R ７ C is a straight-chain or branched-chain C ３ ~C ６ The monofunctional silicone monomer according to claim 1, wherein it is an alkyl group, x is 2 to 4, and y is 3 to 5.

6. An ophthalmic device which is a polymerization product of a monomer mixture, wherein the monomer mixture is (a) Equation I: [Chemistry I] One or more monofunctional silicone monomers represented by the structure shown. (In the formula, R １ , R ２ , R ３ and R ４ R is independently hydrogen, alkyl group, haloalkyl group, cycloalkyl group, heterocycloalkyl group, alkenyl group, haloalkenyl group, aryl group and heteroaryl group, ５ , R ６ and R ７ (where x is independently a linear or branched alkyl group, x is 1 to 6, and y is 3 to 5), and (b) An ophthalmic device comprising one or more ophthalmic device-forming hydrophilic comonomers.

7. In the monofunctional silicone monomer, R １ ,R ２ ,R ３ and R ４ are independently hydrogen, C １ -C １２ alkyl group, C １ -C １２ haloalkyl group, C ３ -C １２ cycloalkyl group, C ３ -C １２ heterocycloalkyl group, C ２ -C １２ alkenyl group, C ２ -C １２ haloalkenyl group, C ６ -C １２ aromatic group and C ６ -C<​​​​​​​​​​​

8. In the monofunctional silicone monomer, R １ , R ２ , R ３ and R ４ Hydrogen and C are independent of each other. １ ~C ６ It is an alkyl group, R ５ , R ６ and R ７ C is independently a linear or branched chain １ ~C ６ The ophthalmic device according to claim 6, wherein it is an alkyl group, x is 1 to 6, and y is 3 to 5.

9. In the monofunctional silicone monomer, R １ , R ２ , R ３ and R ４ C is independent １ ~C ３ It is an alkyl group, R ５ and R ６ C is independent １ ~C ３ It is an alkyl group, R ７ C is a straight-chain or branched-chain C ３ ~C ６ The ophthalmic device according to claim 6, wherein it is an alkyl group, x is 2 to 4, and y is 3 to 5.

10. In the monofunctional silicone monomer, R １ , R ２ , R ３ , R ４ , R ５ and R ６ is methyl, R ７ C is a straight-chain or branched-chain C ３ ~C ６ The ophthalmic device according to claim 6, wherein it is an alkyl group, x is 2 to 4, and y is 3 to 5.

11. The ophthalmic device according to any one of claims 6 to 10, wherein the one or more ophthalmic device-forming hydrophilic comonomers are selected from the group consisting of unsaturated carboxylic acids, acrylamides, vinyl lactams, hydroxyl group-containing (meth)acrylates, hydrophilic vinyl carbonates, hydrophilic vinyl carbamates, hydrophilic oxazolones, and poly(alkene glycols) functionalized with polymerizable groups.

12. The ophthalmic device according to any one of claims 6 to 10, wherein the one or more ophthalmic device-forming hydrophilic comonomers are selected from the group consisting of acrylamide, vinyl lactam, and hydroxyl group-containing (meth)acrylate.

13. The monomer mixture is Based on the total weight of the monomer mixture, approximately 1% by weight to approximately 40% by weight of one or more of the monofunctional silicone monomers, An ophthalmic device according to any one of claims 6 to 12, comprising about 10% to 80% by weight of one or more of the ophthalmic device-forming hydrophilic comonomers based on the total weight of the monomer mixture.

14. The ophthalmic device according to any one of claims 6 to 13, wherein the monomer mixture further comprises one or more non-functionalized comfort polymers.

15. The ophthalmic device according to claim 14, wherein the one or more non-functionalized comfort polymers include a polyvinylpyrrolidone polymer.

16. The ophthalmic device according to claim 15, wherein the weight-average molecular weight of the polyvinylpyrrolidone polymer is at least about 10,000.

17. The ophthalmic device according to claim 15, wherein the weight-average molecular weight of the polyvinylpyrrolidone polymer is approximately 10,000 to approximately 250,000.

18. The ophthalmic device according to any one of claims 15 to 17, wherein the one or more non-functionalized comfort polymers are present in the monomer mixture in an amount of at least 6% by weight, based on the total weight of the monomer mixture.

