Method for manufacturing a wettable silicone hydrogel contact lens

Abstract

The present invention provides a method for producing coated silicone hydrogel contact lenses in a cost-effective and environmentally friendly manner, which does not include a lens extraction step and includes thermally or actinically curing a polymerizable composition in a lens mold, the polymerizable composition including at least one hydrophilized polysiloxane vinyl crosslinker, hydroxyethyl methacrylate, C1-C2 alkoxyethyl (meth)acrylate, at least one free radical initiator, and at least one solvent selected from the group consisting of water, propylene glycol, and / or low molecular weight polyethylene glycol, and heating a cast molded silicone hydrogel contact lens in an aqueous coating solution to form a coated silicone hydrogel contact lens including a bulk silicone hydrogel material and a layer of crosslinked hydrophilic polymeric material covalently bonded to the bulk silicone hydrogel material. The resulting contact lens is optically clear and wettable and has relatively high oxygen permeability.

Description

Technical Field

[0001] The present invention relates to a method for manufacturing optically transparent and wettable silicone hydrogel contact lenses in a cost - effective and environmentally friendly manner. The present invention also relates to wettable silicone hydrogel contact lenses produced according to the method of the present invention.

Background Art

[0002] Recently, soft silicone hydrogel contact lenses have become increasingly popular due to their high oxygen permeability and comfort. "Soft" contact lenses can fit precisely to the shape of the eye, and thus oxygen cannot easily penetrate through the lens. Since the cornea does not receive oxygen from a blood supply like other tissues, soft contact lenses must allow oxygen from the surrounding air (i.e., oxygen) to reach the cornea. If sufficient oxygen does not reach the cornea, corneal swelling occurs. Long - term oxygen deprivation causes undesirable growth of blood vessels in the cornea. By having high oxygen permeability, silicone hydrogel ("SiHy") contact lenses enable sufficient oxygen to permeate through the lens to the cornea and minimize adverse effects on corneal health.

[0003] Most commercially available SiHy contact lenses are manufactured according to conventional casting techniques involving the use of disposable plastic molds and generally a SiHy lens - forming composition (or, SiHy lens formulation) containing one or more silicone - containing polymerizable components and at least one hydrophilic polymerizable component. However, the silicone - containing polymerizable component and the hydrophilic polymerizable component do not have sufficient miscibility (compatibility with each other) to form an optically transparent lens formulation for making optically transparent SiHy contact lenses. Further, silicone - containing components are typically not soluble in water or ophthalmically compatible solvents (as non - reactive diluents). Therefore, one or more ophthalmically incompatible organic solvents must be used in the SiHy lens formulation.

[0004] Furthermore, some of the polymerizable components in the SiHy lens formulation may not be ophthalmically compatible. Unreacted and partially reacted polymerizable components left in the SiHy contact lens resulting from the formation from the SiHy lens formulation need to be removed in an extraction process involving the use of one or more ophthalmically incompatible organic solvents. Such lens extraction increases production costs and decreases production efficiency.

[0005] Due to the use of one or more ophthalmically incompatible organic solvents in the SiHy lens formulation and in the extraction process, solvent exchange or hydration processes have been carried out in manufacturing. Such solvent exchange or hydration processes also increase production costs and decrease production efficiency.

[0006] The use of ophthalmically incompatible organic solvents in the manufacture of SiHy contact lenses is costly and not environmentally friendly. The process for manufacturing SiHy contact lenses desirably does not involve the use of any ophthalmically incompatible organic solvents.

[0007] In addition, SiHy materials are typically hydrophobic (non-wetting) and have a surface, or at least some regions of the surface, that are prone to adsorbing lipids or proteins from the ocular environment and may adhere to the eye. Thus, SiHy contact lenses generally require surface modification. Recently, a new cost-effective approach for applying a non-silicone hydrogel coating to SiHy contact lenses has been described in U.S. Patent Nos. 8,529,057 and 10,449,740, which includes forming a base coating on the SiHy contact lens, one or more steps of rinsing the SiHy contact lens having the base coating thereon with a solvent (e.g., water, a mixture of water and an organic solvent, and / or buffered saline), and covalently bonding a hydrophilic polymer material that is partially cross-linked in an autoclave directly to the base coating within the lens package. The formation and rinsing steps of the base coating may be environmentally unfriendly and / or increase production costs and decrease production efficiency.

[0008] Accordingly, there remains a need for a cost-effective and environmentally friendly method for manufacturing SiHy contact lenses, particularly wettable SiHy contact lenses. SUMMARY OF THE INVENTION MEANS FOR SOLVING THE PROBLEM

[0009] In one aspect, the present invention is a method for manufacturing a coated silicone hydrogel contact lens, the method comprising: (1) introducing a polymerizable composition into a lens mold, the polymerizable composition comprising: (a) at least one hydrophilic polysiloxane vinyl-based crosslinking agent, (b) optionally, hydroxyethyl methacrylate, and (c) at least one C 1 ~C 2An alkoxyethyl (meth)acrylate, and (d) at least one carboxy-containing (meth)acryloxy monomer in an amount of about 2 wt% to about 10 wt% based on the total amount of all polymerizable components, and (e) at least one free radical, and (f) optionally, at least one solvent selected from the group consisting of water, propylene glycol, polyethylene glycol having a molecular weight of 400 daltons or less, and combinations thereof, introducing step; (2) thermally curing or chemically curing the polymerizable composition in a lens forming mold to form a silicone hydrogel lens precursor comprising a bulk silicone hydrogel material containing carboxyl groups; (3) optionally, hydrating the silicone hydrogel lens precursor obtained in step (2) in water or an aqueous solution to obtain a hydrated silicone hydrogel contact lens; (4) directly heating the silicone hydrogel lens precursor obtained in step (2) or the hydrated silicone hydrogel contact lens obtained in step (3) in an aqueous solution having a pH of about 6.5 to about 9.5 to include at least one water-soluble, thermally crosslinkable hydrophilic polymer material 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 layer of a crosslinked hydrophilic polymer material covalently bonded onto the bulk silicone hydrogel material, A method is provided, wherein the coated silicone hydrogel contact lens exhibits a water film break-up time (WBUT) of at least about 5 seconds and an oxygen permeability of at least 50 barrers.

[0010] In another aspect, the present invention provides a silicone hydrogel contact lens comprising a bulk silicone hydrogel material and a layer of a non-silicone hydrogel material (i.e., a crosslinked hydrophilic polymer material) thereon, wherein the bulk silicone hydrogel material comprises (a) repeating units of at least one hydrophilized polysiloxane vinyl-based crosslinking agent, and (b) optionally, repeating units of hydroxyethyl methacrylate, and (c) at least one C 1 ~C 2The repeating unit of alkoxyethyl (meth)acrylate and the carboxyl-containing repeating unit of (d) at least one carboxyl-containing (meth)acryloxy monomer, wherein a layer of the non-silicone hydrogel material is covalently bonded to the bulk silicone hydrogel material through the carboxyl groups of the carboxyl-containing repeating unit, and the silicone hydrogel contact lens has a water break-up time (WBUT) of at least 5 seconds, an oxygen permeability of at least about 50 barrers, and an elastic modulus of 0.2 MPa to 1.8 MPa.

Mode for Carrying Out the Invention

[0011] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In general, the nomenclature and experimental procedures used herein are well known and commonly employed in the art. Conventional methods, such as those provided in the art and various general references, are used for these procedures. When a term is given in the singular, the inventors also contemplate the plural of that term. The nomenclature used herein and the laboratory procedures described below are well known and commonly employed in the art.

