Coated silicone hydrogel contact lenses and methods for manufacturing the same

Abstract

The present invention provides a cost-effective method for manufacturing coated silicone hydrogel contact lenses. The method includes: obtaining a preformed silicone hydrogel contact lens comprising a bulk silicone hydrogel material comprising repeating units of at least one carboxyl-containing vinyl monomer and at least one repeating unit of arylborono-containing vinyl monomer; and heating the preformed silicone hydrogel contact lens in an aqueous coating solution containing a water-soluble, heat-crosslinkable polymer material having azetidinium groups or epoxide groups and a diol-containing hydrophilic polymer having 1,2- or 1,3-diol moieties to form a coated silicone hydrogel contact lens comprising a bulk silicone hydrogel material, a crosslinked polymer material covalently bonded to the bulk silicone hydrogel material, and a grafted diol-containing hydrophilic polymer covalently bonded to the bulk silicone hydrogel material and distributed within the crosslinked polymer material.

Description

[Technical Field]

[0001] The present invention relates to a method for manufacturing coated silicone hydrogel contact lenses in a cost-effective and environmentally friendly manner. The present invention also relates to coated silicone hydrogel contact lenses manufactured according to the method of the present invention. [Background technology]

[0002] A new type of soft contact lens, the moisture gradient silicone hydrogel contact lens (e.g., DAILIES® TOTAL1® (Alcon), PRECISION1® (Alcon), and TOTAL30® (Alcon)), has been developed and successfully introduced to the market. This new class of soft contact lenses has a moisture gradient structure, characterized by an increasing water content from 33% to over 80% from the core to the surface (see, for example, U.S. Patent Nos. 8480227, 11061168, and 11256003). This class of moisture gradient silicone hydrogel contact lenses is highly flexible, contains a large amount of water, and has a relatively thick and smooth hydrogel coating, providing patients with superior comfort.

[0003] As described in U.S. Patent No. 8,480,227 and U.S. Patent No. 1,125,6003, methods for manufacturing moisture gradient contact lenses often involve forming a non-silicone hydrogel coating on a contact lens coated with a base coating having reactive functional groups (e.g., carboxylic acid groups), or on a contact lens made of a silicone hydrogel material having reactive functional groups (e.g., carboxylic acid groups). When a reactive base coating is required, the method for manufacturing moisture gradient contact lenses may require an additional step to form the reactive base coating. If the silicone hydrogel material of the contact lens has reactive functional groups (e.g., carboxylic acid groups), such silicone hydrogel contact lenses may be prone to degradation due to the large amount of carboxylic acid groups present in the silicone hydrogel contact lens. However, while reducing the carboxylic acid content can improve the shelf life of the lens, it may impair the uniformity of the coating.

[0004] Therefore, in the manufacture of moisture gradient contact lenses, it is desirable to develop a new process for forming a uniform non-silicone hydrogel coating while maintaining a low acid content in the silicone hydrogel lens material. [Overview of the project] [Means for solving the problem]

[0005] In one aspect, the present invention relates to a method for producing a coated silicone hydrogel contact lens, comprising the steps of: (1) obtaining a pre-formed silicone hydrogel contact lens comprising a bulk silicone hydrogel material, wherein the bulk silicone hydrogel material comprises: (a) repeating units of at least one polysiloxane vinyl crosslinking agent and / or at least one siloxane-containing vinyl monomer; (b) repeating units of at least one carboxyl-containing vinyl monomer in an amount of about 0.5% to about 3.5% by weight relative to the total amount of all polymerizable components; (c) repeating units of at least one hydrophilic vinyl monomer; and (d) about 2.5% to about 12% by weight.(1) A step comprising: (2) a step comprising: (3) a step comprising: (4) a step comprising: (5 wt) repeating units of at least one arylborono-containing vinyl monomer having an arylborono group; and (5) an optional but preferred at least one non-silicone vinyl crosslinking agent; and (6) a step comprising: (7) a step comprising: (8) a step comprising: (9) a step comprising: (1) a step comprising: (1) a step comprising: (1) a step comprising: (22) a step comprising: (1) a step comprising: (1) a step comprising: (2) a step comprising: (1) a step comprising: (2) a step comprising: (1) a step comprising: (2) a step comprising: (1) a step comprising: (2) a step comprising: (1) a step comprising: (2) a step comprising: (1) a step comprising: (2) The present invention provides a method comprising the steps of: a zetidinium group and / or epoxide group, wherein the reactive functional group is a primary amino group, a secondary amino group, a carboxylic acid group, a thiol group, or a combination thereof; a non-silicone hydrogel coating comprising a crosslinked polymer material and a grafted hydrophilic polymer, wherein the crosslinked hydrophilic polymer material is derived from the at least one water-soluble, thermally crosslinkable hydrophilic polymer material and covalently bonded to the bulk silicone hydrogel material via a first bond formed between one carboxylic acid group and one azetidinium group or epoxide group, respectively; and the grafted hydrophilic polymer is derived from the at least one diol-containing hydrophilic polymer and covalently bonded to the bulk silicone hydrogel material via a second bond formed between one arylborono group and one 1,2- or 1,3-diol moiety, respectively.

[0006] In another aspect, the present invention provides a coated silicone hydrogel contact lens comprising a bulk silicone hydrogel material and a non-silicone hydrogel coating thereon, wherein the bulk silicone hydrogel material comprises (a) repeating units of at least one polysiloxane vinyl crosslinking agent and / or at least one siloxane-containing vinyl monomer, (b) repeating units of at least one carboxyl-containing vinyl monomer relative to the total amount of all polymerizable components, (c) repeating units of at least one hydrophilic vinyl monomer, (d) repeating units of at least one arylborono-containing vinyl monomer having an arylborono group, and (e) repeating units of at least one non-silicone vinyl crosslinking agent, which is optionally but preferably. The non-silicone hydrogel coating comprises a crosslinked polymer material The present invention provides a coated silicone hydrogel contact lens comprising a grafted diol-containing hydrophilic polymer distributed within a crosslinked polymer material but not covalently bonded, wherein the crosslinked hydrophilic polymer material is covalently bonded to the bulk silicone hydrogel material via a first bond formed between one carboxylic acid group and one azetidinium group or epoxide group, respectively, and the grafted diol-containing hydrophilic polymer contains 1,2- and / or 1,3-diol moieties and is covalently bonded to the bulk silicone hydrogel material via a second bond formed between one arylborono group and one 1,2- or 1,3-diol moiety, respectively, wherein a fully hydrated coated silicone hydrogel contact lens exhibits a coating integrity of approximately 90% or more and a friction grade of approximately 2.0 or less. [Modes for carrying out the invention]

[0007] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art to which the invention pertains. In general, the nomenclature and experimental procedures used herein are well known and commonly used in the art. Conventional methods, such as those provided in the art and various general references, are used for these procedures. Where a term is given in the singular form, the inventors also assume that the plural form of that term exists. The nomenclature and laboratory procedures described below herein are well known and commonly used in the art.

[0008] In this application, the term “about” as used herein means that the number referred to as “about” includes 1 to 10% of the stated number plus or minus the stated number.

[0009] "Contact lenses" refer to structures that can be placed over or inside the eyes of a wearer. Contact lenses may, but are not required to, correct, improve, or alter the wearer's vision.

[0010] "Hydrogel contact lenses" refer to contact lenses that contain a hydrogel bulk (core) material. The hydrogel bulk material can be a non-silicone hydrogel material, or preferably a silicone hydrogel material.

[0011] A "hydrogel" or "hydrogel material" refers to a crosslinked polymer material having a three-dimensional polymer network (i.e., a polymer matrix), which is insoluble in water but can hold at least 10% by weight of water in its polymer matrix when fully hydrated (or in equilibrium).

[0012] "Silicone hydrogel" or "SiHy" refers to a silicone-containing hydrogel obtained by copolymerization of a polymerizable composition comprising at least one silicone-containing monomer, at least one silicone-containing macromer, or at least one crosslinkable silicone-containing prepolymer.

[0013] Siloxanes, often also called silicones, refer to molecules that have at least one -Si-O-Si- moiety, where each Si atom has two organic groups as substituents.

[0014] As used in this application, the terms “non-silicone hydrogel” or “non-silicone hydrogel material” are interchangeable and refer to a hydrogel that theoretically does not contain silicon.

[0015] As used herein, "hydrophilic" refers to a material or part thereof that associates more readily with water than with lipids.

[0016] The term "room temperature" refers to a temperature range of approximately 17°C to 26°C.

[0017] In relation to compounds or materials in a solvent, the term "soluble" means that the compound or material can dissolve in the solvent at room temperature to give a solution with a concentration of at least about 0.5% by weight.

[0018] In relation to compounds or materials in a solvent, the term "insoluble" means that the compound or material can dissolve in the solvent at room temperature (as defined above) to give a solution with a concentration of less than about 0.01% by weight.

[0019] "Vinyl monomer" refers to a compound that has a single ethylenically unsaturated group, is soluble in solvents, and can be polymerized by chemical radiation or thermally.

[0020] The terms “olefinic unsaturated group” or “ethylenically unsaturated group” are used herein in a broad sense and are intended to encompass any group containing at least one >C=CH2 group. Exemplary ethylenically unsaturated groups include, but are not limited to, (meth)acryloyl [ka] It contains allyl, vinyl, styrenyl, or other C=CH2-containing groups.

[0021] "Acrylic monomer" refers to a vinyl monomer having a single (meth)acryloyl group. Examples of acrylic monomers include (meth)acryloyloxy [or (meth)acryloyloxy] monomers and (meth)acrylamide monomers.

[0022] "(meth)acryloyloxymonomer" or "(meth)acryloyloxymonomer" is [ka] This refers to a vinyl monomer that has only one group.

[0023] "(meth)acrylamide monomer" is [ka] This refers to a vinyl monomer having only one group, where R is the sole group in the formula. o It is either H or a C1-C4 alkyl group.

[0024] The term "(meth)acrylamide" refers to methacrylamide and / or acrylamide.

[0025] The term "(meth)acrylate" refers to methacrylate and / or acrylate.

[0026] "N-vinylamide monomer" refers to an amide compound that has a vinyl group (-CH=CH2) directly bonded to the nitrogen atom of the amide group.

[0027] "En monomer" refers to a vinyl monomer that has only one ene group.

[0028] When used herein, “hydrophilic vinyl monomer,” “hydrophilic acrylic monomer,” “hydrophilic (meth)acryloxy monomer,” or “hydrophilic (meth)acrylamide monomer” means, respectively, a vinyl monomer, an acrylic monomer, a (meth)acryloxy monomer, or a (meth)acrylamide monomer, which typically results in a homopolymer that is water-soluble or capable of absorbing at least 10 weight percent of water.

[0029] When used herein, “hydrophobic vinyl monomer,” “hydrophobic acrylic monomer,” “hydrophobic (meth)acryloxy monomer,” or “hydrophobic (meth)acrylamide monomer” refers, respectively, to vinyl monomer, acrylic monomer, (meth)acryloxy monomer, or (meth)acrylamide monomer, which typically result in a homopolymer that is insoluble in water and can absorb less than 10% by weight of water.

[0030] In this application, "arylborono-containing vinyl monomer" refers to a vinyl monomer containing only one arylborono group that is bonded to only one ethylene-based unsaturated group by a single bond.

[0031] In this application, the "arylborono" group is defined as follows: [ka] (In the formula, R B This is a monovalent radical (preferably H, NO2, F, Cl, Br, CF3, CH2OH, or CH2NR) o R o ' and R o and R o' refers to a monovalent radical that is H or C1-C4 alkyl independently of each other). R B is CH2OH, or CH2NR o R o ', which is in the ortho position of the boronic acid and is understood to be able to form an intramolecular B-O or B-N coordination to lower the pKa of the boronic acid.

[0032] As used in this application, the term "vinyl crosslinking agent" refers to an organic compound having at least two ethylenically unsaturated groups. The "vinyl crosslinking agent" refers to a vinyl crosslinking agent having a molecular weight of 700 daltons or less.

[0033] The "acrylic crosslinking agent" refers to a vinyl crosslinking agent having at least two (meth)acryloyl groups.

[0034] The term "acrylic repeating unit" refers to a repeating unit of a polymer material, each of which is derived from an acrylic monomer or crosslinking agent by free radical polymerization to form a polymer material.

[0035] The term "terminal (meth)acryloyl group" refers to one (meth)acryloyl group at one of the two terminals of the main chain (or skeleton) of an organic compound.

[0036] As used herein, in connection with the curing, crosslinking or polymerization of a polymerizable composition, prepolymer or material, "by actinic radiation" means that the curing (e.g., crosslinking and / or polymerization) is effected by actinic radiation such as UV / visible irradiation, ionizing radiation (e.g., gamma ray or X-ray irradiation), microwave irradiation, etc. Thermal curing or actinic radiation curing methods are well known to those skilled in the art.

[0037] As used in this application, the term "polymer" means a material formed by polymerizing or crosslinking one or more monomers or macromers or prepolymers or combinations thereof.

[0038] A "macromer" or "prepolymer" refers to a compound or polymer containing ethylenically unsaturated groups and having a number-average molecular weight of over 700 daltons.

[0039] As used in this application, the term "molecular weight" of a polymer material (including monomer or macromer material) refers to the number-average molecular weight unless otherwise specified or indicated by the test conditions. Those skilled in the art will know of known methods, such as GPC (gel permeation chromatography) equipped with one or more of the following: refractive index detectors, low-angle laser light scattering detectors, multi-angle laser light scattering detectors, differential viscosity detectors, UV detectors, and infrared (IR) detectors; and MALDI-TOF MS (matrix-assisted desorption / ionization time-of-flight mass spectrometry); 1 I am familiar with methods for determining the molecular weight of polymers using techniques such as 1H NMR (proton nuclear magnetic resonance) spectroscopy.

[0040] "Polysiloxane segments" or "polydiorganosiloxane segments" are [ka] The polymer chain segments (i.e., divalent radicals) are interchangeably pointed to, where SN is an integer greater than or equal to 3, and R S1 and R S2 Each of these is independent of the others, C1~C 10 Alkyl; Phenyl; C1-C4 alkyl-substituted phenyl; C1-C4 alkoxy-substituted phenyl; Phenyl-C1-C6 alkyl; C1-C 10 Fluoroalkyl; C1~C 10 Fluoroethers; aryls; aryl C1-C 18 Alkyl;-Alk-(OC2H4) γ1 -OR o (Here, ALC is a C1-C6 alkylened radical, R o (where γ1 is an integer from 1 to 10); hydroxyl group (-OH), carboxyl group (-COOH), amino group (-NR) N1 R N1 '), -NRN1 -amino bond, -CONR N1 -amide bond, -CONR N1 R N1 C2-C4 having at least one functional group selected from the group consisting of amides, -OCONH- urethane bonds, and C1-C4 alkoxy groups. 40 Selected from the group consisting of organic radicals or linear hydrophilic polymer chains, where R N1 and R N1 ' are independent of each other, hydrogen or C1~C 15 It is alkyl.

[0041] A "polysiloxane vinyl monomer" refers to a compound containing at least one polysiloxane segment and one single ethylene-based unsaturated group.

[0042] "Polydiorganosiloxane vinyl crosslinking agent" or "polysiloxane vinyl crosslinking agent" refers to a compound that interchangeably comprises at least one polysiloxane segment and at least two ethylene-based unsaturated groups.

[0043] "Linear polydiorganosiloxane vinyl crosslinking agent" or "linear polysiloxane vinyl crosslinking agent" refers to a compound comprising a main chain that interchangeably contains at least one polysiloxane segment and is terminated with one ethylene-based unsaturated group at each of the two ends of the main chain.

[0044] "Chain-extended polydiorganosiloxane vinyl crosslinking agent" or "chain-extended polysiloxane vinyl crosslinking agent" means the same thing and refers to a compound comprising at least two ethylenically unsaturated groups and at least two polysiloxane segments, each pair of which is linked by a divalent radical.

[0045] As used herein, the term "fluid" indicates that a material can flow like a liquid.

[0046] As used in this application, the term "optically transparent" with respect to a polymerizable composition means that the polymerizable composition is a transparent solution or liquid mixture (i.e., has a light transmittance of 85% or more, preferably 90% or more, in the range of 400 to 700 nm).

[0047] The term "monovalent radical" refers to an organic radical obtained by removing a hydrogen atom from an organic compound, and which forms one bond with one other group in the organic compound. Examples, but not limited to, include alkyl (by removing a hydrogen atom from an alkane), alkoxy (or alkoxyl) (by removing one hydrogen atom from the hydroxyl group of an alkyl alcohol), thiyl (by removing one hydrogen atom from the thiol group of an alkylthiol), cycloalkyl (by removing a hydrogen atom from a cycloalkane), cycloheteroalkyl (by removing a hydrogen atom from a cycloheteroalkane), aryl (by removing a hydrogen atom from the aromatic ring of an aromatic hydrocarbon), heteroaryl (by removing a hydrogen atom from any ring atom), and amino (by removing one hydrogen atom from an amine).

[0048] The term "divalent radical" refers to an organic radical obtained by removing two hydrogen atoms from an organic compound and forming two bonds with two other groups in the organic compound. For example, an alkylene divalent radical (i.e., alkylenyl) is obtained by removing two hydrogen atoms from an alkane, and a cycloalkylene divalent radical (i.e., cycloalkylenyl) is obtained by removing two hydrogen atoms from a cyclic ring.

[0049] In this application, the term “substituted” in relation to alkyl or alkylenyl means that the alkyl or alkylenyl replaces one hydrogen atom of the alkyl or alkylenyl and includes at least one substituent selected from the group consisting of hydroxyl (-OH), carboxyl (-COOH), -NH2, sulfhydryl (-SH), C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkylthio (alkyl sulfide), C1-C4 acylamino, C1-C4 alkylamino, di-C1-C4 alkylamino, and combinations thereof.

[0050] In this application, the term "polyoxazoline" means [ka] Refers to a polymer or polymer segment, where R ox1 This is hydrogen, methyl, ethyl, N-pyrrolidonylmethyl, N-pyrrolidonylethyl, N-pyrrolidonylpropyl, or -alk-(OC2H4) m3 -OR ” The formula is a monovalent radical (wherein alk is a C1-C4 alkyl diradical; R'' is a C1-C4 alkyl (preferably methyl); m3 is an integer from 1 to 10 (preferably 1 to 5); and x is an integer from 5 to 500.

[0051] In this application, the term "poly(2-oxazoline-co-ethyleneimine)" means [ka] This refers to a statistical copolymer or polymer segment thereof having the formula, where R ox1 This is hydrogen, methyl, ethyl, N-pyrrolidonylmethyl, N-pyrrolidonylethyl, N-pyrrolidonylpropyl, or -alk-(OC2H4) m3 -OR ”The formula is a monovalent radical (wherein alk is a C1-C6 alkyl diradical; R'' is a C1-C4 alkyl (preferably methyl); m3 is an integer from 1 to 10 (preferably 1 to 5); x is an integer from 5 to 500; and z is an integer less than or equal to x. Poly(2-oxazoline-co-ethyleneimine) is obtained by hydrolysis of polyoxazoline.

[0052] In this application, the term "poly(2-oxazoline-co-ethyleneimine)-epichlorohydrin" refers to a polymer obtained by reacting poly(2-oxazoline-co-ethyleneimine) with epichlorohydrin to convert all or a significant percentage (≧90%) of the secondary amine groups of poly(2-oxazoline-co-ethyleneimine) into azetidinium groups. An example of poly(2-oxazoline-co-ethyleneimine)-epichlorohydrin is disclosed in U.S. Patent Application Publication No. 2016 / 0061995A1.

[0053] "Epichlorohydrin-functionalized polyamine" or "epichlorohydrin-functionalized polyamidoamine" refers to a polymer obtained by reacting a polyamine or polyamidoamine with epichlorohydrin to convert all or a significant percentage of the secondary amine groups of the polyamine or polyamidoamine into azetidinium groups.

[0054] The term "polyamidoamine-epichlorohydrin" refers to an adipic acid-diethylenetriamine copolymer functionalized with epichlorohydrin.

[0055] In this application, the terms "azetidinium" or "3-hydroxyazetidinium" are defined as follows: [ka] This refers to a positively charged (i.e., cationic), divalent radical (or group or site).

[0056] The term "thermally crosslinkable" in relation to polymer materials or functional groups means that the polymer material or functional group can crosslink (or coupling) with another material or functional group at relatively high temperatures (approximately 40°C to 140°C), but cannot crosslink (or coupling) with another material or functional group to a detectable extent in approximately one hour at temperatures of approximately 5°C to 15°C.

[0057] The term "phosphorylcholine" as used in this application means [ka] This refers to the zwitterionic group, where n is an integer from 1 to 5, and R 2 , R 3 , and R 4 These are, independently of each other, C1-C8 alkyl or C1-C8 hydroxyalkyl.

[0058] As used in this application, the term “reactive vinyl monomer” refers to any vinyl monomer having at least one reactive functional group selected from the group consisting of carboxyl groups, primary amino groups, and secondary amino groups.

[0059] As used in this application, the term "unreactive vinyl monomer" refers to any vinyl monomer (either hydrophilic or hydrophobic) that does not contain a carboxyl group, primary amino group, secondary amino group, epoxide group, isocyanate group, azulactone group, or aziridine group.

[0060] Free radical initiators can be either photoinitiators or thermal initiators. A "photoinitiator" is a chemical substance that initiates a free radical crosslinking / polymerization reaction using light. A "thermal initiator" is a chemical substance that initiates a free radical crosslinking / polymerization reaction using thermal energy.

[0061] As used herein, the term “bulk silicone hydrogel material” in relation to contact lenses is mutually interchangeable and means a layer of silicone hydrogel material substantially having the three-dimensional shape of a contact lens.

[0062] The inherent "oxygen permeability" of the material Dk i Oxygen permeability is the rate at which oxygen passes through a material. Oxygen permeability is usually expressed in units of bars, where a bar is [(cm²]. 3 Oxygen) (mm) / (cm 2 )(sec)(mmHg)]×10 -10 It is defined as follows.

[0063] The "oxygen permeability coefficient" Dk / t of an insert or material is the rate at which oxygen passes through a particular insert or material with an average thickness t [in mm] over the entire area being measured. Oxygen permeability is usually expressed in units of bars / mm, where "bars / mm" is [(cm 3 Oxygen) / (cm 2 )(sec)(mmHg)]×10 -9 It is defined as follows.

[0064] In relation to contact lenses or materials, the term "modulus" or "elastic modulus" refers to the tensile modulus, or Young's modulus, which is a measure of the embedding properties of the contact lens or material.

[0065] The term "dry lens precursor" refers to cast contact lenses obtained by casting a polymerizable composition in a mold and which have not undergone an extraction and / or hydration post-molding process (i.e., have not come into contact with water, any organic solvent, or any liquid after molding).

[0066] The term “wet-resistant silicone hydrogel contact lens” means that the silicone hydrogel contact lens has a water film breakdown time ("WBUT") of at least about 10 seconds, preferably at least about 15 seconds, more preferably at least about 20 seconds, and even more preferably at least about 25 seconds. The WBUT can be measured according to the procedure described in Example 1.

[0067] The term "optically transparent silicone hydrogel contact lens" means that the silicone hydrogel contact lens has a light transmittance of at least 85%, preferably at least 90%, more preferably at least 93%, and even more preferably at least 95% in the range of 400 to 700 nm. The light transmittance of the contact lens in the range of 400 to 700 nm can be measured according to the procedure described in Example 1.

[0068] "Average water contact angle" refers to the water contact angle (measured by the sessile drop method), which is obtained by averaging the measurements of at least three individual contact lens or silicone hydrogel material samples.

[0069] In general, the present invention relates to a cost-effective method for producing coated SiHy contact lenses having non-silicone hydrogel coatings on each. The present invention is partly based on the discovery that pre-formed SiHy contact lenses (or other hydrophobic plastic molded articles) having two types of moldable reactive functional groups (carboxylic acid groups and arylborono groups) can be coated by packaging and autoclaving them in a packaging saline solution containing two different coating materials. The first type of coating material is a lightly crosslinked (or branched) thermocrosslinkable hydrophilic polymer material containing thermocrosslinkable groups (azetidinium groups and / or epoxide groups) that can react with carboxylic acid groups during autoclaving. The other type of coating material is a diol-containing hydrophilic polymer containing 1,2- or 1,3-diol moieties that can react with arylborono groups. Having two different types of coating materials makes it possible to form a hybrid coating with excellent integrity on pre-formed SiHy contact lenses with relatively low amounts of carboxylic acid. As a result, the resulting coated SiHy contact lenses can have reduced susceptibility to degradation induced by carboxylic acids, thereby providing increased stability (longer shelf life).