19. The ophthalmic device according to any one of claims 15 to 17, wherein the one or more non-functionalized comfort polymers are present in the monomer mixture in an amount ranging from 6% by weight to about 10% by weight, based on the total weight of the monomer mixture.

20. The ophthalmic device according to any one of claims 6 to 19, wherein the monomer mixture further comprises one or more functionalized comfort polymers.

21. The ophthalmic device according to claim 20, wherein the one or more functionalized comfort polymers include one or more functionalized poloxamers and functionalized poloxamines.

22. The ophthalmic device according to claim 20 or 21, wherein the one or more functionalized comfort polymers are present in the monomer mixture in an amount ranging from about 1% by weight to about 10% by weight, based on the total weight of the monomer mixture.

23. The ophthalmic device according to any one of claims 6 to 22, wherein the monomer mixture further comprises one or more ophthalmic device-forming silicone comonomers.

24. The ophthalmic device according to claim 23, wherein the one or more ophthalmic device-forming silicone comonomers include a hydroxyl group-containing silicone comonomer.

25. The ophthalmic device according to claim 24, wherein the hydroxyl group-containing silicone comonomer comprises (3-methacryloxy-2-hydroxypropoxy)propylbis(trimethylsiloxy)methylsilane.

26. The ophthalmic device according to any one of claims 23 to 25, wherein the one or more ophthalmic device-forming silicone comonomers comprises one or more bulky silicone comonomers.

27. The one or more bulky silicone comonomers are defined by formula II: 【Chemistry II】 One or more bulky silicone-containing comonomers represented by the structure (In the formula, X is -O- or -NR) １９ - represents (R １９ is hydrogen or C １ ~C ４ Each R is an alkyl group. １７ R independently represents hydrogen or methyl, and each R １８ C is independent １ ~C ６ Represents an alkyl group, a phenyl group, or a group represented below. 【Chemical Si】 (In the formula, each R １８’ C is independent １ ~C ６ (representing an alkyl radical or a phenyl radical), and h is 1 to 10), or formula III: 【Chemistry III】 One or more bulky silicone-containing comonomers represented by the structure (In the formula, X is -NR) １９ - represents (R １９ is hydrogen or C １ ~C ４ (It is an alkyl group), R １７ represents hydrogen or methyl, and each R represents hydrogen or methyl. １８ C is independent １ ~C ６ Represents an alkyl group, a phenyl group, or a group represented below. 【Chemical Si】 (In the formula, each R １８’ C is independent １ ~C ６ The ophthalmic device according to claim 26, comprising an alkyl group or a phenyl group, and where h is 1 to 10.

28. The ophthalmic device according to any one of claims 23 to 27, wherein the one or more ophthalmic device-forming silicone comonomers are present in the monomer mixture in an amount ranging from about 5% by weight to about 50% by weight, based on the total weight of the monomer mixture.

29. The ophthalmic device according to any one of claims 6 to 28, wherein the monomer mixture further comprises one or more crosslinking agents, one or more reactive ultraviolet absorbers, and one or more reactive blue light absorbers.

30. An ophthalmic device according to any one of claims 6 to 29, wherein the equilibrium water content is approximately 35% by weight to approximately 80% by weight.

31. An ophthalmic device according to any one of claims 6 to 30, wherein the silicone hydrogel has optical transparency.

32. A method for fabricating ophthalmic devices, (a) Curing a monomer mixture in a mold, wherein the monomer mixture is (i) Equation I: [Chemistry I] One or more monofunctional silicone monomers represented by the structure shown. (In the formula, R １ , R ２ , R ３ and R ４ R is independently hydrogen, alkyl group, haloalkyl group, cycloalkyl group, heterocycloalkyl group, alkenyl group, haloalkenyl group, aryl group and heteroaryl group, ５ , R ６ and R ７ (where x is independently a linear or branched alkyl group, x is 1 to 6, and y is 3 to 5), and (ii) A hydrophilic comonomer containing one or more ophthalmic device-forming compounds, which can be cured. (b) A method comprising dry demolding an ophthalmic device from a mold.