[0012] In this application, the term "about" as used herein means that the number referred to as "about" includes the recited number plus or minus 1 to 10% of the recited number.

[0013] "Contact lens" refers to a structure that can be placed on or in the eye of a wearer. A contact lens can correct, improve, or change the vision of a user, but it is not necessary to do so.

[0014] "Hydrogel contact lens" refers to a contact lens containing a hydrogel bulk (core) material. The hydrogel bulk material can be a non-silicone hydrogel material or preferably a silicone hydrogel material.

[0015] "Hydrogel" or "hydrogel material" refers to a crosslinked polymer material having a three-dimensional polymer network (i.e., polymer matrix), being insoluble in water, but capable of retaining at least 10% by weight of water in its polymer matrix when fully hydrated (or equilibrated).

[0016] "Silicone hydrogel" or "SiHy" refers to a silicone-containing hydrogel obtained by copolymerization of a polymerizable composition containing at least one silicone-containing monomer or at least one silicone-containing macromer or at least one crosslinkable silicone-containing prepolymer.

[0017] Siloxane, often also called silicone, refers to a molecule having at least one -Si-O-Si- moiety, with each Si atom having two organic groups as substituents.

[0018] As used in this application, the terms "non-silicone hydrogel" or "non-silicone hydrogel material" are interchangeable and theoretically refer to a hydrogel that does not contain silicon.

[0019] "Hydrophilic", as used herein, refers to a material or a part thereof that associates more readily with water than with lipids.

[0020] The term "room temperature" refers to a temperature of about 17°C to about 26°C.

[0021] The term "soluble" with respect to a compound or substance in a solvent means that the compound or substance can dissolve in the solvent to give a solution having a concentration of at least about 0.5% by weight at room temperature (i.e., a temperature of about 17°C to about 26°C).

[0022] In relation to a compound or material in a solvent, the term "insoluble" means that the compound or material is capable of dissolving in the solvent at room temperature (as defined above) to give a solution with a concentration of less than about 0.01% by weight.

[0023] "Vinyl monomer" refers to a compound having one and only one ethylenically unsaturated group, being soluble in a solvent, and capable of polymerizing either by actinic radiation or thermally.

[0024] The terms "olefinically unsaturated group" or "ethylenically unsaturated group" are used herein in a broad sense and are intended to include any group containing at least one >C=CH 2 group. Exemplary ethylenically unsaturated groups include, but are not limited to, (meth)acryloyl

Chemical formula

[0025] "Acrylic monomer" refers to a vinyl monomer having one and only one (meth)acryloyl group. Examples of acrylic monomers include (meth)acryloxy [or (meth)acryloyloxy] monomers and (meth)acrylamide monomers.

[0026] "(Meth)acryloxy monomer" or "(meth)acryloyloxy monomer" refers to

Chemical formula

[0027] "(Meth)acrylamide monomer" refers to

Chemical formula

[0028] The term "(meth)acrylamide" refers to methacrylamide and / or acrylamide.

[0029] The term "(meth)acrylate" refers to methacrylate and / or acrylate.

[0030] "N-vinylamide monomer" refers to an amide compound having a vinyl group (-CH=CH 2 ) directly bonded to the nitrogen atom of the amide group.

[0031] "En monomer" refers to a vinyl monomer having one unique en group.

[0032] "Hydrophilic vinyl monomer", "hydrophilic acrylic monomer", "hydrophilic (meth)acryloxy monomer", or "hydrophilic (meth)acrylamide monomer", as used herein, refers to a vinyl monomer, an acrylic monomer, a (meth)acryloxy monomer, or a (meth)acrylamide monomer, respectively, which typically results in a homopolymer that is water-soluble or can absorb at least 10 weight percent of water.

[0033] "Hydrophobic vinyl monomer", "hydrophobic acrylic monomer", "hydrophobic (meth)acryloxy monomer", or "hydrophobic (meth)acrylamide monomer", as used herein, refers to a vinyl monomer, an acrylic monomer, a (meth)acryloxy monomer, or a (meth)acrylamide monomer, respectively, which typically results in a homopolymer that is insoluble in water and can absorb less than 10 weight percent of water.

[0034] As used in this application, the term "vinyl crosslinking agent" refers to an organic compound having at least two ethylenically unsaturated groups. "Vinyl crosslinking agent" refers to a vinyl crosslinking agent having a molecular weight of 700 daltons or less.

[0035] "Acrylic crosslinking agent" refers to a vinyl crosslinking agent having at least two (meth)acryloyl groups.

[0036] The term "acrylic repeating unit" refers to a repeating unit of a polymer material each derived from an acrylic monomer or crosslinking agent by free radical polymerization to form a polymer material.

[0037] The term "terminal (meth)acryloyl group" refers to one (meth)acryloyl group at one of the two terminals of the main chain (or backbone) of an organic compound, as known to those skilled in the art.

[0038] As used herein, "chemically" with respect to the curing, crosslinking or polymerization of a polymerizable composition, prepolymer or material means that the curing (e.g., crosslinking and / or polymerization) is effected by irradiation with 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.

[0039] As used in this application, the term "polymer" means a material formed by polymerizing / crosslinking one or more monomers or macromers or prepolymers or combinations thereof.

[0040] "Macromer" or "prepolymer" refers to a compound or polymer containing an ethylenically unsaturated group and having a number average molecular weight of more than 700 daltons.

[0041] As used in this application, the term "molecular weight" of a polymeric material (including monomeric materials or macromeric materials) refers to the number average molecular weight, unless otherwise specified or the test conditions are otherwise indicated. Those skilled in the art are familiar with methods for determining the molecular weight of polymers according to known methods, such as gel permeation chromatography (GPC) equipped with one or more of a refractive index detector, a low angle laser light scattering detector, a multi-angle laser light scattering detector, a differential viscosity measurement detector, a UV detector, and an infrared (IR) detector; matrix-assisted desorption / ionization time-of-flight mass spectrometry (MALDI-TOF MS); 1 1H NMR (proton nuclear magnetic resonance) spectroscopy, etc.

[0042] "Polysiloxane segment" or "polydiorganosiloxane segment" are interchangeable with each other, [Chemical formula] refers to a polymer chain segment (i.e., a divalent radical) of, where SN is an integer of 3 or more, and R S1 and R S2 each independently of the other is C 1 ~C 10 alkyl; phenyl; C 1 ~C 4 alkyl-substituted phenyl; C 1 ~C 4 alkoxy-substituted phenyl; phenyl-C 1 ~C 6 alkyl; C 1 ~C 10 fluoroalkyl; C 1 ~C 10 fluoroether; aryl; arylC 1 ~C 18 alkyl; -alk-(OC 2 H 4 ) γ1 -OR o (where alk is a C 1 ~C 6 alkylenediradical, and R o is H or C 1 ~C 4is alkyl, and γ1 is an integer from 1 to 10); a hydroxyl group (-OH), a carboxyl group (-COOH), an amino group (-NR N1 R N1 ’), -NR N1 -amino bond of -, -CONR N1 -amide bond of -, -CONR N1 R N1 ’amide of, -OCONH-urethane bond, and C 1 ~C 4 organic radical having at least one functional group selected from the group consisting of an alkoxy group, or a C 2 ~C 40 organic radical selected from the group consisting of a linear hydrophilic polymer chain, where R N1 and R N1 ’ are, independently of each other, hydrogen or C 1 ~C 15 alkyl.

