Silicone hydrogel

Abstract

The silicone hydrogel is a polymerization product of a monomer mixture containing (a) one or more monofunctional silicone monomers represented by the structure of formula I [Chemical 1] JPEG2026514358000072.jpg26114 (wherein, R 1 , R 2 , R 3 and R 4 are independently hydrogen, a C1-C 12 alkyl group, a C1-C 12 haloalkyl group, a C3-C 12 cycloalkyl group, a C3-C 12 heterocycloalkyl group, a C2-C 12 alkenyl group, a C2-C 12 haloalkenyl group, a C6-C 12 aryl group and a C6-C 12 heteroaryl group, and R 5 , R 6 and R 7 are independently a linear or branched C1-C 12 alkyl group, x is 1-6, and y is 3-15), and (b) one or more silicone hydrogel-forming silicone comonomers.

Description

Technical Field

[0001] Priority Claim This application claims the priority of U.S. Provisional Patent Application No. 63 / 453,851, entitled "Silicone Hydrogels," filed on March 22, 2023, the entire content of which is incorporated herein by reference.

Background Art

[0002] Hydrogels are a desirable class of materials for many biomedical applications, including contact lenses and intraocular lenses. A hydrogel is a hydrated cross-linked polymer system that contains water in an equilibrium state. Silicone hydrogels are a known class of hydrogels and are characterized by containing silicone-containing substances. Typically, a silicone-containing monomer is copolymerized with a hydrophilic monomer by free radical polymerization, and either the silicone-containing monomer or the hydrophilic monomer functions as a cross-linking agent (a cross-linking agent defined as a monomer having multiple polymerizable functional groups), or another cross-linking agent can be used.

Summary of the Invention

[0003] In an exemplary embodiment, the silicone hydrogel comprises

[0004] (a) one or more monofunctional silicone monomers represented by the structure of Formula I

Chemical Formula

[0005] (b) A polymerization product of a monomer mixture containing one or more silicone hydrogel-forming silicone comonomers.

[0006] In another exemplary embodiment, a method for preparing a silicone hydrogel is:

[0007] (a) Curing a monomer mixture in a mold, wherein the monomer mixture is

[0008] (i) One or more monofunctional silicone monomers represented by the structure of formula I [ka] (In the formula, R1, R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , x and y are as defined herein), and

[0009] (ii) A material containing one or more silicone hydrogel-forming silicone comonomers, which is cured,

[0010] (b) The process of releasing the silicone hydrogel from the mold is included. [Modes for carrying out the invention]

[0011] Various exemplary embodiments described herein relate to silicone hydrogels with improved oxygen permeability and methods for producing the same.

[0012] Hydrogels are a desirable class of material for contact lenses. Hydrogels are hydrated, cross-linked polymer systems that contain water in equilibrium. Hydrogel lenses offer relatively high oxygen permeability, as well as desirable biocompatibility and comfort.

[0013] Oxygen permeability (Dk) is a crucial factor in contact lens design for maintaining the eye health of contact lens wearers. For example, contact lenses must allow sufficient oxygen to reach the cornea for long-term corneal health. Since the cornea does not receive oxygen from the blood supply like other tissues, contact lenses must also allow oxygen from the surrounding air to reach the cornea. Because "soft" contact lenses fit snugly to the shape of the eye, oxygen cannot easily bypass the lens. Therefore, soft contact lenses must allow oxygen to diffuse through the lens and reach the cornea.

[0014] Another ophthalmic fit requirement for soft contact lenses is that the lens must not adhere too strongly to the eye. For example, consumers must be able to easily remove the lens from their eye for disinfection, cleaning, or disposal. However, the lens must also be mobile on the eye to facilitate tear flow between the lens and the eye. This tear flow between the lens and the eye allows debris such as foreign particles or dead epithelial cells to be swept away from under the lens and eventually through the tear film. Therefore, contact lenses must not adhere so strongly to the eye that proper movement of the lens on the eye is hindered.

[0015] Soft contact lens materials are manufactured by polymerizing and crosslinking hydrophilic monomers such as 2-hydroxyethyl methacrylate (HEMA) and N-vinylpyrrolidone (NVP). Polymers produced by polymerizing these hydrophilic monomers exhibit significant hydrophilicity themselves and can absorb large amounts of water into the polymer matrix. Because of their water-absorbing ability, these polymers are often called "hydrogels." These hydrogels are optically transparent and have high hydration water levels, making them useful materials for manufacturing soft contact lenses. However, these hydrogels are known to have low oxygen permeability.

[0016] Silicone hydrogels (SiHy), such as contact lenses, manufactured from hydrated cross-linked polymer materials containing silicone and a certain amount of water in a lens polymer matrix in equilibrium, are becoming increasingly popular compared to conventional hydrogels due to their high oxygen permeability and minimal adverse effects on corneal health. However, incorporating silicone into contact lens materials can undesirably affect the hydrophilicity and wettability of the silicone hydrogel because silicone is hydrophobic and tends to migrate to the lens surface exposed to air. Therefore, optimal contact lenses need to possess at least both excellent oxygen permeability and excellent tear film wettability.

[0017] The exemplary embodiments described herein overcome the above-mentioned drawbacks by using one or more monofunctional silicone monomers of formula I to form a silicone hydrogel with improved oxygen permeability.

[0018] As used herein, the term "SiHy" is understood to mean silicone hydrogel.

[0019] As used herein, the terms “hydrogel” or “hydrogel material” refer to a crosslinked polymer material having a three-dimensional polymer network (i.e., polymer matrix) that is insoluble in water but can hold at least about 10 weight percent of water in the polymer matrix when fully hydrated.

[0020] As used herein, “silicone hydrogel” or “SiHy” interchangeably refers to a silicone-containing hydrogel. Silicone hydrogels (SiHy) are typically obtained by copolymerizing 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.

[0021] As used herein, the term "(meth)" represents any methyl substituent. Therefore, terms such as "(meth)acrylate" represent methacrylate or acrylate, and "(meth)acrylamide" represent methacrylamide or acrylamide.

[0022] In non-limiting exemplary embodiments, the silicone hydrogels disclosed herein are:

[0023] (a) Monofunctional silicone monomer 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 R 7 (where x is independently a linear or branched alkyl group, x is 1-6, and y is 3-15), and

[0024] (b) A polymerization product of a monomer mixture containing one or more silicone hydrogel-forming silicone comonomers.

[0025] In some embodiments, the monofunctional silicone monomer R represented by the structure of formula I 1 , R 2 , R 3 and R 4 These are independently 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 8.

[0026] In some embodiments, the monofunctional silicone monomer R represented by the structure of formula I 1 , R 2 , R 3 and R 4 R is independently hydrogen, C1-C6 alkyl, and 5 , R 6 and R 7 is independently a linear or branched C1-C6 alkyl group, x is 1-6, and y is 3-8.

[0027] In some embodiments, 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, 7is a linear or branched C3-C6 alkyl group, x is 2-4, and y is 3-15.

[0028] Typical examples of alkyl groups for use 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 the rest of the molecule, such as methyl, ethyl, n-propyl, 1-methylethyl (isopropyl), n-butyl, n-pentyl, methylene, ethylene, etc., which 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.

[0029] Typical examples of cycloalkyl groups for use herein include, for example, substituted or unsubstituted non-aromatic monocyclic or polycyclic ring systems of 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, adamantylnorbornyl group, bridging cyclic group, or spirobicyclo group (e.g., spiro-(4,4)-non-2-yl), which optionally include one or more heteroatoms (e.g., O and N) to form heterocycloalkyl groups.

[0030] Typical examples of cycloalkylalkyl groups for use herein include, for example, substituted or unsubstituted cyclic ring-containing groups containing about 4 to about 30 carbon atoms directly bonded to an alkyl group, or 3 to about 6 carbon atoms, where any carbon of the alkyl group forms a stable structure bonded to the main structure of the monomer, such as cyclopropylmethyl, cyclobutylethyl, and cyclopentylethyl, where the cyclic ring can optionally contain one or more heteroatoms (e.g., O and N) to form a heterocycloalkylalkyl group.

