Contact lenses containing UV-blocking agents that have been removed.

Abstract

A method for preparing a contact lens containing an ultraviolet (UV) blocking agent is disclosed. This method comprises (a) polymerizing a monomer mixture containing (i) one or more contact lens forming comonomers and (ii) one or more UV blocking agents containing a phenol group having a protected hydroxyl moiety and one or more ethylenically unsaturated reactive groups to obtain a polymerization product containing one or more UV blocking agents containing a phenol group having a protected hydroxyl moiety, and (b) deprotecting the protected hydroxyl moiety of one or more UV blocking agents of the polymerization product.

Description

[Technical Field]

[0001] Claim of priority This application claims priority to U.S. Provisional Patent Application No. 63 / 450,744, filed on 8 March 2023, entitled “Contact Lens Containing Deprotected UV Blocker,” the contents of which are incorporated herein by reference in their entirety. [Background technology]

[0002] It is well known that sunlight can damage the human eye, particularly in connection with the formation of cataracts and age-related macular degeneration, which can lead to vision loss. To minimize UV ​​damage to the eyes, individuals can wear eyeglasses or contact lenses that protect them from peripheral radiation. However, the degree of protection depends on the type of lens and the design of the sunglasses. Most styles of sunglasses do not provide complete protection from UV radiation, thereby allowing UV rays to reach the eye from around the frame. Wearing UV-blocking contact lenses that cover the entire cornea can provide full-angle UV protection.

[0003] In the realm of sunlight, the long-wavelength and near-ultraviolet (UVA and UVB) range, characterized by wavelengths of 280–380 nanometers (nm), is of greatest concern. The U.S. Food and Drug Administration (FDA) has established standards for UV-blocking contact lenses based on the standards of the American National Standards Institute (ANSI). Specifically, the FDA classifies UV-blocking contact lenses into two categories, Class I and Class II, depending on the degree of protection. Class I contact lenses must block more than 90% of UVA (i.e., 316–380 nm) and more than 99% of UVB (i.e., 280–315 nm). Class II lenses must block more than 50% of UVA and more than 95% of UVB. UVA irradiation corresponds to the wavelength range of 316–400 nm, but only the 316–380 nm wavelength is considered in the classification of contact lenses. [Overview of the Initiative]

[0004] According to one exemplary embodiment, a method for preparing contact lenses containing an ultraviolet (UV) blocking agent is:

[0005] (a) Polymerizing a monomer mixture containing (i) one or more comonomers for contact lens formation, and (ii) one or more UV blocking agents containing a phenol group having a protected hydroxyl moiety and one or more ethylenically unsaturated reactive groups, under ultraviolet polymerization conditions, to obtain a polymerization product containing one or more UV blocking agents containing a phenol group having a protected hydroxyl moiety, and

[0006] (b) comprising deprotecting the protected hydroxyl group portion of one or more UV-blocking agents in the polymerization product.

[0007] In another exemplary embodiment, the contact lens is an extracted and / or autoclaved ultraviolet (UV) cured polymerization product of a monomer mixture comprising (a) one or more contact lens forming comonomers and (b) one or more ultraviolet (UV) blocking agents comprising a phenol group having a deprotected hydroxyl moiety and one or more ethylenically unsaturated reactive groups. [Modes for carrying out the invention]

[0008] The various exemplary embodiments described herein relate to contact lenses containing ultraviolet (UV) blocking agents and methods for preparing them.

[0009] In the field of contact lenses, UV blocking properties are a desired feature. The UV blocking properties of contact lenses are typically improved by adding one or more UV blocking agents to the monomer mixture for contact lens formation. Generally, contact lenses can be prepared by a curing process utilizing either UV irradiation or heat, depending on the type of initiator in the monomer mixture for contact lens formation (i.e., photoinitiator or thermal initiator). When forming contact lenses with desired UV blocking properties, UV blocking agents are essential components in the monomer mixture. However, the presence of UV blocking agents in the monomer mixture can significantly inhibit the initiation reaction of UV radical initiators and the growth reaction of radical polymerization by blocking UV exposure and shortening the lifetime of UV radical species.

[0010] For example, UV blockers are generally aromatic compounds consisting of at least a phenol group and a (hetero) aromatic ring, and have strong absorption peaks in the UVA (316-400 nm) and UVB (280-315 nm) ranges. Phenolic compounds are usually used as radical inhibitors due to their well-known radical scavenging ability (e.g., butylated hydroxytoluene, hydroquinone, etc.). Because these UV blockers possess both UV blocking and radical inhibitory abilities, they limit the efficiency of the UV curing process during polymerization to form contact lenses.

[0011] Accordingly, the non-limiting exemplary embodiments described herein overcome the above drawbacks by using a UV-blocking agent protected in the monomer mixture during the formation of the contact lenses described herein, thereby inhibiting and / or preventing the above-mentioned capabilities of the UV-blocking agent during the UV curing process. By functionalizing the hydroxyl group on the phenol group of the UV-blocking agent with a protecting group, the hydroxyl-protected UV-blocking agent significantly reduces the radical scavenging ability and can shift the UV absorption range to the blue side through intramolecular hydrogen bonding. The presence of intramolecular hydrogen bonding increases the planarity of the conjugated system and shifts the UV absorption peak to the red side. By functionalizing the hydroxyl group on the phenol group of the UV-blocking agent with a hydrolyzable bulky protecting group (e.g., trimethylsilyl group, ethoxycarbonyloxy group, and t-butyloxycarbonyl group), intramolecular hydrogen bonding can be broken and steric hindrance between aromatic rings can be enhanced, thereby shifting the UV absorption peak to the blue side outside the range of the UV-absorbing photoinitiator (e.g., Irgacure 819). Furthermore, the exemplary embodiments described herein are based on the remarkable finding that, after the protected UV-blocking agent is deprotected by extraction and / or autoclaving techniques, the resulting deprotected UV-blocking contact lenses demonstrate sufficient UV blocking to meet both FDA Class I and II specifications for UV blocking.

[0012] In non-limiting exemplary embodiments, a contact lens containing one or more UV-blocking agents described herein can be obtained by (a) polymerizing a monomer mixture containing (i) one or more contact lens-forming comonomers and (ii) one or more UV-blocking agents comprising a phenol group having a protected hydroxyl moiety and one or more ethylenically unsaturated reactive groups under UV curing to obtain a UV-cured polymerization product containing one or more UV-blocking agents comprising a phenol group having a protected hydroxyl moiety, and (b) deprotecting the protected hydroxyl moiety of one or more UV-blocking agents in the polymerization product.

[0013] In non-limiting exemplary embodiments, one or more contact lens-forming comonomers may be present in the monomer mixture in a majority amount. In non-limiting exemplary embodiments, one or more contact lens-forming comonomers may be present in the monomer mixture in an amount ranging from about 70% to about 95% by weight, based on the total weight of the monomer mixture. In another exemplary embodiment, one or more contact lens-forming comonomers may be present in the monomer mixture in an amount ranging from about 85% to about 95% by weight, based on the total weight of the monomer mixture.

[0014] One or more contact lens-forming comonomers used in the monomer mixture can be any contact lens-forming comonomer material known in the art that is capable of forming the above-mentioned contact lenses. In one exemplary embodiment, one or more contact lens-forming comonomers can be one or more hydrophilic contact lens-forming comonomers. Suitable one or more hydrophilic contact lens-forming comonomers include, for example, unsaturated carboxylic acids, acrylamides, vinyl lactams, hydroxyl group-containing (meth)acrylates, hydrophilic vinyl carbonates, hydrophilic vinyl carbamates, hydrophilic oxazolones, and poly(alkene glycols) functionalized with polymerizable groups, as well as mixtures thereof.

[0015] As used herein, the term "(meth)" represents an optional methyl substituent. Thus, terms such as "(meth)acrylate" refer to either methacrylate or acrylate, and "(meth)acrylamide" refer to either methacrylamide or acrylamide.

[0016] 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, N-vinyl-2-piperidone, and mixtures thereof. Typical examples of hydroxyl-containing (meth)acrylates include, but are not limited to, 2-hydroxyethyl methacrylate (HEMA), glycerol methacrylate, and mixtures thereof. Other hydrophilic comonomers for contact lens formation 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 hydrophilic comonomers for contact lens formation will be apparent to those skilled in the art. The monomer mixture described herein may also be a mixture of the above-mentioned hydrophilic comonomers for contact lens formation.

[0017] 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 for contact lens formation may be present in the monomer mixture in an amount ranging from about 20% to about 80% by weight, based on the total weight of the monomer mixture. In another exemplary embodiment, one or more hydrophilic comonomers for contact lens formation may be present in the monomer mixture in an amount ranging from about 30% to about 60% by weight, based on the total weight of the monomer mixture.

[0018] In one or more additional non-limiting exemplary embodiments, which may be combined with one or more of the preceding paragraphs, one or more contact lens forming comonomers may be one or more contact lens forming silicone comonomers. For example, typical contact lens forming silicone comonomers used for forming silicone hydrogels are well known in the art, and numerous examples are provided in U.S. Patents No. 4,136,250, No. 4,153,641, No. 4,740,533, No. 5,034,461, No. 5,070,215, No. 5,260,000, No. 5,310,779, and No. 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.

[0019] In exemplary embodiments, which may be combined with one or more of the preceding items, the silicone comonomer for contact lens formation may include one or more non-bulky organosilicon-containing monomers as a representative class of silicone comonomers for contact lens formation. As used herein, “organosilicon-containing monomer” contains at least one [siloxanil] or at least one [silylalkylsiloxanil] repeating unit in the monomer, macromer, or prepolymer. In exemplary embodiments, an example of a non-bulky organosilicon-containing monomer is represented by the structure of formula Ia: [ka]

[0020] 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 , R6 , R 7 , R 8 and R 9 are, independently, hydrogen, an alkyl group, a haloalkyl group, a cycloalkyl group, a heterocycloalkyl group, an alkenyl group, a haloalkenyl group or an aryl group, and R\ 10 and R 11 are independently hydrogen or an alkyl group, where at least one of R 10 and R 11 is hydrogen, y is from 2 to 7, and n is from 1 to 100 or from 1 to 20.

[0021] Ethylenically unsaturated polymerizable groups are well known to those skilled in the art. Suitable ethylenically unsaturated polymerizable groups include, for example, (meth)acrylate, vinyl carbonate, O-vinyl carbamate, N-vinyl carbamate, and (meth)acrylamide.

[0022] The linking group can be any divalent radical or moiety, for example, a substituted or unsubstituted C1-C 12 alkyl group, an alkyl ether group, an alkenyl group, an alkenyl ether group, a haloalkyl group, a substituted or unsubstituted siloxane group, and a monomer capable of propagating ring opening.

[0023] In one embodiment, V is (meth)acrylate, L is a C1-C 12 alkylene group, and R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , and R 9 are, independently, C1-C 12 alkyl groups, and R 10 and R 11 are independently H or a C1-C 12 alkyl group, y is from 2 to 7, and n is from 3 to 8.\

[0024] In one embodiment, V is a (meth)acrylate, L is a C1-C6 alkyl group, and R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , and R 9 R is independently a C1-C6 alkyl group. 10 and R 11 is independently H or a C1-C6 alkyl group, y is 2-7, and n is 1-20.

[0025] Non-bulky organosilicon-containing monomers represented by the structure of formula Ia are known in the art; see, for example, U.S. Patents 7,915,323, 7,994,356, 8,420,711, 8,827,447, and 9,039,174, which are incorporated herein by reference.

[0026] In one exemplary embodiment, which may be combined with one or more of the preceding items, one or more non-bulky organosilicon-containing monomers may also include compounds represented by the structure of formula Ib: [ka]

[0027] In the formula, R 12 is H or methyl, and X is O or NR 16 And here, R 16 R is selected from C1-C4 alkyl groups which may be further substituted with H or one or more hydroxyl groups, and in some embodiments is H or methyl, 13is a divalent alkyl group which may be further functionalized with a group selected from the group consisting of an ether group, a hydroxyl group, a carbamate group and combinations thereof, in another embodiment it is a C1-C6 alkylene group which may be substituted with an ether group, a hydroxyl group and combinations thereof, in yet another embodiment it is a C1 or C3-C4 alkylene group which may be substituted with an ether group, a hydroxyl group and combinations thereof, and each R 14 In one embodiment, each R is 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, and a is 2-50, and in some embodiments it is 5-15.