[0043] "Polysiloxane vinyl monomer" refers to a compound containing at least one polysiloxane segment and one single ethylenically unsaturated group.

[0044] "Polydiorganosiloxane vinyl crosslinking agent" or "polysiloxane vinyl crosslinking agent" interchangeably refers to a compound containing at least one polysiloxane segment and at least two ethylenically unsaturated groups.

[0045] "Linear polydiorganosiloxane vinyl crosslinking agent" or "linear polysiloxane vinyl crosslinking agent" interchangeably refers to a compound containing at least one polysiloxane segment and having a main chain terminated with one ethylenically unsaturated group at each of the two ends of the main chain.

[0046] "Chain extension polydiorganosiloxane vinyl crosslinking agent" or "chain extension polysiloxane vinyl crosslinking agent" interchangeably refers to a compound containing at least two ethylenically unsaturated groups and at least two polysiloxane segments, with each pair thereof linked by a single divalent radical.

[0047] As used herein, the term "fluid" indicates that the material can flow like a liquid.

[0048] 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., having a light transmittance of 85% or more, preferably 90% or more in the range of 400 - 700 nm).

[0049] The term "monovalent radical" refers to an organic radical obtained by removing a hydrogen atom from an organic compound and forming one bond with another group in the organic compound. Examples include, without limitation, 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), thioyl (by removing one hydrogen atom from the thiol group of an alkyl thiol), 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 an aromatic ring of an aromatic hydrocarbon), heteroaryl (by removing a hydrogen atom from any ring atom), amino (by removing one hydrogen atom from an amine), etc.

[0050] 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., alkenylenyl) is obtained by removing two hydrogen atoms from an alkane, and a cycloalkylene divalent radical (i.e., cycloalkenylenyl) is obtained by removing two hydrogen atoms from a cyclic ring.

[0051] In this application, the term "substituted" in relation to alkyl or alkenylenyl means that the alkyl or alkenylenyl is replaced with one hydrogen atom of the alkyl or alkenylenyl, and hydroxyl (-OH), carboxyl (-COOH), -NH 2, sulfhydryl (-SH), C 1 ~C 4 alkyl, C 1 ~C 4 alkoxy, C 1 ~C 4 alkylthio (alkyl sulfide), C 1 ~C 4 acylamino, C 1 ~C 4 alkylamino, di-C 1 ~C 4 It means containing at least one substituent selected from the group consisting of alkylamino and combinations thereof.

[0052] In the present application, the term "polyoxazoline" refers to [Chemical formula] (wherein: R 1 is hydrogen, methyl, ethyl, N - pyrrolidonylmethyl, N - pyrrolidonylethyl, N - pyrrolidonylpropyl or -alk-(OC 2 H 4 ) m3 -OR ” a monovalent radical (where alk is a C 1 ~C 4 alkyl diradical; R” is a C 1 ~C 4 alkyl (preferably methyl); m3 is an integer from 1 to 10 (preferably 1 to 5); and x is an integer from 5 to 500) of a polymer or polymer segment.

[0053] In the present application, the term "poly(2 - oxazoline - co - ethyleneimine)" refers to [Chemical formula] (wherein: R 1 is hydrogen, methyl, ethyl, N - pyrrolidonylmethyl, N - pyrrolidonylethyl, N - pyrrolidonylpropyl or -alk-(OC 2 H4 ) m3 -OR ” a monovalent radical (where alk is C 1 ~C 4 alkyl diradical; R” is C 1 ~C 4 alkyl (preferably methyl); m3 is an integer from 1 to 10 (preferably from 1 to 5); x is an integer from 5 to 500; z is an integer less than or equal to x), or a polymer segment thereof. Poly(2-oxazoline-co-ethyleneimine) is obtained by hydrolyzing polyoxazoline.

[0054] 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 substantial percentage (≧90%) of the secondary amine groups of poly(2-oxazoline-co-ethyleneimine) to azetidinium groups. An example of poly(2-oxazoline-co-ethyleneimine)-epichlorohydrin is disclosed in co-pending U.S. Patent Application Publication No. 2016 / 0061995A1.

[0055] "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 substantial percentage of the secondary amine groups of the polyamine or polyamidoamine to azetidinium groups.

[0056] The term "polyamidoamine-epichlorohydrin" refers to an adipic acid-diethylenetriamine copolymer functionalized with epichlorohydrin.

[0057] In this application, the term "azetidinium" or "3-hydroxyazetidinium"

Chemical formula

[0058] The term "thermocrosslinkable" with respect to a polymeric material or functional group means that the polymeric material or functional group can undergo a crosslinking reaction (or coupling reaction) with another material or functional group at a relatively high temperature (about 40 °C to about 140 °C), while this polymeric material or functional group cannot undergo the same crosslinking reaction (or coupling reaction) with another material or functional group to a detectable extent at a temperature of about 5 °C to about 15 °C for about 1 hour.

[0059] As used in this application, the term "phosphorylcholine" [Chemical formula] (wherein n is an integer from 1 to 5, and R 1 , R 2 and R 3 are each independently C 1 -C 8 alkyl or C 1 -C 8 hydroxyalkyl) refers to a zwitterionic group.

[0060] 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 a carboxyl group, a primary amino group, and a secondary amino group.

[0061] As used in this application, the term "non-reactive vinyl monomer" refers to any vinyl monomer (either a hydrophilic or hydrophobic vinyl monomer) that does not contain a carboxyl group, a primary amino group, a secondary amino group, an epoxide group, an isocyanate group, an azlactone group, or an aziridine group.

[0062] The free radical initiator can be either a photoinitiator or a thermal initiator. "Photoinitiator" refers to a chemical substance that initiates a free radical crosslinking / polymerization reaction by the use of light. "Thermal initiator" refers to a chemical substance that initiates a free radical crosslinking / polymerization reaction by the use of thermal energy.

[0063] As used herein, the term "bulk silicone hydrogel material" with respect to a contact lens is interchangeable and means a layer of silicone hydrogel material that substantially has the three-dimensional shape of the contact lens.

[0064] The intrinsic "oxygen permeability" Dk of the material i is the rate at which oxygen passes through the material. Oxygen permeability is typically expressed in units of barrers, where a "barrer" is defined as [(cm 3 oxygen)(mm) / (cm 2 )(sec)(mmHg)]×10 -10 .

[0065] The "oxygen permeability coefficient" Dk / t of an insert or material is the rate at which oxygen passes through a specific insert or material of average thickness t [in mm units] over the entire region being measured. The oxygen permeability coefficient is typically expressed in units of barrers / mm, where a "barrer / mm" is defined as [(cm 3 oxygen) / (cm 2 )(sec)(mmHg)]×10 -9 .

[0066] The "ionic permeability" through the lens correlates with the ion flux diffusion coefficient. The ion flux diffusion coefficient D (in units of [mm 2 / min]) is determined by applying Fick's law as follows: D=-n’ / (A×dc / dx) (where n’ = ion transport rate [mol / min]; A = exposed lens area [mm 2 ; dc = concentration difference [mol / L]; dx = lens thickness [mm]).

[0067] For a contact lens or a material, the term "modulus" or "elastic modulus" means the tensile modulus, i.e., Young's modulus, which is a measure of the indentation of the contact lens or the material. The modulus can be measured according to the procedure described in Example 1.

[0068] The term "dry lens precursor" refers to a cast contact lens obtained by casting a polymerizable composition in a mold and not having undergone an extraction and / or hydration post-molding process (i.e., not in contact with water or any organic solvent or any liquid after molding).