33. In the monofunctional silicone monomer, R １ , R ２ , R ３ and R ４ Hydrogen and C are independent of each other. １ ~C １２ alkyl group, C １ ~C １２ Haloalkyl group, C ３ ~C １２ Cycloalkyl groups, C ３ ~C １２ Heterocycloalkyl groups, C ２ ~C １２ Alkenyl group, C ２ ~C １２ Haloalkenyl group, C ６ ~C １２ Aromatic group and C ６ ~C １２ It is a heteroaromatic group, R ５ , R ６ and R ７ C is independently a linear or branched chain １ ~C １２ The method according to claim 32, wherein the alkyl group is 1 to 6 and y is 3 to 5.

34. In the monofunctional silicone monomer, R １ , R ２ , R ３ and R ４ Hydrogen and C are independent of each other. １ ~C ６ It is an alkyl group, R ５ , R ６ and R ７ C is independently a linear or branched chain １ ~C ６ The method according to claim 32, wherein the alkyl group is 1 to 6 and y is 3 to 5.

35. In the monofunctional silicone monomer, R １ , R ２ , R ３ , R ４ , R ５ and R ６ is methyl, R ７ C is a straight-chain or branched-chain C ３ ~C ６ The method according to claim 32, wherein the alkyl group is 2 to 4 and y is 3 to 5.

36. The method according to any one of claims 32 to 35, wherein the one or more ophthalmic device-forming hydrophilic comonomers are selected from the group consisting of unsaturated carboxylic acids, acrylamides, vinyl lactams, hydroxyl group-containing (meth)acrylates, hydrophilic vinyl carbonates, hydrophilic vinyl carbamates, hydrophilic oxazolones, and poly(alkene glycols) functionalized with polymerizable groups.

37. The monomer mixture is Based on the total weight of the monomer mixture, approximately 1% by weight to approximately 40% by weight of one or more of the monofunctional silicone monomers, The method according to any one of claims 32 to 36, comprising about 10% to 80% by weight of one or more ophthalmic device-forming hydrophilic comonomers based on the total weight of the monomer mixture.

38. The method according to any one of claims 32 to 37, wherein the monomer mixture further comprises one or more non-functionalized comfort polymers.

39. The method according to claim 38, wherein the one or more non-functionalized comfort polymers include a polyvinylpyrrolidone polymer.

40. The method according to claim 39, wherein the weight-average molecular weight of the polyvinylpyrrolidone polymer is at least about 10,000.

41. The method according to any one of claims 38 to 40, wherein the one or more non-functionalized comfort polymers are present in the monomer mixture in an amount of at least 6% by weight, based on the total weight of the monomer mixture.

42. The method according to any one of claims 38 to 40, wherein the one or more non-functionalized comfort polymers are present in the monomer mixture in an amount ranging from 6% by weight to about 10% by weight, based on the total weight of the monomer mixture.

43. The method according to any one of claims 32 to 42, wherein the monomer mixture further comprises one or more functionalized comfort polymers.

44. The method according to claim 43, wherein the one or more functionalized comfort polymers include one or more functionalized poloxamers and functionalized poloxamines.

45. The method according to any one of claims 32 to 44, wherein the monomer mixture further comprises one or more ophthalmic device-forming silicone comonomers.

46. The method according to claim 45, wherein the one or more ophthalmic device-forming silicone comonomers include (3-methacryloxy-2-hydroxypropoxy)propylbis(trimethylsiloxy)methylsilane.

47. The method according to claim 45 or 46, wherein the one or more ophthalmic device-forming silicone comonomers include one or more bulky silicone comonomers.

48. The method according to any one of claims 45 to 47, wherein the one or more ophthalmic device-forming silicone comonomers are present in the monomer mixture in an amount ranging from about 5% by weight to about 50% by weight, based on the total weight of the monomer mixture.

49. The method according to any one of claims 32 to 48, wherein the monomer mixture further comprises one or more crosslinking agents, one or more reactive ultraviolet absorbers, and one or more reactive blue light absorbers.

50. The method according to any one of claims 32 to 49, wherein the equilibrium water content of the ophthalmic device is about 35% by weight to about 80% by weight.

51. The method according to any one of claims 32 to 49, wherein the ophthalmic device is an optically transparent silicone hydrogel.

Images