[0028] Non-bulky organosilicon-containing monomers represented by the structure of formula Ib 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, which are incorporated herein by reference.

[0029] Typical examples of non-bulky organosilicon-containing monomers include at least the following compounds:

[0030] M1EDS6: A compound having the following structure, available from Gelest: [ka]

[0031] MCR-M11: A compound having the following structure: [ka]

[0032] M1-MCR-C12: A compound having the following structure: [ka] (In the formula, n has a mean of 12).

[0033] The aforementioned non-bulky organosilicon-containing monomers are merely examples, and any other known or future-developed non-bulky organosilicon-containing monomers are incorporated herein.

[0034] According to one exemplary embodiment, which may be combined with one or more of the preceding items, one or more silicone comonomers for contact lens formation may include one or more bulky silicone-containing monomers as a representative class of silicone comonomers for contact lens formation. Suitable one or more bulky silicone monomers include, for example, one or more bulky siloxane monomers such as polysiloxanyl alkyl (meth)acrylic monomers, bulky polysiloxanyl alkyl carbamate monomers, and mixtures thereof. In one embodiment, a typical example of a bulky silicon-containing monomer is represented by the structure of formula II: [ka]

[0035] In the formula, X is -O- or -NR 19 - indicates (where each R 19 (is hydrogen or a C1-C4 alkyl group), R 17 Each R independently represents hydrogen or methyl, and each R 18 This independently represents a lower alkyl radical such as a C1-C6 group, a phenyl radical, or a group represented by the following structure: [ka]

[0036] In the formula, each R 18′ Each of these independently represents a lower alkyl radical or a phenyl radical, where h is 1 to 10, or represented by the structure of formula III: [ka]

[0037] In the formula, X is -NR 19 -shows (where R 19 (is hydrogen or a C1-C4 alkyl group), R 17 R represents hydrogen or methyl, and each R 18 These independently represent a lower alkyl radical, a phenyl radical, or a group represented by the following structure: [ka]

[0038] In the formula, each R 18′ Each of these independently represents a lower alkyl radical or a phenyl radical, and h is between 1 and 10.

[0039] Typical examples of bulky silicon-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), and 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.

[0040] Such bulky monomers may be copolymerized with silicone macromonomers, which are poly(organosiloxanes) capped with unsaturated groups at two or more ends of the molecule. U.S. Patent No. 4,153,641 discloses various unsaturated groups, such as acryloxy or methacryloxy groups.

[0041] The aforementioned bulky organosilicon-containing monomers are merely examples, and any other known or future-developed bulky organosilicon-containing monomers are also included herein.

[0042] In one exemplary embodiment, which may be combined with one or more of the preceding items, one or more silicone comonomers for contact lens formation may include one or more silicon-containing vinyl carbonate or vinyl carbamate monomers as a representative class of silicone comonomers for contact lens formation. Suitable silicon-containing vinyl carbonate or vinyl carbamate monomers include, for example, 1,3-bis[4-vinyloxycarbonyloxy)butan-1-yl]tetramethyldisiloxane, 3-(trimethylsilyl)propyl vinyl carbonate, 3-(vinyloxycarbonylthio)propyl-[tris(trimethylsiloxy)silane], 3-[tris(trimethylsiloxy)silyl]propyl vinyl carbamate, 3-[tris(trimethylsiloxy)silyl]propyl allyl carbamate, 3-[tris(trimethylsiloxy)silyl]propyl vinyl carbonate, t-butyldimethylsiloxyethyl vinyl carbonate, trimethylsilylethyl vinyl carbonate, trimethylsilylmethyl vinyl carbonate, and mixtures thereof.

[0043] In one exemplary embodiment, which may be combined with one or more of the preceding items, one or more silicone comonomers for contact lens formation may include one or more polyurethane-polysiloxane macromonomers (sometimes called prepolymers) that may have a rigid-soft-rigid block, similar to conventional urethane elastomers, as a representative class of silicone comonomers for contact lens formation. These may be end-capped with hydrophilic monomers such as HEMA. Examples of such silicone urethanes are disclosed in various publications, including Lai, Yu-Chin, “The Role of Bulky Polysiloxanylalkyl Methacryates in Polyurethane-Polysiloxane Hydrogels,” Journal of Applied Polymer Science, Vol. 60, 1193-1199 (1996). PCT Publication Application WO96 / 31792 discloses examples of such monomers, the disclosure of which is incorporated herein by reference in its entirety. Further examples of silicone urethane monomers are represented by formulas IV and V. [ka] [ka] During the ceremony, D independently represents an alkyldi group, alkylcycloalkyldi group, cycloalkyldi group, aryldi group, or alkylaryldi group having 6 to approximately 30 carbon atoms. G independently represents an alkyldi group, cycloalkyldi group, alkylcycloalkyldi group, aryldi group, or alkylaryldi group having 1 to about 40 carbon atoms, and may contain ether, thio, or amine bonds in the main chain. * indicates a urethane or ureid bond. a is at least 1, A independently represents the divalent polymer group of formula VI. [ka] In the formula, each R s This independently represents an alkyl group or fluorine-substituted alkyl group of 1 to about 10 carbon atoms that may contain ether bonds between carbon atoms, m' is at least 1, and p is a number that provides about 400 to about 10,000 partial weights. Each of E and E' independently represents a polymerizable unsaturated organic group represented by formula VII: [ka] In the formula, R 3 is hydrogen or methyl, R 4 This includes hydrogen, an alkyl group having 1 to 6 carbon atoms, or -CO-YR 6 It is a base, and Y is -O-, -S-, or -NH-. R 5 It is a divalent alkylene radical having 1 to approximately 10 carbon atoms. R 6 It is an alkyl radical having 1 to approximately 12 carbon atoms. X represents -CO- or -OCO-, Z represents -O- or -NH-, Ar represents an aromatic group having approximately 6 to 30 carbon atoms. w is between 0 and 6, x is 0 or 1, y is 0 or 1, and z is 0 or 1.

[0044] In one exemplary embodiment, which may be combined with one or more of the preceding items, one or more silicone comonomers for contact lens formation may include, as a representative class of silicone comonomers for contact lens formation, one or more silicon-containing urethane monomers represented by formula VIII: [ka] In the formula, m is at least 1, preferably 3 or 4, a is at least 1, preferably 1, p is a number that provides part weights of about 400 to about 10,000, preferably at least 30, R 7 This is a diradical obtained by removing the isocyanate group from a diisocyanate (for example, the diradical of isophorone diisocyanate), and each E'' is a group represented as follows. [ka]

[0045] In another embodiment, the silicone hydrogel material comprises about 5 to about 50 weight percent (or about 10 to about 25 weight percent) of one or more silicone macromonomers, 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 (overall, i.e., in the copolymerized monomer mixture). 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 structures, U.S. Patent No. 4,153,641 discloses additional unsaturated groups including acryloxy or methacryloxy. Fumarate-containing materials, such as those disclosed in U.S. Patents No. 5,310,779, No. 5,449,729 and No. 5,512,205, are also useful substrates according to the non-limiting embodiments described herein. The silane macromonomer may be a silicon-containing vinyl carbonate or vinyl carbamate, or a polyurethane-polysiloxane having one or more rigid-flexible-rigid blocks and terminally capped with a hydrophilic monomer.

[0046] In one exemplary embodiment, which may be combined with one or more of the preceding items, one or more silicone comonomers for contact lens formation may include one or more monomers of formula IX as a representative class of silicone comonomers for contact lens formation: [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.

[0047] Ring-opening agents are well known in the literature. Non-exclusive examples of anionic ring-opening agents include alkyllithium, alkoxides, and trialkylsiloxylithium (where the alkyl group may or may not contain a halogen atom).

[0048] The linking group can be any divalent radical or moiety and may include substituted or unsubstituted alkyls, alkyl ethers, alkenyls, alkenyl ethers, haloalkyls, substituted or unsubstituted siloxanes, and monomers capable of propagating ring opening.

[0049] Ethylene-based unsaturated polymerizable groups are well known to those skilled in the art. Non-limiting examples of ethylene-based unsaturated polymerizable groups include acrylates, methacrylates, vinyl carbonates, O-vinylcarbamates, N-vinylcarbamates, acrylamides, and methacrylamides.

[0050] In one exemplary embodiment, which may be combined with one or more of the preceding items, one or more silicone comonomers for contact lens formation may include one or more monomers of formula X as a representative class of silicone comonomers for contact lens formation: [ka] In the formula, L is the same or different, a linking group or bond; V is the same or different, an ethylenically unsaturated polymerizable group; R1, R2, R3, R4, R5, R6, and R9 are independently hydrogen, alkyl groups, haloalkyl groups, cycloalkyl groups, heterocycloalkyl groups, alkenyl groups, haloalkenyl groups, or aromatic groups; R7 and R8 are independently hydrogen or alkyl groups (where at least one of R7 or R8 is hydrogen); y is 2 to 7; and n is 1 to 100.

[0051] In one exemplary embodiment, which may be combined with one or more of the preceding items, one or more silicone comonomers for contact lens formation may include one or more monomers from formulas XI and XII as a representative class of silicone comonomers for contact lens formation: [ka] In the formula, R9, R 10 and R 11 n is independently hydrogen, an alkyl group, a haloalkyl group, or another substituted alkyl group, where n is as defined above, 1 It ranges from 0 to 10, and also, [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.

[0052] In one exemplary embodiment, which may be combined with one or more of the preceding items, one or more silicone comonomers for contact lens formation may include one or more monomers from formulas XIII to XVII as a representative class of silicone comonomers for contact lens formation: [ka] [ka] [ka] [ka] [ka]

[0053] In one exemplary embodiment, which may be combined with one or more of the preceding items, one or more silicone comonomers for contact lens formation may include one or more monomers from formulas XVIII to XX as a representative class of silicone comonomers for contact lens formation: [ka] [ka] [ka]

[0054] In the formula, R9, R 10 and R 11 These are independently hydrogen, alkyl groups, haloalkyl groups, or other substituted alkyl groups, and n and n 1 This is defined as above.

[0055] In one exemplary embodiment, which may be combined with one or more of the preceding items, one or more silicone comonomers for contact lens formation may include one or more monomers from formulas XXI to XXIII as a representative class of silicone comonomers for contact lens formation: [ka] [ka] [ka]

[0056] In the formula, n is as defined above, X - It is a counterion that provides an overall neutral charge.

[0057] Counterions capable of providing an overall neutral charge are well known to those skilled in the art and would include, for example, halide ions.

[0058] In one exemplary embodiment, which may be combined with one or more of the preceding items, one or more silicone comonomers for contact lens formation may include one or more monomers of formula XXIV as a representative class of silicone comonomers for contact lens formation. [ka]

[0059] In one exemplary embodiment, which may be combined with one or more of the preceding items, one or more silicone comonomers for contact lens formation may include one or more polysiloxane prepolymers represented by the structure of formula XXV, as a representative class of silicone comonomers for contact lens formation: [ka] In the formula, each V is independently a reactive functional end group, and includes, 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 alkyl groups, 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-C30 Aryl groups, and substituted or unsubstituted C7-C 30 It is an arylalkyl group, and L is independently a linking group.

[0060] In exemplary embodiments, the hydroxyl group-containing reactive functional end groups used herein may be 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.

[0061] The linking group L is independently a linear or branched alkyl group, a cycloalkyl group, an aryl group, an ether or polyether group, and an ester group as defined herein.

[0062] In exemplary embodiments, typical examples of polysiloxane prepolymers are as follows: [ka]

[0063] The methods for preparing the polysiloxane prepolymers described herein are well known and within the scope of the art. In addition, polysiloxane prepolymers are commercially available from sources such as Gelest, Silar, Shin-Etsu, Momentive, and Siltech.

[0064] Other types of typical silicone comonomers for contact lens formation include, for example, fluorinated monomers. Such monomers have been used in the formation of fluorosilicone hydrogels to reduce deposit accumulation on contact lenses made therefrom, as shown, for example, in U.S. Patents 4,954,587, 5,010,141, and 5,079,319. Furthermore, the use of silicone-containing monomers having a specific fluorinated side group, i.e., -(CF2)-H, has been found to improve compatibility between hydrophilic monomer units and silicone-containing monomer units. See, for example, U.S. Patents 5,321,108 and 5,387,662.