[0069] The term "wettable silicone hydroge (hydroge) contact lens" means that the silicone hydrogel contact lens has a water break-up time ("WBUT") of at least about 5 seconds, preferably at least about 10 seconds, more preferably at least about 15 seconds, and even more preferably at least about 20 seconds. The water break-up time ("WBUT") can be measured according to the procedure described in Example 1.

[0070] 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 - 700 nm. The light transmittance of the contact lens in the range of 400 - 700 nm can be measured according to the procedure described in Example 1.

[0071] "Average water contact angle" refers to the water contact angle (measured by the Sessile Drop method), which is obtained by averaging the measured values of at least three individual contact lenses or samples of silicone hydrogel materials.

[0072] Generally, the present invention aims at a method for producing an optically transparent and wettable silicone hydrogel contact lens in a cost-effective and environmentally friendly manner. The present invention is based in part on the discovery that selected polymerizable components such as hydroxyethyl methacrylate, alkoxyethyl methacrylate (e.g., ethoxyethyl methacrylate or methoxyethyl methacrylate), carboxyl-containing (meth)acryloxy monomer (e.g., acrylic acid or methacrylic acid), and a hydrophilic polysiloxane vinyl-based crosslinking agent can be formulated in an ophthalmically compatible organic solvent (e.g., propylene glycol) to form a lens formulation capable of producing an optically transparent silicone hydrogel contact lens having a relatively high oxygen permeability (at least 50 barrers). The present invention is also based in part on the discovery that a cast silicone hydrogel contact lens need not be subjected to an extraction and hydration process and can be directly surface-modified in the packaging solution within the lens package in an autoclave.

[0073] The present invention provides the following advantages. First, an ophthalmically incompatible organic solvent is not used in the method of the present invention. By eliminating the ophthalmically incompatible organic solvent, the post-molding extraction and hydration steps can be eliminated. Therefore, the manufacturing is significantly simplified, the production cost can be significantly reduced, and the manufacturing process becomes environmentally friendly. Second, the step of forming a base coating on the silicone hydrogel contact lens is eliminated. The production costs associated with the base coating step and the rinsing step are eliminated.

[0074] In one aspect, the present invention is a method for producing a coated silicone hydrogel contact lens, comprising: (1) introducing a polymerizable composition into a lens mold, wherein the polymerizable composition comprises: (a) at least one hydrophilic polysiloxane vinyl-based crosslinking agent; (b) optionally, hydroxyethyl methacrylate; and (c) at least one C 1 ~C 2An alkoxyethyl (meth)acrylate, (d) at least one carboxyl-containing (meth)acryloxy monomer in an amount of about 2% to about 10% by weight based on the total amount of all polymerizable components, (e) at least one free radical, and (f) optionally, at least one solvent selected from the group consisting of water, propylene glycol, polyethylene glycol having a molecular weight of 400 daltons or less, and combinations thereof, and introducing; (2) thermally curing or chemically curing the polymerizable composition in a lens mold to form a silicone hydrogel lens precursor comprising a bulk silicone hydrogel material containing a carboxyl group; (3) optionally, hydrating the silicone hydrogel lens precursor obtained in step (2) in water or an aqueous solution to obtain a hydrated silicone hydrogel contact lens; (4) directly heating the silicone hydrogel lens precursor obtained in step (2) or the hydrated silicone hydrogel contact lens obtained in step (3) in an aqueous solution having a pH of about 6.5 to about 9.5 and containing at least one water-soluble and thermally crosslinkable hydrophilic polymer material 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 layer of a crosslinked hydrophilic polymer material covalently bonded to the bulk silicone hydrogel material, and providing a method, wherein the coated silicone hydrogel contact lens exhibits a water break-up time (WBUT) of at least about 5 seconds (preferably at least about 10 seconds, more preferably at least about 15 seconds, even more preferably at least about 20 seconds) and an oxygen permeability of at least about 50 barrers (preferably at least about 60 barrers, more preferably at least about 70 barrers, even more preferably at least about 80 barrers).

[0075] According to a preferred embodiment of the present invention, the total amount of components (a) to (e) is at least about 90% by weight, preferably at least about 92% by weight, more preferably at least about 94% by weight, even more preferably at least about 96% by weight based on the total amount of all polymerizable components in the polymerizable composition.

[0076] According to any of the preceding embodiments of the present invention, the polymerizable composition comprises hydroxyethyl methacrylate.

[0077] According to any of the preceding embodiments of the present invention, the polymerizable composition comprises at least one solvent selected from the group consisting of water, polyethylene glycol, polyethylene glycol having a molecular weight of about 400 Daltons or less, and combinations thereof.

[0078] According to the present invention, any hydrophilized polysiloxane vinyl-based crosslinking agent can be used in the present invention as long as it contains a hydrophilic moiety of at least about 1.50 (preferably at least about 2.0, more preferably at least about 2.5, even more preferably at least about 3.0) milliequivalents / gram ("meq / g"), and the hydrophilic moiety preferably comprises a hydroxyl group (-OH), a carboxyl group (-COOH), an amino group (-NHR N1 (wherein R N1 is H or C 1 ~C 2 alkyl)), an amide moiety (-CO-NR N1 R N2 (wherein R N1 is H or C 1 ~C 2 alkyl and R N2 is a covalent bond, H, or C 1 ~C 2 alkyl)), an N-C 1 ~C 3 acylamino group, a urethane moiety (-NH-CO-O-), a urea moiety (-NH-CO-NH-), [Chemical formula] (wherein N is an integer from 2 to 20 and T 1 is H, methyl or acetyl or a phosphorylcholine group, or a combination thereof) is a polyethylene glycol chain.

[0079] In any of the preceding embodiments, the at least one hydrophilic polysiloxane vinyl crosslinking agent comprises: (1) a polysiloxane segment containing dimethylsiloxane units and hydrophilic siloxane units each having one methyl substituent and one monovalent C 4 ~C 40 organic radical substituent and (2) two terminal (meth)acryloyl groups. More preferably, the at least one hydrophilic polysiloxane vinyl crosslinking agent has the formula (1)

Chemical formula

Chemical formula

Chem.

Chem.

[0080] In any of the preceding embodiments, R 4 is one of the monovalent radicals of formula (2a) to (2y)

Chemical formula

[0081] In any of the preceding embodiments, alternatively, R 4 is one of the monovalent radicals of formula (3a) to (3y)

Chemical formula

Chemical formula

[0082] In any of the preceding embodiments, alternatively, R 4 is a monovalent radical of formula (4a) or (4b).

Chemical formula

[0083] In any of the preceding embodiments, alternatively, R 4 is a monovalent radical of one of formulas (5a) to (5c).

Chemical formula

[0084] In any of the preceding embodiments, alternatively, the monovalent radical R 4 is a radical of formula (6), where m1 is 3, p1 is 1, and R 7 is hydrogen. Such a preferred first polysiloxane vinyl-based crosslinking agent has the formula (A)

Chemical formula

[0085] In any of the preceding embodiments, alternatively, R 4 is a radical of formula (7a)

Chemical formula

[0086] The procedure for preparing the polysiloxane vinyl-based crosslinking agent of formula (1) is described in detail in U.S. Patent No. 10,081,697 and U.S. Patent Application No. 63 / 147624 (filed on February 9, 2021).

[0087] According to the present invention, any carboxyl-containing (meth)acryloxy monomer can be used in the present invention. Examples of carboxyl-containing (meth)acryloxy monomers include, but are not limited to, acrylic acid, methacrylic acid, ethylacrylic acid, propyacrylic acid, (meth)acryloyloxyacetic acid, mono-2-[(meth)acryloyloxy]ethyl succinate, (meth)acryloyloxypropanoic acid, and (meth)acryloyloxybutanoic acid.