[0031] Typical examples of cycloalkenyl groups for use herein include, for example, substituted or unsubstituted cyclic ring-containing groups having at least one carbon-carbon double bond and containing about 3 to about 30 or 3 to about 6 carbon atoms, such as cyclopropenyl, cyclobutenyl, and cyclopentenyl, where the cyclic ring can optionally contain one or more heteroatoms (e.g., O and N) to form a heterocycloalkenyl group.

[0032] Typical examples of aryl groups for use herein include, for example, substituted or unsubstituted monocyclic or polycyclic aromatic 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, which optionally contain one or more heteroatoms (e.g., O and N) to form heteroaryl groups.

[0033] In exemplary embodiments, the monofunctional silicone monomer represented by the structure of formula I is commercially available from suppliers such as Shin-Etsu Chemical Co., Ltd., or can be produced by methods within the technical scope of those skilled in the art. For example, in exemplary embodiments, the monofunctional silicone monomer represented by the structure of formula I can be prepared according to the following reaction scheme I. [ka]

[0034] In some embodiments, 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 5% 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 7% to about 15% by weight, based on the total weight of the monomer mixture.

[0035] The monomer mixture further comprises one or more silicone hydrogel-forming silicone comonomers as component (b). Typical silicone hydrogel-forming silicone comonomers for use in forming silicone hydrogels according to exemplary embodiments are well known in the art, and many 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.

[0036] In exemplary embodiments, which may be combined with one or more of the preceding paragraphs, one or more silicone hydrogel-forming silicone comonomers may include one or more non-bulky organosilicon-containing monomers as a representative class of silicone hydrogel-forming silicone comonomers. As used herein, “organosilicon-containing monomer” contains at least one [siloxanyl] or at least one [silyl-alkyl-siloxanyl] 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: [ka]

[0037] In the formula, L is an ethylenically unsaturated polymerizable group, V is a linking group or bond, and R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7, R 8 and R 9 R is independently hydrogen, alkyl group, haloalkyl group, cycloalkyl group, heterocycloalkyl group, alkenyl group, haloalkenyl group, or aryl group. 10 and R 11 R is independently a hydrogen atom or an alkyl group (where R 10 and R 11 (At least one of them is hydrogen), y is between 2 and 7, and n is between 1 and 100 or 1 and 20.

[0038] Ethylene-unsaturated polymerizable groups are well known to those skilled in the art. Suitable ethylenically unsaturated polymerizable groups include, for example, (meth)acrylates, vinyl carbonates, O-vinylcarbamates, N-vinylcarbamates, and (meth)acrylamides.

[0039] The linking group can be any divalent radical or part, for example, a substituted or unsubstituted C1-C 12 The material comprises alkyl groups, alkyl ether groups, alkenyl groups, alkenyl ether groups, haloalkyl groups, substituted or unsubstituted siloxane groups, and ring-opening polymerizable monomers.

[0040] In some embodiments, V is (meth)acrylate and L is C1-C 12 It is an alkylene group, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 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.

[0041] In some embodiments, V is a (meth)acrylate, L is a C1-C6 alkyl group, and R 1 , R2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 are independently C1-C6 alkyl groups, R 10 and R 11 are independently H or a C1-C6 alkyl group, y is 2-7, and n is 1-20.

[0042] The non-bulky organosilicon-containing monomer represented by the structure of Formula IIa is known in the art. For example, see U.S. Patent Nos. 7,915,323, 7,994,356, 8,420,711, 8,8,27,447, and 9,039,174, the contents of which are incorporated herein by reference.

[0043] In exemplary embodiments that may be combined with one or more of the foregoing paragraphs, one or more non-bulky organosilicon-containing monomers may further comprise a compound represented by the structure of Formula IIb:

Chemical Formula

[0044] In the formula, R 12 is H or methyl, X is O or NR 16 , in the formula, R<000,0101>is selected from H or C1-C4 alkyl optionally further substituted with one or more hydroxyl groups, and in some embodiments is H or methyl, R 13 is 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, and in another embodiment is a C1-C6 alkylene group optionally substituted with ether, hydroxyl groups, and combinations thereof, and in yet another embodiment is a C1 or C3-C4 alkylene group optionally substituted with ether, hydroxyl groups, and combinations thereof, each R 14R is independently a C1-C4 alkyl group which may be substituted with phenyl or fluorine, a hydroxyl group or an ether, and 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, and R 15 is a C1-C4 alkyl group, a is 2-50, and in some embodiments it is 5-15.

[0045] 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.

[0046] Typical examples of non-bulky organosilicon-containing monomers include the following:

[0047] M1EDS6: A compound having the following structure, available from Gelest: [ka]

[0048] MCR-M11: A compound having the following structure: [ka]

[0049] M1-MCR-C12: A compound having the following structure: [ka] (In the formula, the mean of n is 12).

[0050] In exemplary embodiments, which may be combined with one or more of the preceding paragraphs, one or more silicone hydrogel-forming silicone comonomers may include one or more polysiloxane prepolymers represented by the structure of Formula III, as a representative class of silicone hydrogel-forming silicone comonomers: [ka] In the formula, each V is independently a reactive functional end group, including, for example, a hydroxyl group-containing reactive functional end group and an amine-containing reactive functional end group, R 17 ~R 22 These are independently linear or branched, substituted or unsubstituted C1-C12 30 Alkyl, substituted or unsubstituted C3-C 30 Cycloalkyl groups, substituted or unsubstituted C4-C 30 Cycloalkylalkyl groups, substituted or unsubstituted C3-C 30 Cycloalkenyl group, substituted or unsubstituted C6-C 30 Aryl groups, and substituted or unsubstituted C7-C 30 It is an arylalkyl group, and L is an independent linking group.

[0051] The hydroxyl-containing reactive functional end groups used herein are groups of the general formula -OH. Typical examples of amine-containing reactive functional end groups used herein include, for example, (meth)acrylamide-containing reactive functional end groups.

[0052] The linking group L is independently a linear or branched alkyl group, cycloalkyl group, aryl group, ether group or polyether group, and ester group, as defined herein.

[0053] Typical examples of polysiloxane prepolymers are as follows: [ka]

[0054] The methods for producing the polysiloxane prepolymers described herein are well known and within the technical scope of those skilled in the art. Furthermore, polysiloxane prepolymers are commercially available from suppliers such as Gelest, Silar, Shin-Etsu, Momentive, and Siltech.

[0055] In exemplary embodiments, which may be combined with one or more of the preceding paragraphs, one or more silicone hydrogel-forming silicone comonomers may include one or more bulky silicone-containing monomers as a representative class of silicone hydrogel-forming silicone comonomers. In one embodiment, preferred 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 silicone-containing monomer represented by the structure of formula IV: [ka]

[0056] In the formula, X is -O- or -NR 19 - represents (each R 19 (is hydrogen or a C1-C4 alkyl group), R 17 R independently represents hydrogen or methyl, and each R 18 The following groups are independently represented: lower alkyl radicals such as C1-C6 groups, phenyl radicals, or groups represented by the following structures: [ka]

[0057] (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 V: [ka]

[0058] (In the formula, X is -NR) 19 - represents (R 19 (where represents hydrogen or C1-C4 alkyl), R 17 represents hydrogen or methyl, and each R represents hydrogen or methyl. 18 represents independently a lower alkyl radical, a phenyl radical, or a group represented by the following structure: [ka]

[0059] (In the formula, each R 18’ (where is independently a lower alkyl radical or a phenyl radical, and h is 1 to 10).

[0060] 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, and methyldi(trimethylsiloxy)methacryloxymethylsilane, (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, such as a tris(trimethylsiloxy)silylpropyl methacrylate-containing monomer.

[0061] Such bulky silicone-containing 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.