[0065] The silicone materials described above are merely illustrative, and other materials can also be used as substrates, which are disclosed in various publications and are continuously being developed for use in contact lenses and other medical devices, and which may provide beneficial effects by incorporating UV-blocking agents according to exemplary embodiments. For example, contact lenses can be formed from cationic monomers, such as at least cationic silicone-containing monomers or cationic fluorinated silicone-containing monomers.

[0066] In one or more additional non-limiting and exemplary embodiments, which may be combined with one or more of the preceding paragraphs, one or more silicone comonomers for contact lens formation may be present in the monomer mixture in an amount of about 10% to about 90% by weight, based on the total weight of the monomer mixture. In another exemplary embodiment, one or more silicone comonomers for contact lens formation may be present in the monomer mixture in an amount of about 30% to about 70% by weight, based on the total weight of the monomer mixture.

[0067] In exemplary embodiments which may be combined with one or more of the preceding items, the monomer mixture further contains, in addition to one or more comonomers for contact lens formation, one or more UV blocking agents comprising a phenol group having a protected hydroxyl moiety and one or more ethylenically unsaturated reactive groups. In non-limiting exemplary embodiments, the one or more UV blocking agents comprising a phenol group having a protected hydroxyl moiety and one or more ethylenically unsaturated reactive groups can be represented by a benzotriazole compound having the structure of formula XXVI. [ka] In the formula, each R is independently hydrogen, halogen, -O- group, nitro group, nitrile group, substituted or unsubstituted alkoxy group, substituted or unsubstituted hydroxyl group, substituted or unsubstituted amine group, substituted or unsubstituted carbonyl group, and substituted or unsubstituted hydrocarbyl group, * R is a hydrogen or a substituted or unsubstituted hydrocarbyl group. ** is an ethylenically unsaturated reactive group, and PG is the protected hydroxyl group moiety.

[0068] As used herein, the term "substituted" means a group such as an alkyl group, cycloalkyl group, heterocycloalkyl group, aryl group and / or heteroaryl group, in which at least one hydrogen atom is optionally substituted with a group other than hydrogen water, such as halogen groups (e.g., F, Cl, I, and Br), hydroxyl groups, ether groups, thiol groups, thioether groups, carboxylic acid groups, carboxylic acid ester groups, phosphoric acid groups, phosphoric acid ester groups, sulfonic acid groups, sulfonic acid ester groups, nitro groups, cyano groups, hydrocarbyl groups (e.g., alkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups including polycyclic condensed ring cycloalkyl and polycyclic cycloalkyl groups, heterocycloalkyl groups, hydroxyl-substituted aryl groups such as phenol, aryl groups including polycyclic condensed ring aryl groups, heteroaryl groups including polycyclic condensed ring heteroaryl groups, and aralkyl groups), and amine groups.

[0069] As used herein, the description of a "linear or branched" group, such as a linear or branched alkyl group, means, for example, linear C2-C 30 Linear groups such as alkyl groups, and branched C3-C3 groups. 30 It is understood to include appropriately branched groups such as alkyl groups.

[0070] Typical examples of halogen groups include Cl, I, F, and Br.

[0071] Typical examples of hydrocarbyl groups include linear or branched alkyl groups, linear or branched alkenyl groups, linear or branched alkynyl groups, cycloalkyl groups, heterocyclic alkyl groups, aryl groups (including polycyclic aryl groups), heteroaryl groups (having at least one heteroatom in the aromatic ring), and aralkyl groups as defined herein.

[0072] Typical examples of alkoxy groups for use herein include alkyl groups as defined herein, i.e., those of the general formula -OR, which are bonded to the rest of the molecule via oxygen bonds. 1 (In the formula, R 1 The alkyl group (which is an alkyl group, cycloalkyl group, or aromatic group as defined herein) includes, for example, -OCH3, -OC2H5, or -OC6H5, which may be substituted or unsubstituted.

[0073] Typical examples of alkyl groups for use herein include, for example, linear or branched hydrocarbon chain radicals containing 1 to about 30 carbon atoms, or 1 to 12 carbon atoms, or 1 to 6 carbon atoms and hydrogen atoms, which may or may not be unsaturated with respect to the rest of the molecule, such as methyl groups, ethyl groups, n-propyl groups, 1-methylethyl groups (isopropyl groups), n-butyl groups, and n-pentyl groups.

[0074] Typical examples of alkenyl groups for use herein include, for example, linear or branched hydrocarbon chain radicals containing about 3 to about 30 carbon atoms and having at least one carbon-carbon double bond, such as propenyl, butenyl, and pentenyl groups.

[0075] Typical examples of alkynyl groups for use herein include, for example, linear or branched hydrocarbon chain radicals containing about 3 to about 30 carbon atoms and having at least one carbon-carbon triple bond, such as propynyl, butynyl, and pentynyl groups.

[0076] 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 12 carbon atoms, or 3 to 6 carbon atoms, which optionally include one or more heteroatoms (e.g., O and N), such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, perhydronaphthyl, adamantyl, and norbornyl groups, as well as bridging ring groups or spirodicyclic groups (e.g., spiro-(4,4)-non-2-yl).

[0077] Typical examples of heterocyclic groups for use herein include, for example, stable substituted or unsubstituted 3- to about 15-membered ring radicals containing a carbon atom and 1 to 5 heteroatoms (e.g., nitrogen, phosphorus, oxygen, sulfur, and mixtures thereof). Suitable heterocyclic ring groups for use herein may be monocyclic, bicyclic, or tricyclic ring systems, and may include fused ring systems, bridging ring systems, or spiro ring systems, and the nitrogen, phosphorus, carbon, oxygen, or sulfur atoms in the heterocyclic ring group may be optionally oxidized to a variety of oxidation states. Examples of such heterocyclic groups include, but are not limited to, azetidinyl, acridinyl, benzodioxolyl, benzodioxanil, benzofuryl, carbazolyl, synnolinyl, dioxolanil, indolidinyl, naphthilidinyl, perhydroazepinyl, phenadinyl, phenothiazinyl, phenoxadinyl, phthalazinyl, pyridyl, pteridinyl, purinyl, quinazolinyl, noxalinyl, quinolinyl, isoquinolinyl, tetrazoyl, imidazolyl, tetrahydroisoquinolyl, piperidinyl, piperazinyl, 2-oxopiperazinyl, 2-oxopiperidinyl, 2-oxopyrrolidinyl, 2-oxoazepinyl, azepinyl, pyrrolyl, 4-piperidonyl, pyrrolidinyl, pyrazinyl, pyrimidinyl, pyridadinyl, oxazolyl, oxazolinyl, oxazolyl This includes zolidinyl, triazolyl, indanyl, isoxazolyl, isoxazolidinyl, morpholinyl, thiazolyl, thiazolinyl, thiazolidinyl, isothiazolyl, quinuclidinyl, isothiazolidinyl, indolyl, isoindolyl, indlinyl, isoindolyl, octahydroindolyl, octahydroisoindolyl, quinolyl, isoquinolyl, decahydroisoquinolyl, benzimidazolyl, thiadiazolyl, benzopyranil, benzothiazolyl, benzoxazolyl, furyl, tetrahydrofuryl, tetrahydropyranil, thienyl, benzothienyl, thiamorpholinyl, thiamorpholinyl sulfoxide, thiamorpholinyl sulfone, dioxaphosphoranyl, oxadiazolyl, chromanil, isochromanil, and mixtures thereof.

[0078] Representative examples of aryl groups for use herein include, for example, substituted or unsubstituted monoaromatic or polyaromatic radicals containing from about 5 to about 30 carbon atoms, or 5 to 12 carbon atoms, or 5 to 8 carbon atoms, optionally containing one or more heteroatoms (such as O and N, etc.), such as phenyl, naphthyl, tetrahydronaphthyl, indenyl, biphenyl, and the like.

[0079] Representative examples of heteroaryl groups for use herein include, for example, substituted or unsubstituted stable 5- to about 30-membered monoaromatic or polyaromatic radicals containing carbon atoms and 1 to 5 heteroatoms (such as nitrogen, phosphorus, oxygen, sulfur, and mixtures thereof).

[0080] Representative examples of similar terms such as fused-ring polycyclic-aryl-alkyl groups, fused-ring polycyclic-alkyl-aryl groups, fused-ring polycyclic cyclo-aryl-alkyl groups, and fused-ring polycyclic cyclo-alkyl-aryl groups mean fused-ring polycyclic groups containing at least one aryl ring and at least one cycloalkyl ring that are fused together to form a fused-ring structure. For purposes of non-limiting illustration, examples of fused-ring polycyclic-aryl-alkyl groups include, but are not limited to, indenyl, 9H-fluorenyl, cyclopentanaphthyl, and indacenyl groups.

[0081] Representative examples of aralkyl groups for use herein include, according to some embodiments, but not limited to, C6-C 10 C6-C such as aralkyl 24 An aralkyl-containing group in which an aryl group is substituted with an alkyl group.

[0082] Representative examples of amine groups for use herein include, for example, amines of the general formula -R 2 NR 3 R 4 wherein R 2 , R 3 and R 4is independently a hydrogen atom or a C1-C hydrocarbon such as an alkyl group, an aromatic group, or a cycloalkyl group as defined herein 30 is a hydrocarbon.

[0083] Representative examples of ethylenically unsaturated reactive groups for use herein include, for example, (meth)acrylate-containing reactive end groups, (meth)acrylamide-containing reactive end groups, allyl-containing reactive end groups, vinyl-containing reactive end groups, vinyl carbonate-containing reactive end groups, vinyl carbamate-containing reactive end groups, styrene-containing reactive end groups, itaconate-containing reactive end groups, vinyloxy-containing reactive end groups, fumarate-containing reactive end groups, maleimide-containing reactive end groups, vinylsulfonyl reactive end groups, and the like. In non-limiting exemplary embodiments, the (meth)acrylate-containing reactive end group can be represented by the following structure:

Chemical formula

[0084] Representative examples of suitable protecting groups for protecting the hydroxyl moiety of the phenolic group of the UV blocker include, for example, trialkylsilanes such as trimethylsilane, triethylsilane, branched alkyloxycarbonyls such as t-butyloxycarbonyl (also referred to as BOC), vinyloxycarbonyl, dialkyl dicarbonates such as methoxymethyl, ethoxycarbonyloxy, di-t-butyldicarbonate, and the like.

[0085] In one exemplary embodiment, R and R * Each of these is a hydrogen atom, and R ** This is a (meth)acrylate-containing reactive terminal group.

[0086] In another exemplary embodiment, which may be combined with one or more of the preceding items, R ** It is located on the aromatic ring in the para position relative to the protected OH moiety.

[0087] In a non-limiting exemplary embodiment, one class of UV-blocking agents comprising a phenol group containing a hydroxyl moiety and one or more ethylenically unsaturated reactive groups can be represented by a benzotriazole compound having the structure of formula XXVII: [ka]

[0088] In the formula, R, R * and R ** This is defined as above.

[0089] The UV-blocking agents used herein are known and commercially available from sources such as Aldrich, Polysciences, Gelest, and Melrob, or can be prepared by methods within the scope of the knowledge of those skilled in the art.

[0090] The above-mentioned UV-blocking agents comprising a phenol group having a hydroxyl moiety and one or more ethylenically unsaturated reactive groups are merely examples and not intended to be limiting. Known UV-blocking agents comprising a phenol group having a hydroxyl moiety and one or more ethylenically unsaturated reactive groups, or UV-blocking agents later developed comprising a phenol group having a hydroxyl moiety and one or more ethylenically unsaturated reactive groups, are intended for use herein.

[0091] In exemplary embodiments, one or more UV-blocking agents comprising a phenol group having a protected hydroxyl moiety and one or more ethylenically unsaturated reactive groups can be obtained by protecting the hydroxyl moiety of the phenol group with a suitable protecting group as discussed above. Methods for protecting the hydroxyl moiety with a protecting group are within the scope of knowledge of those skilled in the art.

[0092] Typical examples of various synthetic routes for preparing the above UV blocking agent, which contains a phenol group with a protected hydroxyl moiety and one or more ethylenically unsaturated reactive groups, are as follows. [ka] [ka] [ka]

[0093] In one or more additional, non-limiting, and exemplary embodiments, which may be combined with one or more of the preceding paragraphs, one or more UV-blocking agents comprising a phenol group having a protected hydroxyl moiety and one or more ethylenically unsaturated reactive groups may be present in the monomer mixture in an amount ranging from about 0.1 weight percent to about 5 weight percent based on the total weight of the monomer mixture. In another exemplary embodiment, one or more UV-blocking agents comprising a phenol group having a protected hydroxyl moiety and one or more ethylenically unsaturated reactive groups may be present in the monomer mixture in an amount ranging from about 0.5 weight percent to about 3 weight percent based on the total weight of the monomer mixture.