[0070] The present invention relates to a method for manufacturing a coated silicone hydrogel contact lens, comprising the steps of (1) obtaining a pre-formed silicone hydrogel contact lens comprising a bulk silicone hydrogel material, wherein the bulk silicone hydrogel material comprises (a) repeating units of at least one polysiloxane vinyl crosslinking agent and / or at least one siloxane-containing vinyl monomer, (b) repeating units of at least one carboxyl-containing vinyl monomer in an amount of about 0.5% to about 3.5% by weight relative to the total amount of all polymerizable components, (c) repeating units of at least one hydrophilic vinyl monomer, and (d) about 2.5% to about 12% by weight.(1) A step comprising: (2) a step comprising: (3) a step comprising: (4) a step comprising: (5 wt) repeating units of at least one arylborono-containing vinyl monomer having an arylborono group; and (5) an optional but preferred at least one non-silicone vinyl crosslinking agent; and (6) a step comprising: (7) heating a pre-formed silicone hydrogel contact lens in an aqueous coating solution at a temperature of about 60°C to about 140°C to form a coated silicone hydrogel contact lens comprising a bulk silicone hydrogel material and a non-silicone hydrogel coating thereon, wherein the aqueous coating solution comprises: (a) at least one diol-containing hydrophilic polymer having 1,2- and / or 1,3-diol moieties; and (b) at least one water-soluble, heat-crosslinkable hydrophilic polymer material comprising branched or slightly crosslinked, heat-crosslinkable groups and optional reactive functional groups, wherein the heat-crosslinkable groups are azetidinium The present invention provides a method comprising the steps of: a reactive functional group being a primary amino group, a secondary amino group, a carboxylic acid group, a thiol group, or a combination thereof, wherein the non-silicone hydrogel coating comprises a crosslinked polymer material and a grafted diol-containing hydrophilic polymer, wherein the crosslinked hydrophilic polymer material is derived from the at least one water-soluble, thermally crosslinkable hydrophilic polymer material and is covalently bonded to the bulk silicone hydrogel material via a first bond formed between one carboxylic acid group and one azetidinium group or epoxide group, respectively; and the grafted diol-containing hydrophilic polymer is derived from the at least one diol-containing hydrophilic polymer and is covalently bonded to the bulk silicone hydrogel material via a second bond formed between one arylborono group and one 1,2- or 1,3-diol moiety, respectively.

[0071] A pre-formed SiHy contact lens can be any SiHy contact lens that has not undergone any surface treatment after being manufactured according to any lens manufacturing process, any contact lens that has been plasma-treated or treated with chemical or physical surface modification, or any commercially available contact lens, as long as there is no hydrogel coating on the surface of the pre-formed SiHy contact lens. Those skilled in the art are very familiar with the methods of manufacturing pre-formed contact lenses. Those skilled in the art are very familiar with the methods of manufacturing pre-formed contact lenses. For example, a pre-formed contact lens can be manufactured in a conventional “spin-casting mold,” such as described in U.S. Patent No. 3,408,429, or by a static, full-scale casting process, such as described in U.S. Patents No. 4,347,198, 5508,317, 5583,463, 5789,464, and 5849810, or by turning polymer material buttons, as used in the manufacture of customized contact lenses. In casting, polymerizable compositions (i.e., lens formulations) are typically dispensed into a mold and cured (i.e., polymerized and / or crosslinked) within the mold to manufacture contact lenses.

[0072] Lens molds for manufacturing contact lenses, such as hydrocontact lenses, are well known to those skilled in the art and are used, for example, in casting or spin casting. For example, a mold (for casting) generally comprises at least two mold pieces (or parts) or mold halves, namely a first and a second mold half. The first mold half has a first molding (or optical) surface that is in direct contact with the polymerizable composition for casting the contact lens and defines the rear surface (concave) of the molded contact lens, and the second mold half has a second molding (or optical) surface that is in direct contact with the polymerizable composition and defines the front surface (convex) of the molded contact lens. The first and second mold halves are configured to receive each other so that a lens forming cavity is formed between the first molding surface and the second molding surface.

[0073] Methods for manufacturing mold pieces for casting contact lenses are generally well known to those skilled in the art. The method of the present invention is not limited to a specific method for forming a mold. In fact, any method for forming a mold can be used in the present invention.

[0074] The mold halves can be formed by various methods, such as injection molding. Methods for manufacturing mold halves for casting contact lenses are generally well known to those skilled in the art. The method of the present invention is not limited to a specific method for forming a mold. In fact, any method of forming a mold can be used in the present invention. The first and second mold halves can be formed by various methods, such as injection molding or turning. Examples of preferred processes for forming mold halves are disclosed in U.S. Patent Nos. 4,444,711, 4,460,534, 5,843,346, and 5,894,002.

[0075] Virtually all materials known in the art for manufacturing molds can be used to manufacture molds for manufacturing contact lenses. For example, polymer materials such as polyethylene, polypropylene, polystyrene, PMMA, and Topas® COC grade 8007-S10 (a transparent amorphous copolymer of ethylene and norbornene, manufactured by Ticona GmbH in Frankfurt, Germany and Summit, New Jersey) can be used. Other UV light-transmitting materials such as quartz glass and sapphire may also be used.

[0076] According to the present invention, a pre-formed SiHy contact lens comprises (a) at least one polysiloxane vinyl crosslinking agent and / or at least one siloxane-containing vinyl monomer, (b) at least one carboxyl-containing vinyl monomer in an amount of about 0.5% to about 3.5% (preferably about 0.7% to about 3.5% by weight, more preferably about 0.9% to about 3.0% by weight, and even more preferably about 1.0% to about 2.8% by weight) relative to the total amount of all polymerizable components, and (c) at least one parent It can be produced from a polymerizable composition containing an aqueous vinyl monomer, (d) about 2.5% to about 12.5% ​​(preferably about 2.5% to about 10% by weight, more preferably about 3.0% to about 8.0% by weight, and even more preferably about 3.5% to about 7.0% by weight) of at least one arylborono-containing vinyl monomer having an arylborono group, (e) at least one optional but preferred non-silicone vinyl crosslinking agent, and (f) at least one free radical initiator.

[0077] According to the present invention, the silicone-containing (e.g., siloxane-containing) vinyl monomer can be any silicone-containing vinyl monomer known to those skilled in the art. Examples of preferred silicone-containing vinyl monomers, but are not limited to, vinyl monomers having a bis(trialkylsilyloxy)alkylsilyl group (preferably a bis(trimethylsilyloxy)alkylsilyl group) or a tris(trialkylsilyloxy)silyl group (preferably a tris(trimethylsilyloxy)silyl group), polysiloxane vinyl monomers, 3-methacryloxypropylpentamethyldisiloxane, t-butyldimethylsiloxyethyl vinyl carbonate, trimethylsilylethyl vinyl carbonate, trimethylsilylmethyl vinyl carbonate, and combinations thereof.

[0078] Preferred siloxane-containing vinyl monomers having a bis(trialkylsilyloxy)alkylsilyl group or a tris(trialkylsilyloxy)silyl group, respectively, include, but are not limited to, tris(trimethylsilyloxy)-silylpropyl(meth)acrylate, [3-(meth)acrylooxy-2-hydroxypropyloxy]propyl-bis(trimethylsiloxy)-methylsilane, and [3-(meth)acrylooxy-2-hydroxypropyloxy]propylbis(trimethyl-siloxy) Chilsilane, 3-(meth)acryloxy-2-(2-hydroxyethoxy)propyloxy)-propylbis(trimethylsiloxy)-methylsilane, 3-(meth)acryloxy-2-hydroxypropyloxy)propyl-tris(trimethylsiloxy)silane, N-[tris(trimethylsiloxy)-silylpropyl]-(meth)acrylamide, N-(2-hydroxy-3-(3-(bis(trimethylsilyloxy)methylsilyl)-propyloxy)-propyl)-2-methyl(meth)acrylamide, N-(2-hydroxy-3-(3-(bis(trimethyl-silyloxy)methylsilyl)-propyloxy)propyl)(meth)acrylamide, N-(2-hydroxy-3-(3-(tris(trimethyl-silyloxy)silyl)propyloxy)-propyl)-2-methylacrylamide, N-(2-hydroxy-3-(3-(tris(trimethylsilyloxy)-silyl)propyloxy)propyl)(meth)acrylamide, N-[tris(dimethylpropylsiloxy)-silylpropyl]-(meth)acryl Luamide, N-[tris(dimethylphenylsiloxy)silylpropyl](meth)acrylamide, N-[tris(dimethyl-ethylsiloxy)silylpropyl](meth)acrylamide, N,N-bis[2-hydroxy-3-(3-(bis(trimethyl-silyloxy)methyl-silyl)propyloxy)propyl]-2-methyl(meth)acrylamide, N,N-bis[2-hydroxy-3-(3-(bis(trimethylsilyloxy)-methylsilyl)propyloxy)-propyl](meth)acrylamide, N,N-bis[2-hydroxy-3-(3-(tris(trimethylsilyloxy)-silyl)propyloxy)propyl]-2-methyl(meth)acrylamide, N,N-bis[2-hydroxy-3-(3-(tris(trimethylsilyloxy)-silyl)propyloxy)propyl](meth)acrylamide, N-[2-hydroxy-3-(3-(t-butyldimethylsilyl)propyloxy)propyl]-2-methyl(meth)acrylamide, N-[2-hydroxy-3-(3-(t-butyldimethylsilyl)propyloxy)propyl](meth)acrylamide, N,N-bis[2-hydroxy-3-(3-(t-butyldimethylsilyl)propyloxy)propyl]-2-methyl(meth Examples include acrylamide, N-2-(meth)acryloxyethyl-O-(methyl-bis-trimethylsiloxy-3-propyl)silylcarbamate, 3-(trimethylsilyl)propyl vinyl carbonate, 3-(vinyloxy-carbonylthio)propyl-tris(trimethyl-siloxy)silane, 3-[tris(trimethylsiloxy)silyl]propyl vinylcarbamate, 3-[tris(trimethylsiloxy)silyl]propyl allylcarbamate, 3-[tris(trimethylsiloxy)silyl]propyl vinyl carbonate, those disclosed in U.S. Patent No. 9097840, No. 9103965, and No. 9475827, and mixtures thereof. The above preferred silicone-containing vinyl monomers can be obtained from commercial suppliers or prepared according to the procedures described in U.S. Patent Nos. 5070215, 6166236, 6867245, 7214809, 8415405, 8475529, 8614261, 8658748, 9097840, 9103965, 9217813, 9315669, and 9475827.

[0079] Preferred polysiloxane vinyl monomers include, but are not limited to, polysiloxanes of formula (I) with mono-(meth)acryloyl or monoalkyl terminators, including, but are not limited to, α-(meth)acryloylpropyl-terminated ω-butyl (or ω-methyl)-terminated polydimethylsiloxanes, α-(meth)acryloxy-2-hydroxypropyloxypropyl-terminated ω-butyl (or ω-methyl)-terminated polydimethylsiloxanes, and α-(2-hydroxy-methacryloxypropyloxypropyl)-ω-butyl- Decamethylpentasiloxane, α-[3-(meth)acryloxyethoxy-2-hydroxypropyloxypropyl]-terminated ω-butyl (or ω-methyl)-terminated polydimethylsiloxane, α-[3-(meth)acryloxy-propyloxy-2-hydroxypropyloxypropyl]-terminated ω-butyl (or ω-methyl)-terminated polydimethylsiloxane, α-[3-(meth)acryloxyisopropyloxy-2-hydroxypropyloxypropyl]-terminated ω-butyl (or ω-methyl)-terminated polydimethylsiloxane, α-[3-(meth)acrylo [Xybutyloxy-2-hydroxypropyloxypropyl]-terminated ω-butyl (or ω-methyl)-terminated polydimethylsiloxane, α-[3-(meth)acryloxyethylamino-2-hydroxypropyloxypropyl]-terminated ω-butyl (or ω-methyl)-terminated polydimethylsiloxane, α-[3-(meth)acryloxypropylamino-2-hydroxypropyloxypropyl]-terminated ω-butyl (or ω-methyl)-terminated polydimethylsiloxane, α-[3-(meth)acryloxy-butylamino-2-hydroxypropyloxypropyl ]-Terminal ω-butyl (or ω-methyl)-terminated polydimethylsiloxane, α-(meth)acryloxy(polyethyleneoxy)-2-hydroxypropyloxypropyl]-Terminal ω-butyl (or ω-methyl)-terminated polydimethylsiloxane, α-[(meth)acryloxy-2-hydroxypropyloxyethoxypropyl]-Terminal ω-butyl (or ω-methyl)-terminated polydimethylsiloxane, α-[(meth)acryloxy-2-hydroxypropyl-N-ethylaminopropyl]-Terminal ω-butyl (or ω-methyl)-terminated polydimethylsiloxane,α-[(meth)acryloxy-2-hydroxypropylaminopropyl]-terminal ω-butyl (or ω-methyl)-terminated polydimethylsiloxane, α-[(meth)acryloxy-2-hydroxypropyloxy-(polyethyleneoxy)propyl]-terminal ω-butyl (or ω-methyl)-terminated polydimethylsiloxane, α-(meth)acryloylamidopropyloxypropyl-terminal ω-butyl (or ω-methyl)-terminated polydimethylsiloxane, α-N-methyl-(meth)acryloylamidopropyloxypropyl-terminal ω-butyl (or ω-methyl )Terminal polydimethylsiloxane, α-[3-(meth)acrylamide ethoxy-2-hydroxypropyloxypropyl]-terminated ω-butyl (or ω-methyl)-terminated polydimethylsiloxane, α-[3-(meth)acrylamide propyloxy-2-hydroxypropyloxypropyl]-terminated ω-butyl (or ω-methyl)-terminated polydimethylsiloxane, α-[3-(meth)acrylamide isopropyloxy-2-hydroxypropyloxypropyl]-terminated ω-butyl (or ω-methyl)-terminated polydimethylsiloxane, α-[3-( [meth)acrylamidobutyloxy-2-hydroxypropyloxypropyl]-terminal ω-butyl (or ω-methyl)-terminal polydimethylsiloxane, α-[3-(meth)acryloylamide-2-hydroxypropyloxypropyl]-terminal ω-butyl (or ω-methyl) polydimethylsiloxane, α-[3-[N-methyl-(meth)acryloylamide]-2-hydroxypropyloxypropyl]-terminal ω-butyl (or ω-methyl)-terminal polydimethylsiloxane, N-methyl-N'-(propyltetra(dimethylsiloxy)dimethyl propyl Examples include (meth)acrylamide (Cylsilane), N-(2,3-dihydroxypropane)-N'-(propyltetra(dimethylsiloxy)dimethylbutylsilane)(meth)acrylamide, (meth)acryloylamide-propyltetra(dimethylsiloxy)dimethylbutylsilane, monovinyl carbonate-terminated monoalkyl-terminated polydimethylsiloxane, monovinyl carbamate-terminated monoalkyl-terminated polydimethylsiloxane, those disclosed in U.S. Patent No. 9,097,840 and 9,103,965, and mixtures thereof. The above preferred polysiloxane vinyl monomers are:It can be obtained from commercial suppliers (e.g., Shin-Etsu Chemical Co., Ltd., Gelest, etc.), or prepared according to the procedures described in, for example, U.S. Patent Publication Nos. 6166236, 6867245, 8415405, 8475529, 8614261, 9217813, and 9315669, or prepared according to coupling reactions well known to those skilled in the art, by hydroxyalkyl (meth)acrylate or (meth)acrylamide or (meth It can be prepared by reacting acrylicoxypolyethylene glycol with monoepoxypropyloxypropyl-terminated polydimethylsiloxane, or by reacting glycidyl (meth)acrylate with monocarbinol-terminated polydimethylsiloxane, monoaminopropyl-terminated polydimethylsiloxane, or monoethylaminopropyl-terminated polydimethylsiloxane, or by reacting isocyanatoethyl (meth)acrylate with monocarbinol-terminated polydimethylsiloxane.

[0080] According to the present invention, any polysiloxane vinyl crosslinking agent can be used. Preferred polysiloxane vinyl crosslinking agents include, but are not limited to, α,ω-(meth)acrylooxy-terminated polydimethylsiloxanes of various molecular weights; α,ω-(meth)acrylamide-terminated polydimethylsiloxanes of various molecular weights; α,ω-vinylcarbonate-terminated polydimethylsiloxanes of various molecular weights; α,ω-vinylcarbamate-terminated polydimethylsiloxanes of various molecular weights; bis-3-methacrylooxy-2-hydroxypropyloxypropylpolydimethylsiloxanes of various molecular weights; and N,N,N',N'-tetrakis(3-methacrylooxy-2-hydroxypropyl) (Loxypropyl)-alpha,omega-bis-3-aminopropyl-polydimethylsiloxane; reaction product of glycidyl methacrylate and diamino-terminated polydimethylsiloxane; reaction product of glycidyl methacrylate and dihydroxy-terminated polydimethylsiloxane; reaction product of azulactone-containing vinyl monomer (any one of the above) and dihydroxy-terminated polydimethylsiloxane; reaction product of isocyanatoethyl (meth)acrylate and dihydroxyl-terminated polydimethylsiloxane; reaction product of isocyanatoethyl (meth)acrylate and diamino-terminated polydimethylsiloxane;U.S. Patent Nos. 5760100, 4136250, 4153641, 4182822, 4189546, 4259467, 4260725, 4261875, 4343927, 4254248, 4355147, 4276402, and 4327203 4341889, 4486577, 4543398, 4605712, 4661575, 4684538, 4703 Specification No. 097, Specification No. 4833218, Specification No. 4837289, Specification No. 4954586, Specification No. 4954587, Specification No. 5010141, Specification No. 5034461, Specification No. 5070170, Specification No. 5079319, Specification No. 5039761, Specification No. 5346946, Specification No. 5358995, Specification No. 5387632, Specification No. 541613 Specification No. 2, Specification No. 5449729, Specification No. 5451617, Specification No. 5486579, Specification No. 5962548, Specification No. 5981675, Specification No. 6039913, Specification No. Examples include the polysiloxane vinyl crosslinking agents disclosed in Specification No. 6762264, No. 7423074, No. 8163206, No. 8480227, No. 8529057, No. 8835525, No. 8993651, No. 9187601, No. 10081697, No. 10301451, and No. 10465047.

[0081] One preferred classification of polysiloxane vinyl crosslinking agents is vinyl crosslinking agents prepared by reacting glycidyl (meth)acrylate or (meth)acryloyl chloride with diamino-terminated polydimethylsiloxane or dihydroxyl-terminated polydimethylsiloxane, or by reacting isocyanatoethyl (meth)acrylate with dihydroxyl-terminated polydimethylsiloxane, or by reacting amino-containing acrylic monomers with dicarboxyl-terminated polydimethylsiloxane in the presence of a coupling agent (carbodiimide), or by reacting carboxyl-containing acrylic monomers with diamino-terminated polydimethylsiloxane in the presence of a coupling agent (carbodiimide), or by reacting hydroxyl-containing acrylic monomers with dihydroxyl-terminated polydisiloxane in the presence of a diisocyanate or diexope coupling agent.

[0082] Examples of such preferred polysiloxane vinyl crosslinking agents include α,ω-bis[3-(meth)acrylamidopropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acryloxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acryloxy-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane, and α,ω-bis[3-(meth)acryloxyethoxy-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane. [Propyloxy-2-hydroxypropyloxypropyl]-terminal polydimethylsiloxane, α,ω-bis[3-(meth)acrylooxyisopropyloxy-2-hydroxypropyloxypropyl]-terminal polydimethylsiloxane, α,ω-bis[3-(meth)acrylooxybutyloxy-2-hydroxypropyloxypropyl]-terminal polydimethylsiloxane, α,ω-bis[3-(meth)acrylamideethoxy-2-hydroxypropyloxypropyl]-terminal polydimethylsiloxane, α,ω-bis[3-(meth) [Crylamidopropyloxy-2-hydroxypropyloxypropyl]-terminal polydimethylsiloxane, α,ω-bis[3-(meth)acrylamideisopropyloxy-2-hydroxypropyloxypropyl]-terminal polydimethylsiloxane, α,ω-bis[3-(meth)acrylamidebutyloxy-2-hydroxypropyloxypropyl]-terminal polydimethylsiloxane, α,ω-bis[3-(meth)acryloxyethylamino-2-hydroxypropyloxypropyl]-terminal polydimethylsiloxane, α,ω-bis [3-(meth)acryloxypropylamino-2-hydroxypropyloxypropyl]-terminal polydimethylsiloxane, α,ω-bis[3-(meth)acryloxybutylamino-2-hydroxypropyloxypropyl]-terminal polydimethylsiloxane, α,ω-bis[(meth)acrylamideethylamino-2-hydroxypropyloxypropyl]-terminal polydimethylsiloxane, α,ω-bis[3-(meth)acrylamidepropylamino-2-hydroxypropyloxypropyl]-terminal polydimethylsiloxane, α,These include ω-bis[3-(meth)acrylamide-butylamino-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane, α,ω-bis[(meth)acryloxy-2-hydroxypropyloxy-ethoxypropyl]-terminated polydimethylsiloxane, α,ω-bis[(meth)acryloxy-2-hydroxypropyl-N-ethylaminopropyl]-terminated polydimethylsiloxane, α,ω-bis[(meth)acryloxy-2-hydroxypropyl-aminopropyl]-polydimethylsiloxane, α,ω-bis[(meth)acryloxy-2-hydroxypropyloxy-(polyethyleneoxy)propyl]-terminated polydimethylsiloxane, α,ω-bis[(meth)acryloxyethylamino-carbonyloxy-ethoxypropyl]-terminated polydimethylsiloxane, α,ω-bis[(meth)acryloxyethylamino-carbonyloxy-(polyethyleneoxy)propyl]-terminated polydimethylsiloxane, and combinations thereof.

[0083] Other preferred polysiloxane vinyl crosslinkers are chain-extended polysiloxane vinyl crosslinkers, each containing at least two polysiloxane segments, which can be prepared according to the procedures described in U.S. Patent Nos. 5,034,461, 5,416,132, 5,449,729, 5,760,100, 7,423,074, 8,529,057, 8,835,525, 8,993,651, and 1,0301,451, as well as U.S. Patent Publication No. 2018-0100038A1.

[0084] A further classification of preferred polysiloxane vinyl crosslinkers is a hydrophilized polysiloxane vinyl crosslinker, each containing at least about 1.50 (preferably at least about 2.0, more preferably at least about 2.5, and even more preferably at least about 3.0) milliequivalents / gram ("meq / g") of hydrophilic moieties, wherein the hydrophilic moieties are preferably hydroxyl groups (-OH), carboxyl groups (-COOH), and amino groups (-NHR). N1 , R N1(H or C1-C2 alkyl), amide moiety (-CO-NR) N1 R N2 , R N1 is H or C1-C2 alkyl, R N2 The covalent bond is H, or C1-C2 alkyl, N-C1-C3 acylamino group, urethane moiety (-NH-CO-O-), urea moiety (-NH-CO-NH-), [ka] The polyethylene glycol chain (where n is an integer from 2 to 20, and T1 is H, methyl, or acetyl), or a phosphorylcholine group, or a combination thereof.