[0062] In exemplary embodiments, which may be combined with one or more of the preceding paragraphs, one or more silicone hydrogel-forming silicone comonomers may include one or more silicone-containing vinyl carbonate or vinyl carbamate monomers as a representative class of silicone hydrogel-forming silicone comonomers. Suitable silicone-containing vinyl carbonate or vinyl carbamate monomers include, for example, 1,3-bis[4-vinyloxycarbonyloxy)buta-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, trimethylsilylmethyl vinyl carbonate, and mixtures thereof.

[0063] In exemplary embodiments, which may be combined with one or more of the preceding paragraphs, one or more silicone hydrogel-forming silicone comonomers may include, as a representative class of silicone hydrogel-forming silicone comonomers, one or more polyurethane-polysiloxane macromonomers (sometimes also called prepolymers) that may have hard-soft-hard blocks, such as 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 Methacrylates 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 entirety of which is incorporated herein by reference. Further examples of silicone urethane monomers are represented by formulas VI and VII: [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 approximately 40 carbon atoms and potentially containing ether bonds, thio bonds, or amine bonds in the main chain. * represents a urethane bond or ureid bond. a is at least 1, A independently represents the divalent polymer radical of formula VIII. [ka] (In the formula, each R s (Independently, represents an alkyl group or fluorine-substituted alkyl group having 1 to about 10 carbon atoms and potentially containing ether bonds between carbon atoms, m' is at least 1, and p is a number that gives a partial weight of about 400 to about 10,000) Each of E and E' independently represents a polymerizable unsaturated organic radical represented by formula IX: [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 radical having approximately 6 to 30 carbon atoms. (where w is between 0 and 6, x is 0 or 1, y is 0 or 1, and z is 0 or 1)

[0064] In exemplary embodiments which may be combined with one or more of the preceding paragraphs, one or more silicone hydrogel-forming silicone comonomers may include, as a representative class of silicone hydrogel-forming silicone comonomers, one or more silicone-containing urethane monomers represented by formula X: [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 gives a partial 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 by the following: [ka]

[0065] In another embodiment, the silicone hydrogel material (in bulk, i.e., in the copolymerized monomer mixture) comprises about 5 to about 50 weight percent, or about 10 to about 25 weight percent, of one or more silicone macromonomers; 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 above structural formulas, U.S. Patent No. 4,153,641 discloses additional unsaturated groups, including acryloxy or methacryloxy groups. Fumarate-containing materials, such as those disclosed in U.S. Patents No. 5,310,779, No. 5,449,729 and No. 5,512,205, are also useful substrates in 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 terminally capped with a hydrophilic monomer.

[0066] In exemplary embodiments which may be combined with one or more of the preceding paragraphs, one or more silicone hydrogel-forming silicone comonomers may include one or more monomers of formula XI as a representative class of silicone hydrogel-forming silicone comonomers: [ka] In the formula, X is a ring-opening agent residue, L is the same or different linking 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.

[0067] Ring-opening agents are well known in the literature. Non-limiting examples of anionic ring-opening agents include alkyllithium, alkoxides, and trialkylsiloxylithium, in which the alkyl group may or may not contain a halo atom.

[0068] The linking group can be any divalent radical or moiety, and includes substituted or unsubstituted alkyl groups, alkyl ether groups, alkenyl groups, alkenyl ether groups, haloalkyl groups, substituted or unsubstituted siloxane groups, and ring-opening polymerizable monomers.

[0069] 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.

[0070] In exemplary embodiments, which may be combined with one or more of the preceding paragraphs, one or more silicone hydrogel-forming silicone comonomers may include one or more monomers of formula XII as a representative class of silicone hydrogel-forming silicone comonomers: [ka] In the formula, L is the same or different and is a linking group or bond, V is the same or different and is an 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.

[0071] In exemplary embodiments, which may be combined with one or more of the preceding paragraphs, one or more silicone hydrogel-forming silicone comonomers may include one or more monomers from formulas XIII and XIV as representative classes of silicone hydrogel-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, and n 1 (is between 0 and 10) and, [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)

[0072] In exemplary embodiments, which may be combined with one or more of the preceding paragraphs, one or more silicone hydrogel-forming silicone comonomers may include one or more monomers from formulas XV to XIX as a representative class of silicone hydrogel-forming silicone comonomers: [ka] [ka] [ka] [ka] and [ka]

[0073] In exemplary embodiments, which may be combined with one or more of the preceding paragraphs, one or more silicone hydrogel-forming silicone comonomers may include one or more monomers from formulas XX to XXII as a representative class of silicone hydrogel-forming silicone comonomers: [ka] [ka] [ka]

[0074] In the formula, R9, R 10 and R 11 independently of n and n are hydrogen, alkyl groups, haloalkyl groups or other substituted alkyl groups, and n and n 1 This is defined as described above.

[0075] In exemplary embodiments, which may be combined with one or more of the preceding paragraphs, one or more silicone hydrogel-forming silicone comonomers may include one or more monomers from formulas XXIII to XXV as a representative class of silicone hydrogel-forming silicone comonomers: [ka] [ka] [ka]

[0076] In the formula, n is as defined above, and X - This is the counterion that gives the overall charge a neutral charge.

[0077] Counterions capable of providing an overall neutral charge are well known to those skilled in the art, and include, for example, halide ions.

[0078] In exemplary embodiments, which may be combined with one or more of the preceding paragraphs, one or more silicone hydrogel-forming silicone comonomers may include one or more monomers from formula XXVI as a representative class of silicone hydrogel-forming silicone comonomers: [ka]

[0079] In one or more additional non-limiting exemplary embodiments, which may be combined with one or more of the preceding paragraphs, one or more silicone hydrogel-forming silicone comonomers may be present in the monomer mixture in a principal amount. In one or more additional non-limiting exemplary embodiments, which may be combined with one or more of the preceding paragraphs, one or more silicone hydrogel-forming silicone comonomers may be present in the monomer mixture in an amount greater than about 50% by weight, based on the total weight of the monomer mixture. In some embodiments, one or more silicone hydrogel-forming silicone comonomers may be present in the monomer mixture in an amount greater than about 50% by weight and up to 95% by weight, based on the total weight of the monomer mixture.

[0080] In one or more additional non-limiting exemplary embodiments, which may be combined with one or more of the preceding paragraphs, one or more silicone hydrogel-forming silicone comonomers may be present in the monomer mixture in an amount ranging from about 10% to about 60% by weight, based on the total weight of the monomer mixture. In another exemplary embodiment, one or more silicone hydrogel-forming silicone comonomers may be present in the monomer mixture in an amount ranging from about 15% to about 50% by weight, based on the total weight of the monomer mixture.

[0081] 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 being continuously developed for use in contact lenses and other silicone hydrogels. For example, silicone hydrogels can be formed from at least one cationic monomer, such as a cationic silicone-containing monomer or a cationic fluorinated silicone-containing monomer.

[0082] 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 hydrophilic comonomers. Suitable hydrophilic comonomers 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, and mixtures thereof. Typical examples of unsaturated carboxylic acids include, but are not limited to, methacrylic acid, acrylic acid, and mixtures thereof. Typical examples of acrylamides include, but are not limited to, alkylamides such as N,N-dimethylacrylamide and N,N-dimethylmethacrylamide, and mixtures thereof. Typical examples of cyclic lactams include, but are not limited to, N-vinyl-2-pyrrolidone, N-vinylcaprolactam, and N-vinyl-2-piperidone, and mixtures thereof. Typical examples of hydroxyl group-containing (meth)acrylates include, but are not limited to, 2-hydroxyethyl methacrylate (HEMA), glycerol methacrylate, and mixtures thereof.

[0083] Additional 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 silicone hydrogel-forming hydrophilic comonomers will be apparent to those skilled in the art. Mixtures of the above hydrophilic comonomers may also be used in the monomer mixtures herein.

[0084] In one or more additional non-limiting exemplary embodiments, which may be combined with one or more of the preceding paragraphs, one or more hydrophilic comonomers may be present in the monomer mixture in an amount ranging from about 20% to about 60% by weight, based on the total weight of the monomer mixture. In another exemplary embodiment, one or more hydrophilic comonomers may be present in the monomer mixture in an amount ranging from about 25% to about 45% by weight, based on the total weight of the monomer mixture.