[0094] In an exemplary embodiment, which may be combined with one or more of the preceding items, the monomer mixture further contains one or more contact lens-forming comonomers and one or more UV-blocking agents comprising a phenol group having a protected hydroxyl moiety and one or more ethylenically unsaturated reactive groups, in addition to one or more blue light-blocking agents comprising a phenol group having a protected hydroxyl moiety and one or more ethylenically unsaturated reactive groups. In an exemplary embodiment, the one or more blue light-blocking agents comprising a phenol group having a protected hydroxyl moiety and one or more ethylenically unsaturated reactive groups can be represented by an acridone compound having the structure of formula XXVIII: [ka] In the formula, R * R is a hydrogen atom or a substituted or unsubstituted hydrocarbyl group as defined above, ** is the ethylenically unsaturated reactive group as defined above, and PG is the protected hydroxyl group moiety as defined above.

[0095] In an exemplary embodiment, R * R is a hydrogen atom, ** This is a (meth)acrylate-containing reactive terminal group as defined above.

[0096] In another exemplary embodiment, which may be combined with one or more of the preceding items, R ** It is located on the aromatic ring in the para position relative to the OH moiety.

[0097] In non-limiting exemplary embodiments, a series of blue light blocking agents comprising a phenol group containing a hydroxyl moiety and one or more ethylenically unsaturated reactive groups can be represented by acridone compounds having the structure of formula XXIX: [ka] In the formula, R * and R ** This is defined as above.

[0098] The blue light blocking agents used herein are known and commercially available from sources such as Vishwa-Syntharo PharmaCompany, or can be prepared by methods within the technical scope of those skilled in the art.

[0099] The above-mentioned blue light blocking agents comprising a phenol group having a hydroxyl moiety and one or more ethylenically unsaturated reactive groups are merely examples and not intended to be limiting. Any known blue light blocking agent comprising a phenol group having a hydroxyl moiety and one or more ethylenically unsaturated reactive groups, or blue light blocking agents comprising a phenol group having a hydroxyl moiety and one or more ethylenically unsaturated reactive groups to be developed in the future, are intended for use herein.

[0100] In exemplary embodiments, one or more blue light blocking agents can be obtained by protecting the hydroxyl moiety of a phenol group with a suitable protecting group, as discussed above. Representative examples of various synthetic routes for preparing the above blue light blocking agent, which comprises a phenol group containing the protected hydroxyl moiety and one or more ethylenically unsaturated reactive groups, are shown below. [ka] [ka] [ka]

[0101] In one or more additional, non-limiting, and exemplary embodiments which may be combined with one or more of the preceding paragraphs, one or more blue light blocking agents may be present in the monomer mixture in an amount ranging from about 0.1 weight percent to about 2 weight percent based on the total weight of the monomer mixture.

[0102] In non-limiting and exemplary embodiments, which may be combined with one or more of the preceding items, 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 comprising 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.

[0103] 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 di, tri, or tetra(meth)acrylate-containing crosslinking agents include, for example, di, tri, or tetra(meth)acrylate-containing crosslinking agents of alkane polyols (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).

[0104] 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, butylene glycol di(meth)acrylate, and the like. In one embodiment, one or more alkanediol di(meth)acrylate crosslinking agents include butanediol di(meth)acrylate crosslinking agents and hexanediol di(meth)acrylate, and the like. 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.

[0105] 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.

[0106] 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).

[0107] 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 exemplary embodiments, one or more crosslinking agents may be allyl methacrylate.

[0108] In non-limiting and exemplary embodiments, which may be combined with one or more of the crosslinking agents described in the preceding paragraph, one or more crosslinking agents may be present in the monomer mixture in a contact lens-forming amount. In non-limiting and exemplary embodiments, which may be combined with one or more of the crosslinking agents described in the preceding paragraph, one or more crosslinking agents may be present in the monomer mixture in an amount of about 2% to about 30% by weight, based on the total weight of the monomer mixture. In non-limiting and exemplary embodiments, which may be combined with one or more of the crosslinking agents described in the preceding paragraph, one or more crosslinking agents may be present in the monomer mixture in an amount of about 5% to about 20% by weight, based on the total weight of the monomer mixture.

[0109] In non-limiting and exemplary embodiments, which may be combined with one or more of the preceding items, 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 1-5 carbon atoms, such as methanol, ethanol, isopropyl alcohol, 1-propanol, tert-butyl alcohol, 2-butyl alcohol, 2-methyl-1-propanol, tert-amyl alcohol, and other C5 isomers.

[0110] In exemplary embodiments, which are not limiting and may be combined with one or more of the preceding provisions, the monomer mixture contains about 5% to about 50% by weight of diluent based on the total weight of the monomer mixture. In one embodiment, the monomer mixture contains about 15% to about 30% by weight of diluent based on the total weight of the monomer mixture.

[0111] The monomer mixture may further contain, as necessary, various additives such as antioxidants, colorants, lubricants, internal wetting agents, and reinforcing agents, as well as other components well known in the art, to the extent that they do not impair the purpose and effect of the exemplary embodiments.

[0112] Contact lenses according to the non-limiting exemplary embodiments described herein can be prepared using various prior art techniques to obtain molded articles having desired rear and front lens surfaces. Various processes are known for curing monomer mixtures in the preparation of contact lenses, including, for example, rotary casting and static casting. For example, in rotary casting, the monomer mixture is placed in an open mold (i.e., a one-piece mold) having a concave bottom surface, and the mold is rotated in a controlled manner while the monomer mixture is exposed to UV curing conditions such as UV light. In static casting, the monomer mixture is placed between two mold pieces (one mold piece having a shape that forms the front lens surface, and the other mold piece having a shape that forms the rear lens surface), and the monomer mixture is cured while held in the mold assembly, for example, by UV free radical polymerization of the mixture, to form a lens. Rotary casting methods are disclosed in U.S. Patents No. 3,408,429 and No. 3,660,545, while static casting methods are disclosed in U.S. Patents No. 4,113,224, No. 4,197,266 and No. 5,271,875. Furthermore, monomer mixtures may be cast in the form of rods or buttons, and then machined on a lathe to the desired lens shape.

[0113] Polymerization of monomer mixtures is accelerated by exposing the mixture to UV curing conditions, such as UV irradiation. Polymerization initiators may be included in the mixture to accelerate the polymerization step. Typical examples of UV initiators, though not limited to those known in the art, include benzoin methyl ether, benzoin ethyl ether, Darocure 1173, 1164, 2273, 1116, 2959, 3331 (EM Industries) and Irgacure 184, 651, and 819 (BASF), as well as Darocure TPO (BASF), Lucirin TPO, Lucirin TPO-L (BASF). Generally, UV initiators are used in the mixture at a concentration of approximately 0.01% to 5% by weight of the total monomer mixture.

[0114] Generally, polymerization under UV curing conditions can be carried out for approximately 5 to 50 minutes in an inert atmosphere such as nitrogen or argon.

[0115] After casting, the polymerization product (contact lens) is dry-released from the mold. For example, the polymerization product can be dry-released simply by removing it from the mold while it is dry. In another embodiment, dry release is achieved by mechanical action, using a mechanical gripper such as tweezers to mechanically remove the polymerization product from the mold, taking care not to break it. If mechanical removal is not possible, the mold half containing the polymerization product is mechanically deformed to forcibly dry-release it.

[0116] Next, the protected hydroxyl group portion of the phenol group of the UV-blocking agent and the blue-light-blocking agent is deprotected when used. In a non-limiting exemplary embodiment, the protected hydroxyl group portion of the phenol group is completely deprotected. In a non-limiting exemplary embodiment, the protected hydroxyl group portion of the phenol group can be deprotected by extraction and / or autoclaving when the contact lens is immersed in an aqueous packaging solution and placed in a packaging system as described below.

[0117] In an exemplary embodiment for deprotecting the protected hydroxyl group portion of the phenol group of a UV-blocking agent and an optional blue-light-blocking agent, a contact lens is dry-released and then subjected to an extraction process involving immersion in a series of solutions. In a non-limiting exemplary embodiment, the contact lens is first immersed in a first solvent solution, which includes, for example, a low molecular weight alcohol solvent, an aliphatic hydrocarbon solvent, an alicyclic hydrocarbon solvent, a ketone solvent, a nitrile solvent, an ether solvent, an amide group-containing solvent, and mixtures thereof. Suitable low molecular weight alcohols include, for example, low molecular weight alcohols having about 1 to about 13 carbon atoms and / or low molecular weight alcohols with a molecular weight of about 200 or less. Suitable low molecular weight alcohols can be selected from a variety of low molecular weight monohydric alcohols, each containing about 1 to about 13 carbon atoms. Suitable monohydric alcohols include, for example, methanol, ethanol, propanol, isopropyl alcohol, butanol, isobutyl alcohol, tert-butyl alcohol, hexanol, 2-ethylhexanol, dodecanol, and the like. Suitable aliphatic or alicyclic hydrocarbon solvents include, for example, pentane, hexane, heptane, and cyclohexane.

[0118] Suitable ketone solvents include, for example, acetone, methyl ethyl ketone, diethyl ketone, methyl propyl ketone, methyl isopropyl ketone, ethyl propyl ketone, ethyl isopropyl ketone, dipropyl ketone, diisopropyl ketone, methyl butyl ketone, methyl isobutyl ketone, methyl sec-butyl ketone, methyl tert-butyl ketone, ethyl butyl ketone, ethyl isobutyl ketone, ethyl sec-butyl ketone, ethyl tert-butyl ketone, propyl butyl ketone, isopropyl sec-butyl ketone, isopropyl tert-butyl ketone, dibutyl ketone, diisobutyl ketone, di-sec-butyl ketone, di-tert-butyl ketone, butyl isobutyl ketone, butyl sec-butyl ketone, butyl tert-butyl ketone, isobutyl sec-butyl ketone, isobutyl tert-butyl ketone, sec-butyltert-butylketone, 5-heptanone, 5-methyl-2-hexanone (methylisoamylketone), 4-methyl-2-hexanone, 3-methyl-2-hexanone, 3,4-dimethyl-2-pentanone, 3,3-dimethyl-2-pentanone, 4,4-dimethyl-2-pentanone, 3-octanone, 4-methyl-3-heptanone, 5-methyl-3-heptanone, 6-methyl-3-heptanone, 4,4-dimethyl-3-hexanone, 4,5-dimethyl-3-hexanone, 5,5-dimethyl This includes til-3-hexanone, 4-nonanone, 5-methyl-4-octanone, 6-methyl-4-octanone, 7-methyl-4-octanone, 5,5-dimethyl-4-neptanone, 5,6-dimethyl-4-heptanone, 6,6-dimethyl-4-heptanone, 2-undecanone, cyclopropanone, cyclobutanone, cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, cyclononanone, cyclodecanone, cycloundecanone, cyclododecanone, etc., and combinations thereof. In one embodiment, the ketone solvent is acetone.

[0119] Suitable nitrile solvents include, for example, saturated or unsaturated aliphatic, alicyclic, or aromatic compounds containing a nitrile group. Nitriles include compounds containing heteroatoms selected from groups 13, 14, 15, 16, and 17 of the periodic table. Typical examples of nitriles for use herein include acetonitrile, propionitrile, isopropionitrile, butyronitrile, isobutyronitrile, valeronitrile, isovaleronitrile, trimethylacetonitrile, hexanenitrile, heptanenitrile, heptyl cyanide, octyl cyanide, undecanenitrile, malononitrile, succinonitrile, glutalonitrile, adiponitrile, sebaconitrile, allyl cyanide, acrylonitrile, crotononitrile, methacrylonitrile, fumaronitrile, tetracyanoethylene, cyclopentanecarbonile, cyclohexanecarbonile, dichloroacetonitrile, fluoroacetonitrile, trichloroacetonitrile, benzonitrile, benzyl cyanide, 2-methylbenzyl cyanide, 2-chlorobenzonitrile, 3-chlorobenzonitrile, 4-chlorobenzonitrile, o-tolunitrile, m-tolunitrile, p-tolunitrile, and mixtures thereof. In one embodiment, the nitrile solvent is acetonitrile.