[0085] An example of such a preferred hydrophilized polysiloxane vinyl crosslinking agent is that of the compound of formula (1): [ka] (In the formula, Provided that ω1 / υ1 is approximately 0.035 to approximately 0.15 (preferably approximately 0.040 to approximately 0.12, and more preferably approximately 0.045 to approximately 0.10), υ1 is an integer between 30 and 500, and ω1 is an integer between 1 and 75; X 01 is O or NR n And here R n is hydrogen or C1~C 10 -It is alkyl; R o is hydrogen or methyl; R2 and R3 are independently substituted or unsubstituted C1-C 10 A divalent alkylene radical or a divalent radical of -R5-O-R6-, where R5 and R6 are independently substituted or unsubstituted C1-C 10 It is an alkylene divalent radical; R4 is given by equations (2) to (7) [ka] It is one of the following monovalent radicals: p1 is zero or 1; m1 is an integer between 2 and 4; m2 is an integer between 1 and 5; m3 is an integer between 3 and 6; m4 is an integer between 2 and 5; R7 is either hydrogen or methyl; R8 is a C2-C6 hydrocarbon radical with a valency of (m2+1); R9 is a C2-C6 hydrocarbon radical with a valency of (m4+1); R 10 is ethyl or hydroxymethyl; R 11 It is methyl or hydromethyl; R 12 is hydroxyl or methoxy; X3 is either a -S- sulfur bond or an -NR 13 - is a tertiary amino bond, where R 13 These are C1-C1 alkyl, hydroxyethyl, hydroxypropyl, or 2,3-dihydroxypropyl; The X4 is [ka] It is an amide bond, R 14 is hydrogen or C1~C 10 It is alkyl, L PC teeth, [ka] It is a divalent radical, where q1 is an integer from 1 to 20, and R 15 C1~C is a straight chain or branched C1~C 10 It is an alkylene divalent radical, R 16 C3~C is either a straight chain or a branched C3~C 10 It is an alkylene divalent radical, R 17 (These are directly bonded, linear, or branched C1-C4 alkylene divalent radicals.)

[0086] The procedure for preparing the polysiloxane vinyl crosslinking agent of formula (1) is described in detail in U.S. Patent No. 10,081,697 and U.S. Patent Application Publication No. 2022 / 0251302A1.

[0087] According to the present invention, any carboxyl-containing vinyl monomer can be used. Preferred carboxyl-containing (meth)acryloxy monomers include, but are not limited to, acrylic acid, C1-C4 alkylacrylic acid (e.g., methacrylic acid, ethylacrylic acid, propylacrylic acid, butylacrylic acid), (meth)acryloxy-C1-C6 alkanic acid (e.g., (meth)acryloyloxyacetic acid, (meth)acryloyloxypropanoic acid, (meth)acryloyloxybutanoic acid, (meth)acryloyloxypentanoic acid, (meth)acryloyloxyhexanoic acid), mono-2-[(meth)acryloxy]-ethyl succinate, (meth)acrylamide-C1-C6 alanoic acid (3-(meth)acrylamidepropionic acid, 4-(meth)acrylamidebutanoic acid, 5-(meth)acrylamidepentanoic acid, 6-(meth)acrylamidehexanoic acid), 2-acrylamide glycolic acid, and combinations thereof.

[0088] Any hydrophilic vinyl monomer can be used in the present invention. Preferred hydrophilic vinyl monomers include alkyl(meth)acrylamide (described later in this application), hydroxyl-containing acrylic monomers (described below), amino-containing acrylic monomers (described later in this application), N-vinylamide monomers (described later in this application), methylene-containing pyrrolidone monomers (i.e., pyrrolidone derivatives each having a methylene group bonded to a pyrrolidone ring at the 3- or 5-position) (described later in this application), acrylic monomers having C1-C4 alkoxyethoxy groups (described later in this application), vinyl ether monomers (described later in this application), allyl ether monomers (described later in this application), phosphorylcholine-containing vinyl monomers (described later in this application), N-2-hydroxyethyl vinylcarbamate, N-carboxyvinyl-β-alanine (VINAL), N-carboxyvinyl-α-alanine, and combinations thereof.

[0089] Examples of alkyl(meth)acrylamides, though not limited to them, include (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N-ethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-propyl(meth)acrylamide, N-isopropyl(meth)acrylamide, N-3-methoxypropyl(meth)acrylamide, and combinations thereof.

[0090] Examples of hydroxyl-containing acrylic monomers include, but are not limited to, N-2-hydroxyethyl(meth)acrylamide, N,N-bis(hydroxyethyl)(meth)acrylamide, N-3-hydroxypropyl(meth)acrylamide, N-2-hydroxypropyl(meth)acrylamide, N-2,3-dihydroxypropyl(meth)acrylamide, N-tris(hydroxymethyl)methyl(meth)acrylamide, 2-hydroxyethyl(meth)acrylate, 3-hydroxypropyl(meth)acrylate, 2-hydroxypropyl(meth)acrylate, glycerol methacrylate (GMA), di(ethylene glycol)(meth)acrylate, tri(ethylene glycol)(meth)acrylate, tetra(ethylene glycol)(meth)acrylate, poly(ethylene glycol)(meth)acrylate with a number average molecular weight of up to 1500, poly(ethylene glycol)ethyl(meth)acrylamide with a number average molecular weight of up to 1500, and combinations thereof.

[0091] Examples of preferred N-vinylamide monomers include, but are not limited to, N-vinylpyrrolidone (also known as N-vinyl-2-pyrrolidone), N-vinyl-3-methyl-2-pyrrolidone, N-vinyl-4-methyl-2-pyrrolidone, N-vinyl-5-methyl-2-pyrrolidone, N-vinyl-6-methyl-2-pyrrolidone, N-vinyl-3-ethyl-2-pyrrolidone, N-vinyl-4,5-dimethyl-2-pyrrolidone, N-vinyl-5,5-dimethyl-2-pyrrolidone, N-vinyl-3,3,5-trimethyl-2-pyrrolidone, N-vinylpiperidone (also known as N-vinyl-2-piperidone), N-vinyl-3-methyl-2-piperidone, N-vinyl-4-methyl-2-piperidone, N-vinyl-5-methyl-2-piperidone, N-vinyl-6-methyl-2-piperidone, and N-vinyl-6-ethyl-2- Examples include piperidone, N-vinyl-3,5-dimethyl-2-piperidone, N-vinyl-4,4-dimethyl-2-piperidone, N-vinylcaprolactam (also known as N-vinyl-2-caprolactam), N-vinyl-3-methyl-2-caprolactam, N-vinyl-4-methyl-2-caprolactam, N-vinyl-7-methyl-2-caprolactam, N-vinyl-7-ethyl-2-caprolactam, N-vinyl-3,5-dimethyl-2-caprolactam, N-vinyl-4,6-dimethyl-2-caprolactam, N-vinyl-3,5,7-trimethyl-2-caprolactam, N-vinyl-N-methylacetamide, N-vinylformamide, N-vinylacetamide, N-vinylisopropylamide, N-vinyl-N-ethylacetamide, N-vinyl-N-ethylformamide, and mixtures thereof. Preferably, the N-vinylamide monomer is N-vinylpyrrolidone, N-vinyl-N-methylacetamide, or a combination thereof.

[0092] Preferred methylene-containing (=CH2) pyrrolidone monomers include, but are not limited to, 1-methyl-3-methylene-2-pyrrolidone, 1-ethyl-3-methylene-2-pyrrolidone, 1-methyl-5-methylene-2-pyrrolidone, 1-ethyl-5-methylene-2-pyrrolidone, 5-methyl-3-methylene-2-pyrrolidone, 5-ethyl-3-methylene-2-pyrrolidone, 1-n-propyl-3-methylene-2-pyrrolidone, 1-n-propyl-5-methylene-2-pyrrolidone, 1-isopropyl-3-methylene-2-pyrrolidone, 1-isopropyl-5-methylene-2-pyrrolidone, 1-n-butyl-3-methylene-2-pyrrolidone, 1-tert-butyl-3-methylene-2-pyrrolidone, and combinations thereof.

[0093] Preferred acrylic monomers having C1-C4 alkoxyethoxy groups include, but are not limited to, ethylene glycol methyl ether (meth)acrylate, di(ethylene glycol) methyl ether (meth)acrylate, tri(ethylene glycol) methyl ether (meth)acrylate, tetra(ethylene glycol) methyl ether (meth)acrylate, C1-C4 alkoxy poly(ethylene glycol) (meth)acrylate with a weight-average molecular weight of up to 1500, methoxy-poly(ethylene glycol) ethyl (meth)acrylamide with a number-average molecular weight of up to 1500, and combinations thereof.

[0094] Examples of preferred vinyl ether monomers include, but are not limited to, ethylene glycol monovinyl ether, di(ethylene glycol) monovinyl ether, tri(ethylene glycol) monovinyl ether, tetra(ethylene glycol) monovinyl ether, poly(ethylene glycol) monovinyl ether, ethylene glycol methyl vinyl ether, di(ethylene glycol) methyl vinyl ether, tri(ethylene glycol) methyl vinyl ether, tetra(ethylene glycol) methyl vinyl ether, poly(ethylene glycol) methyl vinyl ether, and combinations thereof.

[0095] Preferred allyl ether monomers include, but are not limited to, allyl alcohol, ethylene glycol monoallyl ether, di(ethylene glycol) monoallyl ether, tri(ethylene glycol) monoallyl ether, tetra(ethylene glycol) monoallyl ether, poly(ethylene glycol) monoallyl ether, ethylene glycol methyl allyl ether, di(ethylene glycol) methyl allyl ether, tri(ethylene glycol) methyl allyl ether, tetra(ethylene glycol) methyl allyl ether, poly(ethylene glycol) methyl allyl ether, and combinations thereof.

[0096] Preferred phosphorylcholine-containing vinyl monomers include, but are not limited to, (meth)acryloyloxyethyl phosphorylcholine (also known as MPC or 2-((meth)acryloyloxy)ethyl-2'-(trimethylammonio)ethyl phosphate), (meth)acryloyloxypropyl phosphorylcholine (also known as 3-((meth)acryloyloxy)propyl-2'-(trimethylammonio)ethyl phosphate), 4-((meth)acryloyloxy)butyl-2'-(trimethylammonio)ethyl phosphate, 2-[(meth)acryloylamino]ethyl-2'-(trimethylammonio)-ethyl phosphate, 3-[(meth)acryloylamino]propyl-2'-(trimethylammonio)ethyl phosphate, 4-[(meth)acryloylamino]butyl-2'-(trimethylammonio)ethyl phosphate, 5-((meth)acryloyloxy)pentyl-2'-(trimethylammonio)ethyl phosphate, 6-((meth)acryloyloxy)hexyl-2'-(trimethylammonio)-ethyl phosphate, 2-((meth) Cryloyloxy)ethyl-2'-(triethylammonio)ethyl phosphate, 2-((meth)acryloyloxy)ethyl-2'-(tripropylammonio)ethyl phosphate, 2-((meth)acryloyloxy)ethyl-2'-(tributylammonio)ethyl phosphate, 2-((meth)acryloyloxy)propyl-2'-(trimethylammonio)-ethyl phosphate, 2-((meth)acryloyloxy)butyl-2'-(trimethylammonio)ethyl phosphate, 2-((meth)acryloyloxy) Nthyl-2'-(trimethylammonio)ethyl phosphate, 2-((meth)acryloyloxy)hexyl-2'-(trimethylammonio)ethyl phosphate, 2-(vinyloxy)ethyl-2'-(trimethylammonio)ethyl phosphate, 2-(allyloxy)ethyl-2'-(trimethylammonio)ethyl phosphate, 2-(vinyloxycarbonyl)ethyl-2'-(trimethylammonio)ethyl phosphate, 2-(allyloxycarbonyl)ethyl-2'-(trimethylammonio)-ethyl phosphate,Examples include 2-(vinylcarbonylamino)ethyl-2'-(trimethylammonio)ethyl phosphate, 2-(allyloxycarbonylamino)ethyl-2'-(trimethylammonio)ethyl phosphate, 2-(butenoyloxy)ethyl-2'-(trimethylammonio)ethyl phosphate, and combinations thereof.

[0097] In preferred embodiments, the arylborono group-containing vinyl monomer is represented by formula (I): [ka] (In the formula: R B This is a monovalent radical (preferably H, NO2, F, Cl, Br, CF3, CH2OH, or CH2NR) o R o ' and R o and R o ' is independently H or C1-C4 alkyl; Q is, [ka] It is a monovalent radical; L B This refers to direct bonding, C1-C4 alkylene divalent radicals, or [ka] It is a divalent radical, where Y1 is a CH(OH) or C1-C4 alkylene divalent radical, Y2 is a C1-C4 alkylene divalent radical, and p2 is an integer from 0 to 3. o (H is H or C1-C4 alkyl).

[0098] Examples of preferred arylborono group-containing vinyl monomers of formula (I) include, but are not limited to, 3-vinylphenylboronic acid, 4-vinylphenylboronic acid (pKa approx. 8.8), 3-(meth)acrylamidephenylboronic acid (pKa approx. 8.2), 4-(meth)acrylamidephenylboronic acid, 4-(1,6-dioxo-2,5-diaza-7-oxamyl)phenylboronic acid (pKa approx. 7.8), 2-dimethylaminomethyl-5-vinylphenylboronic acid (pKa < 7.8), 4-(N-allyl sulfamoyl)phenylboronic acid (pKa approx. 7.4), and 4-(3-butenylsulfonyl)phenylboronic acid (pKa approx. 7.1) 3-(meth)acrylamide-5-nitrophenylboronic acid, 4-(meth)acrylamide-5-nitrophenylboronic acid, 4-(meth)acrylamide-3-nitrophenylboronic acid, 3-[(meth)acrylamide-C2~C5-alkylaminocarbonyl]-5-nitrophenylboronic acid, 3-[(meth)acryloyloxy-C2~C5-alkylaminocarbonyl]-5-nitrophenylboronic acid, 3-(meth)acrylamide-6-hydroxymethylphenylboronic acid, 3-(meth)acrylamide-6-dimethylaminomethylphenylboronic acid, 4-(meth)acrylamide-6-hydroxymethylphenylboronic acid, 4-(meth)acrylamide-6-dimethylaminomethylphenylboronic acid, carbodiimide (e.g., 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (EDC), N,N'-disic Examples include reaction products of amino-containing phenylboronic acid derivatives and (meth)acrylic acid halides or epoxide-containing vinyl monomers or carboxy-containing vinyl monomers in the presence of N-hydroxysuccinimide (e.g., 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (EDC), N,N'-dicyclohexylcarbodiimide (DCC), 1-cyclohexyl-3-(2-morpholinoethyl)carbodiimide, diisopropylcarbodiimide, or mixtures thereof) and carboxy-containing phenylboronic acid derivatives and amino group-containing vinyl monomers in the presence of N-hydroxysuccinimide, as well as combinations thereof.

[0099] Preferred carboxyl-containing phenylboronic acid derivatives include, but are not limited to, 3-carboxyphenylboronic acid, 4-carboxyphenylboronic acid, 3-boronophenylacetic acid, 4-boronophenylacetic acid, 2-(4-boronophenyl)-2-methylpropanoic acid, 3-(4-boronophenyl)propanoic acid, 3-(3-boronophenyl)propanoic acid, 5-(3-boronophenyl)pentanoic acid, 5-(4-boronophenyl)pentanoic acid, 4-(2-carboxyethyl)-3-nitrophenylboronic acid, 3-carboxy-5-nitrophenylboronic acid, 4-carboxy-30-chlorophenylboronic acid, 3-carboxy-4-fluorophenylboronic acid (bornic acid), 3-(3-carboxypropionylamino)phenylboronic acid, 3-amino-3-(4-boronophenyl)propanoic acid, and combinations thereof.

[0100] Examples of preferred amino-containing phenylboronic acid derivatives include, but are not limited to, 3-aminophenylboronic acid, 4-aminophenylboronic acid, 4-amino-3-nitrophenylboronic acid, 3-amino-6-hydroxymethylphenylboronic acid, 3-amino-6-(dimethylaminomethyl)phenylboronic acid, 4-amino-2-hydroxymethylphenylboronic acid, 4-amino-2-(dimethylaminomethyl)phenylboronic acid, 3-amino-4-fluorophenylboronic acid, 4-(aminomethyl)-5-nitrophenylboronic acid, 3-(aminomethyl)-phenylboronic acid, 3-amino-5-nitrophenylboronic acid, 3-amino-3-(4-boronophenyl)propanoic acid, and combinations thereof.

[0101] Preferred acetal-containing phenylboronic acid derivatives include, but are not limited to, 2-acetoxyphenylboronic acid, 3-acetoxyphenylboronic acid, 4-acetoxyphenylboronic acid, 2-formylphenylboronic acid, 3-formylphenylboronic acid, 4-formylphenylboronic acid, 5-formyl-2-methoxyphenylboronic acid, 3-fluoro-4-formylphenylboronic acid, 4-fluoro-3-formylphenylboronic acid, and combinations thereof.

[0102] Examples of preferred carboxy-containing vinyl monomers include, but are not limited to, those listed above.

[0103] Examples of preferred amino-containing vinyl monomers include, but are not limited to, amino-C2~C4 alkyl (meth)acrylates (e.g., 2-aminoethyl (meth)acrylate, 3-aminopropyl (meth)acrylate, 3-amino-2-hydroxypropyl (meth)acrylate) and C1~C3 alkylamino-C2~C4 alkyl (meth)acrylates (e.g., 2-methylaminoethyl (meth)acrylate, 2-ethylaminoethyl (meth)acrylate, 3-methylaminopropyl (meth)acrylate, 3-ethylaminopropyl (meth)acrylate). Examples include acrylates, amino-C2-C4 alkyl(meth)acrylamides (e.g., N-2-aminoethyl(meth)acrylamide, N-3-aminopropyl(meth)acrylamide, N-4-aminobutyl(meth)acrylamide), C1-C3 alkylamino-C2-C4 alkyl(meth)acrylamides (e.g., N-2-methylaminoethyl(meth)acrylamide, N-2-ethylaminoethyl(meth)acrylamide, N-3-methylaminopropyl(meth)acrylamide), vinylamines, allylamines, and combinations thereof.

[0104] Examples of preferred epoxide-containing vinyl monomers include, but are not limited to, glycidyl(meth)acrylamide, hydroxyethyl(meth)acrylamide glycidyl ether, 3-hydroxypropyl(meth)acrylamide glycidyl ether, 4-hydroxybutyl(meth)acrylamide glycidyl ether, glycidyl(meth)acrylate, hydroxyethyl(meth)acrylate glycidyl ether, 3-hydroxypropyl(meth)acrylate glycidyl ether, 4-hydroxybutyl(meth)acrylate glycidyl ether, and combinations thereof.

[0105] According to the present invention, any non-silicone vinyl crosslinking agent can be included within the scope of the present invention. Examples of preferred non-silicone vinyl crosslinking agents include, but are not limited to, ethylene glycol di-(meth)acrylate, diethylene glycol di-(meth)acrylate, triethylene glycol di-(meth)acrylate, tetraethylene glycol di-(meth)acrylate, polyethylene glycol di-(meth)acrylate having a number average molecular weight of 200 to 10,000 daltons, glycerol di-(meth)acrylate, 1,3-propanediol di-(meth)acrylate, 1,3-butanediol di-(meth)acrylate, 1,4-butanediol-(meth)acrylate, glycerol 1,3-diglycerolate di-(meth)acrylate, ethylene bis[oxy(2-hydroxypropane-1,3-diyl)] di-(meth)acrylate, bis[2-(meth)acryloyloxyethyl]phosphate, trimethylolpropane di-(meth)acrylate, and 3,4-bis[(meth)acryloyl] [L]tetrahydrofuran, diacrylamide (i.e., N-(1-oxo-2-propenyl)-2-propenamide), dimethacrylamide (i.e., N-(1-oxo-2-methyl-2-propenyl)-2-methyl-2-propenamide), N,N-di(meth)acryloyl-N-methylamine, N,N-di(meth)acryloyl-N-ethylamine, N,N'-methylenebis(meth)acrylamide, N,N'-ethylenebis(meth)acrylamide, N ,N'-dihydroxyethylenebis(meth)acrylamide, N,N'-propylenebis(meth)acrylamide, N,N'-2-hydroxypropylenebis(meth)acrylamide, N,N'-2,3-dihydroxybutylenebis(meth)acrylamide, 1,3-bis(meth)acrylamide-propane-2-yl dihydrogen phosphate (i.e., N,N'-2-phosphonyloxypropylenebis(meth)acrylamide), piperazinediacrylamide (or 1,Examples include 4-bis(meth)acryloylpiperazine), triallyl isocyanurate, triallyl cyanurate, and combinations thereof, more preferably selected from the group consisting of ethylene glycol di-(meth)acrylate, diethylene glycol di-(meth)acrylate, triethylene glycol di-(meth)acrylate, tetraethylene glycol di-(meth)acrylate, polyethylene glycol di-(meth)acrylate having a number-average molecular weight of 200 to 10,000 daltons, and combinations thereof.

[0106] According to the present invention, the free radical initiator can be either a photoinitiator or a thermal initiator. A "photoinitiator" refers to a chemical substance that initiates a free radical crosslinking / polymerization reaction using light. A "thermal initiator" refers to a chemical substance that initiates a free radical crosslinking / polymerization reaction using thermal energy.

[0107] Any thermal polymerization initiator can be used in the present invention. Suitable thermal polymerization initiators are known to those skilled in the art and include, for example, peroxides, hydroperoxides, azo-bis(alkyl- or cycloalkylnitriles), persulfates, percarbonates, or mixtures thereof.Examples of preferred thermal polymerization initiators include, but are not limited to, benzoyl peroxide, t-butyl peroxide, t-amyl peroxybenzoate, 2,2-bis(tert-butylperoxy)butane, 1,1-bis(tert-butylperoxy)cyclohexane, 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane, 2,5-bis(tert-butylperoxy)-2,5-dimethyl-3-hexine, and bis(1-(tert-butylperoxy)-1-methylethyl Benzene, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, di-t-butyl-diperoxyphthalate, t-butylhydroperoxide, t-butylperacetate, t-butylperoxybenzoate, t-butylperoxyisopropylcarbonate, acetylperoxide, lauroylperoxide, decanoylperoxide, dicetylperoxydicarbonate, di(4-t-butylcyclohexyl)peroxydicarbonate (Perkadox 16) Di(2-ethylhexyl)peroxydicarbonate, t-butylperoxypivalate (Lupersol 11); t-butylperoxy-2-ethylhexanoate (Trigonox 21-C50), 2,4-pentanedione peroxide, dicumyl peroxide, peracetic acid, potassium persulfate, sodium persulfate, ammonium persulfate, 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile) (VAZO 33), 2,2'-azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride (VAZO 44), 2,2'-azobis(2-amidinopropane) dihydrochloride (VAZO 50), 2,2'-azobis(2,4-dimethylvaleronitrile) (VAZO 52), 2,2'-azobis(isobutyronitrile) (VAZO Examples include VAZO 64 (or AIBN), 2,2'-azobis-2-methylbutyronitrile (VAZO 67), 1,1-azobis(1-cyclohexanecarbonitride) (VAZO 88); 2,2'-azobis(2-cyclopropylpropionitrile), 2,2'-azobis(methylisobutyrate), 4,4'-azobis(4-cyanovaleric acid), and combinations thereof.Preferably, the thermal initiator is 2,2'-azobis(isobutyronitrile) (AIBN or VAZO 64).

[0108] Suitable photoinitiators include benzoin methyl ether, diethoxyacetophenone, benzoylphosphine oxide, 1-hydroxycyclohexylphenyl ketone, and Darocur and Irgacur type, preferably Darocur 1173® and Darocur 2959®, and germanium-based Norish type I photoinitiators (e.g., those described in U.S. Patent No. 7,605,190). Examples of benzoylphosphine initiators include 2,4,6-trimethylbenzoyldiphenylphosphine oxide; bis-(2,6-dichlorobenzoyl)-4-N-propylphenylphosphine oxide; and bis-(2,6-dichlorobenzoyl)-4-N-butylphenylphosphine oxide. Reactive photoinitiators that can be incorporated into macromers or used as special monomers are also preferred. Examples of reactive photoinitiators are disclosed in European Patent No. 632329.

[0109] SiHy lens formulations (i.e., polymerizable compositions) include other necessary components known to those skilled in the art, such as one or more non-silicone hydrophobic vinyl monomers, ultraviolet-absorbing vinyl monomers, polymerizable ultraviolet / high-energy ultraviolet ("HEVL") absorbing compounds (including UV / HEVL absorbing vinyl monomers described later, and / or polymerizable Cu(II)-porphyrin as described in U.S. Patent Application Publication No. 20150316688), polymerizable photochromic compounds, visibility colorants (e.g., reactive dyes, polymerizable dyes, pigments, or mixtures thereof as known to those skilled in the art), antimicrobial agents (e.g., preferably silver nanoparticles), bioactive agents, eluting lubricants (e.g., non-polymerizable hydrophilic polymers), eluting tear stabilizers (e.g., phospholipids, monoglycerides, diglycerides, triglycerides, glycolipids, glyceroglycolipids, sphingolipids, sphingoglycolipids, etc.), and mixtures thereof.