[0085] 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. Suitable crosslinking agents for use herein are known in the art. For example, in non-limiting exemplary embodiments, 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.

[0086] 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).

[0087] In exemplary embodiments, 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, 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.

[0088] 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.

[0089] 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).

[0090] 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.

[0091] 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 a silicone hydrogel-forming amount. 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.

[0092] In one or more additional 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 additional comonomers. In exemplary embodiments, one or more additional comonomers may include, for example, both ethylenically unsaturated groups (which enable the monomer to copolymerize with hydrophilic comonomers) and epoxide groups (which do not react with hydrophilic comonomers but remain to react with copolymers). Suitable additional comonomers include, for example, glycidyl methacrylate, glycidyl acrylate, glycidyl vinyl carbonate, glycidyl vinyl carbamate, and 4-vinyl-1-cyclohexene-1,2-epoxide.

[0093] In a non-limiting exemplary embodiment, one or more additional comonomers may be present in the monomer mixture in an amount ranging from about 1% by weight to about 20% by weight, based on the total weight of the monomer mixture. In another exemplary embodiment, one or more additional comonomers may be present in the monomer mixture in an amount ranging from about 3% by weight to about 10% by weight, based on the total weight of the monomer mixture.

[0094] In a non-limiting exemplary embodiment, which may be combined with one or more of the foregoing paragraphs, the monomer mixture can further contain a reactive (polymerizable) ultraviolet (UV) absorber and / or a reactive blue light absorber. Suitable reactive UV absorbers can be any known reactive UV absorber. In a non-limiting exemplary embodiment, suitable reactive UV absorbers include, for example, 2-(2'-hydroxy-3'-methallyl-5'-methylphenyl)benzotriazole (commercially available as o-Methallyl Tinuvin P ("oMTP") from Polysciences, Inc. (Warrington, Pa.)), 3-(2H-benzotriazol-2-yl)-4-hydroxyphenyl ethyl methacrylate, and 2-(3-(tert-butyl)-4-hydroxy-5-(5-methoxy-2H-benzotriazol-2-yl)phenoxy)ethyl methacrylate.

[0095] In an exemplary embodiment, suitable UV absorbers include, for example, one or more compounds of the following formulae.

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0096] In an exemplary embodiment, the UV absorber can be present in the monomer mixture in an amount ranging from about 0.1 to about 5 wt% based on the total weight of the monomer mixture. In another exemplary embodiment, the UV absorber can be present in the monomer mixture in an amount ranging from about 1.5 to about 2.5 wt% based on the total weight of the monomer mixture. In yet another non-limiting exemplary embodiment, the UV absorber can be present in the monomer mixture in an amount ranging from about 1.5 to about 2 wt% based on the total weight of the monomer mixture.

[0097] Many reactive blue light-absorbing compounds are known. Preferred reactive blue light-absorbing compounds are those described in U.S. Patent Nos. 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 an exemplary embodiment, the blue light absorber can be present in the monomer mixture in an amount ranging from about 0.005 to about 1 wt% based on the total weight of the monomer mixture. In another exemplary embodiment, the blue light absorber can be present in the monomer mixture in an amount ranging from about 0.01 to about 1 wt% 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 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.

[0099] In non-limiting exemplary embodiments, which may be combined with one or more of the preceding paragraphs, the monomer mixture may contain about 5% to about 50% by weight of diluent, based on the total weight of the monomer mixture. In one embodiment, the monomer mixture may contain about 15% to about 30% by weight of diluent, based on the total weight of the monomer mixture.

[0100] The monomer mixture may further contain various additives, such as antioxidants, colorants, lubricants, internal wetting agents, and reinforcing agents, and other components well known in the art, as needed and within limits that do not impair the purpose and effect of the exemplary embodiments.

[0101] The silicone hydrogels of exemplary embodiments (e.g., contact lenses or intraocular lenses) can be manufactured by polymerizing the above monomer mixture to form a product, and then shaping it into an appropriate 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 may then be cut into a button shape. This button may then be turned into a contact lens.

[0102] Alternatively, silicone hydrogels such as contact lenses may be cast directly from a mixture in a mold, such as a polypropylene mold, by rotary casting or 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 pouring a 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 UV rays. Static casting involves pouring a monomer mixture between two mold portions (one mold portion having a shape that forms the front lens surface and the other mold portion having a shape that forms the rear lens surface) and curing the mixture in the mold assembly, for example by free radical polymerization of the mixture, to form a lens. Examples of free radical reaction techniques for curing lens materials include, or may be used in combination, thermal radiation, infrared radiation, electron beam radiation, gamma ray radiation, ultraviolet (UV) radiation, etc. U.S. Patent No. 5,271,875 describes a static casting method in which a finished lens can be formed in 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 method of curing an excess monomer mixture by rotary casting in a mold to form an article with a front lens surface and a relatively thick shape, and then turning the rear surface of the cured rotary-cast article to provide a contact lens with a desired thickness and rear lens surface.

[0103] Polymerization can be accelerated by exposing the mixture to heat (thermosetting) and / or radiation such as ultraviolet light, visible light, or high-energy radiation. Polymerization initiators may be included in the mixture to accelerate the polymerization step. Typical examples of free radical thermal polymerization initiators include organic peroxides such as acetyl peroxide, lauroyl peroxide, decanoyl peroxide, stearoyl peroxide, benzoyl peroxide, tert-butyl peroxypivalate, and peroxydicarbonate. Typical examples of diazo initiators include VAZO64 and VAZO67. Typical UV initiators known in the art include benzoin methyl ether, benzoin ethyl ether, Darocure® 1173, 1164, 2273, 1116, 2959, 3331 (EM Industries), and Irgacure® 651 and 184 (Ciba-Geigy). Typical visible light initiators include IRGACURE 819 and other phosphine oxide-type initiators. Generally, initiators are used in monomer mixtures at a concentration of about 0.01 to about 5% by weight of the total mixture.

[0104] 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, or 2-propanol. Any mixture of the above solvents may also be used.

[0105] Generally, polymerization can be carried out over a period of about 15 minutes to about 72 hours, under an inert gas atmosphere, for example, nitrogen or argon. If desired, the resulting polymerization product can be dried under vacuum for, for example, about 5 to about 72 hours, or held in an aqueous solution before use.

[0106] Polymerization of the mixture yields a polymer, which is then hydrated to form a hydrogel. When producing a hydrogel lens, the mixture may further contain at least the diluents discussed above, which are ultimately replaced by water when the polymerization product is hydrated to form a hydrogel. In non-limiting exemplary embodiments, which may be combined with one or more of the preceding paragraphs, the silicone hydrogels disclosed herein can be high-water-content silicone hydrogels having an equilibrium water content of at least about 50% by weight. In another exemplary embodiment, the silicone hydrogels disclosed herein can be high-water-content silicone hydrogels having an equilibrium water content of at least about 60% by weight. In another exemplary embodiment, the silicone hydrogels disclosed herein can be high-water-content silicone hydrogels having an equilibrium water content of at least about 70% by weight. In another exemplary embodiment, the silicone hydrogels disclosed herein can be high-water-content silicone hydrogels having an equilibrium water content of about 50% to about 80% by weight.

[0107] In non-limiting exemplary embodiments, which may be combined with one or more of the preceding paragraphs, the silicone hydrogels disclosed herein may have an oxygen permeability of more than about 120 bar. In exemplary embodiments, the silicone hydrogels disclosed herein may have an oxygen permeability of more than about 80 bar (e.g., about 100 to about 150 bar).

[0108] The amount of diluent used should be less than approximately 50% by weight, and in most cases, the diluent content is less than approximately 30% by weight. However, in certain polymer systems, the actual limit is determined by the solubility of the various monomers in the diluent. To produce optically transparent copolymers, it is important that no phase separation occurs between the comonomers and the diluent, or between the diluent and the final copolymer, which would cause visual opacity.