[0120] Suitable ether solvents include, for example, dialkyl ethers with the same or different alkyl groups and containing 1 to about 12 carbon atoms. Typical examples of ether solvents include dimethyl ether, diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran, pyran, and mixtures thereof. In one embodiment, the ether solvent is tetrahydrofuran.

[0121] Suitable amide group-containing solvents include, for example, dimethylformamide, N-methylformanilide, N-formylpiperidine, N-formylmorpholine, dimethylacetamide, N-methylpyrrolidone, N,N-dimethylbenzamide, and mixtures thereof. In one embodiment, the amide group-containing solvent is N-methylpyrrolidone.

[0122] In one embodiment, the first solvent solution may further contain water in combination with any of the first solvents described above. In another embodiment, the first solvent solution may be a blend of water in combination with a low molecular weight alcohol solvent. For example, the first solvent solution may be a blend containing about 25 to about 75 weight percent of the first solvent solution and about 75 to about 25 weight percent of water. In another embodiment, the blend may contain about 40 to about 60 weight percent of the first solvent solution and about 60 to about 40 weight percent of water.

[0123] The contact lens is immersed in the first solvent solution or a blend of water and the first solvent solution for about 5 to 60 minutes. In one embodiment, the contact lens is immersed in the first solvent solution or a blend of water and the first solvent solution for about 10 to 30 minutes.

[0124] According to one or more additional non-limiting exemplary embodiments, which may be combined with one or more of the preceding paragraphs, the contact lens can then be immersed in a second solvent solution, which may include, for example, one of the low molecular weight alcohol solvents, aliphatic hydrocarbon solvents, alicyclic hydrocarbon solvents, ketone solvents, nitrile solvents, ether solvents, and amide group-containing solvents discussed above. In one embodiment, the second solvent solution is one of the low molecular weight alcohol solvents.

[0125] According to one or more additional non-limiting exemplary embodiments, which may be combined with one or more of the preceding paragraphs, the contact lens can then be immersed in a third solvent solution, which may include, for example, any of the low molecular weight alcohol solvents, aliphatic hydrocarbon solvents, alicyclic hydrocarbon solvents, ketone solvents, nitrile solvents, ether solvents, and amide group-containing solvents discussed above. In one embodiment, the third solvent solution is any of the low molecular weight alcohol solvents.

[0126] In one embodiment, the third solvent solution may further contain water combined with any of the first solvents described above. In another embodiment, the third solvent solution may be a blend of water and a low molecular weight alcohol solvent. For example, the third solvent solution may be a blend containing about 25 to about 75 weight percent of the third solvent solution and about 75 to about 25 weight percent of water. In another embodiment, the blend may contain about 40 to about 60 weight percent of the third solvent solution and about 60 to about 40 weight percent of water.

[0127] The contact lens is immersed in the third solvent solution or a blend of water and the third solvent solution for about 5 to 60 minutes. In one embodiment, the contact lens is immersed in the third solvent solution or a blend of water and the third solvent solution for about 10 to 30 minutes.

[0128] According to one or more additional non-limiting exemplary embodiments, which may be combined with one or more of the preceding paragraphs, the contact lens can then be immersed in a series of aqueous solutions. The contact lens is immersed in the aqueous solution for about 5 minutes to about 60 minutes. In one embodiment, the contact lens is immersed in the aqueous solution for about 10 minutes to about 30 minutes.

[0129] After subjecting the contact lenses to the extraction process described above, the extracted contact lenses are sterilized. In one embodiment, the extracted contact lenses are sterilized by immersing them in buffered saline (e.g., borate-buffered saline or phosphate-buffered saline) and then subjecting them to autoclaving conditions at a temperature of approximately 120°C or higher for at least approximately 5 minutes, or at least approximately 20 minutes, or at least 24 hours, or up to approximately 72 hours. The sterilized contact lenses are then rinsed with water and placed in their packaging with appropriate buffered saline. The packaging is sealed, and the contact lenses are again subjected to autoclaving conditions in a sealed container at a temperature of approximately 120°C or higher.

[0130] In another exemplary embodiment for deprotecting the protected hydroxyl portion of the phenol group of a UV-blocking agent and an optional blue-light-blocking agent, the contact lens is dry-released and placed in a container containing a receptacle portion for holding the contact lens and a sterile aqueous packaging solution. Examples of containers include conventional blister packaging for biomedical devices. This receptacle, containing the contact lens immersed in the aqueous packaging solution, is airtightly sealed, for example, by sealing a lid material onto the packaging on top of the receptacle. For example, the lid material seals around the storage container. The aqueous packaging solution and the contact lens, while sealed in the packaging container receptacle, are sterilized by autoclaving the packaging at a temperature of at least 100°C or at least 120°C. After autoclaving, the protected hydroxyl portion of the phenol group of the UV-blocking agent and the blue-light-blocking agent is deprotected if to be used.

[0131] In a non-limiting exemplary embodiment, the resulting contact lens demonstrates sufficient UV protection to meet at least the FDA's Class I specification for UV protection. In another non-limiting exemplary embodiment, the resulting contact lens demonstrates sufficient UV protection to meet at least the FDA's Class II specification for UV protection, and the protected hydroxyl moiety at the phenol group of the UV-blocking agent is completely deprotected.

[0132] The following examples are provided to enable those skilled in the art to carry out the present invention and are merely illustrative of the invention. The examples should not be read as limiting the scope of the invention as defined in the claims.

[0133] In the examples, the following abbreviations are used.

[0134] TRIS: Tris(trimethylsiloxy)silylpropyl methacrylate.

[0135] NVP: N-vinyl-2-pyrrolidone.

[0136] EGDMA: Ethylene glycol dimethacrylate

[0137] HEMA: 2-Hydroxyethyl methacrylate

[0138] DMA: N,N-Dimethylacrylamide

[0139] IMVT: 1,4-Bis(4-(2-methacryloyloxyethyl)phenylamino)anthraquinone

[0140] Irgacure 819: A photoinitiator for free radical polymerization available from Sigma Aldrich

[0141] UV416: 2-(4-Benzoyl-3-hydroxyphenoxy)ethyl acrylate

[0142] SA monomer: A compound having the following structure:

CHEMICAL STRUCTURE

[0143] Ma2D37: A compound having the following structure and available from Shin-Etsu and Gelest

CHEMICAL STRUCTURE

[0144] M1EDS6: A compound having the following structure and available from Gelest

CHEMICAL STRUCTURE

[0145] As described below, various polymerization products were formed and their properties were evaluated by the following standard test procedures.

[0146] Contact Angle (CBCA): Captive bubble contact angle data was collected on a First Ten Angstroms FTA-1000 prop Shape Instrument. All samples were rinsed in HPLC-grade water before analysis to remove any packaging solution components from the sample surface. Before data acquisition, the surface tension of the water used in all experiments was measured using the pendant drop method. A surface tension value of 70–72 dynes / cm was expected to indicate that the water was suitable for use. All lens samples were placed on a curved sample holder and immersed in a quartz cell filled with HPLC-grade water. Advance and receding captive bubble contact angles were collected for each sample. Advance contact angle is defined as the angle measured in water when the bubble is receding from the lens surface (water is advancing across the surface). All captive bubble data was collected using a high-speed digital camera focused on the sample / bubble interface. The contact angle was calculated in the digital frame immediately before contact line movement across the sample / bubble interface. The receding contact angle is defined as the angle measured in water when the bubble is swelling across the sample surface (water is receding from the surface).

[0147] UVA transmittance % and UVB transmittance %: Transmittance was measured using a JASCO V-760 equipped with a JASCO PIV-756. A quartz cell sample holder was filled with phosphate buffer solution. The contact lens sample was placed in the center of the holder. The transmittance % passing through the sample was measured in the wavelength range of 200–800 nm. UVA transmittance is the integral value of transmittance % in the range of 316–380 nm. UVB transmittance % is the integral value of transmittance in the range of 280–315 nm. [Examples]

[0148] Example 1 Synthesis of 3-(2H-benzo[d][1,2,3]triazol-2-yl)-4-((trimethylsilyl)oxy)phenethyl methacrylate (TMS-SA) by a general reaction scheme. [ka]

[0149] A 250 mL round-bottom flask fitted with a magnetic stirring bar was dried overnight in a heated oven and cooled to room temperature. 2-[3-(2H-benzotriazol-2-yl)-4-hydroxyphenyl]ethyl methacrylate (5 g, 15.5 mmol, 1 equivalent) and triethylamine (1.88 g, 18.5 mmol, 1.2 equivalents) were added to the septum-filled flask. Next, anhydrous THF (45 mL) was injected into the flask using a syringe. The flask was then cooled in an ice bath at 0°C. Trimethylchlorosilane (2.01 g, 18.6 mmol, 1.2 equivalents) was slowly injected into the flask, and the reaction was stirred overnight. The solvent was removed from the rhodopap, and the solid was dissolved in anhydrous diethyl ether. The solution was passed through a Celite plug to remove triethylamine hydrochloride, then concentrated with a rhodopap, and dried overnight in a vacuum oven to obtain 3-(2H-benzo[d][1,2,3]triazole-2-yl)-4-((trimethylsilyl)oxy)phenethyl methacrylate (4.7 g, 76%) as a light brown liquid.

[0150] 1 ¹H NMR (400MHz, chloroform-d) δ ppm 0.17-0.19 (s,9H) 2.02 (s,3H) 3.119 (m,2H) 4.47-4.51 (m,2H) 5.63-5.64 (s,1H) 6.19 (s,1H) 7.10-7.13 (m,1H) 7.38-7.42 (m,1H) 7.52-7.54 (m,2H) 7.75-7.76 (m,1H) 8.04-8.07 (m,2H).

[0151] Example 2 Synthesis of 3-(2H-benzo[d][1,2,3]triazol-2-yl)-4-((ethoxycarbonyl)oxy)phenethyl methacrylate (Eoc-SA) by a general reaction scheme. [ka]

[0152] A 250 mL round-bottom flask equipped with a magnetic stir bar was dried overnight in a heating oven and cooled to room temperature. Into the flask with a septum, 2-[3-(2H-benzotriazol-2-yl)-4-hydroxyphenyl]ethyl methacrylate (5 g, 15.5 mmol, 1 equivalent) and triethylamine (1.88 g, 18.5 mmol, 1.2 equivalents) were added. Next, anhydrous THF (45 mL) was injected into the flask using a syringe. Then, the flask was cooled in an ice bath at 0 °C. Ethyl chloroformate (2.01 g, 18.6 mmol, 1.2 equivalents) was slowly injected into the flask, and the reaction was stirred overnight. The solvent was removed from the rotary evaporator, and the solid was dissolved in anhydrous diethyl ether. The solution was passed through a Celite plug to remove triethylamine hydrochloride. The product was purified by recrystallization in diethyl ether to obtain 3-(2H-benzo[d][1,2,3]triazol-2-yl)-4-((ethoxycarbonyl)oxy)phenethyl methacrylate (3.9 g, 63.80%) as white crystals.

[0153] 1 H NMR (400 MHz, chloroform-d) δ ppm 1.32 - 1.44 (m, 3H) 1.88 - 1.99 (m, 3H) 3.04 - 3.16 (m, 2H) 4.25 - 4.36 (m, 2H) 4.37 - 4.48 (m, 2H) 5.51 - 5.60 (m, 1H) 6.06 - 6.15 (m, 1H) 7.32 - 7.40 (m, 2H) 7.41 - 7.46 (m, 2H) 7.85 - 7.96 (m, 2H) 8.08 - 8.16 (m, 1H).

[0154] Example 3 Synthesis of 3-(2H-benzo[d][1,2,3]triazol-2-yl)-4-((tert-butoxycarbonyl)oxy)phenethyl methacrylate (Boc-SA) according to a general reaction scheme.