[0110] According to the present invention, any non-silicone hydrophobic vinyl monomer can be included in the present invention. Examples of preferred non-silicone hydrophobic vinyl monomers include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl valerate, styrene, chloroprene, vinyl chloride, vinylidene chloride, (meth)acrylonitrile, 1-butene, butadiene, vinyltoluene, vinyl ethyl ether, perfluorohexylethyl-thio-carbonyl-aminoethyl-methacrylate, isobornyl (meth)acrylate, trifluoroethyl (meth)acrylate, hexafluoroisopropyl (meth)acrylate, hexafluorobutyl (meth)acrylate, and combinations thereof.

[0111] To prepare the preformed SiHy contact lenses of the present invention, any suitable UV-absorbing vinyl monomer and UV / HEVL-absorbing vinyl monomer can be used in the polymerizable composition. Preferred UV-absorbing and UV / HEVL-absorbing vinyl monomers include, but are not limited to, 2-(2-hydroxy-5-vinylphenyl)-2H-benzotriazole, 2-(2-hydroxy-5-acryloxyphenyl)-2H-benzotriazole, 2-(2-hydroxy-3-methacrylamidemethyl-5-tert-octylphenyl)benzotriazole, 2-(2'-hydroxy-5'-methacrylamidephenyl)-5-chlorobenzotriazole, and 2-(2'- Hydroxy-5'-methacrylamidephenyl)-5-methoxybenzotriazole, 2-(2'-hydroxy-5'-methacryloxypropyl-3'-t-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-5'-methacryloxypropylphenyl)benzotriazole, 2-hydroxy-5-methoxy-3-(5-(trifluoromethyl)-2H-benzo[d][1,2,3]triazole-2-yl)benzyl methacrylate (WL-1), 2-hydroxy- 5-Methoxy-3-(5-Methoxy-2H-benzo[d][1,2,3]triazol-2-yl)benzyl methacrylate (WL-5), 3-(5-fluoro-2H-benzo[d][1,2,3]triazol-2-yl)-2-hydroxy-5-methoxybenzyl methacrylate (WL-2), 3-(2H-benzo[d][1,2,3]triazol-2-yl)-2-hydroxy-5-methoxybenzyl methacrylate (WL-3), 3-(5-chloro-2H-benzo[d][1,2,3 ]triazol-2-yl)-2-hydroxy-5-methoxybenzyl methacrylate (WL-4), 2-hydroxy-5-methoxy-3-(5-methyl-2H-benzo[d][1,2,3]triazol-2-yl)benzyl methacrylate (WL-6), 2-hydroxy-5-methyl-3-(5-(trifluoromethyl)-2H-benzo[d][1,2,3]triazol-2-yl)benzyl methacrylate (WL-7), 4-allyl-2-(5-chloro-2H-benzo[d][1,2,3] Triazole-2-yl)-6-methoxyphenol (WL-8), 2-{2'-hydroxy-3'-tert-5'[3”-(4”-vinylbenzyloxy)propoxy]phenyl}-5-methoxy-2H-benzotriazole, phenol, 2-(5-chloro-2H-benzotriazole-2-yl)-6-(1,1-dimethylethyl)-4-ethenyl-(UVAM), 2-[2'-hydroxy-5'-(2-methacryloxyethyl)phenyl)]-2H-benzotriazole(2-propenoic acid, 2-methyl-, 2-[3-(2H-benzotriazole-2-yl)-4-hydroxyphenyl]ethyl ester,Norbloc), 2-{2'-hydroxy-3'-tert-butyl-5'-[3'-methacryloyloxypropoxy]phenyl}-2H-benzotriazole, 2-{2'-hydroxy-3'-tert-butyl-5'-[3'-methacryloyloxypropoxy]phenyl}-5-methoxy-2H-benzotriazole (UV13), 2-{2'-hydroxy-3'-tert-butyl-5'-[3'-methacryloyloxypropoxy]phenyl}-5-chloro-2H- Benzotriazole (UV28), 2-[2'-hydroxy-3'-tert-butyl-5'-(3'-acryloyloxypropoxy)phenyl]-5-trifluoromethyl-2H-benzotriazole (UV23), 2-(2'-hydroxy-5-methacrylamidephenyl)-5-methoxybenzotriazole (UV6), 2-(3-allyl-2-hydroxy-5-methylphenyl)-2H-benzotriazole (UV9), 2-(2-hydroxy-3-methallyl-5-meth (2'-hydroxyphenyl)-2H-benzotriazole (UV12), 2-3'-t-butyl-2'-hydroxy-5'-(3"-dimethylvinylsilylpropoxy)-2'-hydroxyphenyl)-5-methoxybenzotriazole (UV15), 2-(2'-hydroxy-5'-methacryloylpropyl-3'-tert-butylphenyl)-5-methoxy-2H-benzotriazole (UV16), 2-(2'-hydroxy-5'-acryloylpropyl-3'-tert-butylphenyl) (L)-5-methoxy-2H-benzotriazole (UV16A), 2-methylacrylic acid 3-[3-tert-butyl-5-(5-chlorobenzotriazol-2-yl)-4-hydroxyphenyl]propyl ester (16-100, CAS number 96478-15-8), 2-(3-(tert-butyl)-4-hydroxy-5-(5-methoxy-2H-benzo[d][1,2,3]triazol-2-yl)phenoxy)ethyl methacrylate (16-102); phenol,Examples include 2-(5-chloro-2H-benzotriazol-2-yl)-6-methoxy-4-(2-propen-1-yl) (CAS#1260141-20-5); 2-[2-hydroxy-5-[3-(methacryloyloxy)propyl]-3-tert-butylphenyl]-5-chloro-2H-benzotriazol; phenol, 2-(5-ethenyl-2H-benzotriazol-2-yl)-4-methyl-, homopolymer (9CI) (CAS#83063-87-0). According to the present invention, the polymerizable composition contains one or more UV-absorbing vinyl monomers in an amount of about 0.1% to about 3.0% by weight, preferably about 0.2% to about 2.5% by weight, and more preferably about 0.3% to about 2.0% by weight, based on the total amount of polymerizable components in the polymerizable composition.

[0112] Examples of preferred photochromic vinyl monomers include polymerizable naphthopyran, polymerizable benzopyran, polymerizable indenonaphthopyran, polymerizable phenantropyran, polymerizable spiro(benzindoline)-nafthopyran, polymerizable spiro(indoline)benzopyran, polymerizable spiro(indoline)-nafthopyran, polymerizable spiro(indoline)quinoplan, polymerizable spiro(indoline)-pyran, polymerizable naphthoxazine, polymerizable spirobenzopyran; polymerizable spirobenzopyran, polymerizable spirobenzothiopyran, polymerizable naphthacendione, polymerizable spirooxazine, polymerizable spiro(indoline)naphthoxazine, polymerizable spiro(indoline)pyridobenzoxazine, polymerizable spiro(benzindoline)pyridobenzoxazine, polymerizable spiro(benzindoline) Examples include phosphorus naphthoxazines, polymerizable spiro(indoline)-benzoxazines, polymerizable diarylethenes, and combinations thereof, which are specified in U.S. Patent Nos. 4,929,693, 5,166,345, 6,017,121, 7,556,750, 7,584,630, 7,999,989, 8,158,037, and 86 This is disclosed in Specification No. 97770, No. 8741188, No. 9052438, No. 9097916, No. 9465234, No. 9904074, No. 10197707, No. 6019914, No. 6113814, No. 6149841, No. 6296785, and No. 6348604.

[0113] A polymerizable composition (SiHy lens formulation) can be a solvent-free, clear liquid prepared by mixing all polymerizable components with other necessary components, as is known to those skilled in the art, or a solution prepared by dissolving all desired components in any suitable solvent, such as a mixture of water and one or more miscible organic solvents, an organic solvent, or a mixture of one or more organic solvents. The term "solvent" refers to a chemical substance that cannot participate in the free radical polymerization reaction.

[0114] Solvent-free SiHy lens formulations typically contain at least one blending vinyl monomer as a reactive solvent for dissolving all other polymerizable components of the solvent-free SiHy lens formulation. Examples of preferred blending vinyl monomers are described later in this application. Preferably, methyl methacrylate is used as the blending vinyl monomer when preparing solvent-free SiHy lens formulations.

[0115] Any solvent can be used in the present invention. Examples of preferred organic solvents, though not limited to, include tetrahydrofuran, tripropylene glycol methyl ether, dipropylene glycol methyl ether, ethylene glycol n-butyl ether, ketones (e.g., acetone, methyl ethyl ketone, etc.), diethylene glycol n-butyl ether, diethylene glycol methyl ether, ethylene glycol phenyl ether, propylene glycol methyl ether, propylene glycol methyl ether acetate, dipropylene glycol methyl ether acetate, propylene glycol n-propyl ether, dipropylene glycol n-propyl ether, tripropylene glycol n-butyl ether, propylene glycol n-butyl ether, dipropylene glycol n-butyl ether, tripropylene glycol n-butyl ether, propylene glycol Recyclable phenyl ether, dipropylene glycol dimethyl ether, polyethylene glycol, polypropylene glycol, ethyl acetate, butyl acetate, amyl acetate, methyl lactate, ethyl lactate, i-propyl lactate, methylene chloride, 2-butanol, 1-propanol, 2-propanol, menthol, cyclohexanol, cyclopentanol and exonorborneol, 2-pentanol, 3-pentanol, 2-hexanol, 3-hexanol, 3-methyl-2-butanol, 2-heptanol, 2-octanol, 2-nonanol, 2-decanol, 3-octanol, norborneol, tert-butanol, tert-amyl alcohol, 2-methyl-2-pentanol, 2,3-dimethyl-2-butanol, 3-methyl-3-pentanol, 1-methylcyclohexanol, 2-methyl-2-hexanol, 3,7-Dimethyl-3-Octanol, 1-Chloro-2-methyl-2-propanol, 2-Methyl-2-Heptanol, 2-Methyl-2-Octanol, 2-2-Methyl-2-Nonanol, 2-Methyl-2-Decanol, 3-Methyl-3-Heptanol, 3-Methyl-3-Heptanol, 4-Methyl-4-Heptanol, 3-Methyl-3-Nonanol, 4-Methyl-4-Nonanol, 3-Methyl-3-Octanol, 3-Ethyl-3-Heptanol, 3-Methyl-3-Heptanol, 4-Ethyl-4-Heptanol, 4-Propyl-4-Heptanol, 4-Isopropyl-4-Heptanol, 2,4-Dimethyl-2-Pentanol, 1-Methylcyclopentanol Examples include pentanol, 1-ethylcyclopentanol, 1-ethylcyclopentanol, 3-hydroxy-3-methyl-1-butene, 4-hydroxy-4-methyl-1-cyclopentanol, 2-phenyl-2-propanol, 2-methoxy-2-methyl-2-propanol, 2,3,4-trimethyl-3-pentanol, 3,7-dimethyl-3-octanol, 2-phenyl-2-butanol, 2-methyl-1-phenyl-2-propanol and 3-ethyl-3-pentanol, 1-ethoxy-2-propanol, 1-methyl-2-pyrrolidone, N,N-dimethylpropionamide, dimethylformamide, dimethylacetamide, dimethylpropionamide, N-methylpyrrolidone, and mixtures thereof.

[0116] In preferred embodiments, the polymerizable composition comprises (i) at least one hydrophilic polysiloxane vinyl crosslinking agent, (ii) optionally but preferably hydroxyethyl methacrylate, (iii) at least one C1-C2 alkoxyethyl (meth)acrylate, (iv) at least one carboxyl-containing vinyl monomer in an amount of about 0.5% to about 3.5% by weight (preferably about 0.7% to about 3.5% by weight, more preferably about 0.9% to about 3.0% by weight, and even more preferably about 1.0% to about 2.8% by weight) relative to the total amount of all polymerizable components, and (v) about 2.5% to about 1 The composition contains 2.5% by weight (preferably about 2.5% to about 10% by weight, more preferably about 3.0% to about 8.0% by weight, and even more preferably about 3.5% to about 7.0% by weight) of at least one arylborono-containing vinyl monomer having an arylborono group; (vi) at least one non-silicone vinyl crosslinking agent; (vii) at least one free radical initiator; and (viii) at least one solvent optionally selected from the group consisting of water, propylene glycol, polyethylene glycol having a molecular weight of about 400 daltons or less, and combinations thereof. The total amount of components (i) to (vii) is at least about 90% by weight, preferably at least about 92% by weight, more preferably at least about 94% by weight, and even more preferably at least about 96% by weight, based on the total amount of all polymerizable components in the polymerizable composition. According to this preferred embodiment of the present invention, the polymerizable composition may further contain one or more additional polymerizable components (other than components (i) to (iv)) known to those skilled in the art, provided that the total amount of these additional polymerizable components is about 10% by weight or less, preferably about 8% by weight or less, more preferably about 6% by weight or less, and even more preferably about 4% by weight or less, based on the total amount of all polymerizable components in the polymerizable composition. The polymerizable composition can be prepared by blending all the desired components as known to those skilled in the art.

[0117] According to the present invention, the polymerizable composition can be distributed into a lens mold by any known method. For example, a specific amount of polymerizable composition is typically distributed into a female half by a distribution device, then a male half is placed, and the mold is closed. Once the mold is closed, any excess polymerizable composition is pushed into an overflow provided on the female half (or male half).

[0118] The molded assembly (i.e., a closed mold containing the polymerizable composition) is then cured by heat or chemical rays, as is known to those skilled in the art, to form a pre-formed silicone hydrogel lens containing a bulk silicone hydrogel material comprising carboxyl groups and arylborono groups. It is understood that the carboxyl groups on and / or near the surface of the bulk silicone hydrogel material can function as reaction sites that can covalently bond layers of crosslinked hydrophilic polymer material, while the arylborono groups on and / or near the surface of the bulk silicone hydrogel material can function as reaction sites that can covalently bond diol-containing hydrophilic polymers having 1,2- or 1,3-diol moieties.

[0119] After curing, the mold can be opened according to any method known to those skilled in the art. After the mold is separated, the pre-formed silicone hydrogel lens is attached to one of the male and female halves.

[0120] The pre-formed silicone hydrogel lens attached to the lens-attached mold half can be removed from the lens-attached mold half and subjected to one or more post-molding processes.

[0121] According to the present invention, the aqueous coating solution of the present invention must contain two different types of coating materials.

[0122] The first type of coating material is a branched or slightly crosslinked water-soluble, thermocrosslinkable, hydrophilic polymer material comprising thermocrosslinkable groups (azetidinium groups and / or epoxide groups) and optionally but preferably reactive functional groups (primary amino groups, secondary amino groups, carboxylic acid groups, thiol groups, or combinations thereof).

[0123] The term "slightly crosslinked" in relation to polymer materials means that the number of crosslinks between polymer chains in the polymer material is very small, so the polymer material remains water-soluble.

[0124] In preferred embodiments, the water-soluble, heat-crosslinkable, hydrophilic polymer material is a partially crosslinked polymer material comprising a three-dimensional network and heat-crosslinkable groups, preferably azetidinium groups within or linked to the network. The term “partially crosslinked” in relation to the polymer material means that, in the crosslinking reaction, the crosslinkable groups of the starting materials for producing the polymer material are not completely consumed. For example, such a heat-crosslinkable, hydrophilic polymer material is a partial reaction product of at least one azetidinium-containing or epoxide-containing polymer comprising azetidinium groups and following the crosslinking reaction shown in Scheme I, and at least one hydrophilicity enhancer (i.e., wetting agent) having at least one carboxyl, primary amine, secondary amine, or thiol group: [ka] (In the formula, X1 is -S-*, -OC(=O)-*, or -NR'-*, and R' is hydrogen or C1~C) 20 It is an unsubstituted or substituted alkyl group, and * represents an organic radical.

[0125] Examples of preferred water-soluble, heat-crosslinkable, hydrophilic polymer materials containing epoxide groups include, but are not limited to, one or more multi-arm polyethylene glycols, each having a terminal epoxide (i.e., epoxy) group; partial reaction products of multi-arm polyethylene glycols having terminal epoxide groups and one or more polyethylene glycols, each having a terminal functional group selected from the group consisting of primary amine groups, secondary amine groups, carboxyl groups, thiol groups, and combinations thereof; partial reaction products of multi-arm polyethylene having terminal epoxide groups and a hydrophilicity enhancer having at least one reactive functional group selected from the group consisting of amino groups, carboxyl groups, thiol groups, and combinations thereof (such as those disclosed in U.S. Patent No. 9,505,184, and hydrophilic polymers disclosed in U.S. Patent No. 6,440,571); epoxide Examples include a copolymer of a side-containing vinyl monomer (any of the above) and one or more hydrophilic vinyl monomers, and a hydrophilicity enhancer having at least one reactive functional group selected from the group consisting of an amino group, a carboxyl group, a thiol group, and combinations thereof (any of the following); an epoxide-containing vinyl monomer (any of the above), a hydrophilic vinyl monomer, and a copolymer of C1-C4 alkoxy poly(ethylene glycol) ethyl (meth)acrylate having a number average molecular weight of up to 2500 daltons (poly(ethylene glycol) ethyl (meth)acrylate having a number average molecular weight of up to 2500 daltons, C1-C4 alkoxy poly(ethylene glycol) ethyl (meth)acrylamide, or poly(ethylene glycol) ethyl (meth)acrylamide having a number average molecular weight of up to 2500 daltons); or a combination thereof.

[0126] Examples of preferred water-soluble, heat-crosslinkable, hydrophilic polymer materials containing an azetidinium group include, but are not limited to, poly(2-oxazoline-co-ethyleneimine)-epichlorohydrin copolymer (disclosed in U.S. Patent No. 9720138), chemically modified poly(2-oxazoline-co-ethyleneimine)-epichlorohydrin copolymer (disclosed in U.S. Patent No. 9720138), chemically modified polyamidoamine-epichlorohydrin (disclosed in U.S. Patent No. 8529057), copolymers of azetidinium-containing vinyl monomers with one or more hydrophilic vinyl monomers (disclosed in U.S. Patent No. 9422447), chemically modified copolymers of azetidinium-containing vinyl monomers with one or more hydrophilic vinyl monomers (disclosed in U.S. Patent No. 9422447), or combinations thereof.

[0127] According to the present invention, the term "chemically modified" with respect to water-soluble, heat-crosslinkable, hydrophilic polymer materials having azetidinium groups means that the copolymer of poly(2-oxazoline-co-ethyleneimine)-epichlorohydrin copolymer, polyamidoamine-epichlorohydrin, or azetidinium-containing vinyl monomer is partially reacted with a hydrophilicity enhancer having at least one reactive functional group selected from the group consisting of amino groups, carboxyl groups, thiol groups, and combinations thereof (i.e., not all of the azetidinium groups are consumed). Chemically modified poly(2-oxazoline-co-ethyleneimine)-epichlorohydrin copolymer or copolymer of polyamidoamine-epichlorohydrin or azetidinium-containing vinyl monomer can be particularly useful for forming relatively thick and soft non-silicone hydrogel coatings on silicone hydrogel contact lenses.

[0128] Any suitable hydrophilicity enhancer can be used in the present invention, provided that they contain at least one amino group, at least one carboxyl group, and / or at least one thiol group.

[0129] Preferred classes of hydrophilicity enhancers include, but are not limited to, primary amino acids, secondary amino acids, carboxyl or thiol-containing monosaccharides (e.g., 3-amino-1,2-propanediol, 1-thiolglycerol, 5-keto-D-gluconic acid, galaxamine, glucosamine, galacturonic acid, gluconic acid, glucosamic acid, mannosamine, 1,4-lactone saccharic acid, saccharidic acid, ketodeoxynonurosonic acid, N-methyl-D-glucamine, 1-aino-1-deoxy-β-D-galactose, 1-amino-1-deoxysorbitol). Examples include 1-methylamino-1-deoxysorbitol, N-aminoethylgluconamide; primary amino acids, secondary amino acids, carboxyl or thiol-containing disaccharides (e.g., chondroitin disaccharide sodium salt, di(β-D-xylopyranosyl)amine, digalacturonic acid, heparin disaccharide, hyaluronic acid disaccharide, lactobionic acid); and primary amino acids, secondary amino acids, carboxyl or thiol-containing oligosaccharides (e.g., carboxymethyl-β-cyclodextrin sodium salt, trigalacturonic acid); and combinations thereof.

[0130] Another preferred class of hydrophilicity enhancers is a hydrophilic polymer having one or more (primary or secondary) amino, carboxyl, and / or thiol groups. More preferably, the content of amino (-NHR' having R' as defined above), carboxyl (-COOH), and / or thiol (-SH) groups in the hydrophilic polymer as a hydrophilicity enhancer is less than about 40% by weight, preferably less than about 30% by weight, more preferably less than about 20% by weight, and even more preferably less than 10% by weight, based on the total weight of the hydrophilic polymer.

[0131] One preferred class of hydrophilic polymers as hydrophilicity enhancers is (primary or secondary) amino or carboxyl-containing polysaccharides, such as carboxymethylcellulose (repeating unit, -[C6H 10~m O5(CH2CO2H) m-(having a carboxyl content of about 40% or less estimated based on the composition of -(where m is 1 to 3)), carboxymethyl cellulose (repeating unit, -[C6H 10~m O5(C2H4CO2H) m -(having a carboxyl content of about 36% or less estimated based on the composition of -(where m is 1 to 3)), carboxypropyl cellulose (repeating unit, -[C6H 10~m O5(C3H6CO2H) m -(having a carboxyl content of about 32% or less estimated based on the composition of -(where m is 1 to 3)), hyaluronic acid (repeating unit, -(C 13 H 20 O9NCO2H)- having a carboxyl content of about 11% estimated based on the composition), chondroitin sulfate (repeating unit, -(C 12 H 18 O 13 NSCO2H)- having a carboxyl content of about 9.8% estimated based on the composition), or a combination thereof, etc.

[0132] Other preferred classes of hydrophilic polymers as hydrophilicity enhancers include, but are not limited to, poly(ethylene glycol) (PEG) (e.g., PEG-NH2, PEG-SH, PEG-COOH) having mono-amino (primary or secondary amino), carboxyl, or thiol groups; H2N-PEG-NH2; HOOC-PEG-COOH; HS-PEG-SH; H2N-PEG-COOH; HOOC-PEG-SH; H2N-PEG-SH; multi-armed PEG having one or more amino (primary or secondary), carboxyl, or thiol groups; and one or more amino (primary or secondary), carboxyl, or thiol groups. Examples include PEG dendrimers having a group; diamino-(primary or secondary) or dicarboxyl-terminated homopolymers or copolymers of non-reactive hydrophilic vinyl monomers; monoamino-(primary or secondary) or monocarboxyl-terminated homopolymers or copolymers of non-reactive hydrophilic vinyl monomers; copolymers which are polymerization products of compositions comprising (1) one or more reactive vinyl monomers in an amount of about 60% by weight or less, preferably about 0.1% to about 30% by weight, more preferably about 0.5% to about 20% by weight, and even more preferably about 1% to about 15% by weight, and (2) at least one non-reactive hydrophilic vinyl monomer, as well as combinations thereof. The reactive vinyl monomers and non-reactive hydrophilic vinyl monomers are those described above.

[0133] According to the present invention, the reactive vinyl monomer for producing a hydrophilicity enhancer can be a carboxyl-containing vinyl monomer (as described above), or a primary and secondary amino-containing vinyl monomer (as described above).

[0134] According to the present invention, the non-reactive vinyl monomer for producing a hydrophilicity enhancer is a vinyl monomer that does not contain any carboxyl group, primary amino group, secondary amino group, epoxide group, isocyanate group, azulactone group, or aziridine group. The non-reactive vinyl monomer is preferably an uncharged hydrophilic vinyl monomer that does not contain carboxyl or amino groups (any of the above may be used herein), a phosphorylcholine-containing vinyl monomer (any of the above may be used herein), or a combination thereof.