[0109] 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 may cause the copolymer to collapse 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, formamides, ketones, dialkyl sulfoxides, butyl carbitols, and borates described herein, as well as mixtures thereof.

[0110] If necessary, it may be desirable to remove residual diluent from the lens before the edge finishing operation, which can be achieved by evaporation at or near ambient pressure or under vacuum. High temperatures can be used to reduce the time required for diluent evaporation. The time, temperature, and pressure conditions for the solvent removal step vary depending on factors such as the volatility of the diluent and specific monomer components, which can be easily determined by those skilled in the art. If desired, the mixture used in the manufacture of the hydrogel lens may further contain crosslinking agents and wetting agents known in the prior art for producing hydrogel materials.

[0111] 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.

[0112] The silicone hydrogels such as contact lenses obtained herein may be subjected to any machining operation. For example, any machining step may include buffing or polishing of the lens edge and / or surface. Generally, such machining processes may be carried out before or after removing the product from the mold part. For example, the lens is dry removed from the mold by using vacuum tweezers to lift the lens from the mold, and then the lens is transferred to a second vacuum tweezer using mechanical tweezers and placed on a rotating surface to smooth the surface or edge. Thereafter, the lens may be inverted to machine the opposite side of the lens.

[0113] Thereafter, the lens may be transferred to individual lens packages containing buffered saline. The saline may be added to the package either before or after transfer of the lens. Suitable package designs and materials are known in the art. Plastic packages are removably sealed with a film. Suitable sealing films are known in the art and include foils, polymer films and mixtures thereof. Thereafter, the sealed package containing the lens is sterilized to ensure a sterile product. Suitable sterilization means and conditions are known in the art and include, for example, autoclave sterilization.

[0114] As will be readily understood by those skilled in the art, the above molding and packaging processes may include other steps. Such other steps can include, for example, coating of the formed lens, surface treatment of the lens during formation (e.g., by mold transfer), inspection of the lens, rejection of defective lenses, cleaning of the mold halves, and reuse of the mold halves, and combinations thereof.

[0115] The following examples are provided so that those skilled in the art can practice the invention and are merely illustrative. The examples should not be construed as limiting the scope of the invention as defined in the claims.

[0116] In the examples, the following abbreviations are used.

[0117] HEMA: 2-hydroxyethyl methacrylate.

[0118] NVP: N-vinyl-2-pyrrolidone.

[0119] DMA: N,N-dimethylacrylamide.

[0120] EGDMA: Ethylene glycol dimethacrylate.

[0121] TRIS: Tris(trimethylsiloxy)silylpropyl methacrylate.

[0122] UV416: 2-(4-benzoyl-3-hydroxyphenoxy)ethyl acrylate.

[0123] IMVT: 1,4-bis(4-(2-methacryloxyethyl)phenylamino)anthraquinone.

[0124] M1EDS6: A compound with the following structure, available from Gelest: [ka]

[0125] Ma2D37: Compound having the following structure: [ka]

[0126] Various polymerization products were formed as described below and characterized using the following standard test procedures.

[0127] Oxygen permeability (also known as Dk) is measured by the following procedure. Other methods and / or apparatus may be used, but only if the oxygen permeability values ​​obtained are equivalent to those of the method described. The oxygen permeability of silicone hydrogels is measured by polarization (ANSI Z80.20-1998) using an O2 Permeometer Model 201T instrument (Createch, Albany, California, USA) which has a probe containing a central circular gold cathode at its edge and a silver anode insulated from the cathode. The measurement is 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 measurement of the film sample may be measured using a Rehder ET-1 electronic thickness gauge. Generally, the film sample has a disc shape. The measurement is 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, place the film sample on a cathode pre-moistened with equilibrated PBS, center it, and ensure 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 so that the cathode portion of the probe contacts only the film sample. For 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 pre-moistened cathode, then place the film sample on the Teflon film, and ensure there are no air bubbles or excess PBS under the Teflon film or film sample. After collecting the measurements, 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 and R2 values ​​should be obtained for each thickness.

[0128] Using known regression analysis, oxygen permeability (Dk) is calculated from film samples of at least three different thicknesses. Any film samples hydrated in a solution other than PBS are first immersed in purified water for at least 24 hours to equilibrate, and then immersed in PBS for at least 12 hours to equilibrate. The apparatus is cleaned periodically and calibrated periodically 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 of which is incorporated herein by reference in whole.

[0129] Moisture content %: Two sets of six hydration lenses or films are dipped on a piece of filter paper to remove excess water and then weighed (wet weight). The samples are then placed in a jar containing a desiccant and microwaved for 10 minutes. The samples are then left to stand for 30 minutes to equilibrate at room temperature, and their weight is measured again (dry weight). The moisture content is calculated from the wet and dry weights.

[0130] Modulus of elasticity (g / mm²) 2 The measurement was performed using an Instron (Model 4502) instrument in accordance with ASTM 1708, with the film sample immersed in borate-buffered saline. The appropriate size of the film sample was 22 mm in gauge length and 4.75 mm in width, and the sample further had a thickness of 100 ± 50 microns and ends that formed a dogbone shape suitable for gripping the sample with the clamp of the Instron instrument.

[0131] UV blocking was measured using a Jasco V-760 UV-Vis spectrophotometer, employing a transmittance % sweep from 800 nm to 200 nm. Visible light transmittance (VLT), UVA, and UVB blocking were calculated by averaging the transmittance % over the ranges of 381–780 nm for VLT, 316–380 nm for UVA, and 280–315 nm for UVB.

[0132] Example 1 Preparation of silicone monomers having the following structure: [ka] This follows a typical reaction scheme. [ka]

[0133] 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 an N2 atmosphere with stirring. Butyllithium (6.4 g, 0.1 mol) was added to the above reaction mixture, followed by the addition of 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. The reaction mixture was then 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. The filtrate was then concentrated under vacuum (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), NaHCO3 aqueous solution (2 × 100 mL, prepared by dissolving 10 g of NaHCO3 in 200 mL of DI water), saline solution (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. MgSO4 was removed by filtration, 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 through a thin layer of Celite. By removing the residual solvent at 25°C and 0.2 mmHg for 30 minutes, 40 g of the desired product was obtained as a clear oil.

[0134] Example 2 and Comparative Examples A and B A monomer mixture was prepared by mixing the following components listed in Table 1 in amounts equal to their weight. [Table 1]

[0135] The resulting monomer mixture was introduced into a polypropylene mold assembly and cast into a contact lens. The mold assembly and monomer mixture were then heat-cured for approximately 3 hours to form the contact lens. The resulting contact lens was then demolded from the mold assembly.

[0136] The silicone hydrogel of Example 2 had significantly higher oxygen permeability (Dk) compared to the silicone hydrogels of Comparative Examples A and B.

[0137] According to one aspect of this disclosure, a silicone hydrogel is

[0138] (a) One or more monofunctional silicone monomers represented by the structure of formula I [ka]

[0139] (In the formula, R 1 , R 2 , R 3 and R 4 These are independently 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 Aryl group and C6~C 12 It is a heteroaryl 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 1 to 6 and y is 3 to 15), and

[0140] (b) A polymerization product of a monomer mixture containing one or more silicone hydrogel-forming silicone comonomers.

[0141] 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 These are independently 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 15.

[0142] 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 hydrogen, C1-C6 alkyl, and 5 , R 6 and R 7 is independently a linear or branched C1-C6 alkyl group, x is 1-6, and y is 3-15.

[0143] 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 is a linear or branched C3-C6 alkyl group, x is 2-4, and y is 3-15.

[0144] 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 is a linear or branched C3-C6 alkyl group, x is 2-4, and y is 3-15.

[0145] In non-limiting exemplary embodiments, which may be combined with one or more of the preceding paragraphs, one or more silicone hydrogel-forming silicone comonomers include one or more non-bulky organosilicon-containing monomers.

[0146] In non-limiting exemplary embodiments, which may be combined with one or more of the preceding paragraphs, one or more non-bulky organosilicon-containing monomers include at least one [siloxanil] or at least one [silyl-alkyl-siloxanil] repeating unit in the monomer, macromer, or prepolymer.