Chemical formula

[0155] A 250 mL round-bottom flask fitted with a magnetic stirring bar was dried overnight in a heated oven and cooled to room temperature. 2-[3-(2H-benzotriazol-2-yl)-4-hydroxyphenyl]ethyl methacrylate (10 g, 30.9 mmol, 1 equivalent) and 4-dimethylaminopyridine (378 mg, 3.1 mmol, 0.1 equivalent) were added to a flask with a septum. Next, 100 mL of anhydrous THF was injected into the flask using a syringe. Di-tert-butyl dicarbonate (8.1 g, 37.1 mmol, 1.2 equivalents) was dissolved in 20 mL of anhydrous THF in a vial. The di-tert-butyl dicarbonate solution was slowly poured into the flask, and the reaction was stirred overnight. The reaction mixture was washed with 5% HCl solution. The organic layer was collected, dried over anhydrous MgSO4, and then concentrated using a rhodopap to obtain 3-(2H-benzo[d][1,2,3]triazole-2-yl)-4-((tert-butoxycarbonyl)oxy)phenethyl methacrylate (5.03 g, 38.4%) as a white powder.

[0156] 1 H NMR (400MHz, chloroform-d)δ ppm1.4-1.54(m,9H)1.87-1.99(m,3H)3.04-3.18(m,2H)4.35-4.50(m,2H)5.56(s,1H) )6.07-6.15(m,1H)7.30-7.40(m,2H)7.40-7.46(m,2H)7.87-7.97(m,2H)8.10(s,1H).

[0157] Example 4 Synthesis of 5-chloro-9-oxo-1-((trimethylsilyl)oxy)-9,10-dihydroacridine-3-ylmethacrylate (TMS-acridone) by a general reaction scheme [ka]

[0158] A 250 mL round-bottom flask fitted with a magnetic stirring bar was dried overnight in a heated oven and cooled to room temperature. Next, 5-chloro-1-hydroxy-9-oxo-9,10-dihydroacridine-3-yl methacrylate (5 g, 15.1 mmol, 1 equivalent) and triethylamine (1.83 g, 18.1 mmol, 1.2 equivalents) were added to a flask with a septum. Anhydrous THF (100 mL) was injected into the flask using a syringe. The flask was cooled in an ice bath at 0°C. Trimethylchlorosilane (1.97 g, 18.1 mmol, 1.2 equivalents) was slowly injected into the flask. The reaction was stirred overnight, and after removing the solvent from the rhodopap, the solid was dissolved in anhydrous diethyl ether. The solution was passed through a Celite plug to remove triethylamine hydrochloride. The solution was concentrated using a rhodopap and dried overnight in a vacuum oven to obtain 5-chloro-9-oxo-1-((trimethylsilyl)oxy)-9,10-dihydroacridine-3-yl methacrylate (4.9 g, 81%) as a yellow solid.

[0159] Examples 5-8 and Comparative Examples A and B The monomer mixture was prepared by mixing the following components listed in Table 1 in amounts by weight. [Table 1]

[0160] Preparation of monomer mixtures: The monomers listed in Table 1 for each example were mixed and stirred in a brown polypropylene bottle at room temperature for 30 minutes.

[0161] Monomer casting and curing: Each monomer mixture was brought into a nitrogen-filled glove box. The monomer mixture was pipetteed onto the front mold and covered with the rear mold. The assembled mold containing the cast monomer mixture was placed in a UV curing box inside the glove box. The assembled mold was cured under the curing time and UV irradiation conditions described in Table 1. After UV irradiation, the assembled mold was moved out of the glove box.

[0162] Lens extraction and hydration: The contact lenses were removed from their assembled molds and immersed in a series of solutions. The contact lenses were first immersed in a 50:50 isopropanol / water solution for 10 minutes, then in 100% isopropanol for 30 minutes, then in 50:50 isopropanol / water for 10 minutes, followed by two 10-minute immersions in deionized water. The extracted lenses were transferred to borate buffer in glass vials and autoclaved.

[0163] According to one aspect of this disclosure, a method for preparing contact lenses containing an ultraviolet (UV) blocking agent is:

[0164] (a) Polymerizing a monomer mixture containing (i) one or more comonomers for contact lens formation, and (ii) one or more UV blocking agents containing a phenol group having a protected hydroxyl moiety and one or more ethylenically unsaturated reactive groups, under ultraviolet polymerization conditions, to obtain a polymerization product containing one or more UV blocking agents containing a phenol group having a protected hydroxyl moiety, and

[0165] (b) comprising deprotecting the protected hydroxyl group portion of one or more UV-blocking agents in the polymerization product.

[0166] In a non-limiting exemplary embodiment, which may be combined with one or more of the preceding items, the monomer mixture is polymerized under ultraviolet polymerization conditions for 5 to 50 minutes.

[0167] In a non-limiting exemplary embodiment which may be combined with one or more of the preceding items, one or more contact lens forming comonomers include one or more hydrophilic comonomers.

[0168] In non-limiting exemplary embodiments which may be combined with one or more of the preceding items, 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, poly(alkene glycols) functionalized with polymerizable groups, and mixtures thereof.

[0169] In a non-limiting exemplary embodiment which may be combined with one or more of the preceding items, one or more contact lens forming comonomers include one or more silicone-containing comonomers.

[0170] In a non-limiting exemplary embodiment, which may be combined with one or more of the preceding items, one or more silicone-containing comonomers are represented by the structure of formula I: [ka]

[0171] In the formula, V is an ethylenically unsaturated polymerizable group, L 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 These are H, C1~C independently. 12 Alkyl, haloalkyl, C3-C 12 Cycloalkyl, heterocyclic alkyl, C2~C 12 Alkenyl, haloalkenyl, or C6-C 12 It is aromatic, R 10 and R 11 H or C1~C 12 It is alkyl (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.

[0172] In a non-limiting exemplary embodiment, which may be combined with one or more of the preceding items, one or more silicone-containing comonomers are represented by the structure of formula II: [ka]

[0173] In the formula, R 12is H or methyl, and X is O or NR 16 (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 an ether group, a hydroxyl group, a carbamate group, and combinations thereof, and each R 14 R is a C1-C4 alkyl which may be independently substituted with phenyl or fluorine, hydroxyl or ether, and 15 is a C1-C4 alkyl group, a is 2-50, and in some embodiments it is 5-15.

[0174] In a non-limiting exemplary embodiment which may be combined with one or more of the preceding items, one or more silicone-containing comonomers are polysiloxane prepolymers represented by the structure of formula III: [ka]

[0175] In the formula, each V is an independent reactive functional terminal group, and R 17 ~R 22 These are independently linear or branched, substituted or unsubstituted C1-C 30 Alkyl alkyl groups, 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.

[0176] In a non-limiting exemplary embodiment, which may be combined with one or more of the preceding paragraphs, one or more silicone-containing comonomers are represented by the structure of formula IV: [ka]

[0177] In the formula, X is -O- or -NR 19 - indicates, R 19 R is hydrogen or C1-C4 alkyl, and each R 17 R independently represents hydrogen or methyl, and each R 18 These independently represent a C1-C6 alkyl group, a lower alkyl radical, a phenyl radical, or a group represented as follows: [ka]

[0178] In the formula, each R 18’ Each of these independently represents a lower alkyl radical such as a C1-C6 alkyl group or a phenyl radical, and h is between 1 and 10.

[0179] In a non-limiting exemplary embodiment, which may be combined with one or more of the preceding items, one or more silicone-containing comonomers are represented by the structure of formula V: [ka]

[0180] In the formula, X is -NR 19 - indicates, R 19 R represents hydrogen or a C1-C4 alkyl group. 17 R represents hydrogen or methyl, and each R 18 These independently represent lower alkyl groups such as C1-C6 alkyl groups, phenyl groups, or groups represented as follows: [ka]

[0181] In the formula, each R 18’ Each of these independently represents a lower alkyl group such as a C1-C6 alkyl group or a phenyl group, and h is 1-10.

[0182] In a non-limiting exemplary embodiment which may be combined with one or more of the preceding items, one or more UV blocking agents comprising a phenol group having a protected hydroxyl moiety and one or more ethylenically unsaturated reactive groups comprises a benzotriazole compound having the structure of formula VI, [ka]

[0183] In the formula, each R is independently hydrogen, halogen, -O- group, nitro group, nitrile group, substituted or unsubstituted alkoxy group, substituted or unsubstituted hydroxyl group, substituted or unsubstituted amine group, substituted or unsubstituted carbonyl group, and substituted or unsubstituted hydrocarbyl group, * R is a hydrogen or a substituted or unsubstituted hydrocarbyl group. ** is an ethylenically unsaturated reactive group, and PG is the protected hydroxyl moiety.

[0184] In a non-limiting exemplary embodiment, which may be combined with one or more of the preceding items, R and R * Each of them is hydrogen, and R ** This is a (meth)acrylate-containing reactive terminal group.

[0185] In a non-limiting exemplary embodiment which may be combined with one or more of the preceding items, R ** It is located on the aromatic ring in the para position relative to the protected hydroxyl group.

[0186] In non-limiting exemplary embodiments which may be combined with one or more of the preceding items, the protecting group of the protected hydroxyl moiety includes one of a trialkylsilane group, a branched alkyloxycarbonyl group, a vinyloxycarbonyl group, a methoxymethyl group, an ethoxycarbonyloxy group, and a di-t-alkyldicarbonate group.

[0187] In a non-limiting exemplary embodiment which may be combined with one or more of the preceding items, one or more contact lens forming comonomers comprises one or more hydrophilic comonomers, and one or more UV blocking agents comprising a phenol group having a protected hydroxyl moiety and one or more ethylenically unsaturated reactive groups comprises a benzotriazole compound having the structure of formula VI. [ka]

[0188] In the formula, each R is independently hydrogen, halogen, -O- group, nitro group, nitrile group, substituted or unsubstituted alkoxy group, substituted or unsubstituted hydroxyl group, substituted or unsubstituted amine group, substituted or unsubstituted carbonyl group, and substituted or unsubstituted hydrocarbyl group, * R is a hydrogen or a substituted or unsubstituted hydrocarbyl group. ** is an ethylenically unsaturated reactive group, and PG is the protected hydroxyl moiety.

[0189] In a non-limiting exemplary embodiment which may be combined with one or more of the preceding items, the monomer mixture is:

[0190] Based on the total weight of the monomer mixture, approximately 10% to approximately 90% by weight of one or more comonomers for contact lens formation, and

[0191] The monomer mixture contains one or more UV-blocking agents in an amount of approximately 0.1% to 5% by weight, based on the total weight of the monomer mixture.

[0192] In a non-limiting exemplary embodiment which may be combined with one or more of the preceding items, the monomer mixture is:

[0193] Based on the total weight of the monomer mixture, approximately 30% to approximately 70% by weight of one or more comonomers for contact lens formation, and

[0194] The monomer mixture contains one or more UV-blocking agents in an amount of approximately 0.5% to 3% by weight, based on the total weight of the monomer mixture.

[0195] In a non-limiting exemplary embodiment which may be combined with one or more of the above, the monomer mixture further comprises one or more blue light blocking agents comprising a phenol group containing a protected hydroxyl moiety and one or more ethylenically unsaturated reactive groups.

[0196] In a non-limiting exemplary embodiment which may be combined with one or more of the preceding items, the one or more blue light blocking agents are represented by an acridone compound having the structure of formula VII: [ka]

[0197] In the formula, each R is independently hydrogen, halogen, -O- group, nitro group, nitrile group, substituted or unsubstituted alkoxy group, substituted or unsubstituted hydroxyl group, substituted or unsubstituted amine group, substituted or unsubstituted carbonyl group, and substituted or unsubstituted hydrocarbyl group, * R is a hydrogen or a substituted or unsubstituted hydrocarbyl group. ** is an ethylenically unsaturated reactive group, and PG is the protected hydroxyl moiety.

[0198] In a non-limiting exemplary embodiment, which may be combined with one or more of the preceding items, R and R * Each of them is hydrogen, and R ** This is a (meth)acrylate-containing reactive terminal group.

[0199] In a non-limiting exemplary embodiment which may be combined with one or more of the preceding items, R ** It is located on the aromatic ring in the para position relative to the protected hydroxyl group.

[0200] In non-limiting exemplary embodiments, which may be combined with one or more of the preceding items, the protecting group of the protected hydroxyl moiety includes one of trialkylsilane, branched alkyloxycarbonyl, vinyloxycarbonyl, methoxymethyl, and di-t-alkyldicarbonate.

[0201] In an exemplary, non-limiting embodiment which may be combined with one or more of the preceding items, the monomer mixture contains one or more blue light blocking agents in an amount of about 0.1% to about 2% by weight, based on the total weight of the monomer mixture.

[0202] In a non-limiting exemplary embodiment, which may be combined with one or more of the preceding items, the monomer mixture further comprises one or more crosslinking agents.