[0135] More preferably, the hydrophilic polymer used as a hydrophilicity enhancer is Poly(ethylene glycol) having one single functional group of -NH2, -SH, or -COOH; Poly(ethylene glycol) having two terminal functional groups selected from the group consisting of -NH2, -COOH, -SH, and combinations thereof; Multi-armed poly(ethylene glycol) having one or more functional groups selected from the group consisting of -NH2, -COOH, -SH, and combinations thereof; Monoamino, monocarboxyl, diamino, or dicarboxyl-terminated homopolymers or copolymers of nonreactive hydrophilic vinyl monomers; The copolymer is a polymerization product of a composition comprising (1) about 0.1% to about 30% by weight, preferably about 0.5% to about 20% by weight, more preferably about 1% to about 15% by weight of a reactive vinyl monomer, and (2) at least one non-reactive vinyl monomer.

[0136] Examples of preferred reactive vinyl monomers include those listed above.

[0137] Examples of preferred non-reactive hydrophilic vinyl monomers include, but are not limited to, (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N-ethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-propyl(meth)acrylamide, N-isopropyl(meth)acrylamide, N-3-methoxypropyl(meth)acrylamide, N-2-dimethylaminoethyl(meth)acrylamide, dimethylaminoethyl(meth)acrylate, hydroxyl-containing acrylic monomers (any of the above), N-vinylamide monomers (any of the above), methylene-containing pyrrolidone monomers (i.e., pyrrolidone derivatives having a methylene group linked to the pyrrolidone ring at the 3rd or 5th position, respectively) (any of the above), acrylic monomers having C1-C4 alkoxyethoxy groups (any of the above), vinyl ether monomers (any of the above), allyl ether monomers (any of the above), phosphorylcholine-containing vinyl monomers (any of the above), and combinations thereof.

[0138] Preferably, the non-reactive hydrophilic vinyl monomer is (meth)acryloyloxyethyl phosphorylcholine, (meth)acryloyloxypropyl phosphorylcholine, 4-((meth)acryloyloxy)butyl-2'-(trimethylammonio)ethyl phosphate, 2-[(meth)acryloylamino]ethyl-2'-(trimethylammonio)ethyl phosphate, 3-[(meth)acryloylamino]propyl-2'-(trimethylammonio)ethyl phosphate, 4-[(meth)acryloylamino]butyl-2'-(trimethylammonio)ethyl phosphate, (meth)acrylamide, dimethyl(meth)acrylamide, N-2-hydroxyethyl(meth)acrylamide, N,N-bis(hydroxyethyl)(meth)acrylamide, N-2,3-Dihydroxypropyl(meth)acrylamide, N-Tris(hydroxymethyl)methyl(meth)acrylamide, 2-Hydroxyethyl(meth)acrylate, Glycerol methacrylate (GMA), Tetra(ethylene glycol)(meth)acrylate, Poly(ethylene glycol)ethyl(meth)acrylamide with a number average molecular weight of up to 1500, Poly(ethylene glycol)(meth)acrylate with a number average molecular weight of up to 1500, N-Vinylpyrrolidone, N-Vinyl-N-methylacetamide, N-Vinylformamide A selection from the group consisting of N-vinylacetamide, 1-methyl-3-methylene-2-pyrrolidone, 1-methyl-5-methylene-2-pyrrolidone, 5-methyl-3-methylene-2-pyrrolidone, tetra(ethylene glycol)methyl ether (meth)acrylate, methoxypoly(ethylene glycol)ethyl (meth)acrylamide having a number average molecular weight of up to 1500, C1-C4 alkoxy polyethylene glycol (meth)acrylate having a weight average molecular weight of up to 1500, tetra(ethylene glycol) monovinyl ether, poly(ethylene glycol) monovinyl ether, tetra(ethylene glycol) methyl vinyl ether, poly(ethylene glycol) methyl vinyl ether, tetra(ethylene glycol) monoallyl ether, poly(ethylene glycol) monoallyl ether, tetra(ethylene glycol) methyl allyl ether, poly(ethylene glycol) methyl allyl ether, vinyl alcohol, allyl alcohol, and combinations thereof, more preferably (meth)acryloyloxyethyl phosphorylcholine, (meth)acryloyloxypropyl phosphoryl Holylcholine, 4-((meth)acryloyloxy)butyl-2'-(trimethylammonio)ethyl phosphate, 2-[(meth)acryloylamino]ethyl-2'-(trimethylammonio)ethyl phosphate, 3-[(meth)acryloylamino]propyl-2'-(trimethylammonio)ethyl phosphate, 4-[(meth)acryloylamino]butyl-2'-(trimethylammonio)ethyl phosphate, (meth)acrylamide, dimethyl(meth)acrylamide, N-2-hydroxyethyl(meth)acrylamide, N,A selection from the group consisting of N-bis(hydroxyethyl)(meth)acrylamide, N-2,3-dihydroxypropyl(meth)acrylamide, N-tris(hydroxymethyl)methyl(meth)acrylamide, 2-hydroxyethyl(meth)acrylate, glycerol methacrylate (GMA), poly(ethylene glycol)ethyl(meth)acrylamide having a number average molecular weight of up to 1500, poly(ethylene glycol)(meth)acrylate having a number average molecular weight of up to 1500, N-vinylpyrrolidone, N-vinyl-N-methylacetamide, methoxypoly(ethylene glycol)ethyl(meth)acrylamide having a number average molecular weight of up to 1500, methoxypolyethylene glycol(meth)acrylate having a weight average molecular weight of up to 1500, poly(ethylene glycol) monovinyl ether, poly(ethylene glycol) methyl vinyl ether, poly(ethylene glycol) monoallyl ether, poly(ethylene glycol) methyl allyl ether, vinyl alcohol, allyl alcohol, and combinations thereof, more preferably (meth)acryloyloxyethyl phospho Rylcholine, (meth)acryloyloxypropylphosphorylcholine, 2-[(meth)acryloylamino]ethyl-2'-(trimethylammonio)ethyl phosphate, 3-[(meth)acryloylamino]propyl-2'-(trimethylammonio)ethyl phosphate, (meth)acrylamide, dimethyl(meth)acrylamide, N-2-hydroxyethyl(meth)acrylamide, N,N-bis(hydroxyethyl)(meth)acrylamide, N-2,3-dihydroxypropyl(meth)acrylamide, N-tris(hydroxymethyl ) Selected from the group consisting of methyl(meth)acrylamide, poly(ethylene glycol)ethyl(meth)acrylamide with a number average molecular weight of up to 1500, poly(ethylene glycol)(meth)acrylate with a number average molecular weight of up to 1500, N-vinylpyrrolidone, N-vinyl-N-methylacetamide, methoxypoly(ethylene glycol)ethyl(meth)acrylamide with a number average molecular weight of up to 1500, methoxypolyethylene glycol(meth)acrylate with a weight average molecular weight of up to 1500, and combinations thereof.

[0139] Functionalized PEGs and multi-armed functionalized PEGs can be obtained from various commercial suppliers, such as Polyscience and Shearwater Polymers, Inc.

[0140] Monoamino, monocarboxyl, diamino, or dicarboxy-terminated homopolymers or copolymers of one or more nonreactive hydrophilic vinyl monomers, or phosphorylcholine-containing vinyl monomers, can be prepared by following the procedures described in U.S. Patent No. 6,218,508, which is incorporated herein by reference in whole. For example, to prepare diamino or dicarboxyl-terminated homopolymers or copolymers of nonreactive hydrophilic vinyl monomers, a nonreactive vinyl monomer, a chain transfer agent having an amino or carboxyl group (e.g., 2-aminoethanethiol, 2-mercaptopropionic acid, thioglycolic acid, thiobutyric acid, or other hydroxymercaptons, aminomercaptons, or carboxyl-containing mercaptons), and optionally another vinyl monomer are polymerized (thermally or chemically) with a reactive vinyl monomer (having an amino or carboxyl group) in the presence of a free radical initiator. Generally, the molar ratio of the chain transfer agent to all vinyl monomers other than the reactive vinyl monomer is about 1:5 to about 1:100, while the molar ratio of the chain transfer agent to the reactive vinyl monomer is 1:1. In such preparations, a chain transfer agent having an amino or carboxyl group is used to control the molecular weight of the resulting hydrophilic polymer, forming the ends of the resulting hydrophilic polymer to provide a hydrophilic polymer having one terminal amino or carboxyl group, while the reactive vinyl monomer provides other terminal carboxyl or amino groups to the resulting hydrophilic polymer. Similarly, to prepare monoamino or monocarboxyl-terminated homo or copolymers of non-reactive hydrophilic vinyl monomers, a non-reactive vinyl monomer, a chain transfer agent having an amino or carboxyl group (e.g., 2-aminoethanethiol, 2-mercaptopropionic acid, thioglycolic acid, thiobutyric acid, or other hydroxymercaptons, aminomercaptons, or carboxyl-containing mercaptons) and optionally another vinyl monomer are polymerized (thermally or by chemical rays) in the absence of any reactive vinyl monomer.

[0141] Copolymers containing non-reactive hydrophilic vinyl monomers and reactive vinyl monomers (e.g., carboxyl-containing vinyl monomers, primary amino group-containing vinyl monomers, or secondary amino group-containing vinyl monomers) can be prepared by any well-known radical polymerization method or obtained from commercial sources. Copolymers containing methacryloyloxyethyl phosphorylcholine and carboxyl-containing vinyl monomers (or amino-containing vinyl monomers) can be obtained from NOP Corporation (e.g., LIPIDURE®-AC01 and AE).

[0142] A hydrophilic polymer having at least one amino, carboxyl, or thiol group (as a hydrophilicity enhancer) with a weight-average molecular weight M w Preferably, this is about 500 to about 2,000,000, more preferably about 1,000 to about 500,000, and even more preferably about 5,000 to about 250,000 Daltons.

[0143] Water-soluble, heat-crosslinkable, hydrophilic polymer materials can be prepared according to the procedures disclosed in U.S. Patent Nos. 8,529,057, 9,422,447, 9,720,138, and 1,125,6003, and U.S. Patent Publication No. 63 / 371660.

[0144] In a preferred embodiment, a water-soluble, heat-crosslinkable polymer material can be obtained by heating a reactive aqueous solution containing at least one azetidinium-containing polymer and at least one hydrophilicity enhancer (i.e., a wetting agent) having at least one reactive functional group selected from the group consisting of amino groups, carboxyl groups, thiol groups, and combinations thereof, to a temperature of about 35°C to about 85°C and maintaining the temperature for a sufficient amount of time (about 8 hours or less, preferably about 5 hours, more preferably about 2 hours to about 4 hours). The reactive aqueous solution preferably contains one or more ionic components in a concentration of about 70 mM to about 170 mM (preferably about 90 mM to about 150 mM, more preferably about 100 mM to about 130 mM) and has a pH of at least 8.0 (preferably at least 8.5, more preferably at least 9.0, and even more preferably 9.5). It should be understood that the reaction time should be long enough to covalently bond the hydrophilicity enhancer to the polymer chains of the azetidinium-containing polymer, but short enough not to consume all of the azetidinium groups of the azetidinium-containing polymer, and not to form a gel (i.e., non-water soluble) due to too many crosslinks formed between the azetidinium-containing polymer and the hydrophilicity enhancer. The resulting polymer material is a lightly crosslinked polymer material with a highly branched structure and still containing thermally crosslinkable azetidinium groups.

[0145] Those skilled in the art will have a good understanding of how to adjust the pH of a reactive mixture by adding, for example, a base (e.g., NaOH, KOH, NH4OH, or a mixture thereof) or an acid (e.g., HCl, H2SO4, H3PO4, citric acid, acetic acid, boric acid, or a mixture thereof).

[0146] According to the present invention, any ionic compound can be used in a reactive mixture. Preferably, the ionic compound is used as an ionic tonicity regulator and an ionic buffer in ophthalmic solutions. Examples of preferred ionic tonicity regulators include, but are not limited to, sodium chloride, potassium chloride, and combinations thereof. Examples of preferred ionic buffers include various salts of phosphoric acid (e.g., NaH2PO4, Na2HPO4, Na3PO4, KH2PO4, K2HPO4, K3PO4, or mixtures thereof), various salts of boric acid (e.g., sodium borate, potassium borate, or mixtures thereof), various salts of citric acid (e.g., monosodium citrate, disodium citrate, trisodium citrate, monopotassium citrate, dipotassium citrate, tripotassium citrate, or mixtures thereof), and various salts of carboxylic acid (e.g., Na2CO3, NaHCO3, K2CO3, KHCO3, or mixtures thereof).

[0147] A reactive aqueous solution for preparing a water-soluble, heat-crosslinkable polymer material can be prepared by dissolving a desired amount of azetidinium-containing polymer, a desired amount of a hydrophilicity enhancer having at least one reactive functional group, and a desired amount of other components (e.g., an ionic buffer, an ionic tonicity adjuster, etc.) in water (or a mixture of water and a small amount of water-soluble organic solvent) to form an aqueous solution, and then adjusting the pH of the aqueous solution as needed.

[0148] According to the present invention, the concentration ratio of the hydrophilicity enhancer to the azetidinium-containing polymer in the aqueous reactive solution must be selected so as not to render the resulting water-soluble, heat-crosslinkable polymer material water-insoluble (i.e., less than 0.005 g of solubility per 100 ml of water at room temperature), and so as not to consume more than about 99%, preferably about 98%, more preferably about 97%, and even more preferably about 96% of the azetidinium groups of the azetidinium-containing polymer.

[0149] In a preferred embodiment, the reactive aqueous solution comprises 0.01% to about 10% by weight (preferably 0.05% to about 5% by weight, more preferably 0.08% to about 1% by weight, and even more preferably 0.1% to about 0.4% by weight) of an azetidinium-containing polymer and about 0.01% to about 10% by weight (preferably 0.02% to about 5% by weight, more preferably 0.05% to about 2% by weight, and even more preferably 0.08% to about 1.0% by weight) of a hydrophilicity enhancer having at least one reactive functional group (carboxyl, primary amino, or secondary amino group), wherein the concentration ratio of the azetidinium-containing polymer to the hydrophilicity enhancer is about 1000:1 to 1:1000 (preferably about 500:1 to about 1:500, more preferably about 250:1 to about 1:250, and even more preferably about 100:1 to about 1:100).

[0150] In a preferred embodiment, the water-soluble, heat-crosslinkable polymer material comprises (i) a first polymer chain derived from polyamidoamine-epichlorohydrin or poly(2-oxazoline-co-ethyleneimine)-epichlorohydrin in an amount of about 20% to about 95% by weight, and (ii) a hydrophilic moiety or second polymer chain derived from at least one hydrophilicity enhancer having at least one reactive functional group selected from the group consisting of amino groups, carboxyl groups, thiol groups, and combinations thereof (preferably carboxyl or thiol groups) in an amount of about 5% to about 80% by weight. The hydrophilic portion or second polymer chain is covalently bonded to the first polymer chain through one or more covalent bonds formed between one azetidinium group of polyamidoamine-epichlorohydrin or poly(2-oxazoline-co-ethyleneimine)-epichlorohydrin and one amino, carboxyl, or thiol group of the hydrophilicity enhancer, and (iii) an azetidinium group that is part of the first polymer chain or is a pendant or terminal group covalently bonded to the first polymer chain. The composition of the chemically modified poly(2-oxazoline-co-ethyleneimine)-epichlorohydrin or chemically modified polyamidoamine-epichlorohydrin is determined by the composition (based on the total weight of reactants) of the reaction mixture used for such polymer according to the crosslinking reaction shown in Scheme I above. For example, if the reaction mixture contains about 75% by weight of polyamidoamine-epichlorohydrin and about 25% by weight of at least one hydrophilicity enhancer, based on the total weight of the reactants, the resulting chemically modified polyamidoamine-epichlorohydrin will contain a first polymer chain derived from about 75% by weight of polyamioamine-epichlorohydrin and a hydrophilic moiety or second polymer chain derived from about 25% by weight of the at least one hydrophilicity enhancer.

[0151] According to the present invention, the second type of coating material is a diol-containing hydrophilic polymer containing a 1,2- or 1,3-diol moiety. Any diol-containing hydrophilic polymer having a 1,2- or 1,3-diol moiety can be used in the present invention. Examples of preferred diol-containing hydrophilic polymers having a 1,2- or 1,3-diol moiety include, but are not limited to, polyvinyl alcohol, poly(ethylene glycol)-graft-poly(vinyl alcohol), copolymers of vinyl alcohol and hydrophilic vinyl monomers, copolymers of glycerol (meth)acrylate and hydrophilic vinyl monomers, copolymers of 2,3,4-trihydroxybutyl (meth)acrylate and hydrophilic vinyl monomers, copolymers of 2,2-dihydroxypropyl (meth)acrylate and hydrophilic vinyl monomers, copolymers of 2,3-dihydroxybutyl (meth)acrylate and hydrophilic vinyl monomers, copolymers of glycerin-2 (meth)acrylate and hydrophilic vinyl monomers, copolymers of N-2,3-dihydroxypropyl (meth)acrylamide and hydrophilic vinyl monomers, copolymers of 3-allyloxy-1,2-propanediol and hydrophilic vinyl monomers, and combinations thereof.

[0152] According to the present invention, during the heating process, the at least one water-soluble, heat-crosslinkable hydrophilic polymer material is crosslinked by intermolecular and intramolecular crosslinking reactions between azetidinium groups or epoxide groups and carboxyl groups, amino groups, or thiol groups, and is also covalently bonded to the bulk silicone hydrogel material by reactions between azetidinium groups or epoxide groups and carboxyl groups, while the diol-containing hydrophilic polymer is covalently bonded to the bulk silicone hydrogel material by reactions between arylborono groups and 1,2- or 1,3-diol moieties.

[0153] Preferably, the heating step is carried out by autoclaving the pre-formed SiHy contact lenses, which are immersed in a packaging solution (i.e., a buffered aqueous coating solution) in a sealed lens package, at a temperature of about 115°C to about 125°C for about 20 to 90 minutes.

[0154] Lens packages (or containers) are well known to those skilled in the art for autoclaving and storing soft contact lenses. Any lens package can be used in the present invention. Preferably, the lens package is a blister package comprising a base and a cover, wherein the cover is sealed to be removable from the base, and the base comprises a cavity for receiving a sterile packaging solution and a contact lens.

[0155] The lenses are packaged in individual packages, sealed, and sterilized (for example, by autoclaving at approximately 120°C or higher for at least 30 minutes under pressure) before being distributed to users. Those skilled in the art will understand well how to seal and sterilize the lens packages.

[0156] According to the present invention, the packaging solution contains at least one buffering agent and one or more other components known to those skilled in the art. Examples of other materials include, but are not limited to, isotonic agents, surfactants, antimicrobial agents, preservatives, and lubricants (e.g., cellulose derivatives, polyvinyl alcohol, polyvinylpyrrolidone).

[0157] The packaging solution contains a buffer in an amount sufficient to maintain the pH of the packaging solution within the desired range, for example, preferably about 6.8 to about 8.5, more preferably about 7.0 to 8.2, and even more preferably about 7.2 to about 8.0. It has been found that a higher pH is desirable to ensure that all or a substantial portion of the carboxyl groups of the bulk silicone hydrogel material are ionized. As a result, the resulting silicone hydrogel contact lenses may become dimensionally stable in the packaging solution and have improved lubricity during autoclaving and storage.

[0158] Any known physiologically compatible buffer can be used. Suitable buffers as components of the contact lens care composition according to the present invention are known to those skilled in the art. Preferably, a phosphate buffer (essentially consisting of a mixture of monobasic dihydrogen phosphate (e.g., NaH2PO4, KH2PO4, or a mixture thereof) and dibasic monohydrogen phosphate (e.g., Na2HPO4, K2HPO4, or a mixture thereof)) is used to maintain the pH of the packaging solution. In various preferred embodiments, the total concentration of monobasic dihydrogen phosphate and dibasic monohydrogen phosphate is at least 30 mM (preferably at least 35 mM, more preferably at least 40 mM, and even more preferably at least 45 mM).

[0159] The solutions according to the present invention are preferably formulated to be isotonic with tears. A solution isotonic with tears is generally understood to be a solution whose concentration corresponds to that of a 0.9% sodium chloride solution (308 mOsm / kg). Deviations from this concentration are possible throughout.

[0160] Isotonicity with tears, or any other desired tonicity, can be adjusted by adding organic or inorganic substances that affect the tonicity. Suitable ophthalmologically acceptable isotonic agents include, but are not limited to, sodium chloride, potassium chloride, glycerol, propylene glycol, polyols, mannitol, sorbitol, xylitol, and mixtures thereof. The tonicity of the packaging solution is typically adjusted to about 200 to about 450 milliosmoles (mOsm), preferably about 250 to 350 mOsm.

[0161] In preferred embodiments, one or more organic isotonic agents (e.g., glycerol, propylene glycol, polyethylene glycol having a number-average molecular weight of 200-800 daltons, mannitol, sorbitol, xylitol, and mixtures thereof) are present in an amount of at least 70 mM (preferably at least 90 mM, more preferably at least 110 mM, and even more preferably at least 130 mM) to adjust the tension of the packaging solution. It has been found that the resulting silicone hydrogel contact lenses may have improved lubricity when the ionic strength of the packaging solution is reduced (e.g., by replacing some of the NaCl with an organic isotonic agent, e.g., propylene glycol).

[0162] In preferred embodiments, the packaging solution preferably contains about 0.01% to about 2% by weight, more preferably about 0.05% to about 1.5% by weight, even more preferably about 0.1% to about 1% by weight, and most preferably about 0.2% to about 0.5% by weight of a water-soluble, thermally crosslinkable, hydrophilic polymer material having azetidinium groups.

[0163] In another embodiment, the present invention relates to a coated silicone hydrogel contact lens comprising a bulk silicone hydrogel material and a non-silicone hydrogel coating thereon, wherein the bulk silicone hydrogel material comprises (a) repeating units of at least one polysiloxane vinyl crosslinking agent and / or at least one siloxane-containing vinyl monomer, (b) repeating units of at least one carboxyl-containing vinyl monomer relative to the total amount of all polymerizable components, (c) repeating units of at least one hydrophilic vinyl monomer, (d) repeating units of at least one arylborono-containing vinyl monomer having an arylborono group, and (e) repeating units of at least one optional but preferred non-silicone vinyl crosslinking agent, wherein the non-silicone hydrogel coating comprises a crosslinked polymer material and grafts distributed in the crosslinked polymer material but not covalently bonded The present invention provides a coated silicone hydrogel contact lens comprising a hydrophilic polymer, wherein the crosslinked hydrophilic polymer material is covalently bonded to the bulk silicone hydrogel material via a first bond formed between one carboxylic acid group and one azetidinium group or epoxide group, respectively, and the grafted hydrophilic polymer comprises 1,2- and / or 1,3-diol moieties and is covalently bonded to the bulk silicone hydrogel material via a second bond formed between one arylborono group and one 1,2- or 1,3-diol moiety, respectively, wherein the fully hydrated coated silicone hydrogel contact lens exhibits a coating integrity of about 90% or more (preferably about 93% or more, more preferably about 96% or more, even more preferably about 98% or more) and a friction grade of about 2.0 or less (preferably about 1.5 or less, more preferably about 1.0 or less, even more preferably about 0.5 or less).

[0164] Various embodiments, including preferred embodiments of bulk SiHy materials, polysiloxane vinyl crosslinkers, siloxane-containing vinyl monomers, carboxyl-containing vinyl monomers, hydrophilic vinyl monomers, aryl vorono-containing vinyl monomers, non-silicone vinyl crosslinkers, water-soluble, heat-crosslinkable hydrophilic polymer materials, and hydrophilic polymers having 1,2- or 1,3-diol moieties, are described above and can be used in this embodiment of the present invention.

[0165] While various embodiments of the present invention have been described using specific terms, devices, and methods, such descriptions are for illustrative purposes only. The terms used are descriptive rather than restrictive. As will be apparent to those skilled in the art, many variations and modifications of the present invention can be made by those skilled in the art without departing from the spirit and scope of the novel concepts of this disclosure. In addition, it should be understood that the various embodiments of the present invention can be interchangeable in whole or in part, or combined and / or used together in any way, as shown below.