[0088] 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 by the use of light. A "thermal initiator" refers to a chemical substance that initiates a free radical crosslinking / polymerization reaction by the use of thermal energy.

[0089] 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 cycloalkylnitrile), 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-hexyne, bis(1-(tert-butylperoxy)-1-methylethyl)benzene, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, di-t-butyl diperoxyphthalate, t-butyl hydroperoxide, t-butyl peracetate, t-butyl peroxybenzoate, t-butyl peroxyisopropyl carbonate, acetyl peroxide, lauroyl peroxide, decanoyl peroxide, dicetyl peroxydicarbonate, di(4-t-butylcyclohexyl) peroxydicarbonate (Perkadox 16), di(2-ethylhexyl) peroxydicarbonate, t-butyl peroxypivalate (Lupersol 11); t-butyl peroxy-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 64 or AIBN), 2,2'-azobis-2-methylbutyronitrile (VAZO 67), 1,1-azobis(1-cyclohexanecarbonitrile) (VAZO 88); 2,2'-azobis(2-cyclopropylpropionitrile), 2,2'-azobis(methyl isobutyrate), 4,4'-azobis(4-cyanovaleric acid), and combinations thereof.Preferably, the thermal initiator is 2,2'-azobis(isobutyronitrile) (AIBN or VAZO 64).

[0090] Suitable photoinitiators are benzoin methyl ether, diethoxyacetophenone, benzoylphosphine oxide, 1-hydroxycyclohexyl phenyl ketone and Darocur and Irgacur types, preferably Darocur 1173 (registered trademark) and Darocur 2959 (registered trademark), germanium-based Norrish type I photoinitiators (for example, those described in US 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. For example, reactive photoinitiators that can be incorporated into macromers or used as special monomers are also suitable. Examples of reactive photoinitiators are those disclosed in European Patent No. 632329.

[0091] According to any preceding embodiment of the present invention, the polymerizable composition can further include one or more additional polymerizable components (other than components (a) to (e)) 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.

[0092] According to any of the preceding embodiments of the present invention, the polymerizable composition preferably comprises 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)acryloxyethyl]phosphate, trimethylolpropane di-(meth)acrylate, and 3,4-bis[(meth)acryloyl]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), piperazine diacrylamide (or 1,Selected from the group consisting of 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.,

[0093] According to any preceding embodiment of the present invention, the polymerizable composition may also include other polymerizable materials, such as UV-absorbing vinyl monomers, polymerizable UV / high energy violet light (「HEVL」) absorbing compounds (including the UV / HEVL absorbing vinyl monomers described below and / or the polymerizable Cu(II)-porphyrins described in US Patent Application Publication No. 20150316688), polymerizable photochromic compounds, polymerizable colorants (polymerizable dyes), or combinations thereof, as known to those skilled in the art.

[0094] To prepare the preformed SiHy contact lens of the present invention, any suitable UV-absorbing vinyl monomer and UV / HEVL-absorbing vinyl monomer can be used in the polymerizable composition. Examples of 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-acryloyloxyphenyl)-2H benzotriazole, 2-(2-hydroxy-3-methacrylamidomethyl-5-tert-octylphenyl)benzotriazole, 2-(2'-hydroxy-5'-methacrylamidophenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-5'-methacrylamidophenyl)-5-methoxybenzotriazole, 2-(2'-hydroxy-5'-glycidyloxypropyl-3'-t-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-5'-methacryloxypropylphenyl)benzotriazole, 2-hydroxy-5-methoxy-3-(5-(trifluoromethyl)-2H-benzo[d][1,2,3]triazol-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]Triazol-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-benzotriazol-2-yl)-6-(1,1-(1,1-Dimethylethyl)-4-ethenyl-(UVAM), 2-[2'-hydroxy-5'-(2-methacryloyloxyethyl)phenyl)]-2H-benzotriazole (2-propenoic acid, 2-methyl-, 2-[3-(2H-benzotriazol-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-methacrylamidophenyl)-5-methoxybenzotriazole (UV6), 2-(3-allyl-2-hydroxy-5-methylphenyl)-2H-benzotriazole (UV9), 2-(2-hydroxy-3-methallyl-5-methylphenyl)-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)-5-methoxy-2H-benzotriazole (UV16A), 3-[3-tert-butyl-5-(5-chlorobenzotriazol-2-yl)-4-hydroxyphenyl]-propyl 2-methylacrylate (16-100, CAS#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, 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-benzotriazole; Phenol, 2-(5-ethenyl-2H-benzotriazol-2-yl)-4-methyl-, homopolymer (9CI) (CAS#83063-87-0) may be mentioned. According to the present invention, the polymerizable composition contains one or more UV-absorbing vinyl monomers in an amount of about 0.1% by weight to about 3.0% by weight, preferably about 0.2% by weight to about 2.5% by weight, more preferably about 0.3% by weight to about 2.0% by weight based on the total amount of polymerizable components in the polymerizable composition.,

[0095] Examples of preferred photochromic vinyl monomers include polymerizable naphthopyrans, polymerizable benzopyrans, polymerizable indenonaphthopyrans, polymerizable phenanthropyrans, polymerizable spiro(benzindoline)-naphthopyrans, polymerizable spiro(indoline)benzopyrans, polymerizable spiro(indoline)-naphthopyrans, polymerizable spiro(indoline)quinopyrans, polymerizable spiro(indoline)-pyrans, polymerizable naphthoxazines, polymerizable spirobenzopyrans; polymerizable spirobenzothiopyrans, polymerizable naphthacenediones, polymerizable spirooxazines, polymerizable spiro(indoline)naphthoxazines, polymerizable spiro(indoline)pyridobenzoxazines, polymerizable spiro(benzindoline)pyridobenzoxazines, polymerizable spiro(benzindoline)naphthoxazines, polymerizable spiro(indoline)-benzoxazine, polymerizable diarylethene, and combinations thereof. These are as disclosed 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; 8,697,770; 8,741,188; 9,052,438; 9,097,916; 9,465,234; 9,904,074; 10,197,707; 6,019,914; 6,113,814; 6,149,841; 6,296,785; and 6,348,604.

[0096] According to any of the preceding embodiments, the polymerizable composition preferably comprises component (a) in an amount of about 30 wt% to about 65 wt% (more preferably about 35 wt% to about 60 wt%, even more preferably about 40 wt% to about 60 wt%) based on the total amount of all polymerizable components, component (b) and (c) in an amount of preferably about 30 wt% to about 65 wt% (more preferably about 35 wt% to about 60 wt%, even more preferably about 40 wt% to about 60 wt%), and component (d) in an amount of preferably about 2 wt% to about 10 wt% (more preferably about 3 wt% to about 9 wt%, even more preferably about 4 wt% to about 8 wt%).

[0097] In any of the preceding embodiments, the weight ratio of component (c) to component (b) in the polymerizable composition is from about 40 to about 10, preferably from about 35 to about 15, more preferably from about 30 to about 15, and even more preferably from about 23 to about 11.

[0098] Other polymerizable components (materials) including various silicone-containing vinyl monomers, polysiloxane vinyl crosslinkers, hydrophilic vinyl monomers, and hydrophobic vinyl monomers are well known to those skilled in the art. One or more such polymerizable components can be used in the polymerizable composition of the present invention as long as their amounts are less than about 10% by weight (preferably less than about 8% by weight, more preferably less than about 6% by weight, and even more preferably less than about 4% by weight) based on the total amount of all polymerizable components in the polymerizable composition.