[0147] In an exemplary, non-limiting embodiment which may be combined with one or more of the preceding paragraphs, one or more non-bulky organosilicon-containing monomers include one or more non-bulky organosilicon-containing monomers represented by the structure of formula II: [ka]

[0148] In the formula, L is an ethylenically unsaturated polymerizable group, V is a linking group or bond, and R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9R is independently hydrogen, alkyl group, haloalkyl group, cycloalkyl group, heterocycloalkyl group, alkenyl group, haloalkenyl group, or aryl group. 10 and R 11 R is independently a hydrogen atom or an alkyl group (where R 10 and R 11 (At least one of them is hydrogen), y is between 2 and 7, and n is between 1 and 100 or 1 and 20.

[0149] In a non-limiting exemplary embodiment, which may be combined with one or more of the preceding paragraphs, V is a (meth)acrylate and L is C1-C 12 It is an alkylene group, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 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.

[0150] In a non-limiting exemplary embodiment which may be combined with one or more of the preceding paragraphs, 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.

[0151] In an exemplary, non-limiting embodiment which may be combined with one or more of the preceding paragraphs, one or more non-bulky organosilicon-containing monomers include one or more non-bulky organosilicon-containing monomers represented by the structure of Formula III: [ka]

[0152] In the formula, R 12 is H or methyl, and X is O or NR 16 And (here, R 16 (Selected from C1-C4 alkyl groups, which may be further substituted with H or one or more hydroxyl groups), R 13 R is 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, and in another embodiment, it is a C1-C6 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 or fluorine, a hydroxyl group or an ether, and 15 is a C1-C4 alkyl group, and a is between 2 and 50.

[0153] In a non-limiting exemplary embodiment, which may be combined with one or more of the preceding paragraphs, one or more silicone hydrogel-forming silicone comonomers include one or more polysiloxane prepolymers represented by the structure of formula IV: [ka]

[0154] In the formula, each V is independently a reactive functional terminal group, including, for example, a hydroxyl group-containing reactive functional terminal group and an amine-containing reactive functional terminal group, R 17 ~R 22 These are independently linear or branched, substituted or unsubstituted C1-C12 30 Alkyl, substituted or unsubstituted C3-C 30 Cycloalkyl groups, substituted or unsubstituted C4-C30 Cycloalkylalkyl groups, substituted or unsubstituted C3-C 30 Cycloalkenyl group, substituted or unsubstituted C6-C 30 Aryl groups, and substituted or unsubstituted C7-C 30 It is an arylalkyl group, and L is an independent linking group.

[0155] In non-limiting exemplary embodiments, which may be combined with one or more of the preceding paragraphs, V is an amine-containing reactive functional terminal group.

[0156] In a non-limiting exemplary embodiment, which may be combined with one or more of the preceding paragraphs, the amine-containing reactive functional terminal group is a (meth)acrylamide-containing reactive functional terminal group.

[0157] In non-limiting exemplary embodiments, which may be combined with one or more of the preceding paragraphs, one or more silicone hydrogel-forming silicone comonomers include one or more bulky silicone comonomers.

[0158] In non-limiting exemplary embodiments, which may be combined with one or more of the preceding paragraphs, one or more bulky silicone comonomers are one or more bulky silicone-containing comonomers represented by the structure of formula V: [ka]

[0159] (In the formula, X is -O- or -NR) 19 - represents (R 19 (where R is hydrogen or a C1-C4 alkyl group), each R 17 Each R independently represents hydrogen or methyl, and each R 18 These are independently C1-C6 alkyl groups, phenyl groups, or [ka] It represents a base that is expressed as

[0160] (In the formula, each R18’ (where is independently a C1-C6 alkyl or phenyl radical, and h is 1-10), and comprises one or more bulky silicone-containing comonomers represented by the structure of formula VI: [ka]

[0161] (In the formula, X is -NR) 19 - represents (R 19 (where represents hydrogen or a C1-C4 alkyl group), R 17 represents hydrogen or methyl, and each R represents hydrogen or methyl. 18 These are independently C1-C6 alkyl groups, phenyl groups, or [ka] It represents a base that is expressed as

[0162] (In the formula, each R 18’ (where 'h' independently represents a C1-C6 alkyl group or a phenyl group, and h is 1-10).

[0163] In a non-limiting exemplary embodiment, which may be combined with one or more of the preceding paragraphs, the monomer mixture is:

[0164] (a) Based on the total weight of the monomer mixture, one or more monofunctional silicone monomers in an amount of about 5% to about 40% by weight, and

[0165] (b) Based on the total weight of the monomer mixture, the mixture contains one or more silicone hydrogel-forming silicone comonomers in an amount of about 10% to about 60% by weight.

[0166] In a non-limiting exemplary embodiment, which may be combined with one or more of the preceding paragraphs, the monomer mixture is:

[0167] (a) Based on the total weight of the monomer mixture, one or more monofunctional silicone monomers in an amount of about 7% to about 15% by weight, and

[0168] (b) Based on the total weight of the monomer mixture, the mixture contains one or more silicone hydrogel-forming silicone comonomers in an amount of about 15% to about 50% by weight.

[0169] 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 hydrophilic comonomers.

[0170] In non-limiting exemplary embodiments, which may be combined with one or more of the preceding paragraphs, one or more 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.

[0171] In non-limiting exemplary embodiments, which may be combined with one or more of the preceding paragraphs, one or more hydrophilic comonomers are selected from the group consisting of acrylamides, vinyl lactams, and hydroxyl group-containing (meth)acrylates.

[0172] In a non-limiting exemplary embodiment, which may be combined with one or more of the preceding paragraphs, the monomer mixture comprises one or more hydrophilic comonomers in an amount of about 20% to 50% by weight, based on the total weight of the monomer mixture.

[0173] 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.

[0174] In non-limiting exemplary embodiments, which may be combined with one or more of the preceding paragraphs, the silicone hydrogel has an equilibrium water content of about 50% to about 80% by weight.

[0175] In a non-limiting exemplary embodiment, which may be combined with one or more of the preceding paragraphs, the silicone hydrogel has an oxygen permeability of about 120 or more.

[0176] According to another aspect of this disclosure, a method for producing a silicone hydrogel is:

[0177] (a) Curing a monomer mixture in a mold, wherein the monomer mixture is

[0178] (i) One or more monofunctional silicone monomers represented by the structure of formula I [ka]

[0179] (In the formula, R 1 , R 2 , R 3 and R 4 These are independently 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 Aryl group and C6~C 12 It is a heteroaryl 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 1 to 6 and y is 3 to 15), and

[0180] (ii) A material containing one or more silicone hydrogel-forming silicone comonomers, which is cured,

[0181] (b) The process of releasing the silicone hydrogel from the mold is included.

[0182] 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 These are independently 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 15.

[0183] 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 hydrogen, C1-C6 alkyl, and 5 , R 6 and R 7 is independently a linear or branched C1-C6 alkyl group, x is 1-6, and y is 3-15.

[0184] 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 is a linear or branched C3-C6 alkyl group, x is 2-4, and y is 3-15.

[0185] 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 is a linear or branched C3-C6 alkyl group, x is 2-4, and y is 3-15.

[0186] In non-limiting exemplary embodiments, which may be combined with one or more of the preceding paragraphs, one or more silicone hydrogel-forming silicone comonomers include one or more non-bulky organosilicon-containing monomers.

[0187] In non-limiting exemplary embodiments, which may be combined with one or more of the preceding paragraphs, one or more non-bulky organosilicon-containing monomers include at least one [siloxanil] or at least one [silyl-alkyl-siloxanil] repeating unit in the monomer, macromer, or prepolymer.