[0166] 1. A coated silicone hydrogel contact lens comprising a bulk silicone hydrogel material and a non-silicone hydrogel coating thereon, It comprises a bulk silicone hydrogel material and a layer of non-silicone hydrogel material on top thereof, The bulk silicone hydrogel material comprises (a) repeating units of at least one polysiloxane vinyl crosslinking agent and / or at least one siloxane-containing vinyl monomer, (b) repeating units of at least one carboxyl-containing vinyl monomer relative to the total amount of all polymerizable components, (c) repeating units of at least one hydrophilic vinyl monomer, (d) repeating units of at least one arylborono-containing vinyl monomer having an arylborono group, and (e) repeating units of at least one non-silicone vinyl crosslinking agent, which is optional but preferred. The non-silicone hydrogel coating comprises a crosslinked polymer material and a grafted hydrophilic polymer distributed within the crosslinked polymer material but not covalently bonded, wherein the crosslinked hydrophilic polymer material is covalently bonded to the bulk silicone hydrogel material via first bonds formed between one carboxylic acid group and one azetidinium group or epoxide group, respectively, and the grafted hydrophilic polymer contains 1,2- and / or 1,3-diol moieties and is covalently bonded to the bulk silicone hydrogel material via second bonds formed between one arylborono group and one 1,2- or 1,3-diol moiety, respectively. A coated silicone hydrogel contact lens that exhibits a coating integrity of approximately 90% or more and a friction rating of approximately 2.0 or less when fully hydrated. 2. The coated silicone hydrogel contact lens according to Embodiment 1, wherein the coated silicone hydrogel contact lens exhibits a coating integrity of approximately 93% or more when fully hydrated. 3. The coated silicone hydrogel contact lens according to Embodiment 1, wherein the coated silicone hydrogel contact lens exhibits a coating integrity of approximately 96% or more when fully hydrated. 4. The coated silicone hydrogel contact lens according to Embodiment 1, wherein the coated silicone hydrogel contact lens exhibits a coating integrity of approximately 98% or more when fully hydrated. 5. A coated silicone hydrogel contact lens according to any one of Embodiments 1 to 4, wherein the coated silicone hydrogel contact lens in a fully hydrated state exhibits a friction rating of 1.5 or less. 6. A coated silicone hydrogel contact lens according to any one of Embodiments 1 to 4, wherein the coated silicone hydrogel contact lens exhibits a friction grade of 1.0 or less when fully hydrated. 7. The coated silicone hydrogel contact lens in any one of Embodiments 1 to 4, wherein the coated silicone hydrogel contact lens in a fully hydrated state exhibits a friction grade of 0.5 or less. 8. The coated silicone hydrogel contact lens according to any one of Embodiments 1 to 7, wherein the at least one carboxyl-containing vinyl monomer is selected from the group consisting of acrylic acid, C1-C4 alkylacrylic acid, (meth)acryloxy-C1-C6 alkanoic acid, mono-2-[(meth)acryloxy]-ethyl succinate, 2-acrylamidoglycolic acid, (meth)acrylamide-C1-C6 alanic acid, and combinations thereof. 9. The coated silicone hydrogel contact lens according to any one of Embodiments 1 to 8, wherein the at least one arylborono group-containing vinyl monomer is represented by Formula (I): [Chemical Formula] (In the formula: R B is a monovalent radical (preferably H, NO2, F, Cl, Br, CF3, CH2OH, or CH2NR o R o ’ where R o and R o ’ are independently of each other H or C1-C4 alkyl); Q is [Chemical Formula] a monovalent radical of; L B is a direct bond, a C1-C4 alkylene divalent radical, or [Chemical Formula] a divalent radical of, Y1 is CH(OH) or a C1-C4 alkylene divalent radical, Y2 is a C1-C4 alkylene divalent radical, p2 is an integer from 0 to 3, and R o is H or C1-C4 alkyl). 10. The above at least one arylborono-containing vinyl monomer is 3-vinylphenylboronic acid, 4-vinylphenylboronic acid, 3-(meth)acrylamidephenylboronic acid, 4-(meth)acrylamidephenylboronic acid, 4-(1,6-dioxo-2,5-diaza-7-oxamyl)phenylboronic acid, 2-dimethylaminomethyl-5-vinylphenylboronic acid, 4-(N-allylsulfamoyl)phenylboronic acid, 4-(3-butenylsulfonyl)phenylboronic acid, 3-(meth)acrylamide-5-nitrophenylboronic acid, 4-(meth)acrylamide-5-nitrophenylboronic acid, 4-(meth)acrylamide-3-nitrophenylboronic acid, 3-[(meth)acrylamide-C2~C5-alkylaminocarbonyl]-5-nitrophenylboronic acid, 3-[(meth)acryloyloxy-C2~C5-alkylaminocarbonyl A coated silicone hydrogel contact lens according to any one of Embodiments 1 to 8, comprising: 1-5-nitrophenylboronic acid, 3-(meth)acrylamide-6-hydroxymethylphenylboronic acid, 3-(meth)acrylamide-6-dimethylaminomethylphenylboronic acid, 4-(meth)acrylamide-6-hydroxymethylphenylboronic acid, 4-(meth)acrylamide-6-dimethylaminomethylphenylboronic acid, reaction product of an amino-containing phenylboronic acid derivative with a (meth)acrylic acid halide or epoxide-containing vinyl monomer or carboxy-containing vinyl monomer in the presence of carbodiimide and N-hydroxysuccinimide, reaction product of a carboxy-containing phenylboronic acid derivative with an amino group-containing vinyl monomer in the presence of carbodiimide and N-hydroxysuccinimide, or a combination thereof. 11. Amino-containing phenylboronic acid derivatives include 3-carboxyphenylboronic acid, 4-carboxyphenylboronic acid, 3-boronophenylacetic acid, 4-boronophenylacetic acid, 2-(4-boronophenyl)-2-methylpropanoic acid, 3-(4-boronophenyl)propanoic acid, 3-(3-boronophenyl)propanoic acid, 5-(3-boronophenyl)pentanoic acid, 5-(4-boronophenyl)pentanoic acid, 4-(2-carboxyethyl)-3-nitrophenylboronic acid, 3-carboxy-5-nitrophenylboronic acid, 4-carboxy-3-chlorophenylboronic acid, and 3-carboxy-4-fluorophenylboronic acid (bornic The coated silicone hydrogel contact lens according to Embodiment 10, wherein the carboxy-containing phenylboronic acid derivative is 3-aminophenylboronic acid, 4-aminophenylboronic acid, 4-amino-3-nitrophenylboronic acid, 3-amino-6-hydroxymethylphenylboronic acid, 3-amino-6-(dimethylaminomethyl)phenylboronic acid, 4-amino-2-hydroxymethylphenylboronic acid, 4-amino-2-(dimethylaminomethyl)phenylboronic acid, 3-amino-4-fluorophenylboronic acid, 4-(aminomethyl)-5-nitrophenylboronic acid, 3-(aminomethyl)-phenylboronic acid, 3-amino-5-nitrophenylboronic acid, or 3-amino-3-(4-boronophenyl)propanoic acid. 12. The crosslinked polymer material comprises (1) a poly(ethylene glycol) chain called a PEG chain, (2) a polymer chain derived from a copolymer, or (3) a combination thereof, wherein the copolymer comprises (i) at least one reactive vinyl monomer containing at least one reactive functional group selected from the group consisting of carboxylic acids, primary amino groups, secondary amino groups, epoxide groups, and combinations thereof, in an amount of 60% by weight or less, and (ii) acrylamide, methacrylamide, N,N-dimethylacrylamide, N,N-dimethylmethacrylamide N-vinylpyrrolidone, N,N-dimethylaminoethyl methacrylate, N,N-dimethylaminoethyl acrylate, N,N-dimethylaminopropyl methacrylamide, N,N-dimethylaminopropyl acrylamide, glycerol methacrylate, 3-acryloylamino-1-propanol, N-hydroxyethyl acrylamide, N-[tris(hydroxymethyl)methyl]acrylamide, N-methyl-3-methylene-2-pyrrolidone, 1-ethyl-3-methylene-2-pyrrolidone, 1-methyl-5-methylene-2- Pyrrolidone, 1-ethyl-5-methylene-2-pyrrolidone, 5-methyl-3-methylene-2-pyrrolidone, 5-ethyl-3-methylene-2-pyrrolidone, 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, phosphorylcholine-containing vinyl monomer, C1-C4 alkoxypoly(ethylene glycol)ethyl (meth)acrylate with a weight-average molecular weight of up to 1500 daltons, C1-C4 alkoxypoly(ethylene glycol)ethyl (meth)acrylate with a weight-average molecular weight of up to 1500 daltons A polymerization product of a composition containing acrylamide, poly(ethylene glycol)ethyl (meth)acrylate having a weight-average molecular weight of up to 1500 daltons, poly(ethylene glycol)ethyl (meth)acrylamide having a weight-average molecular weight of up to 1500 daltons, N-vinylformamide, N-vinylacetamide, N-vinylisopropylamide, N-vinyl-N-methylacetamide, allyl alcohol, vinyl alcohol, and at least one nonreactive vinyl monomer selected from the group consisting of combinations thereof;The at least one reactive vinyl monomer is selected from the group consisting of amino-C2-C4 alkyl (meth)acrylate, C1-C3 alkylamino-C2-C4 alkyl (meth)acrylate, allylamine, vinylamine, amino-C2-C4 alkyl (meth)acrylamide, C1-C3 alkylamino-C2-C4 alkyl (meth)acrylamide, acrylic acid, C1-C4 alkyl acrylic acid, (meth)acryloxy-C2-C6 alkanoic acid, 2-acrylamidoglycolic acid, (meth)acrylamide-C2-C6 alkanoic acid, epoxide-containing vinyl monomer, and combinations thereof, and the epoxide-containing vinyl monomer A coated silicone hydrogel contact lens according to any one of Embodiments 1 to 11, selected from the group consisting of glycidyl (meth)acrylamide, hydroxyethyl (meth)acrylamide glycidyl ether, 3-hydroxypropyl (meth)acrylamide glycidyl ether, 4-hydroxybutyl (meth)acrylamide glycidyl ether, glycidyl (meth)acrylate, hydroxyethyl (meth)acrylate glycidyl ether, 3-hydroxypropyl (meth)acrylate glycidyl ether, 4-hydroxybutyl (meth)acrylate glycidyl ether, and combinations thereof. 13. The crosslinked polymer material comprises a polymer chain derived from a copolymer which is a polymerization product of a composition containing (i) 0.1% to 30% by weight of at least one reactive vinyl monomer and (ii) at least one non-reactive vinyl monomer selected from the group consisting of acrylamide, methacrylamide, N,N-dimethylacrylamide, N,N-dimethylmethacrylamide, N,N-dimethylaminopropylmethacrylamide, N,N-dimethylaminopropylacrylamide, and combinations thereof, wherein the at least one reactive vinyl monomer is amino-C2~C4 alkyl (meth)acrylate, C1~C3 alkylamino-C2~C4 alkyl (meth)acrylate, allylamine, vinylamine, amino-C2~C4 alkyl (meth)acrylamide, C1~C3 alkylamino-C2~C4 alkyl (meth)acrylamide, acrylic acid, C1~C4 alkyl acrylate A coated silicone hydrogel contact lens according to any one of Embodiments 1 to 11, wherein the epoxide-containing vinyl monomer is selected from the group consisting of glycidyl (meth)acrylamide, hydroxyethyl (meth)acrylamide glycidyl ether, 3-hydroxypropyl (meth)acrylamide glycidyl ether, 4-hydroxybutyl (meth)acrylamide glycidyl ether, glycidyl (meth)acrylate, hydroxyethyl (meth)acrylate glycidyl ether, 3-hydroxypropyl (meth)acrylate glycidyl ether, 4-hydroxybutyl (meth)acrylate glycidyl ether, and combinations thereof. 14. The crosslinked polymer material comprises a polymer chain derived from a copolymer which is a polymerization product of a composition containing (i) at least one reactive vinyl monomer in an amount of 0.1% to 30% by weight, and (ii) at least one non-reactive vinyl monomer selected from the group consisting of N,N-dimethylaminoethyl methacrylate, N,N-dimethylaminoethyl acrylate, C1-C4 alkoxy polyethylene glycol (meth)acrylate having a weight-average molecular weight of up to 1500 daltons, and combinations thereof, wherein the at least one reactive vinyl monomer is amino-C2-C4 alkyl (meth)acrylate, C1-C3 alkylamino-C2-C4 alkyl (meth)acrylate, allylamine, vinylamine, amino-C2-C4 alkyl (meth)acrylamide, C1-C3 alkylamino-C2-C4 alkyl (meth)acrylamide, acrylic acid, C1-C4 alkyl acrylate A coated silicone hydrogel contact lens according to any one of Embodiments 1 to 11, wherein the epoxide-containing vinyl monomer is selected from the group consisting of glycidyl (meth)acrylamide, hydroxyethyl (meth)acrylamide glycidyl ether, 3-hydroxypropyl (meth)acrylamide glycidyl ether, 4-hydroxybutyl (meth)acrylamide glycidyl ether, glycidyl (meth)acrylate, hydroxyethyl (meth)acrylate glycidyl ether, 3-hydroxypropyl (meth)acrylate glycidyl ether, 4-hydroxybutyl (meth)acrylate glycidyl ether, and combinations thereof. 15. The crosslinked polymer material comprises a polymer chain derived from a copolymer which is a polymerization product of a composition containing (i) 0.1% to 30% by weight of at least one reactive vinyl monomer and (ii) at least one non-reactive vinyl monomer selected from the group consisting of glycerol methacrylate, 3-acryloylamino-1-propanol, N-hydroxyethylacrylamide, N-[tris(hydroxymethyl)methyl]acrylamide, 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, allyl alcohol, vinyl alcohol, and combinations thereof, wherein the at least one reactive vinyl monomer is amino-C2~C4 alkyl (meth)acrylate, C1~C3 alkylamino-C2~C4 alkyl (meth)acrylate, allylamine, vinylamine, amino-C2~C4 alkyl (meth)acrylamide, C1~C3 alkylamino-C2~C4 alkyl (meth)acrylate A coated silicone hydrogel contact lens according to any one of Embodiments 1 to 11, wherein the epoxide-containing vinyl monomer is selected from the group consisting of amides, acrylic acids, C1-C4 alkylacrylic acids, (meth)acryloxy-C2-C6 alkanic acids, 2-acrylamidoglycolic acid, (meth)acrylamide-C2-C6 alkanic acids, epoxide-containing vinyl monomers, and combinations thereof, wherein the epoxide-containing vinyl monomer is selected from the group consisting of glycidyl (meth)acrylamide, hydroxyethyl (meth)acrylamide glycidyl ether, 3-hydroxypropyl (meth)acrylamide glycidyl ether, 4-hydroxybutyl (meth)acrylamide glycidyl ether, glycidyl (meth)acrylate, hydroxyethyl (meth)acrylate glycidyl ether, 3-hydroxypropyl (meth)acrylate glycidyl ether, 4-hydroxybutyl (meth)acrylate glycidyl ether, and combinations thereof. 16. The crosslinked polymer material comprises (i) 0.1% to 30% by weight of at least one reactive vinyl monomer and (ii) N-methyl-3-methylene-2-pyrrolidone, 1-ethyl-3-methylene-2-pyrrolidone, 1-methyl-5-methylene-2-pyrrolidone, 1-ethyl-5-methylene-2-pyrrolidone, 5-methyl-3-methylene-2-pyrrolidone, 5-ethyl-3-methylene-2-pyrrolidone, N-vinylpyrrolidone, N-vinylformamide, N-vinylacetamide, N-vinylisopropyl The polymer chain is derived from a copolymer which is a polymerization product of a composition containing at least one non-reactive vinyl monomer selected from the group consisting of pyramide, N-vinyl-N-methylacetamide, and combinations thereof, wherein the at least one reactive vinyl monomer is amino-C2~C4 alkyl(meth)acrylate, C1~C3 alkylamino-C2~C4 alkyl(meth)acrylate, allylamine, vinylamine, amino-C2~C4 alkyl(meth)acrylamide, C1~ A coated silicone hydrogel contact lens according to any one of Embodiments 1 to 11, wherein the epoxide-containing vinyl monomer is selected from the group consisting of C3 alkylamino-C2-C4 alkyl(meth)acrylamide, acrylic acid, C1-C4 alkylacrylic acid, (meth)acryloxy-C2-C6 alkanoic acid, 2-acrylamide glycolic acid, (meth)acrylamide-C2-C6 alkanoic acid, epoxide-containing vinyl monomer, and combinations thereof, wherein the epoxide-containing vinyl monomer is selected from the group consisting of glycidyl(meth)acrylamide, hydroxyethyl(meth)acrylamide glycidyl ether, 3-hydroxypropyl(meth)acrylamide glycidyl ether, 4-hydroxybutyl(meth)acrylamide glycidyl ether, glycidyl(meth)acrylate, hydroxyethyl(meth)acrylate glycidyl ether, 3-hydroxypropyl(meth)acrylate glycidyl ether, 4-hydroxybutyl(meth)acrylate glycidyl ether, and combinations thereof. 17. The crosslinked polymer material comprises a polymer chain derived from a copolymer which is a polymerization product of a composition containing (i) 0.1% to 30% by weight of at least one reactive vinyl monomer and (ii) at least one phosphorylcholine-containing vinyl monomer, wherein the at least one reactive vinyl monomer is amino-C2-C4 alkyl (meth)acrylate, C1-C3 alkylamino-C2-C4 alkyl (meth)acrylate, allylamine, vinylamine, amino-C2-C4 alkyl (meth)acrylamide, C1-C3 alkylamino-C2-C4 alkyl (meth)acrylamide, acrylic acid, C1-C4 alkylacrylic acid, (meth)acryloxy-C2-C6 alkanoic acid, 2-acrylamide glycolic acid, (meth)acrylamide-C2 A coated silicone hydrogel contact lens according to any one of Embodiments 1 to 11, wherein the epoxide-containing vinyl monomer is selected from the group consisting of C6 alkanic acid, epoxide-containing vinyl monomer, and combinations thereof, and the epoxide-containing vinyl monomer is selected from the group consisting of glycidyl (meth)acrylamide, hydroxyethyl (meth)acrylamide glycidyl ether, 3-hydroxypropyl (meth)acrylamide glycidyl ether, 4-hydroxybutyl (meth)acrylamide glycidyl ether, glycidyl (meth)acrylate, hydroxyethyl (meth)acrylate glycidyl ether, 3-hydroxypropyl (meth)acrylate glycidyl ether, 4-hydroxybutyl (meth)acrylate glycidyl ether, and combinations thereof. 18. The coated silicone hydrogel contact lens according to Embodiment 17, wherein the phosphorylcholine-containing vinyl monomer is (meth)acryloyloxyethyl phosphorylcholine. 19. A coated silicone hydrogel contact lens according to any one of Embodiments 1 to 11, wherein the crosslinked polymer material comprises poly(ethylene glycol) chains represented as PEG chains, which are derived from at least one selected from the group consisting of PEG-NH2; H2N-PEG-NH2; H2N-PEG-COOH; multi-armed PEG having one or more amino groups; PEG dendrimers having one or more amino groups; and combinations thereof. 20. A coated silicone hydrogel contact lens according to any one of Embodiments 1 to 11, wherein the crosslinked polymer material comprises poly(ethylene glycol) chains represented as PEG chains, which are derived from at least one selected from the group consisting of PEG-COOH; HOOC-PEG-COOH; multi-armed PEG having one or more carboxyl groups; PEG dendrimers having one or more carboxyl groups; and combinations thereof. 21. A coated silicone hydrogel contact lens according to any one of Embodiments 1 to 11, wherein the crosslinked polymer material comprises poly(ethylene glycol) chains represented as PEG chains, which are derived from at least one selected from the group consisting of PEG-SH; HS-PEG-SH; HOOC-PEG-SH; H2N-PEG-SH; multi-armed PEG having one or more thiol groups; PEG dendrimers having one or more thiol groups; and combinations thereof. 22. The crosslinked polymer material contains poly(ethylene glycol) chains represented as PEG chains, and these are [ka] A coated silicone hydrogel contact lens according to any one of embodiments 1 to 11, derived from at least one selected from the group consisting of a multi-armed PEG having one or more epoxide groups; a PEG dendrimer having one or more epoxide groups; and combinations thereof. 23. A coated silicone hydrogel contact lens according to any one of Embodiments 1 to 22, wherein a fully hydrated coated silicone hydrogel contact lens has a water content of about 10% to about 70%, an oxygen permeability of about 50 to 180 bars, and a water film breakdown time of at least 10 seconds. 24. A coated silicone hydrogel contact lens according to any one of Embodiments 1 to 23, wherein the grafted hydrophilic polymer is derived from at least one hydrophilic polymer having a 1,2- or 1,3-diol moiety. 25. A method for manufacturing coated silicone hydrogel contact lenses, (1) A step to obtain a pre-formed silicone hydrogel contact lens containing a bulk silicone hydrogel material, wherein the bulk silicone hydrogel material is (a) repeating units of at least one polysiloxane vinyl crosslinking agent and / or at least one siloxane-containing vinyl monomer, (b) Repeating units of at least one carboxyl-containing vinyl monomer in an amount of approximately 0.5% to approximately 3.5% by weight, (c) A repeating unit of at least one hydrophilic vinyl monomer, (d) Approximately 2.5% to approximately 12.5% ​​by weight of repeating units of at least one arylborono-containing vinyl monomer having an arylborono group, (e) at least one non-silicone vinyl crosslinking agent, which is optional but preferred, A process that includes; and (2) A step of forming a coated silicone hydrogel contact lens comprising a bulk silicone hydrogel material and a non-silicone hydrogel coating thereon, wherein the aqueous coating solution comprises (a) at least one hydrophilic polymer having 1,2- and / or 1,3-diol moieties, and (b) at least one water-soluble, heat-crosslinkable hydrophilic polymer material comprising branched or slightly crosslinked, heat-crosslinkable groups and optionally reactive functional groups, wherein the heat-crosslinkable groups are azetidinium groups and / or epoxide groups, and the reactive functional groups are primary amino groups, secondary amino groups, etc. The non-silicone hydrogel coating comprises a crosslinked polymer material and a grafted hydrophilic polymer, wherein the crosslinked hydrophilic polymer material is derived from the at least one water-soluble, thermally crosslinkable hydrophilic polymer material and is covalently bonded to the bulk silicone hydrogel material via a first bond formed between one carboxylic acid group and one azetidinium group or epoxide group, respectively, and the grafted hydrophilic polymer is derived from the at least one hydrophilic polymer and is covalently bonded to the bulk silicone hydrogel material via a second bond formed between one arylborono group and one 1,2- or 1,3-diol moiety; A method that includes this. 26. The method according to Embodiment 25, wherein the heating step is preferably carried out by autoclaving a pre-formed silicone hydrogel contact lens immersed in an aqueous coating solution in a sealed lens package at a temperature of about 115°C to about 125°C for about 20 to 90 minutes, and the aqueous coating solution further comprises one buffer and one or more isotonic agents to maintain the pH at about 6.8 to about 8.5. 27. The method according to Embodiment 25 or 26, wherein the aqueous solution has a pH of about 7.0 to about 8.2 and comprises about 0.01% to about 2% by weight (preferably about 0.05% to about 1.5% by weight, more preferably about 0.1% to about 1% by weight, and even more preferably about 0.2% to about 0.5% by weight) of the at least one water-soluble, heat-crosslinkable, hydrophilic polymer material. 28. The method according to any one of Embodiments 25 to 27, wherein the aqueous solution contains a mixture of monobasic dihydrogen phosphate and dibasic monohydrogen phosphate to maintain the pH of the aqueous solution, and the total concentration of monobasic dihydrogen phosphate and dibasic monohydrogen phosphate is at least 30 mM. 29. The coated silicone hydrogel contact lens according to Embodiment 24 or the method according to any one of Embodiments 25 to 28, wherein the at least one diol-containing hydrophilic polymer includes polyvinyl alcohol, poly(ethylene glycol)-graft-poly(vinyl alcohol), copolymer of vinyl alcohol and hydrophilic vinyl monomer, copolymer of glycerol (meth)acrylate and hydrophilic vinyl monomer, copolymer of 2,3,4-trihydroxybutyl (meth)acrylate and hydrophilic vinyl monomer, copolymer of 2,2-dihydroxypropyl (meth)acrylate and hydrophilic vinyl monomer, copolymer of 2,3-dihydroxybutyl (meth)acrylate and hydrophilic vinyl monomer, copolymer of glycerin-2 (meth)acrylate and hydrophilic vinyl monomer, copolymer of N-2,3-dihydroxypropyl (meth)acrylamide and hydrophilic vinyl monomer, copolymer of 3-allyloxy-1,2-propanediol and hydrophilic vinyl monomer, or a combination thereof. 30. The method according to any one of Embodiments 25 to 29, wherein the bulk silicone hydrogel material contains about 0.7% to about 3.5% by weight of repeating units of at least one carboxyl-containing vinyl monomer. 31. The method according to any one of Embodiments 25 to 29, wherein the bulk silicone hydrogel material contains about 0.9% to about 3.0% by weight of repeating units of at least one carboxyl-containing vinyl monomer. 32. The method according to any one of Embodiments 25 to 29, wherein the bulk silicone hydrogel material contains about 1.0% to about 2.8% by weight of repeating units of at least one carboxyl-containing vinyl monomer. 33. The method according to any one of Embodiments 25 to 32, wherein the at least one carboxyl-containing vinyl monomer is selected from the group consisting of acrylic acid, C1-C4 alkylacrylic acid, (meth)acryloxy-C1-C6 alkanoic acid, mono-2-[(meth)acryloxy]-ethyl succinate, 2-acrylamidoglycolic acid, (meth)acrylamido-C1-C6 alanoic acid, and combinations thereof. 34. The method according to any one of embodiments 25 to 33, wherein the bulk silicone hydrogel material contains about 2.5% to about 10% by weight of repeating units of at least one arylborono-containing vinyl monomer. 35. The method according to any one of Embodiments 25 to 33, wherein the bulk silicone hydrogel material contains about 3.0% to about 8.0% by weight of repeating units of at least one arylborono-containing vinyl monomer. 36. The method according to any one of embodiments 25 to 33, wherein the bulk silicone hydrogel material contains about 3.5% to about 7.0% by weight of repeating units of at least one arylborono-containing vinyl monomer. 37. The method according to any one of Embodiments 25 to 36, wherein the at least one arylborono group-containing vinyl monomer is represented by formula (I): [ka] (In the formula: R B This is a monovalent radical (preferably H, NO2, F, Cl, Br, CF3, CH2OH, or CH2NR) o R o ' and R o and R o ' is independently H or C1-C4 alkyl; Q is, [ka] It is a monovalent radical; L B This refers to direct bonding, C1-C4 alkylene divalent radicals, or [ka] It is a divalent radical, where Y1 is a CH(OH) or C1-C4 alkylene divalent radical, Y2 is a C1-C4 alkylene divalent radical, and p2 is an integer from 0 to 3. o (H is H or C1-C4 alkyl). 38. The above-mentioned at least one arylborono-containing vinyl monomer is 3-vinylphenylboronic acid, 4-vinylphenylboronic acid, 3-(meth)acrylamidephenylboronic acid, 4-(meth)acrylamidephenylboronic acid, 4-(1,6-dioxo-2,5-diaza-7-oxamyl)phenylboronic acid, 2-dimethylaminomethyl-5-vinylphenylboronic acid, 4-(N-allylsulfamoyl)phenylboronic acid, 4-(3-butenylsulfonyl)phenylboronic acid, 3-(meth)acrylamide-5-nitrophenylboronic acid, 4-(meth)acrylamide-5-nitrophenylboronic acid, 4-(meth)acrylamide-3-nitrophenylboronic acid, 3-[(meth)acrylamide-C2~C5-alkylaminocarbonyl]-5-nitrophenylboronic acid, 3-[(meth)acryloyloxy-C2~C5 The method according to any one of Embodiments 25 to 36, comprising -alkylaminocarbonyl]-5-nitrophenylboronic acid, 3-(meth)acrylamide-6-hydroxymethylphenylboronic acid, 3-(meth)acrylamide-6-dimethylaminomethylphenylboronic acid, 4-(meth)acrylamide-6-hydroxymethylphenylboronic acid, 4-(meth)acrylamide-6-dimethylaminomethylphenylboronic acid, reaction products of an amino-containing phenylboronic acid derivative with a (meth)acrylic acid halide or epoxide-containing vinyl monomer or carboxy-containing vinyl monomer in the presence of carbodiimide and N-hydroxysuccinimide, reaction products of a carboxy-containing phenylboronic acid derivative with an amino group-containing vinyl monomer in the presence of carbodiimide and N-hydroxysuccinimide, or a combination thereof. 39. Amino-containing phenylboronic acid derivatives include 3-carboxyphenylboronic acid, 4-carboxyphenylboronic acid, 3-boronophenylacetic acid, 4-boronophenylacetic acid, 2-(4-boronophenyl)-2-methylpropanoic acid, 3-(4-boronophenyl)propanoic acid, 3-(3-boronophenyl)propanoic acid, 5-(3-boronophenyl)pentanoic acid, 5-(4-boronophenyl)pentanoic acid, 4-(2-carboxyethyl)-3-nitrophenylboronic acid, 3-carboxy-5-nitrophenylboronic acid, 4-carboxy-30-chlorophenylboronic acid, and 3-carboxy-4-fluorophenylboronic acid (bornic The method according to Embodiment 38, wherein the carboxy-containing phenylboronic acid derivative is 3-aminophenylboronic acid, 4-aminophenylboronic acid, 4-amino-3-nitrophenylboronic acid, 3-amino-6-hydroxymethylphenylboronic acid, 3-amino-6-(dimethylaminomethyl)phenylboronic acid, 4-amino-2-hydroxymethylphenylboronic acid, 4-amino-2-(dimethylaminomethyl)phenylboronic acid, 3-amino-4-fluorophenylboronic acid, 4-(aminomethyl)-5-nitrophenylboronic acid, 3-(aminomethyl)-phenylboronic acid, 3-amino-5-nitrophenylboronic acid, or 3-amino-3-(4-boronophenyl)propanoic acid. 40. The method according to any one of Embodiments 25 to 39, wherein the at least one water-soluble, heat-crosslinkable, hydrophilic polymer material comprises an epoxide group. 41. The at least one water-soluble, heat-crosslinkable, hydrophilic polymer material may be: (i) one or more multi-arm polyethylene glycols, each having a terminal epoxide group; (ii) a partial reaction product of a multi-arm polyethylene glycol having a terminal epoxide group and one or more polyethylene glycols, each having a terminal functional group selected from the group consisting of a primary amine group, a secondary amine group, a carboxyl group, a thiol group, and combinations thereof; (iii) a partial reaction product of a multi-arm polyethylene having a terminal epoxide group and a hydrophilicity enhancer having at least one reactive functional group selected from the group consisting of an amino group, a carboxyl group, a thiol group, and combinations thereof; (iv) an epoxide-containing vinyl monomer and one or more hydrophilic vinyl monomers (v) A partial reaction product of a copolymer with a hydrophilicity enhancer having at least one reactive functional group selected from the group consisting of an amino group, a carboxyl group, a thiol group, and combinations thereof; (v) a copolymer of an epoxide-containing vinyl monomer, a hydrophilic vinyl monomer, and a C1-C4 alkoxy poly(ethylene glycol) ethyl (meth)acrylate having a number average molecular weight of up to 2500 daltons, a polyethylene glycol) ethyl (meth)acrylate having a number average molecular weight of up to 2500 daltons, a C1-C4 alkoxy poly(ethylene glycol) ethyl (meth)acrylamide, or a poly(ethylene glycol) ethyl (meth)acrylamide having a number average molecular weight of up to 2500 daltons; or (vi) the method according to Embodiment 40, comprising a combination thereof. 42. The method according to any one of Embodiments 25 to 39, wherein the at least one water-soluble, heat-crosslinkable, hydrophilic polymer material contains an azetidinium group. 43. The method according to Embodiment 42, wherein the at least one water-soluble, thermally crosslinkable, hydrophilic polymer material is a three-dimensional network and thermally crosslinkable groups in or connected to the network. 44. The method according to Embodiment 42, wherein the at least one water-soluble, heat-crosslinkable, hydrophilic polymer material is one or more multi-arm polyethylene glycols, each having a terminal epoxide group; a mixture of a multi-arm polyethylene glycol having a terminal epoxide group and one or more polyethylene glycols, each having a terminal functional group selected from the group consisting of a primary amine group, a secondary amine group, a carboxyl group, a thiol group, and combinations thereof; a partial reaction product of a multi-arm polyethylene having a terminal epoxide group and a hydrophilicity enhancer having at least one reactive functional group selected from the group consisting of an amino group, a carboxyl group, and a thiol group; or a combination thereof. 45. The method according to Embodiment 42, wherein the at least one water-soluble, heat-crosslinkable hydrophilic polymer material contains an azetidinium group, and is a partial reaction product of an azetidinium-containing polymer and a hydrophilicity enhancer having at least one reactive functional group selected from the group consisting of primary amine groups, secondary amine groups, carboxyl groups, thiol groups, and combinations thereof. 46. ​​The method according to Embodiment 45, wherein the azetidinium-containing polymer is a poly(2-oxazoline-co-ethyleneimine)-epichlorohydrin copolymer, a polyamidoamine-epichlorohydrin, a copolymer of an azetidinium-containing vinyl monomer and one or more hydrophilic vinyl monomers, or a combination thereof. 47. The method according to Embodiment 45 or 46, wherein the hydrophilicity enhancer is a primary amino, secondary amino, carboxyl, or thiol-containing monosaccharide; a primary amino, secondary amino, carboxyl, or thiol-containing disaccharide; a primary amino, secondary amino, carboxyl, or thiol-containing oligosaccharide; or a combination thereof. 48. The method according to Embodiment 45 or 46, wherein the hydrophilicity enhancer is a hydrophilic polymer having one or more primary or secondary amino groups, one or more carboxyl groups, one or more thiol groups, or a combination thereof. 49. The method according to Embodiment 48, wherein the hydrophilicity enhancer is a polysaccharide having a primary amine group, a secondary amine group, a carboxyl group, or a combination thereof. 50. Hydrophilicity enhancers, Poly(ethylene glycol) having one single functional group of -NH2, -SH, or -COOH; Poly(ethylene glycol) having two terminal functional groups selected from the group consisting of -NH2, -COOH, -SH, and combinations thereof; Multi-armed poly(ethylene glycol) having one or more functional groups selected from the group consisting of -NH2, -COOH, -SH, and combinations thereof; Monoamino, monocarboxyl, diamino, or dicarboxyl-terminated homopolymers or copolymers of nonreactive hydrophilic vinyl monomers; A copolymer which is a polymerization product of a composition comprising (1) about 0.1% to about 30% (preferably about 0.5% to about 20%, more preferably about 1% to about 15%) of a reactive vinyl monomer, and (2) at least one non-reactive hydrophilic vinyl monomer, The at least one reactive vinyl monomer is a vinyl monomer having a functional group selected from the group consisting of a carboxyl group, a primary amine group, and a secondary amine group. A copolymer in which the non-reactive hydrophilic monomer is a hydrophilic vinyl monomer that does not contain any carboxyl group, primary amine group, secondary amine group, epoxide group, isocyanate group, azulactone group, or aziridine group; The method according to Embodiment 48. 51. The method according to Embodiment 50, wherein the reactive vinyl monomer is amino-C2~C4 alkyl(meth)acrylate, C1~C3 alkylamino-C2~C4 alkyl(meth)acrylate, allylamine, vinylamine, amino-C2~C4 alkyl(meth)acrylamide, C1~C3 alkylamino-C2~C4 alkyl(meth)acrylamide, acrylic acid, C1~C4 alkylacrylic acid, (meth)acryloxy-C2~C6 alkanoic acid, 2-acrylamidoglycolic acid, (meth)acrylamide-C2~C6 alkanoic acid, and combinations thereof. 52. Non-reactive hydrophilic vinyl monomers include (meth)acryloyloxyethyl phosphorylcholine, (meth)acryloyloxypropyl phosphorylcholine, 4-((meth)acryloyloxy)butyl-2'-(trimethylammonio)ethyl phosphate, 2-[(meth)acryloylamino]ethyl-2'-(trimethylammonio)ethyl phosphate, 3-[(meth)acryloylamino]propyl-2'-(trimethylammonio)ethyl phosphate, 4-[(meth)acryloylamino]butyl-2'-(trimethylammonio)ethyl phosphate, (meth)acrylamide, dimethyl(meth)acrylamide, N-2-hydroxyethyl(meth)acrylamide, N,N-bis(hydroxyethyl)(meth)acrylamide, N-2,3-Dihydroxypropyl(meth)acrylamide, N-Tris(hydroxymethyl)methyl(meth)acrylamide, 2-Hydroxyethyl(meth)acrylate, Glycerol methacrylate (GMA), Tetra(ethylene glycol)(meth)acrylate, Poly(ethylene glycol)ethyl(meth)acrylamide with a number average molecular weight of up to 1500, Poly(ethylene glycol)(meth)acrylate with a number average molecular weight of up to 1500, N-Vinylpyrrolidone, N-Vinyl-N-methylacetamide, N-Vinylformamide, N-Vinylacetamide, 1-Methyl-3-methylene-2-pyrrolidone, 1-Methyl-5-methylene-2-pyrrolidone, 5-Methyl-3-methylene-2-pyrrolidone, Tetra(ethylene glycol)methyl ether(meth)acrylate The method according to Embodiment 50 or 51, selected from the group consisting of methoxypoly(ethylene glycol)ethyl(meth)acrylamide having a number average molecular weight of up to 1500, C1-C4-alkoxy polyethylene glycol (meth)acrylate having a weight average molecular weight of up to 1500, tetra(ethylene glycol) monovinyl ether, poly(ethylene glycol) monovinyl ether, tetra(ethylene glycol) methyl vinyl ether, poly(ethylene glycol) methyl vinyl ether, tetra(ethylene glycol) monoallyl ether, poly(ethylene glycol) monoallyl ether, tetra(ethylene glycol) methyl allyl ether, poly(ethylene glycol) methyl allyl ether, vinyl alcohol, allyl alcohol, and combinations thereof.