[0099] According to any of the preceding embodiments, the polymerizable composition may also contain, for example, bioactive agents (e.g., drugs, amino acids, polypeptides, proteins, nucleic acids, 2-pyrrolidone-5-carboxylic acid (PCA), alpha-hydroxy acids, linoleic acid and gamma-linolenic acid, vitamins, or any combination thereof), leachable lubricants (e.g., non-crosslinkable hydrophilic polymers having an average molecular weight of 5,000 to 500,000, preferably 10,000 to 300,000, more preferably 20,000 to 100,000 daltons), leachable tear stabilizers (e.g., phospholipids, monoglycerides, diglycerides, triglycerides, glycolipids, glyceroglycolipids, sphingolipids, sphingoglycolipids, fatty acids having 8 to 36 carbon atoms, fatty alcohols having 8 to 36 carbon atoms, or mixtures thereof), release agents, and other necessary components known to those skilled in the art such as mixtures thereof.

[0100] The polymerizable composition of the present invention can be prepared by blending all of the desired components, as is known to those skilled in the art.

[0101] Lens molding dies for manufacturing contact lenses such as hydro contact lenses are well known to those skilled in the art and are used, for example, in cast molding or spin casting. For example, a molding die (for injection molding) generally includes at least two molding die pieces (or parts) or molding die halves, i.e., a first and a second molding die half. The first molding die half defines a first molding (or optical) surface, and the second molding die half defines a second molding (or optical) surface. The first and second molding die halves are configured to receive each other such that a lens forming cavity is formed between the first molding surface and the second molding surface. The molding surface of the molding die half is the cavity forming surface of the molding die and is in direct contact with the polymerizable composition.

[0102] Methods for manufacturing molding die pieces for injection molding 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 of forming the molding die. In fact, in the present invention, any method for forming the molding die can be used.

[0103] Generally, a lens molding die for injection molding contact lenses includes at least two molding die halves (or molding die pieces), a male molding die half and a female molding die half. The male molding die half has a first molding (or optical) surface that is in direct contact with the polymerizable composition for injection molding contact lenses and defines the rear surface (concave surface) of the molded contact lens. The female molding die half has a second molding (e.g., optical) surface that is in direct contact with the polymerizable composition and defines the front surface (convex surface) of the molded contact lens. The male molding die and the female molding die half are configured to receive each other such that a lens forming cavity is formed between the first molding surface and the second molding surface.

[0104] The mold half can be formed by various methods such as injection molding. Methods for manufacturing a mold half for casting a contact lens are generally well known to those skilled in the art. The method of the present invention is not limited to a specific method of forming the mold. In fact, in the present invention, any method for forming the mold can be used. The first and second mold halves can be formed by various methods such as injection molding or lathe work. Examples of suitable processes for forming the mold half are disclosed in U.S. Patent Nos. 4,444,711, 4,460,534, 5,843,346, and 5,894,002.

[0105] Virtually all materials known in the art for manufacturing a mold can be used for manufacturing a mold for making a contact lens. For example, polymeric materials such as polyethylene, polypropylene, polystyrene, PMMA, Topas® COC grade 8007-S10 (a transparent amorphous copolymer of ethylene and norbornene, manufactured by Ticona GmbH, Frankfurt, Germany and Summit, New Jersey) can be used. Other materials that are transmissive to UV light, such as fused silica and sapphire, could be used.

[0106] According to the present invention, the polymerizable composition can be dispersed into the lens mold by any known technique. For example, a specific amount of the polymerizable composition is typically dispensed into the female mold half by a dispensing device, and then the male mold half is placed and the mold is closed. When the mold is closed, any excess polymerizable composition is pushed into an overflow provided on the female mold half (or on the male mold half).

[0107] The forming assembly (i.e., a closed mold that encloses the second polymerizable fluid composition and the partially cross-linked annular layer immersed therein) is then thermally cured or radiation cured as known to those skilled in the art to form a silicone hydrogel lens precursor comprising a bulk silicone hydrogel material containing carboxyl groups. It is understood that carboxyl groups on and / or near the surface of the bulk silicone hydrogel material can function as reactive sites to which a layer of cross-linked hydrophilic polymer material can be covalently bonded.

[0108] After curing, the mold can be opened according to any technique known to those skilled in the art. After the mold is separated, the silicone hydrogel lens precursor adheres to one of the male and female mold halves.

[0109] The silicone hydrogel lens precursor adhered to the lens-adhering mold half is removed from the lens-adhering mold half and can then be subjected to one or more post-forming treatments.

[0110] According to the present invention, the water-soluble and thermally cross-linkable hydrophilic polymer material preferably contains azetidinium groups or epoxy groups or a combination thereof. Preferably, the water-soluble and cross-linkable hydrophilic polymer material is a partially cross-linked polymer material containing a three-dimensional network and thermally cross-linkable groups, preferably azetidinium groups within or linked to the network. The term "partially cross-linked" with respect to the polymer material means that in the cross-linking reaction, the cross-linkable groups of the starting material for making the polymer material are not completely consumed. For example, such a thermally cross-linkable hydrophilic polymer material is a partial reaction product of at least one azetidinium-containing polymer containing azetidinium groups and following the cross-linking reaction shown in Scheme I, and at least one hydrophilic enhancer (i.e., wetting agent) having at least one carboxyl, primary amine, secondary amine, or thiol group,

Chemical formula

[0111] Examples of preferred water-soluble and thermally crosslinkable hydrophilic polymer materials containing an epoxy group include, without limitation, one or more multi-arm polyethylene glycols each having a terminal epoxy group; a mixture of a multi-arm polyethylene glycol having a terminal epoxy group and one or more polyethylene glycols 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 epoxy group and a hydrophilic 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 (a hydrophilic polymer as disclosed in U.S. Patent No. 6,440,571 as disclosed in U.S. Patent No. 9,505,184), or combinations thereof.

[0112] Examples of preferred water-soluble and thermally crosslinkable hydrophilic polymer materials containing an azetidinium group include, without limitation, poly(2-oxazoline-co-ethyleneimine)-epichlorohydrin copolymer (disclosed in U.S. Patent No. 9,720,138), chemically modified poly(2-oxazoline-co-ethyleneimine)-epichlorohydrin copolymer (disclosed in U.S. Patent No. 9,720,138), chemically modified polyamidoamine-epichlorohydrin (disclosed in U.S. Patent No. 8,529,057), a copolymer of an azetidinium-containing vinyl monomer and one or more hydrophilic vinyl monomers (disclosed in U.S. Patent No. 9,422,447), a chemically modified copolymer of an azetidinium-containing vinyl monomer and one or more hydrophilic vinyl monomers (disclosed in U.S. Patent No. 9,422,447), or combinations thereof.

[0113] According to the present invention, the term "chemically modified" with respect to a water-soluble and thermally crosslinkable hydrophilic polymer material having an azetidinium group means that a poly(2-oxazoline-co-ethyleneimine)-epichlorohydrin copolymer, a polyamidoamine-epichlorohydrin or a copolymer of an azetidinium-containing vinyl monomer is partially reacted with a hydrophilic 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 (i.e., not consuming all of the azetidinium groups). The chemically modified poly(2-oxazoline-co-ethyleneimine)-epichlorohydrin copolymer or polyamidoamine-epichlorohydrin or copolymer of an azetidinium-containing vinyl monomer can be particularly useful for forming a relatively thick and soft non-silicone hydrogel coating on a silicone hydrogel contact lens.