[0203] In an exemplary, non-limiting embodiment which may be combined with one or more of the preceding items, the one or more crosslinking agents include a bifunctional crosslinking agent.

[0204] In an exemplary, non-limiting embodiment which may be combined with one or more of the preceding items, the monomer mixture contains one or more crosslinking agents in an amount of about 3% to about 20% by weight, based on the total weight of the monomer mixture.

[0205] In a non-limiting exemplary embodiment, which may be combined with one or more of the preceding paragraphs, deprotecting the protected hydroxyl group portion of one or more UV-blocking agents of the polymerization product includes subjecting the polymerization product to an extraction process.

[0206] In a non-limiting exemplary embodiment, which may be combined with one or more of the preceding items, the extraction process includes immersing the polymerization product in a series of solvent solutions.

[0207] In an exemplary, non-limiting embodiment which may be combined with one or more of the preceding items, the polymerization product is immersed in a first solution comprising one or more of the following: a first low molecular weight alcohol solvent, an aliphatic hydrocarbon solvent, an alicyclic hydrocarbon solvent, a ketone solvent, a nitrile solvent, an ether solvent, and an amide group-containing solvent, or a blend of water and one or more of the first solvents.

[0208] In a non-limiting exemplary embodiment, which may be combined with one or more of the preceding items, the polymerization product is immersed for about 10 to about 40 minutes in a first solution comprising a blend of water and a first low molecular weight alcohol solvent, wherein the first low molecular weight alcohol solvent is a low molecular weight monohydric alcohol having about 1 to about 13 carbon atoms and / or a low molecular weight monohydric alcohol having a molecular weight of about 200 or less.

[0209] In a non-limiting exemplary embodiment which may be combined with one or more of the preceding items, the polymerization product is immersed in a second solution containing a second low molecular weight alcohol solvent for about 10 to about 40 minutes, wherein the second low molecular weight alcohol solvent is a low molecular weight monohydric alcohol having about 1 to about 13 carbon atoms and / or a low molecular weight monohydric alcohol having a molecular weight of about 200 or less.

[0210] In a non-limiting exemplary embodiment, which may be combined with one or more of the preceding items, the polymerization product is immersed for about 10 to about 40 minutes in a third solution containing a third solvent comprising a mixture of water and a third low molecular weight alcohol solvent, wherein the third low molecular weight alcohol solvent is a low molecular weight monohydric alcohol having about 1 to about 13 carbon atoms and / or a low molecular weight monohydric alcohol having a molecular weight of about 200 or less.

[0211] In a non-limiting exemplary embodiment, which may be combined with one or more of the preceding steps, the polymerization product is immersed in a series of aqueous solutions one or more times.

[0212] In a non-limiting exemplary embodiment, which may be combined with one or more of the preceding paragraphs, the method further includes autoclaving the polymerization product after the extraction process.

[0213] In a non-limiting exemplary embodiment, which may be combined with one or more of the preceding provisions, deprotection of protected hydroxyl groups in one or more UV-blocking agents of the polymerization product includes autoclaving the polymerization product.

[0214] In a non-limiting exemplary embodiment, which may be combined with one or more of the preceding paragraphs, the method further includes applying a lid material to a package containing a polymerization product immersed in an aqueous packaging solution before subjecting the contact lenses to the step of autoclaving.

[0215] In a non-limiting exemplary embodiment, which may be combined with one or more of the preceding items, the polymerization product is autoclaved at a temperature of about 120°C or higher for at least about 5 minutes.

[0216] In a non-limiting exemplary embodiment, which may be combined with one or more of the preceding items, the contact lens is a soft contact lens.

[0217] In a non-limiting exemplary embodiment, which may be combined with one or more of the preceding items, the contact lens is a hydrogel contact lens.

[0218] In a non-limiting exemplary embodiment, which may be combined with one or more of the preceding items, the contact lens is a gas-permeable hard contact lens.

[0219] In a non-limiting exemplary embodiment, which may be combined with one or more of the preceding provisions, the contact lens demonstrates sufficient UV protection to meet at least the FDA's Class I specification for UV protection.

[0220] According to another aspect of the present disclosure, the contact lens is an extracted and / or autoclaved ultraviolet-curable polymerization product of a monomer mixture comprising (a) one or more contact lens forming comonomers and (b) one or more ultraviolet (UV) blocking agents comprising a phenol group having a protected hydroxyl moiety and one or more ethylenically unsaturated reactive groups.

[0221] In a non-limiting exemplary embodiment which may be combined with one or more of the preceding items, one or more contact lens forming comonomers include one or more hydrophilic comonomers.

[0222] In non-limiting exemplary embodiments which may be combined with one or more of the preceding items, 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, poly(alkene glycols) functionalized with polymerizable groups, and mixtures thereof.

[0223] In a non-limiting exemplary embodiment which may be combined with one or more of the preceding items, one or more contact lens forming comonomers include one or more silicone-containing comonomers.

[0224] In a non-limiting exemplary embodiment, which may be combined with one or more of the preceding items, one or more silicone-containing comonomers are represented by the structure of formula I: [ka]

[0225] In the formula, V is an ethylenically unsaturated polymerizable group, L is a linking group or bond, and R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R9 These are H, C1~C independently. 12 Alkyl, haloalkyl, C3-C 12 Cycloalkyl, heterocyclic alkyl, C2~C 12 Alkenyl, haloalkenyl, or C6-C 12 It is aromatic, R 10 and R 11 H or C1~C 12 It is alkyl (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.

[0226] In a non-limiting exemplary embodiment, which may be combined with one or more of the preceding items, one or more silicone-containing comonomers are represented by the structure of formula II: [ka]

[0227] In the formula, R 12 is H or methyl, and X is O or NR 16 (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 an ether group, a hydroxyl group, a carbamate group, and combinations thereof, and each R 14 R is a C1-C4 alkyl which may be independently substituted with phenyl or fluorine, hydroxyl or ether, and 15 is a C1-C4 alkyl group, a is 2-50, and in some embodiments it is 5-15.

[0228] In an exemplary, non-limiting embodiment which may be combined with one or more of the preceding items, one or more silicone-containing comonomers are polysiloxane prepolymers represented by the structure of formula III, [ka]

[0229] In the formula, each V is an independent reactive functional terminal group, and R 17 ~R 22 These are independently linear or branched substituted or unsubstituted C1-C 30 Alkyl alkyl groups, 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.

[0230] In a non-limiting exemplary embodiment, which may be combined with one or more of the preceding paragraphs, one or more silicone-containing comonomers are represented by the structure of formula IV: [ka]

[0231] In the formula, X is -O- or -NR 19 - indicates (where R 19 Each R is either hydrogen or a C1-C4 alkyl group. 17 R independently represents hydrogen or methyl, and each R 18 These independently represent a C1-C6 alkyl group, a lower alkyl radical, a phenyl radical, or a group represented as follows: [ka]

[0232] In the formula, each R 18’ Each of these independently represents a lower alkyl radical such as a C1-C6 alkyl group or a phenyl radical, and h is between 1 and 10.

[0233] In a non-limiting exemplary embodiment, which may be combined with one or more of the preceding items, one or more silicone-containing comonomers are represented by the structure of formula V: [ka]

[0234] In the formula, X is -NR 19 - indicates (where R 19 (R is hydrogen or C1-C4 alkyl) 17 R represents hydrogen or methyl, and each R 18 These independently represent lower alkyl groups such as C1-C6 alkyl groups, phenyl groups, or groups represented as follows: [ka]

[0235] In the formula, each R 18’ Each of these independently represents a lower alkyl radical such as a C1-C6 alkyl group or a phenyl radical, and h is between 1 and 10.

[0236] In a non-limiting exemplary embodiment which may be combined with one or more of the preceding items, one or more UV blocking agents comprising a phenol group having a protected hydroxyl moiety and one or more ethylenically unsaturated reactive groups comprises a benzotriazole compound having the structure of formula VI, [ka]

[0237] In the formula, each R is independently hydrogen, halogen, -O- group, nitro group, nitrile group, substituted or unsubstituted alkoxy group, substituted or unsubstituted hydroxyl group, substituted or unsubstituted amine group, substituted or unsubstituted carbonyl group, and substituted or unsubstituted hydrocarbyl group, * R is a hydrogen or a substituted or unsubstituted hydrocarbyl group. ** is an ethylenically unsaturated reactive group, and PG is the protected hydroxyl group moiety.

[0238] In a non-limiting exemplary embodiment, which may be combined with one or more of the preceding items, R and R * Each of them is hydrogen, and R ** This is a (meth)acrylate-containing reactive terminal group.

[0239] In a non-limiting exemplary embodiment which may be combined with one or more of the preceding items, R ** It is located on the aromatic ring in the para position relative to the protected hydroxyl group.

[0240] In non-limiting exemplary embodiments which may be combined with one or more of the preceding items, the protecting group of the protected hydroxyl moiety includes one of a trialkylsilane group, a branched alkyloxycarbonyl group, a vinyloxycarbonyl group, a methoxymethyl group, an ethoxycarbonyloxy group, and a di-t-alkyldicarbonate group.

[0241] In a non-limiting exemplary embodiment which may be combined with one or more of the above, the one or more contact lens forming comonomers comprises one or more hydrophilic comonomers, and the one or more UV blocking agents comprising a protected hydroxyl moiety and a phenol group having one or more ethylenically unsaturated reactive groups comprises a benzotriazole compound having the structure of formula VI. [ka]

[0242] In the formula, each R is independently hydrogen, halogen, -O- group, nitro group, nitrile group, substituted or unsubstituted alkoxy group, substituted or unsubstituted hydroxyl group, substituted or unsubstituted amine group, substituted or unsubstituted carbonyl group, and substituted or unsubstituted hydrocarbon group, * R is hydrogen or a substituted or unsubstituted hydrocarbon group. ** is an ethylenically unsaturated reactive group, and PG is the protected hydroxyl moiety.

[0243] In a non-limiting exemplary embodiment which may be combined with one or more of the preceding items, the monomer mixture is:

[0244] Based on the total weight of the monomer mixture, approximately 10% to approximately 90% by weight of one or more comonomers for contact lens formation, and

[0245] The monomer mixture contains one or more UV-blocking agents in an amount of approximately 0.1% to 5% by weight, based on the total weight of the monomer mixture.

[0246] In a non-limiting exemplary embodiment which may be combined with one or more of the preceding items, the monomer mixture is:

[0247] Based on the total weight of the monomer mixture, approximately 30% to approximately 70% by weight of one or more contact lens-forming comonomers, and

[0248] The monomer mixture contains one or more UV-blocking agents in an amount of approximately 0.5% to 3% by weight, based on the total weight of the monomer mixture.

[0249] In non-limiting exemplary embodiments, which may be combined with one or more of the preceding paragraphs, the monomer mixture further comprises one or more blue light blocking agents comprising a phenol group containing a protected hydroxyl moiety and one or more ethylenically unsaturated reactive groups.

[0250] In a non-limiting exemplary embodiment which may be combined with one or more of the preceding items, the one or more blue light blocking agents are represented by an acridone compound having the structure of formula VII: [ka]

[0251] In the formula, each R is independently hydrogen, halogen, -O- group, nitro group, nitrile group, substituted or unsubstituted alkoxy group, substituted or unsubstituted hydroxyl group, substituted or unsubstituted amine group, substituted or unsubstituted carbonyl group, and substituted or unsubstituted hydrocarbyl group, * R is a hydrogen or a substituted or unsubstituted hydrocarbyl group. ** is an ethylenically unsaturated reactive group, and PG is the protected hydroxyl moiety.

[0252] In a non-limiting exemplary embodiment, which may be combined with one or more of the preceding items, R and R * Each of them is hydrogen, and R **This is a (meth)acrylate-containing reactive terminal group.

[0253] In a non-limiting exemplary embodiment which may be combined with one or more of the preceding items, R ** It is located on the aromatic ring in the para position relative to the protected hydroxyl group.

[0254] In a non-limiting exemplary embodiment, which may be combined with one or more of the preceding items, the protecting group of the protected hydroxyl group includes one of trialkylsilane, branched alkyloxycarbonyl, vinyloxycarbonyl, methoxymethyl, and di-t-alkyldicarbonate.

[0255] In an exemplary, non-limiting embodiment which may be combined with one or more of the preceding items, the monomer mixture contains one or more blue light blocking agents in an amount of about 0.1% to about 2% by weight, based on the total weight of the monomer mixture.