[0188] In an exemplary, non-limiting embodiment which may be combined with one or more of the preceding paragraphs, one or more non-bulky organosilicon-containing monomers include one or more non-bulky organosilicon-containing monomers represented by the structure of formula II: [ka]

[0189] In the formula, L is an ethylenically unsaturated polymerizable group, V is a linking group or bond, and R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9R is independently hydrogen, alkyl group, haloalkyl group, cycloalkyl group, heterocycloalkyl group, alkenyl group, haloalkenyl group, or aryl group. 10 and R 11 R is independently a hydrogen atom or an alkyl group (where R 10 and R 11 (At least one of them is hydrogen), y is between 2 and 7, and n is between 1 and 100 or 1 and 20.

[0190] In a non-limiting exemplary embodiment, which may be combined with one or more of the preceding paragraphs, V is a (meth)acrylate and L is C1-C 12 It is an alkylene group, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 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.

[0191] In a non-limiting exemplary embodiment which may be combined with one or more of the preceding paragraphs, 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.

[0192] In an exemplary, non-limiting embodiment which may be combined with one or more of the preceding paragraphs, one or more non-bulky organosilicon-containing monomers include one or more non-bulky organosilicon-containing monomers represented by the structure of Formula III: [ka]

[0193] In the formula, R 12 is H or methyl, and X is O or NR 16 And (here, R 16 (Selected from C1-C4 alkyl groups, which may be further substituted with H or one or more hydroxyl groups) 13 is 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, and in another embodiment, is a C1-C6 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 or fluorine, a hydroxyl group or an ether, and 15 is a C1-C4 alkyl group, and a is between 2 and 50.

[0194] In a non-limiting exemplary embodiment, which may be combined with one or more of the preceding paragraphs, one or more silicone hydrogel-forming silicone comonomers include one or more polysiloxane prepolymers represented by the structure of formula IV: [ka]

[0195] In the formula, each V is independently a reactive functional terminal group, including, for example, a hydroxyl group-containing reactive functional terminal group and an amine-containing reactive functional terminal group, R 17 ~R 22 These are independently linear or branched, substituted or unsubstituted C1-C12 30 Alkyl, substituted or unsubstituted C3-C 30 Cycloalkyl groups, substituted or unsubstituted C4-C30 Cycloalkylalkyl groups, substituted or unsubstituted C3-C 30 Cycloalkenyl group, substituted or unsubstituted C6-C 30 Aryl groups, and substituted or unsubstituted C7-C 30 It is an arylalkyl group, and L is an independent linking group.

[0196] In non-limiting exemplary embodiments, which may be combined with one or more of the preceding paragraphs, V is an amine-containing reactive functional terminal group.

[0197] In a non-limiting exemplary embodiment, which may be combined with one or more of the preceding paragraphs, the amine-containing reactive functional terminal group is a (meth)acrylamide-containing reactive functional terminal group.

[0198] In non-limiting exemplary embodiments, which may be combined with one or more of the preceding paragraphs, one or more silicone hydrogel-forming silicone comonomers include one or more bulky silicone comonomers.

[0199] 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 V: [ka]

[0200] (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 Each R independently represents hydrogen or methyl, and each R 18 These are independently C1-C6 alkyl groups, phenyl groups, or [ka] It represents a base that is expressed as

[0201] (In the formula, each R 18’(where is independently a C1-C6 alkyl or phenyl radical, and h is 1-10), and comprises one or more bulky silicone-containing comonomers represented by the structure of formula VI: [ka]

[0202] (In the formula, X is -NR) 19 - represents (where R 19 (R represents hydrogen or a C1-C4 alkyl group) 17 represents hydrogen or methyl, and each R represents hydrogen or methyl. 18 These are independently C1-C6 alkyl groups, phenyl groups, or [ka] It represents a base that is expressed as

[0203] (In the formula, each R 18’ (where 'h' independently represents a C1-C6 alkyl group or a phenyl group, and h is 1-10).

[0204] In a non-limiting exemplary embodiment, which may be combined with one or more of the preceding paragraphs, the monomer mixture is:

[0205] (a) Based on the total weight of the monomer mixture, one or more monofunctional silicone monomers in an amount of about 5% to about 40% by weight, and

[0206] (b) Based on the total weight of the monomer mixture, the mixture contains one or more silicone hydrogel-forming silicone comonomers in an amount of about 10% to about 60% by weight.

[0207] In a non-limiting exemplary embodiment, which may be combined with one or more of the preceding paragraphs, the monomer mixture is:

[0208] (a) Based on the total weight of the monomer mixture, one or more monofunctional silicone monomers in an amount of about 7% to about 15% by weight, and

[0209] (b) Based on the total weight of the monomer mixture, the mixture contains one or more silicone hydrogel-forming silicone comonomers in an amount of about 15% to about 50% by weight.

[0210] 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 hydrophilic comonomers.

[0211] In non-limiting exemplary embodiments, which may be combined with one or more of the preceding paragraphs, one or more 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.

[0212] In non-limiting exemplary embodiments, which may be combined with one or more of the preceding paragraphs, one or more hydrophilic comonomers are selected from the group consisting of acrylamides, vinyl lactams, and hydroxyl group-containing (meth)acrylates.

[0213] In an exemplary, non-limiting embodiment which may be combined with one or more of the preceding paragraphs, the monomer mixture further comprises about 20% to 50% by weight of one or more hydrophilic comonomers based on the total weight of the monomer mixture.

[0214] 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.

[0215] In non-limiting exemplary embodiments, which may be combined with one or more of the preceding paragraphs, the silicone hydrogel has an equilibrium water content of about 50% to about 80% by weight.

[0216] In a non-limiting exemplary embodiment, which may be combined with one or more of the preceding paragraphs, the silicone hydrogel has an oxygen permeability of about 120 or more.

[0217] The various features disclosed herein, while described in the context of a single embodiment for the sake of brevity, 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 each and all combinations were disclosed individually and explicitly. Furthermore, all partial combinations enumerated in embodiments describing such variables are also specifically encompassed and disclosed herein by the Composition, as if each and all such partial combinations were disclosed individually and explicitly.

[0218] 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 function described and implemented above as the best mode for carrying out the invention is for illustrative purposes only. Other arrangements and methods may be implemented by those skilled in the art without departing from the scope and spirit of the invention. Furthermore, those skilled in the art will likely recall other modifications within the scope and spirit of the features and advantages appended herein.

Claims

1. A silicone hydrogel which is a polymerization product of a monomer mixture, wherein the monomer mixture is (a) One or more monofunctional silicone monomers represented by the structure of formula I 【Chemistry 1】 (wherein, R １ , １２ , ７ , R ２ , R ３ and R ４ are each 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 aryl group and C ６ -C １２ heteroaryl group, and R ５ , R<000002​​​​​​​ (b) A silicone hydrogel comprising one or more silicone hydrogel-forming silicone comonomers.

2. In the monofunctional silicone monomer, R １ , R ２ , R ３ and R ４ These are independently hydrogen and C 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 groups 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 silicone hydrogel according to claim 1, wherein the alkyl group is 1 to 6 and y is 3 to 15.

3. In the monofunctional silicone monomer, R １ , R ２ , R ３ and R ４ These are independently hydrogen and C 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 silicone hydrogel according to claim 1, wherein the alkyl group is 1 to 6 and y is 3 to 15.

4. 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 silicone hydrogel according to claim 1, wherein the alkyl group is 2 to 4 and y is 3 to 15.

5. 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 silicone hydrogel according to claim 1, wherein the alkyl group is 2 to 4 and y is 3 to 15.

6. The silicone hydrogel according to any one of claims 1 to 5, wherein the one or more silicone hydrogel-forming silicone comonomers comprises one or more non-bulky organosilicon-containing monomers.

7. The silicone hydrogel according to claim 6, wherein the one or more non-bulky organosilicon-containing monomers contain at least one [siloxanil] or at least one [silyl-alkyl-siloxanil] repeating unit in the monomer, macromer, or prepolymer.

8. The aforementioned one or more non-bulky organosilicon-containing monomers include one or more non-bulky organosilicon-containing monomers represented by the structure of formula I: 【Chemistry 2】 In the formula, L is an ethylenically unsaturated polymerizable group, V is a linking 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; 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. The silicone hydrogel according to claim 6.