[0114] Any suitable hydrophilic enhancer can be used in the present invention as long as they contain at least one amino group, at least one carboxyl group, and / or at least one thiol group.

[0115] Preferred classes of hydrophilicity enhancing agents include, without limitation, primary amino, secondary amino, carboxyl or thiol-containing monosaccharides (e.g., 3-amino-1,2-propanediol, 1-thiol glycerol, 5-keto-D-gluconic acid, galactosamine, glucosamine, galacturonic acid, gluconic acid, glucosaminic acid, mannosamine, saccharic acid 1,4-lactone, saccharide acid, ketodeoxynonulosonic acid, N-methyl-D-glucamine, 1-amino-1-deoxy-β-D-galactose, 1-amino-1-deoxysorbitol, 1-methylamino-1-deoxysorbitol, N-aminoethyl gluconeamide); primary amino, secondary amino, carboxyl or thiol-containing disaccharides (e.g., chondroitin disaccharide sodium salt, di(β-D-xylopyranosyl)amine, digalacturonic acid, heparin disaccharides, hyaluronic acid disaccharides, lactobionic acid); and primary amino, secondary amino, carboxyl or thiol-containing oligosaccharides (e.g., carboxymethyl-β-cyclodextrin sodium salt, trigalacturonic acid); and combinations thereof.

[0116] Another preferred class of hydrophilicity enhancing agents are hydrophilic polymers having one or more (primary or secondary) amino, carboxyl and / or thiol groups. More preferably, the content of amino (-NHR' as defined above with R'), carboxyl (-COOH) and / or thiol (-SH) groups in the hydrophilic polymer as a hydrophilicity enhancing agent is less than about 40 wt%, preferably less than about 30 wt%, more preferably less than about 20 wt%, and even more preferably less than about 10 wt% based on the total weight of the hydrophilic polymer.

[0117] One preferred class of hydrophilic polymers as hydrophilicity enhancing agents are (primary or secondary) amino or carboxyl-containing polysaccharides, e.g., carboxymethyl cellulose (repeating unit, ─[C 6 H 10~m O 5 (CH 2 CO 2 H) 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, ─[C 6 H 10~m O 5 (C 2 H 4 CO 2 H) 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, ─[C 6 H 10~m O 5 (C 3 H 6 CO 2 H) 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 O 9 NCO 2 H)─ having a carboxyl content of about 11% estimated based on the composition of), chondroitin sulfate (repeating unit, ─(C 12 H 18 O 13 NSCO 2 H)─ having a carboxyl content of about 9.8% estimated based on the composition of), or combinations thereof, etc.

[0118] Another preferred class of hydrophilic polymers as hydrophilic enhancers includes, without limitation, poly(ethylene glycol) (PEG) having a mono - amino (primary or secondary amino), carboxyl or thiol group (e.g., PEG - NH 2 , PEG - SH, PEG - COOH); H 2 N - PEG - NH 2 ; HOOC - PEG - COOH; HS - PEG - SH; H 2 N - PEG - COOH; HOOC - PEG - SH; H 2N-PEG-SH; multi-arm PEGs having one or more amino (primary or secondary), carboxyl or thiol groups; PEG dendrimers having one or more amino (primary or secondary), carboxyl or thiol groups; diamino- (primary or secondary) or dicarboxyl end homo- or copolymers of non-reactive hydrophilic vinyl monomers; monoamino- (primary or secondary) or monocarboxyl end homo- or copolymers of non-reactive hydrophilic vinyl monomers; copolymers which are polymerization products of compositions comprising (1) one or more reactive vinyl monomers 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, even more preferably about 1% to about 15% by weight, and (2) at least one non-reactive hydrophilic vinyl monomer, and combinations thereof. The reactive vinyl monomers and non-reactive hydrophilic vinyl monomers are those described previously.

[0119] According to the present invention, the reactive vinyl monomer for producing the hydrophilic enhancer can be a carboxyl-containing vinyl monomer, a primary amino-containing vinyl monomer, or a secondary amino-containing vinyl monomer. Examples of preferred carboxyl-containing vinyl monomers include, but are not limited to, acrylic acid, methacrylic ethylacrylic acid, N-2-(meth)acrylamidoglycolic acid, and combinations thereof. Examples of preferred primary and secondary amino-containing vinyl monomers include, but are not limited to, N-2-aminoethyl (meth)acrylamide, N-2-methylaminoethyl (meth)acrylamide, N-2-ethylaminoethyl (meth)acrylamide, N-3-aminopropyl (meth)acrylamide, N-3-methylaminopropyl (meth)acrylamide, 2-aminoethyl (meth)acrylate, 2-methylaminoethyl (meth)acrylate, 2-ethylaminoethyl (meth)acrylate, 3-aminopropyl (meth)acrylate, 3-methylaminopropyl (meth)acrylate, 3-ethylaminopropyl (meth)acrylate, 3-amino-2-hydroxypropyl (meth)acrylate, and combinations thereof.

[0120] According to the present invention, the non-reactive vinyl monomer for producing the hydrophilic enhancer is a vinyl monomer that does not contain any carboxyl group, primary amino group, secondary amino group, epoxide group, isocyanate group, azlactone group, or aziridine group. The non-reactive vinyl monomer is preferably a non-charged hydrophilic vinyl monomer that does not contain a carboxyl or amino group (any of those described above may be used herein), a phosphorylcholine-containing vinyl monomer (any of those described above may be used herein), or a combination thereof.

[0121] More preferably, the hydrophilic polymer as the hydrophilic enhancer is -NH 2 , -SH or poly(ethylene glycol) having a single functional group of -COOH; -NH 2 , -COOH, -SH, and poly(ethylene glycol) having two terminal functional groups selected from the group consisting of combinations thereof; -NH 2 , -COOH, -SH, and multi-arm poly(ethylene glycol) having one or more functional groups selected from the group consisting of combinations thereof; A monoamino, monocarboxyl, diamino or dicarboxyl terminal homo- or copolymer of a non-reactive hydrophilic vinyl monomer; A copolymer which is a polymerization product of a composition containing (1) about 0.1% by weight to about 30% by weight, preferably about 0.5% by weight to about 20% by weight, more preferably about 1% by weight to about 15% by weight of a reactive vinyl monomer and (2) at least one non-reactive vinyl monomer.

[0122] Examples of preferred reactive vinyl monomers include, but are not limited to, acrylic acid, methacrylic acid, ethylacrylic acid, 2-(meth)acrylamidoglycolic acid, N-2-aminoethyl (meth)acrylamide, N-2-methylaminoethyl (meth)acrylamide, N-2-ethylaminoethyl (meth)acrylamide, N-3-aminopropyl (meth)acrylamide, N-3-methylaminopropyl (meth)acrylamide, 2-aminoethyl (meth)acrylate, 2-methylaminoethyl (meth)acrylate, 2-ethylaminoethyl (meth)acrylate, 3-aminopropyl (meth)acrylate, 3-methylaminopropyl (meth)acrylate, 3-amino-2-hydroxypropyl (meth)acrylate, and combinations thereof.