[0256] In a non-limiting exemplary embodiment, which may be combined with one or more of the preceding items, the monomer mixture further comprises one or more crosslinking agents.

[0257] In an exemplary, non-limiting embodiment which may be combined with one or more of the preceding items, the one or more crosslinking agents include a bifunctional crosslinking agent.

[0258] In an exemplary, non-limiting embodiment which may be combined with one or more of the preceding items, the monomer mixture contains one or more crosslinking agents in an amount of about 3% to about 20% by weight, based on the total weight of the monomer mixture.

[0259] In a non-limiting exemplary embodiment, which may be combined with one or more of the preceding items, the contact lens is a soft contact lens.

[0260] In a non-limiting exemplary embodiment, which may be combined with one or more of the preceding items, the contact lens is a hydrogel contact lens.

[0261] In a non-limiting exemplary embodiment, which may be combined with one or more of the preceding items, the contact lens is a gas-permeable hard contact lens.

[0262] In a non-limiting exemplary embodiment, which may be combined with one or more of the preceding provisions, the contact lens demonstrates sufficient UV protection to meet at least the FDA Class I specification for UV protection.

[0263] The various features disclosed herein are described in the context of a single embodiment for the sake of brevity, but may be provided separately or in any suitable partial combination. All combinations of embodiments are specifically encompassed by the exemplary embodiments disclosed herein as if every possible combination were individually and explicitly disclosed. Furthermore, all subcombinations enumerated in embodiments describing such variations are also specifically encompassed in the compositions of the present invention and are disclosed herein as if every possible subcombination were individually and explicitly disclosed herein.

[0264] It will be understood that various modifications are possible to the embodiments disclosed herein. Therefore, the above description should not be construed as limiting, but rather as illustrative examples of preferred embodiments. For example, the functions described and implemented above as best modes for carrying out the invention are for illustrative purposes only. Those skilled in the art can implement other configurations and methods without departing from the scope and spirit of the invention. Furthermore, those skilled in the art will conceive of other modifications within the scope and spirit of the features and advantages appended herein.

Claims

1. A method for preparing contact lenses containing an ultraviolet (UV) blocking agent, (a) (i) one or more comonomers for contact lens formation, and (ii) one or more UV blocking agents comprising a phenol group having a protected hydroxyl moiety and one or more ethylenically unsaturated reactive groups, are polymerized under ultraviolet polymerization conditions to obtain a polymerization product containing the one or more UV blocking agents comprising a phenol group having a protected hydroxyl moiety, and (b) A method comprising deprotecting the protected hydroxyl group portion of the one or more UV-blocking agents of the polymerization product.

2. The method according to claim 1, wherein the monomer mixture is polymerized under ultraviolet polymerization conditions for a period of 5 to 50 minutes.

3. The method according to claim 1 or 2, wherein the one or more comonomers for contact lens formation are selected from the group consisting of one or more hydrophilic comonomers, one or more silicone-containing comonomers, and mixtures thereof.

4. The one or more UV blocking agents comprising a phenol group having a protected hydroxyl moiety and one or more ethylenically unsaturated reactive groups include a benzotriazole compound having the structure of formula I: 【Chemistry 1】 In the formula, each R is independently hydrogen, halogen, -O- group, nitro group, nitrile group, substituted or unsubstituted alkoxy group, substituted or unsubstituted hydroxyl group, substituted or unsubstituted amine group, substituted or unsubstituted carbonyl group, and substituted or unsubstituted hydrocarbyl group, R ＊ R is a hydrogen or a substituted or unsubstituted hydrocarbyl group. ＊＊ The method according to any one of claims 1 to 3, wherein is an ethylenically unsaturated reactive group and PG is a protected hydroxyl moiety.

5. R and R ＊ Each of them is hydrogen, and R ＊＊ The method according to claim 4, wherein is a (meth)acrylate-containing reactive terminal group.

6. R ＊＊ The method according to claim 4 or 5, wherein is located on the aromatic ring in the para position relative to the protected hydroxyl group portion.

7. The method according to any one of claims 4 to 6, wherein the protecting group of the protected hydroxyl group portion comprises one of a trialkylsilane group, a branched alkoxycarbonyl group, a vinyloxycarbonyl group, a methoxymethyl group, an ethoxycarbonyl group, and a di-t-alkyldicarbonate group.

8. The monomer mixture Based on the total weight of the monomer mixture, approximately 10% to approximately 90% by weight of one or more of the above-mentioned comonomers for contact lens formation, and The method according to any one of claims 1 to 7, comprising about 0.1% to 5% by weight of one or more UV-blocking agents based on the total weight of the monomer mixture.

9. The method according to any one of claims 1 to 8, wherein the monomer mixture further comprises one or more blue light blocking agents comprising a phenol group having a protected hydroxyl group moiety and one or more ethylenically unsaturated reactive groups, and the method further comprises deprotecting the protected hydroxyl group moiety of the one or more blue light blocking agents.

10. The above one or more blue light blocking agents are represented by an acridone compound having the structure of formula II: 【Chemistry 2】 In the formula, each R is independently hydrogen, halogen, -O- group, nitro group, nitrile group, substituted or unsubstituted alkoxy group, substituted or unsubstituted hydroxyl group, substituted or unsubstituted amine group, substituted or unsubstituted carbonyl group, and substituted or unsubstituted hydrocarbyl group, R ＊ R is a hydrogen or a substituted or unsubstituted hydrocarbyl group. ＊＊ The method according to claim 9, wherein is an ethylenically unsaturated reactive group and PG is a protected hydroxyl group moiety.

11. R and R ＊ are each hydrogen, and R ＊＊ is a (meth)acrylate-containing reactive end group, the method according to claim 10.

12. R ＊＊ The method according to claim 10 or 11, wherein is located on the aromatic ring in the para position relative to the protected hydroxyl group portion.

13. The method according to any one of claims 10 to 12, wherein the protecting group of the protected hydroxyl group portion comprises one of trialkylsilane, branched alkoxycarbonyl, vinyloxycarbonyl, methoxymethyl, and di-t-alkyldicarbonate.

14. The monomer mixture The method according to any one of claims 9 to 13, comprising about 0.1% by weight to about 2% by weight of one or more blue light blocking agents based on the total weight of the monomer mixture.

15. The method according to any one of claims 1 to 14, wherein the monomer mixture further comprises one or more crosslinking agents.

16. The method according to any one of claims 1 to 15, wherein deprotecting the protected hydroxyl group portion of the one or more UV-blocking agents of the polymerization product is performed by subjecting the polymerization product to an extraction process.

17. The method according to claim 16, wherein the extraction process includes immersing the polymerization product in a series of solvent solutions.

18. The method according to claim 17, wherein the polymerization product is immersed in a first solvent comprising one or more of the following: a first low molecular weight alcohol solvent, an aliphatic hydrocarbon solvent, an alicyclic hydrocarbon solvent, a ketone solvent, a nitrile solvent, an ether solvent, and an amide group-containing solvent, or a first solution comprising a blend of water and one or more of the first solvents.

19. The method according to claim 17, wherein the polymerization product is immersed in a first solution containing a blend of water and a first low molecular weight alcohol solvent for a period of about 10 to about 40 minutes, wherein the first low molecular weight alcohol solvent is a low molecular weight monohydric alcohol having about 1 to about 13 carbon atoms and / or a molecular weight of about 200 or less.

20. The method according to claim 18 or 19, wherein the polymerization product is further immersed in a second solution containing a second low molecular weight alcohol solvent for about 10 to about 40 minutes, the second low molecular weight alcohol solvent being a low molecular weight monohydric alcohol having about 1 to about 13 carbon atoms and / or a molecular weight of about 200 or less.

21. The method according to claim 20, wherein the polymerization product is further immersed for about 10 to about 40 minutes in a third solution containing a third solvent comprising a blend of water and a third low molecular weight alcohol solvent, the third low molecular weight alcohol solvent being a low molecular weight monohydric alcohol having about 1 to about 13 carbon atoms and / or a molecular weight of about 200 or less.

22. The method according to claim 17, wherein the polymerization product is immersed in a series of aqueous solutions once or more times.

23. The method according to any one of claims 16 to 22, further comprising autoclaving the polymerization product after the extraction process.

24. The method according to any one of claims 1 to 15, wherein deprotecting the protected hydroxyl group portion of the one or more UV-blocking agents of the polymerization product is performed by autoclaving the polymerization product.

25. The method according to any one of claims 1 to 24, wherein the contact lens demonstrates sufficient UV protection to satisfy at least the FDA Class I specification for UV protection.

26. A contact lens comprising one or more UV-blocking agents comprising a phenol group having a deprotected hydroxyl moiety, wherein the contact lens is an extracted and / or autoclaved UV-cured polymerization product of a monomer mixture comprising (a) one or more comonomers for contact lens formation and (b) one or more ultraviolet (UV) blocking agents comprising a phenol group having a protected hydroxyl moiety and one or more ethylenically unsaturated reactive groups.

27. The contact lens according to claim 26, wherein the one or more comonomers for forming the contact lens are selected from the group consisting of one or more hydrophilic comonomers, one or more silicone-containing comonomers, and mixtures thereof.

28. The one or more UV blocking agents comprising a phenol group having the protected hydroxyl moiety and one or more ethylenically unsaturated reactive groups include a benzotriazole compound having the structure of formula I: 【Transformation 3】 In the formula, each R is independently hydrogen, halogen, -O- group, nitro group, nitrile group, substituted or unsubstituted alkoxy group, substituted or unsubstituted hydroxyl group, substituted or unsubstituted amine group, substituted or unsubstituted carbonyl group, and substituted or unsubstituted hydrocarbyl group, R ＊ R is a hydrogen or a substituted or unsubstituted hydrocarbyl group. ＊＊ The contact lens according to claim 26 or 27, wherein is an ethylenically unsaturated reactive group and PG is a protected hydroxyl group moiety.

29. R and R ＊ Each of them is hydrogen, and R ＊＊ The contact lens according to claim 28, wherein is a (meth)acrylate-containing reactive end group.

30. R ＊＊ The contact lens according to claim 28 or 29, wherein the protected hydroxyl group portion is located on the aromatic ring in the para position relative to the protected hydroxyl group portion.

31. The contact lens according to any one of claims 28 to 30, wherein the protecting group of the protected hydroxyl group portion comprises one of a trialkylsilane group, a branched alkoxycarbonyl group, a vinyloxycarbonyl group, a methoxymethyl group, an ethoxycarbonyloxy group, and a di-t-alkyldicarbonate group.

32. A contact lens according to any one of claims 26 to 31, further comprising one or more blue light blocking agents comprising a phenol group containing a deprotected hydroxyl moiety, wherein the monomer mixture further comprises one or more blue light blocking agents comprising a phenol group containing a protected hydroxyl moiety and one or more ethylenically unsaturated reactive groups.

33. The above one or more blue light blocking agents are represented by an acridone compound having the structure of formula II: 【Chemistry 4】 In the formula, each R is independently hydrogen, halogen, -O- group, nitro group, nitrile group, substituted or unsubstituted alkoxy group, substituted or unsubstituted hydroxyl group, substituted or unsubstituted amine group, substituted or unsubstituted carbonyl group, and substituted or unsubstituted hydrocarbyl group, R ＊ R is a hydrogen or a substituted or unsubstituted hydrocarbyl group. ＊＊ The contact lens according to claim 32, wherein is an ethylenically unsaturated reactive group and PG is a protected hydroxyl moiety.

34. R and R ＊ Each of them is hydrogen, and R ＊＊ The contact lens according to claim 33, wherein the reactive terminal group contains a (meth)acrylic acid ester.

35. R ＊＊ The contact lens according to claim 33 or 34, wherein the protected hydroxyl group portion is located on the aromatic ring in the para position relative to the protected hydroxyl group portion.

36. The contact lens according to any one of claims 33 to 35, wherein the protecting group of the protected hydroxyl group portion comprises one of trialkylsilane, branched alkoxycarbonyl, vinyloxycarbonyl, methoxymethyl, and di-t-alkyldicarbonate.

37. The contact lens according to any one of claims 26 to 36, wherein the contact lens is one of a soft contact lens, a hydrogel contact lens, and a gas-permeable hard contact lens.

38. The contact lens according to any one of claims 26 to 37, wherein the contact lens demonstrates sufficient UV protection to satisfy at least the FDA Class I specification for UV protection.

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