9. V is a (meth)acrylate, and L is a C １ -C １２ alkylene group, and R １ , R ２ , R ３ , R ４ , R ５ , R ６ , R ７ , R ８ and R ９ are independently C １ -C １２ alkyl groups, R １０ and R １１ are independently H or C １ -C １２ alkyl groups, y is from 2 to 7, and n is from 3 to 8, the silicone hydrogel according to claim 8.

10. V is (meth)acrylate and L is C １ ~C ６ It is an alkyl group, R １ , R ２ , R ３ , R ４ , R ５ , R ６ , R ７ , R ８ and R ９ C is independent １ ~C ６ It is an alkyl group, R １０ and R １１ H or C １ ~C ６ The silicone hydrogel according to claim 8, wherein it is an alkyl group, y is 2 to 7, and n is 1 to 20.

11. The one or more silicone hydrogel-forming silicone comonomers include one or more polysiloxane prepolymers represented by the structure of formula III: 【Transformation 3】 In the formula, each V is independently a reactive functional terminal group, and R １７ ~R ２２ These are independently linear or branched, substituted or unsubstituted C １ ~C ３０ Alkyl, substituted or unsubstituted C ３ ~C ３０ Cycloalkyl groups, substituted or unsubstituted C ４ ~C ３０ Cycloalkylalkyl groups, substituted or unsubstituted C ３ ~C ３０ Cycloalkenyl group, substituted or unsubstituted C ６ ~C ３０ Aryl groups, and substituted or unsubstituted C ７ ~C ３０ The silicone hydrogel according to any one of claims 1 to 10, wherein L is an arylalkyl group and L is a linking group.

12. The silicone hydrogel according to claim 11, wherein V is an amine-containing reactive functional terminal group.

13. The silicone hydrogel according to claim 12, wherein the amine-containing reactive functional terminal group is a (meth)acrylamide-containing reactive functional terminal group.

14. The monomer mixture (a) Based on the total weight of the monomer mixture, about 5% by weight to about 40% by weight of one or more monofunctional silicone monomers, and (b) The silicone hydrogel according to any one of claims 1 to 13, comprising about 10% to about 60% by weight of one or more silicone hydrogel-forming silicone comonomers based on the total weight of the monomer mixture.

15. The monomer mixture (a) Based on the total weight of the monomer mixture, about 7% by weight to about 15% by weight of one or more monofunctional silicone monomers, and (b) The silicone hydrogel according to any one of claims 1 to 13, comprising about 15% to about 50% by weight of one or more silicone hydrogel-forming silicone comonomers based on the total weight of the monomer mixture.

16. The silicone hydrogel according to any one of claims 1 to 15, wherein the monomer mixture further comprises one or more hydrophilic comonomers.

17. The silicone hydrogel according to claim 16, wherein one or more hydrophilic comonomers are selected from the group consisting of acrylamide, vinyl lactam, and hydroxyl group-containing (meth)acrylate.

18. The monomer mixture The silicone hydrogel according to claim 16 or 17, comprising about 20% to 50% by weight of one or more hydrophilic comonomers based on the total weight of the monomer mixture.

19. The silicone hydrogel according to any one of claims 1 to 18, 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.

20. A silicone hydrogel according to any one of claims 1 to 19, having an equilibrium water content of approximately 50% by weight to approximately 80% by weight.

21. A silicone hydrogel according to any one of claims 1 to 20, having an oxygen permeability of approximately 120 or more.

22. A method for preparing a silicone hydrogel, (a) Curing a monomer mixture in a mold, wherein the monomer mixture is (i) One or more monofunctional silicone monomers represented by the structure of formula I 【Chemistry 4】 (In the formula, R １ , R ２ , R ３ and R ４ These are independently hydrogen and C 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 Aryl group and C ６ ~C １２ It is a heteroaryl group, R ５ , R ６ and R ７ These are independently linear or branched C １ ~C １２ It is an alkyl group, where x is 1 to 6 and y is 3 to 15), and (ii) A silicone hydrogel-forming silicone comonomer containing one or more silicone hydrogel-forming silicone comonomers, (b) A method comprising releasing the silicone hydrogel from the mold.

23. In the monofunctional silicone monomer, R １ , R ２ , R ３ and R ４ These are independently hydrogen and C 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 groups 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 22, wherein the alkyl group is 1 to 6 and y is 3 to 15.

24. In the monofunctional silicone monomer, R １ , R ２ , R ３ and R ４ These are independently hydrogen and C 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 22, wherein the alkyl group is 1 to 6 and y is 3 to 15.

25. 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 method according to claim 22, wherein the alkyl group is 2 to 4 and y is 3 to 15.

26. 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 22, wherein the alkyl group is 2 to 4 and y is 3 to 15.

27. The method according to any one of claims 22 to 26, wherein the one or more silicone hydrogel-forming silicone comonomers comprises one or more non-bulky organosilicon-containing monomers.

28. The aforementioned one or more non-bulky organosilicon-containing monomers include one or more non-bulky organosilicon-containing monomers represented by the structure of formula I: 【Transformation 5】 In the formula, L is an ethylenically unsaturated polymerizable group, V is a linking group or bond, and R １ , R ２ , R ３ , R ４ , R ５ , R ６ , R ７ , R ８ , and R ９ R is independently hydrogen, alkyl group, haloalkyl group, cycloalkyl group, heterocycloalkyl group, alkenyl group, haloalkenyl group, or aryl group. １０ and R １１ (R) is independently hydrogen or alkyl group １０ and R １１ The method according to claim 27, wherein at least one of is hydrogen, y is 2 to 7, and n is 1 to 100.

29. The one or more silicone hydrogel-forming silicone comonomers include one or more polysiloxane prepolymers represented by the structure of formula II: 【Transformation 6】 In the formula, each V is independently a reactive functional terminal group, and R １７ ~R ２２ These are independently linear or branched, substituted or unsubstituted C １ ~C ３０ Alkyl, substituted or unsubstituted C ３ ~C ３０ Cycloalkyl groups, substituted or unsubstituted C ４ ~C ３０ Cycloalkylalkyl groups, substituted or unsubstituted C ３ ~C ３０ Cycloalkenyl group, substituted or unsubstituted C ６ ~C ３０ Aryl groups, and substituted or unsubstituted C ７ ~C ３０ The method according to any one of claims 22 to 28, wherein the arylalkyl group is and L is a linking group.

30. The method according to claim 29, wherein V is an amine-containing reactive functional terminal group.

31. The method according to claim 30, wherein the amine-containing reactive functional end group is a (meth)acrylamide-containing reactive functional end group.

32. The monomer mixture (a) Based on the total weight of the monomer mixture, about 5% by weight to about 40% by weight of one or more monofunctional silicone monomers, and (b) The silicone hydrogel according to any one of claims 22 to 31, comprising about 10% to about 60% by weight of one or more silicone hydrogel-forming silicone comonomers based on the total weight of the monomer mixture.

33. The monomer mixture (a) Based on the total weight of the monomer mixture, about 7% by weight to about 15% by weight of one or more monofunctional silicone monomers, and (b) The method according to any one of claims 22 to 31, comprising about 15% to about 50% by weight of one or more silicone hydrogel-forming silicone comonomers based on the total weight of the monomer mixture.

34. The method according to any one of claims 22 to 33, wherein the monomer mixture further comprises one or more hydrophilic comonomers.

35. The method according to claim 34, wherein one or more hydrophilic comonomers are selected from the group consisting of acrylamide, vinyl lactam, and hydroxyl group-containing (meth)acrylate.

36. The monomer mixture The method according to claim 34 or 35, comprising about 20% to 50% by weight of one or more hydrophilic comonomers based on the total weight of the monomer mixture.

37. The method according to any one of claims 22 to 36, 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.

38. The method according to any one of claims 22 to 37, wherein the silicone hydrogel has an equilibrium water content of about 50% to about 80% by weight and / or an oxygen permeability of about 120 or more.

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