[0167] The above disclosure will enable those skilled in the art to implement the invention. Various modifications, changes, and combinations can be implemented in the various embodiments described herein. References to the following examples are proposed to enable the reader to better understand the particular embodiments and their advantages. The specification and examples are intended to be considered illustrative. [Examples]

[0168] Example 1 Measurement of oxygen permeability coefficient Unless otherwise specified, the oxygen permeability coefficient (Dk / t) of the lens and lens material, and the intrinsic (or edge-corrected) oxygen permeability (Dk i or Dk c ) shall be measured according to the procedure described in ISO 18369-4.

[0169] Water film breakdown time (WBUT) test The surface hydrophilicity of a lens is evaluated by measuring the time it takes for the water film on the lens surface to begin to break, using an interfacial dewetting and drainage optical platform (iDDroP), as described in the paper "Influence of Lipid Coatings on Surface Wettability Characteristics of Silicone Hydrogels" by Bhamla et al., published in Langmuir. 2015, 31:3820-3828 (2015(31):3820-3828). During the IDDroP test, the lens is placed on a stage and immersed in PBS. A small surface of the lens is then exposed to air. An electric linear stage and motion controller are used to expose the contact lens to a specified depth. Videos of water film breakdown are recorded to evaluate the water film breakdown time and pattern.

[0170] equilibrium moisture content The equilibrium water content (EWC) of a contact lens (i.e., the water content of a contact lens in a fully hydrated state) is determined according to the procedure described in Example 1 of U.S. Patent Application Publication No. 20210181379A1.

[0171] modulus of elasticity The elastic modulus of the contact lens is determined according to the procedure described in Example 1 of U.S. Patent Application Publication No. 20210181379A1.

[0172] Measurement of Water Contact Angle (WCA). The Water Contact Angle (WCA) is measured using the droplet method with pure water (Fluka, surface tension 72.5 mN / m at 20°C) on a DSA 10 droplet formation analysis system from Kruess GmbH, Germany. For the purpose of measurement, the contact lens is removed from the storage solution using tweezers and excess storage solution is removed by gentle shaking. The contact lens is placed on the male part of the lens mold and gently wiped with a dry, clean cloth. A water droplet (approximately 1 μl) is then placed on the apex of the lens, and the change in the contact angle of this droplet over time (WCA(t), circle fitting mode) is monitored. The WCA is calculated by extrapolating the graph WCA(t) to t=0.

[0173] Lubricity evaluation The lubricity of contact lenses is evaluated using a tactile lubricity test, which qualitatively characterizes the slipperiness of the lens surface on a friction rating scale from 0 to 4. A higher friction rating indicates lower slipperiness (i.e., lower lubricity). In this test, the lens is touched between the thumb and index finger, and a qualitative rating from 0 to 4 is assigned based on the level of friction perceived by the tester. The given rating is compared to five commercially available lenses corresponding to five levels of lubricity, which serve as a benchmark for this test.

[0174] The levels and standards are as follows: DAILIES® TOTAL1® lens (Alcon) is the standard for grade 0 on the scale, and ACUVUE® OASYS TM Johnson & Johnson lenses meet the Grade 1 standard, Bausch & Lamb ULTRA® lenses meet the Grade 2 standard, Alcon DAILIES® Aqua Comfort Plus® lenses meet the Grade 3 standard, and AIR OPTIX® Aqua lenses meet the Grade 4 standard.

[0175] Place the samples in PBS for at least two rinses of 30 minutes each, and then transfer them to fresh PBS before evaluation. Before evaluation, wash hands with soap solution, rinse thoroughly with deionized water, and then dry with a KimWipe (registered trademark) towel. When evaluating the lubricity of the front surface, place the lens on the finger with the back surface facing the index finger, rub the front surface with the thumb, and confirm the feel of the slipperiness (i.e., lubricity) of the front surface. When evaluating the lubricity of the back surface, first invert the lens, then place the inverted front surface on the finger with the front surface facing the index finger, and then rub the inverted back surface with the thumb to confirm the feel of the smoothness (or lubricity) of the back surface.

[0176] Each sample is assigned a friction grade relative to the above-described reference lens. The value of the friction grade is obtained by averaging the results of at least two friction grades of the contact lens by two or more people and / or by averaging the friction grades of two or more contact lenses (from the same batch of lens production) by one person.

[0177] The finger lubricity (i.e., friction grade) of the contact lens can be determined directly out-of-pack (OOP), but can also be determined after immersion in PBS for ≥ 30 minutes according to the procedure described above.

[0178] Coating Integrity Test The coating integrity of coated SiHy contact lenses can be evaluated by the following Sudan Black staining test. Each SiHy contact lens with a coating is immersed in a Sudan Black dye solution (Sudan Black in a mixture of approximately 80% mineral oil and approximately 20% vitamin E oil). Sudan Black dye is hydrophobic and tends to be readily adsorbed by hydrophobic materials, on hydrophobic lens surfaces, or to hydrophobic spots on partially coated surfaces of hydrophobic lenses (e.g., silicone hydrogel contact lenses). If the coating on a hydrophobic lens is perfect, no staining spots should be observed on or inside the lens. All lenses under test are completely hydrated. Fine lines visible on the lens surface may indicate the presence of cracks in the cross-linked coating.

[0179] The image of a contact lens dyed with Sudan Black is recorded with a digital camera and then analyzed by a computer to determine the percentage (%) of the dyed area of a coated SiHy contact lens (SBQ) that is directly taken out of the package ("OOP") or taken out of the package and subjected to an aqueous extraction process ("2xcycling"). Here, "2xcycling" consists of: (1) taking out one SiHy contact lens that is immediately available from a sealed package, wiping off the moisture, and immersing the immediately available SiHy contact lens, while stirring, in 1.0 mL of fresh phosphate buffered saline (PBS) (pH 7.2 ± 0.2 at 25°C, containing approximately 0.077 wt% NaH2PO4·H2O, approximately 0.31 wt% Na2HPO4·2H2O, and approximately 0.77 wt% NaCl) as the extraction medium in a vial at 35°C for 24 hours, which is the first cycle of a simulated 1-day wear extraction; and (2) removing all the PBS used in the previous cycle with a pipette, then adding 1.0 mL of fresh PBS as the extraction medium to the vial, and immersing the immediately available SiHy contact lens, while stirring, in the freshly added 1 mL of PBS as the extraction medium at 35°C for 24 hours, respectively, which are the 2nd to 7th cycles of a simulated 1-day wear extraction. The integrity of the coating is (1 - SBQ) measured immediately after taking it out of the package.

[0180] As a control, SiHy contact lenses without a coating are also tested. Since these SiHy contact lenses in the control experiment do not have a hydrogel coating on them, their surfaces are completely dyed with Sudan Black.

[0181] Chemical substance In the following examples, the following abbreviations are used: HEMA represents hydroxyethyl methacrylate; EOEMA represents ethoxyethyl methacrylate; MAA represents methacrylic acid; NaMAA represents the sodium salt of methacrylic acid; AA represents acrylic acid; TEGDMA represents tri(ethylene glycol) dimethacrylate; APBA represents 3-acrylamidophenylboronic acid (pKa approximately 8.2); VPBA represents 4-vinylphenylboronic acid (pKa approximately 8.8); Vazo67 represents 2,2'-azodi(2-methyl-butyronitrile); Nobloc is 2-[3-(2H-benzotriazole-2-yl)-5-hydroxyphenyl]ethyl methacrylate; RB247 is Reactive Blue 247; PBS represents phosphate-buffered saline with a pH of 7.2 ± 0.2 at 25°C and containing approximately 0.044 wt% NaH2PO4·H2O, approximately 0.388 wt% Na2HPO4·2H2O, and approximately 0.79 wt% NaCl; wt% represents weight percentage; PG represents propylene glycol; EDTA represents ethylenediaminetetraacetic acid; poly(AAm-co-AA) represents poly(AAm-co-AA)(90 / 10) partial sodium salt (Mw approximately 200,000, from Polysciences, Inc.); PAE represents polyamidoamine-epichlorohydrin; "PEG-PDMS" macromer represents dimethacryloyloxypropyl-terminated polysiloxane of formula (A) (Mw approximately 13 kg / mol, x = approximately 85, y = approximately 8, z = approximately 12). [ka]

[0182] Example 2 Phosphate-buffered saline (PBS) Phosphate-buffered saline is prepared by dissolving NaH2PO4·H2O, Na2HPO4·2H2O, and NaCl in a predetermined amount of purified water (distilled or deionized) to have the following composition: approximately 0.044 w / w% NaH2PO4·H2O, approximately 0.388 w / w / % Na2HPO4·2H2O, and approximately 0.79 w / w% NaCl.

[0183] Preparation of in-package coated saline solution Purchase Kymene or PAE solutions with different solid content from Solenis as aqueous solutions and use them as received.

[0184] Polyvinyl alcohol (PVA) (approximately 80,000 Daltons Mw) will be purchased from Sigma Aldrich and used in the condition it was received.

[0185] Poly(ethylene glycol)-grafted-poly(vinyl alcohol) polymer ("PEG-PVA") (MW 45,000 Daltons) is purchased from BASF and used as received.

[0186] Poly(N-vinylpyrrolidone-co-vinyl alcohol) copolymer ("PVP-PVA") is prepared by hydrolysis of poly(N-vinylpyrrolidone-co-vinyl acetate) copolymer ("PVP-PVAc") (MW 50,000 Daltons) purchased from Sigma Aldrich.

[0187] IPC physiological saline (IPC-1) is prepared by dissolving approximately 0.07 wt% poly(AAm-co-AA), approximately 0.05 wt% PAE, 0.776 wt% Na2HPO4·2H2O, 0.044 wt% NaH2PO4·H2O, 0.160 wt% NaCl, and 10 ppm EDTA in water.

[0188] IPC physiological saline (IPC-2) is prepared by dissolving approximately 0.07 wt% poly(AAm-co-AA), approximately 0.05 wt% PAE, 0.2 wt% PVA, 0.776 wt% Na2HPO4·2H2O, 0.044 wt% NaH2PO4·H2O, 0.160 wt% NaCl, and 10 ppm EDTA in water.

[0189] IPC physiological saline (IPC-3) is prepared by dissolving approximately 0.07 wt% poly(AAm-co-AA), approximately 0.05 wt% PAE, 0.05 wt% PVA, 0.776 wt% Na2HPO4·2H2O, 0.044 wt% NaH2PO4·H2O, 0.160 wt% NaCl, and 10 ppm EDTA in water.

[0190] IPC physiological saline (IPC-4) is prepared by dissolving approximately 0.07 wt% poly(AAm-co-AA), approximately 0.05 wt% PAE, 0.1 wt% PEG-PVA, 0.776 wt% Na2HPO4·2H2O, 0.044 wt% NaH2PO4·H2O, 0.160 wt% NaCl, and 10 ppm EDTA in water.

[0191] IPC physiological saline (IPC-5) is prepared by dissolving approximately 0.07 wt% poly(AAm-co-AA), approximately 0.05 wt% PAE, 0.1 wt% PEG-PVA, 0.776 wt% Na2HPO4·2H2O, 0.044 wt% NaH2PO4·H2O, 0.160 wt% NaCl, and 10 ppm EDTA in water.

[0192] Preparation of polymerizable compositions Polymerizable compositions (i.e., SiHy lens formulations) are prepared by placing all components in their target amounts into a clean bottle and mixing them with a stirring bar at 600 rpm for 30 minutes at room temperature. After all solids have dissolved, the formulation is filtered using a 2.7 μm glass microfiber (GMF) filter. Eight SiHy lens formulations having the compositions reported in Table 1 are prepared.

[0193] [Table 1]

[0194] Fabrication of coated SiHy contact lenses Purge the lens formulation prepared above with nitrogen at room temperature for 30 - 35 minutes. Place the N2 - purged lens formulation into a polypropylene mold and thermally cure it in an oven under nitrogen under the following curing conditions: Heat from room temperature to 55°C at a heating rate of about 7°C / min; Hold at 55°C for about 30 minutes; Heat from 55°C to 100°C at a heating rate of about 7°C / min; Hold at 100°C for about 60 minutes. Open the mold and remove the formed lens from the mold.

[0195] Then, hydrate the lens in the IPC physiological saline prepared above for a time longer than 120 minutes, inspect it, and blister - pack it in IPC physiological saline for sterilization (autoclaving at 121°C for 45 minutes).

[0196] Example 3 Follow the procedure described in Example 2 to fabricate a coated SiHy contact lens. Two SiHy lens formulations (SiHy - 1 and SiHy - 2) prepared in Example 2 and two IPC physiological saline solutions (IPC - 1 and IPC - 2) prepared in Example 2 are used in this example.

[0197] Table 2 shows the results of the characteristic evaluation of a coated SiHy contact lens containing a bulk silicone hydrogel material obtained from the SiHy - 1 lens formulation or the SiHy - 2 lens formulation and a non - silicone hydrogel coating obtained from IPC - 1 physiological saline (as a control) or IPC - 2 physiological saline.

[0198]

Table 2

[0199] It has been observed that coating integrity improves when IPC saline (salie) contains a hydrophilic polymer (i.e., PVA) having 1,2- or 1,3-diol moieties (IPC-2 vs. IPC-1). This suggests that a non-silicone hydrogel coating ("hybrid coating") is formed on the pre-formed SiHy contact lens. This non-silicone hydrogel coating is covalently bonded to the bulk SiHy material and consists of a crosslinked polymer material and PVA distributed therein.

[0200] Example 4 The coated SiHy contact lenses are prepared according to the procedure described in Example 2. The two SiHy lens formulations (SiHy-3 and SiHy-4) prepared in Example 2 and the four IPC salines (IPC-1, IPC-3, IPC-4, and IPC-5) prepared in Example 2 are used in this example.

[0201] Table 3 shows the characterization results of coated SiHy contact lenses containing bulk silicone hydrogel material obtained from SiHy-3 lens formulations and non-silicone hydrogel coatings obtained from IPC-1 saline (control), IPC-3, IPC-4, or IPC-5 saline.

[0202] [Table 3]

[0203] Table 4 shows the characterization results of coated SiHy contact lenses containing bulk silicone hydrogel material obtained from SiHy-3 lens formulations and non-silicone hydrogel coatings obtained from IPC-1 saline (control), IPC-3, IPC-4, or IPC-5 saline.

[0204] [Table 4]

[0205] When IPC saline (salie) contains a hydrophilic polymer having 1,2- or 1,3-diol moieties (i.e., PVA, PEG-PVA, or PVP-PVA), the integrity of the coating is improved (compared to IPC-1). This suggests that a non-silicone hydrogel coating ("hybrid coating") is formed on the pre-formed SiHy contact lens. This non-silicone hydrogel coating is covalently bonded to the bulk SiHy material and consists of a crosslinked polymer material and PVA distributed therein.

[0206] Example 5 A coated SiHy contact lens is prepared according to the procedure described in Example 2. The two SiHy lens formulations (SiHy-5 and SiHy-6) prepared in Example 2 and the two IPC salines (IPC-1 and IPC-3) prepared in Example 2 are used in this example.

[0207] Table 5 shows the characterization results of coated SiHy contact lenses, which include bulk silicone hydrogel material obtained from SiHy-5 or SiHy-6 lens formulations and a non-silicone hydrogel coating obtained from IPC-1 physiological saline (control) or IPC-3 physiological saline.

[0208] [Table 5]

[0209] It has been observed that coating integrity improves when IPC saline contains a hydrophilic polymer (i.e., PVA) having 1,2- or 1,3-diol moieties (IPC-3 vs. IPC-1). This suggests that a non-silicone hydrogel coating ("hybrid coating") is formed on the pre-formed SiHy contact lens. This non-silicone hydrogel coating is covalently bonded to the bulk SiHy material and consists of a crosslinked polymer material and PVA distributed within it.

[0210] Example 6 A coated SiHy contact lens is prepared according to the procedure described in Example 2. The two SiHy lens formulations (SiHy-7 and SiHy-8) prepared in Example 2 and the two IPC salines (IPC-1 and IPC-3) prepared in Example 2 are used in this example.

[0211] Table 6 shows the characterization results of coated SiHy contact lenses, which include bulk silicone hydrogel material obtained from SiHy-7 or SiHy-8 lens formulations and a non-silicone hydrogel coating obtained from IPC-1 physiological saline (control) or IPC-3 physiological saline.

[0212] [Table 6]

[0213] It has been observed that coating integrity improves when IPC saline (salie) contains a hydrophilic polymer (such as PVA) having 1,2- or 1,3-diol moieties (IPC-3 vs. IPC-1). This suggests that a non-silicone hydrogel coating ("hybrid coating") is formed on the pre-formed SiHy contact lens. This non-silicone hydrogel coating is covalently bonded to the bulk SiHy material and consists of a crosslinked polymer material and PVA distributed within it.

[0214] All publications, patents, and patent application publications cited herein in this application are incorporated herein by reference in their entirety.

Claims

1. A coated silicone hydrogel contact lens comprising a bulk silicone hydrogel material and a non-silicone hydrogel coating thereon, The bulk silicone hydrogel material comprises (a) repeating units of at least one polysiloxane vinyl crosslinking agent and / or at least one siloxane-containing vinyl monomer; (b) repeating units of at least one carboxyl-containing vinyl monomer relative to the total amount of all polymerizable components; (c) repeating units of at least one hydrophilic vinyl monomer; (d) repeating units of at least one arylborono-containing vinyl monomer having an arylborono group; and (e) repeating units of at least one non-silicone vinyl crosslinking agent, which is optional but preferred. The non-silicone hydrogel coating comprises a crosslinked polymer material and a grafted hydrophilic polymer distributed within the crosslinked polymer material but not covalently bonded, wherein the crosslinked hydrophilic polymer material is covalently bonded to the bulk silicone hydrogel material via a first bond formed between one carboxylic acid group and one azetidinium group or epoxide group, respectively, and the grafted hydrophilic polymer comprises 1,2- and / or 1,3-diol moieties and is covalently bonded to the bulk silicone hydrogel material via a second bond formed between one arylborono group and one 1,2- or 1,3-diol moiety, respectively. A coated silicone hydrogel contact lens in a fully hydrated state exhibits a coating integrity of approximately 90% or more and a friction grade of approximately 2.0 or less.

2. The above at least one carboxyl-containing vinyl monomer is acrylic acid, C １ ~C ４ Alkyl acrylic acid, (meth)acryloxy-C １ ~C ６ Alkano acid, mono-2-[(meth)acryloxy]-ethyl succinate, 2-acrylamidoglycolic acid, (meth)acrylamido-C １ ~C ６ A coated silicone hydrogel contact lens according to claim 1, selected from the group consisting of alanic acid and combinations thereof.

3. A coated silicone hydrogel contact lens according to claim 1 or 2, wherein the at least one arylborono-containing vinyl monomer is represented by formula (I): 【Chemistry 1】 (where: R Ｂ is H, NO ２ , F, Cl, Br, CF ３ , CH ２ OH, or CH ２ NR ｏ R ｏ ’, and R ｏ and R ｏ ’ are independently of each other H or C １ ~C ４ alkyl; Q is 【Chemistry 2】 It is a monovalent radical; L Ｂ Direct bond, C １ ~C ４ Alkylene divalent radical, 【Transformation 3】 It is a divalent radical of Y １ is CH(OH) or C １ ~C ４ It is an alkylene divalent radical, Y ２ is C １ ~C ４ It is an alkylene divalent radical, and p2 is an integer from 0 to 3, R ｏ is H or C １ ~C ４ (It is alkyl.)

4. The aforementioned at least one arylborono-containing vinyl monomer is 3-vinylphenylboronic acid, 4-vinylphenylboronic acid, 3-(meth)acrylamidephenylboronic acid, 4-(meth)acrylamidephenylboronic acid, 4-(1,6-dioxo-2,5-diaza-7-oxamyl)phenylboronic acid, 2-dimethylaminomethyl-5-vinylphenylboronic acid, 4-(N-allylsulfamoyl)phenylboronic acid, 4-(3-butenylsulfonyl)phenylboronic acid, 3-(meth)acrylamide-5-nitrophenylboronic acid, 4-(meth)acrylamide-5-nitrophenylboronic acid, 4-(meth)acrylamide-3-nitrophenylboronic acid, 3-[(meth)acrylamide-C ２ ~C ５ -Alkylaminocarbonyl]-5-nitrophenylboronic acid, 3-[(meth)acryloyloxy-C ２ ~C ５ A coated silicone hydrogel contact lens according to any one of claims 1 to 3, comprising: -alkylaminocarbonyl-5-nitrophenylboronic acid, 3-(meth)acrylamide-6-hydroxymethylphenylboronic acid, 3-(meth)acrylamide-6-dimethylaminomethylphenylboronic acid, 4-(meth)acrylamide-6-hydroxymethylphenylboronic acid, 4-(meth)acrylamide-6-dimethylaminomethylphenylboronic acid, reaction product of an amino-containing phenylboronic acid derivative with a (meth)acrylic acid halide or epoxide-containing vinyl monomer or carboxy-containing vinyl monomer in the presence of carbodiimide and N-hydroxysuccinimide, reaction product of a carboxy-containing phenylboronic acid derivative with an amino-containing vinyl monomer in the presence of carbodiimide and N-hydroxysuccinimide, or a combination thereof.

5. The amino acid-containing phenylboronic acid derivative is 3-carboxyphenylboronic acid, 4-carboxyphenylboronic acid, 3-boronophenylacetic acid, 4-boronophenylacetic acid, 2-(4-boronophenyl)-2-methylpropanoic acid, 3-(4-boronophenyl)propanoic acid, 3-(3-boronophenyl)propanoic acid, 5-(3-boronophenyl)pentanoic acid, 5-(4-boronophenyl)pentanoic acid, 4-(2-carboxyethyl)-3-nitrophenylboronic acid, 3-carboxy-5-nitrophenylboronic acid, 4-carboxy-3-chlorophenylboronic acid, 3-carboxy-4-fluorophenylboronic acid, 3-(3-carboxypropionylamino)phenylboronic acid, or 3-amino-3-(4-boronophenyl)propanoic acid. The coated silicone hydrogel contact lens according to claim 4, wherein the carboxy-containing phenylboronic acid derivative is 3-aminophenylboronic acid, 4-aminophenylboronic acid, 4-amino-3-nitrophenylboronic acid, 3-amino-6-hydroxymethylphenylboronic acid, 3-amino-6-(dimethylaminomethyl)phenylboronic acid, 4-amino-2-hydroxymethylphenylboronic acid, 4-amino-2-(dimethylaminomethyl)phenylboronic acid, 3-amino-4-fluorophenylboronic acid, 4-(aminomethyl)-5-nitrophenylboronic acid, 3-(aminomethyl)-phenylboronic acid, 3-amino-5-nitrophenylboronic acid, or 3-amino-3-(4-boronophenyl)propanoic acid.

6. The crosslinked polymer material comprises (1) a poly(ethylene glycol) chain called a PEG chain, (2) a polymer chain derived from a copolymer, or (3) a combination thereof, wherein the copolymer comprises (i) at least one reactive vinyl monomer containing at least one reactive functional group selected from the group consisting of carboxylic acids, primary amino groups, secondary amino groups, epoxide groups, and combinations thereof, in an amount of 60% by weight or less, and (ii) acrylamide, methacrylamide, N,N-dimethylacrylamide, N,N-dimethylmethacrylamide, N-vinylpyrrolidone, N,N-dimethylaminoethyl methacrylate, N,N-dimethylaminoethyl acrylate, N,N-dimethylaminopropyl methacrylate Luamide, N,N-dimethylaminopropyl acrylamide, glycerol methacrylate, 3-acryloylamino-1-propanol, N-hydroxyethyl acrylamide, N-[tris(hydroxymethyl)methyl]acrylamide, N-methyl-3-methylene-2-pyrrolidone, 1-ethyl-3-methylene-2-pyrrolidone, 1-methyl-5-methylene-2-pyrrolidone, 1-ethyl-5-methylene-2-pyrrolidone, 5-methyl-3-methylene-2-pyrrolidone, 5-ethyl-3-methylene-2-pyrrolidone, 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, phosphorylcholine-containing vinyl monomer, C having a weight-average molecular weight of up to 1500 daltons １ ~C ４ - Alkoxy poly(ethylene glycol) ethyl (meth)acrylate, with a weight-average molecular weight of up to 1500 daltons. １ ~C ４ - A polymerization product of a composition containing alkoxypoly(ethylene glycol)ethyl(meth)acrylamide, poly(ethylene glycol)ethyl(meth)acrylate having a weight-average molecular weight of up to 1500 daltons, poly(ethylene glycol)ethyl(meth)acrylamide having a weight-average molecular weight of up to 1500 daltons, N-vinylformamide, N-vinylacetamide, N-vinylisopropylamide, N-vinyl-N-methylacetamide, allyl alcohol, vinyl alcohol, and at least one non-reactive vinyl monomer selected from the group consisting of these; the at least one reactive vinyl monomer is amino-C ２ ~C ４ Alkyl (meth)acrylate, C １ ~C ３ Alkylamino-C ２ ~C ４ Alkyl (meth)acrylate, allylamine, vinylamine, amino-C ２ ~C ４ Alkyl (meth)acrylamide, C １ ~C ３ Alkylamino-C ２ ~C ４ Alkyl (meth)acrylamide, acrylic acid, C １ ~C ４ Alkyl acrylic acid, (meth)acryloxy-C ２ ~C ６ Alkanic acid, 2-acrylamidoglycolic acid, (meth)acrylamido-C ２ ~C ６ A coated silicone hydrogel contact lens according to any one of claims 1 to 5, wherein the epoxide-containing vinyl monomer is selected from the group consisting of alkanic acid, epoxide-containing vinyl monomer, and combinations thereof, and the epoxide-containing vinyl monomer is selected from the group consisting of glycidyl (meth)acrylamide, hydroxyethyl (meth)acrylamide glycidyl ether, 3-hydroxypropyl (meth)acrylamide glycidyl ether, 4-hydroxybutyl (meth)acrylamide glycidyl ether, glycidyl (meth)acrylate, hydroxyethyl (meth)acrylate glycidyl ether, 3-hydroxypropyl (meth)acrylate glycidyl ether, 4-hydroxybutyl (meth)acrylate glycidyl ether, and combinations thereof.

7. The coated silicone hydrogel contact lens according to any one of claims 1 to 6, wherein the fully hydrated coated silicone hydrogel contact lens has a water content of about 10% to about 70%, an oxygen permeability of about 50 to 180 bars, and a water film breakdown time of at least 10 seconds.

8. The coated silicone hydrogel contact lens according to any one of claims 1 to 7, wherein the grafted hydrophilic polymer is derived from at least one hydrophilic polymer having a 1,2- or 1,3-diol moiety.

9. The coated silicone hydrogel contact lens according to claim 8, wherein the at least one diol-containing hydrophilic polymer includes polyvinyl alcohol, poly(ethylene glycol)-graft-poly(vinyl alcohol), copolymer of vinyl alcohol and hydrophilic vinyl monomer, copolymer of glycerol (meth)acrylate and hydrophilic vinyl monomer, copolymer of 2,3,4-trihydroxybutyl (meth)acrylate and hydrophilic vinyl monomer, copolymer of 2,2-dihydroxypropyl (meth)acrylate and hydrophilic vinyl monomer, copolymer of 2,3-dihydroxybutyl (meth)acrylate and hydrophilic vinyl monomer, copolymer of glycerin-2 (meth)acrylate and hydrophilic vinyl monomer, copolymer of N-2,3-dihydroxypropyl (meth)acrylamide and hydrophilic vinyl monomer, copolymer of 3-allyloxy-1,2-propanediol and hydrophilic vinyl monomer, or a combination thereof.

10. A method for manufacturing coated silicone hydrogel contact lenses, (1) A step of obtaining a pre-formed silicone hydrogel contact lens comprising a bulk silicone hydrogel material, wherein the bulk silicone hydrogel material is (a) repeating units of at least one polysiloxane vinyl crosslinking agent and / or at least one siloxane-containing vinyl monomer, (b) Repeating units of at least one carboxyl-containing vinyl monomer in an amount of about 0.5% to about 3.5% by weight, (c) A repeating unit of at least one hydrophilic vinyl monomer, (d) Approximately 2.5% to approximately 12.5% ​​by weight of repeating units of at least one arylborono-containing vinyl monomer having an arylborono group, (e) at least one non-silicone vinyl crosslinking agent, which is optional but preferred A process including; and (2) A step of heating the pre-formed silicone hydrogel contact lens in an aqueous coating solution at a temperature of about 60°C to about 140°C to form a coated silicone hydrogel contact lens comprising a bulk silicone hydrogel material and a non-silicone hydrogel coating thereon, wherein the aqueous coating solution comprises (a) at least one hydrophilic polymer having 1,2- and / or 1,3-diol moieties, and (b) at least one water-soluble, heat-crosslinkable hydrophilic polymer material comprising branched or slightly crosslinked, heat-crosslinkable groups and optionally reactive functional groups, wherein the heat-crosslinkable groups are azetidinium groups and / or epoxide groups, and the reactive functional groups are primary amino groups, secondary amino groups The non-silicone hydrogel coating comprises a crosslinked polymer material and a grafted hydrophilic polymer, wherein the crosslinked hydrophilic polymer material is derived from the at least one water-soluble, thermally crosslinkable hydrophilic polymer material and is covalently bonded to the bulk silicone hydrogel material via a first bond formed between one carboxylic acid group and one azetidinium group or epoxide group, respectively, and the grafted hydrophilic polymer is derived from the at least one hydrophilic polymer and is covalently bonded to the bulk silicone hydrogel material via a second bond formed between one arylborono group and one 1,2- or 1,3-diol moiety; A method that includes this.

11. The method according to claim 10, wherein the heating step is preferably carried out by autoclaving the pre-formed silicone hydrogel contact lens, which is immersed in the aqueous coating solution in a sealed lens package, at a temperature of about 115°C to about 125°C for about 20 to 90 minutes, and the aqueous coating solution further comprises one buffer and one or more isotonic agents for maintaining a pH of about 6.8 to about 8.

5.

12. The method according to claim 10 or 11, wherein the aqueous solution has a pH of about 7.0 to about 8.2, and the aqueous solution contains about 0.01% to about 2% by weight of at least one water-soluble, heat-crosslinkable, hydrophilic polymer material.

13. The method according to any one of claims 10 to 12, wherein the aqueous solution contains a mixture of monobasic dihydrogen phosphate and dibasic monohydrogen phosphate to maintain the pH of the aqueous solution, and the total concentration of monobasic dihydrogen phosphate and dibasic monohydrogen phosphate is at least 30 mM.

14. The method according to any one of claims 10 to 13, wherein the at least one diol-containing hydrophilic polymer includes polyvinyl alcohol, poly(ethylene glycol)-graft-poly(vinyl alcohol), copolymer of vinyl alcohol and hydrophilic vinyl monomer, copolymer of glycerol (meth)acrylate and hydrophilic vinyl monomer, copolymer of 2,3,4-trihydroxybutyl (meth)acrylate and hydrophilic vinyl monomer, copolymer of 2,2-dihydroxypropyl (meth)acrylate and hydrophilic vinyl monomer, copolymer of 2,3-dihydroxybutyl (meth)acrylate and hydrophilic vinyl monomer, copolymer of glycerin-2 (meth)acrylate and hydrophilic vinyl monomer, copolymer of N-2,3-dihydroxypropyl (meth)acrylamide and hydrophilic vinyl monomer, copolymer of 3-allyloxy-1,2-propanediol and hydrophilic vinyl monomer, or a combination thereof.

15. The above at least one carboxyl-containing vinyl monomer is acrylic acid, C １ ~C ４ Alkyl acrylic acid, (meth)acryloxy-C １ ~C ６ Alkano acid, mono-2-[(meth)acryloxy]-ethyl succinate, 2-acrylamidoglycolic acid, (meth)acrylamido-C １ ~C ６ Selected from the group consisting of allanic acid and combinations thereof, The above at least one arylborono-containing vinyl monomer is of formula (I) 【Chemistry 4】 (In the formula: R Ｂ is a monovalent radical (preferably H, NO) ２ , F, Cl, Br, CF ３ ,CH ２ OH, or CH ２ NR ｏ R ｏ ' and R ｏ and R ｏ ' are H or C, independently of each other. １ ~C ４ Q is alkyl; 【Transformation 5】 It is a monovalent radical; L Ｂ Direct bond, C １ ~C ４ Alkylene divalent radical, 【Transformation 6】 It is a divalent radical of Y １ is CH(OH) or C １ ~C ４ It is an alkylene divalent radical, Y ２ is C １ ~C ４ It is an alkylene divalent radical, and p2 is an integer from 0 to 3, R ｏ is H or C １ ~C ４ (It is alkyl.) The method according to any one of claims 10 to 14, as represented by the following:

16. The method according to any one of claims 10 to 15, wherein the at least one water-soluble, heat-crosslinkable, hydrophilic polymer material comprises an epoxide group.

17. The method according to any one of claims 10 to 15, wherein the at least one water-soluble, heat-crosslinkable, hydrophilic polymer material comprises an azetidinium group.

18. The at least one water-soluble, heat-crosslinkable hydrophilic polymer material is a partially reacted product of: (i) one or more multi-arm polyethylene glycols, each having a terminal epoxide group; (ii) a multi-arm polyethylene glycol having a terminal epoxide group and one or more polyethylene glycols, each having a terminal functional group selected from the group consisting of primary amine groups, secondary amine groups, carboxyl groups, thiol groups, and combinations thereof; (iii) a partially reacted product of a multi-arm polyethylene having a terminal epoxide group and a hydrophilicity enhancer having at least one reactive functional group selected from the group consisting of amino groups, carboxyl groups, thiol groups, and combinations thereof; (iv) a partially reacted product of a copolymer of an epoxide-containing vinyl monomer and one or more hydrophilic vinyl monomers and a hydrophilicity enhancer having at least one reactive functional group selected from the group consisting of amino groups, carboxyl groups, thiol groups, and combinations thereof; (v) an epoxide-containing vinyl monomer, a hydrophilic vinyl monomer, and C having a number average molecular weight of up to 2500 daltons. １ ~C ４ A copolymer of alkoxypoly(ethylene glycol)ethyl (meth)acrylate, poly(ethylene glycol)ethyl (meth)acrylate having a number-average molecular weight of up to 2500 daltons, C １ ~C ４ The method according to any one of claims 10 to 17, comprising (vi) an alkoxy poly(ethylene glycol) ethyl (meth)acrylamide, or a poly(ethylene glycol) ethyl (meth)acrylamide having a number average molecular weight of up to 2500 Daltons; or a combination thereof.

19. The method according to any one of claims 10 to 17, wherein the at least one water-soluble, heat-crosslinkable, hydrophilic polymer material is a three-dimensional network and heat-crosslinkable groups in or connected to the network.

Images