[0123] Examples of preferred non-reactive hydrophilic vinyl monomers include, but are not limited to, alkyl (meth)acrylamide (any one of the above), N-2-dimethylaminoethyl (meth)acrylamide, dimethylaminoethyl (meth)acrylate, hydroxyl-containing acrylic monomer (any one of the above), N-vinylamide monomer (any one of the above), methylene-containing pyrrolidone monomer (i.e., a pyrrolidone derivative having a methylene group linked to the pyrrolidone ring at the 3- or 5-position) (any one of the above), C 1 ~C 4 acrylic monomer having an alkoxyethoxy group (any one of the above), vinyl ether monomer (any one of the above), allyl ether monomer (any one of the above), phosphorylcholine-containing vinyl monomer (any one of the above), and combinations thereof.

[0124] 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 phosphonate, 3-[(meth)acryloylamino]propyl-2'-(trimethylammonio)ethyl phosphonate, 4-[(meth)acryloylamino]butyl-2'-(trimethylammonio)ethyl phosphonate, (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 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, 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, methoxypoly(ethylene glycol) ethyl (meth)acrylamide having a number average molecular weight of up to 1500, C having a weight average molecular weight of up to 1500 1 ~C 4Selected from the group consisting of -alkoxypolyethylene glycol (meth)acrylate, 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 phosphorylcholine, 4-((meth)acryloyloxy)butyl-2'-(trimethylammonio)ethyl phosphonate, 2-[(meth)acryloylamino]ethyl-2'-(trimethylammonio)-ethyl phosphonate, 3-[(meth)acryloylamino]propyl-2'-(trimethylammonio)ethyl phosphonate, 4-[(meth)acryloylamino]butyl-2'-(trimethylammonio)ethyl phosphonate, (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), 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, and more preferably, (meth)acryloyloxyethyl phosphorylcholine, (meth)acryloyloxypropyl phosphorylcholine, 2-[(meth)acryloylamino]ethyl-2'-(trimethylammonio)ethyl phosphonate, 3-[(meth)acryloylamino]propyl-2'-(trimethylammonio)ethyl phosphonate, (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, 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, and combinations thereof.,

[0125] PEGs with functional groups and multi-arm PEGs with functional groups can be obtained from various commercial suppliers, such as Polyscience, and Shearwater Polymers, inc.

[0126] Homopolymers or copolymers of one or more non-reactive hydrophilic vinyl monomers or of phosphorylcholine-containing vinyl monomers having monoamino, monocarboxyl, diamino or dicarboxyl end groups can be prepared according to the procedure described in U.S. Patent No. 6,218,508, which is hereby incorporated by reference in its entirety. For example, to prepare a diamino or dicarboxyl end group homopolymer or copolymer of a non-reactive hydrophilic vinyl monomer, 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 hydroxymercaptone, aminomercaptone, or carboxyl-containing mercaptone) and optionally, other vinyl monomers are polymerized (thermally or by actinic radiation) 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 of the vinyl monomers other than the reactive vinyl monomer is from about 1:5 to about 1:100, whereas the molar ratio of the chain transfer agent to the reactive vinyl monomer is 1:1. In such a preparation, the chain transfer agent having an amino or carboxyl group is used to control the molecular weight of the resulting hydrophilic polymer and to form the ends of the resulting hydrophilic polymer to provide a resulting hydrophilic polymer having one terminal amino or carboxyl group, while the reactive vinyl monomer provides the other terminal carboxyl or amino group to the resulting hydrophilic polymer. Similarly, to prepare a monoamino or monocarboxyl end group homopolymer or copolymer of a non-reactive hydrophilic vinyl monomer, 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 hydroxymercaptone, aminomercaptone, or carboxyl-containing mercaptone) and optionally, other vinyl monomers are polymerized (thermally or by actinic radiation) in the absence of any reactive vinyl monomer.

[0127] Copolymers containing a non-reactive hydrophilic vinyl monomer and a reactive vinyl monomer (e.g., a carboxyl-containing vinyl monomer, a primary amino group-containing vinyl monomer, or a secondary amino group-containing vinyl monomer) can be prepared according to any well-known radical polymerization method or obtained from commercial suppliers. Copolymers containing methacryloyloxyethyl phosphorylcholine and a carboxyl-containing vinyl monomer (or an amino-containing vinyl monomer) can be obtained from NOP Corporation (e.g., LIPIDURE®-AC01 and AE).

[0128] The weight average molecular weight M of a hydrophilic polymer (as a hydrophilic enhancer) having at least one amino, carboxyl, or thiol group w is preferably from about 500 to about 2,000,000, more preferably from about 1,000 to about 500,000, and even more preferably from about 5,000 to about 250,000 Daltons.

[0129] The water-soluble and thermally crosslinkable hydrophilic polymer material can be prepared according to the processes disclosed in U.S. Patent Application Publication No. US2019 / 0179055A1, as well as U.S. Patent Nos. 8,529,057, 9,422,447, and 9,720,138.

[0130] In a preferred embodiment, a water-soluble, thermally crosslinkable polymer material is obtained by heating a reactive aqueous solution containing at least one azetidinium-containing polymer and at least one hydrophilic enhancer (i.e., 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 that temperature for a sufficient 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 at 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, even more preferably 9.5). The reaction time should be long enough to covalently bond the hydrophilic enhancer onto the polymer chains of the azetidinium-containing polymer, but not consume all of the azetidinium groups of the azetidinium-containing polymer and not be so short as to form a gel (i.e., not water-soluble) due to too many crosslinks formed between the azetidinium-containing polymer and the hydrophilic enhancer. The resulting polymer material has a highly branched structure and is a lightly crosslinked polymer material still containing thermally crosslinkable azetidinium groups.

[0131] One skilled in the art fully understands how to adjust the pH of the reactive mixture, for example, by adding a base (e.g., NaOH, KOH, NH 4 OH, or a mixture thereof) or an acid (e.g., HCl, H 2 SO 4 4, H 3 3PO 4 4, citric acid, acetic acid, boric acid, or a mixture thereof).

[0132] According to the present invention, any ionic compound can be used in a reactive mixture. Preferably, the ionic compound is one 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., NaH 2 PO 4 、Na 2 HPO 4 、Na 3 PO 4 、KH 2 PO 4 、K 2 HPO 4 、K 3 PO 4 、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), various salts of carboxylic acid (e.g., Na 2 CO 3 、NaHCO 3 、K 2 CO 3 、KHCO 3 、or mixtures thereof).

[0133] A reactive aqueous solution for preparing a water-soluble, thermally crosslinkable polymer material can be prepared by dissolving a desired amount of an azetidinium-containing polymer, a desired amount of a hydrophilic enhancer having at least one reactive functional group, and a desired amount of other components (e.g., ionic buffer, ionic tonicity regulator, etc.) in water (or in a mixture of water and a small amount of a water-soluble organic solvent) to form an aqueous solution, and then, if necessary, adjusting the pH of the aqueous solution.

[0134] According to the present invention, the concentration ratio of the hydrophilicity improver to the azetidinium-containing polymer in the aqueous reactive solution should be selected so as not to make the resulting water-soluble thermally crosslinkable polymer material water-insoluble (i.e., solubility less than 0.005 g per 100 ml of water at room temperature), and so that the azetidinium groups of the azetidinium-containing polymer are not consumed by more than about 99%, preferably about 98%, more preferably about 97%, and still more preferably about 96%.

[0135] In a preferred embodiment, the reactive aqueous solution contains from 0.01 wt% to about 10 wt% (preferably from 0.05 wt% to about 5 wt%, more preferably from 0.08 wt% to about 1 wt%, and still more preferably from 0.1 wt% to about 0.4 wt%) of an azetidinium-containing polymer and from about 0.01 wt% to about 10 wt% (preferably from 0.02 wt% to about 5 wt%, more preferably from 0.05 wt% to about 2 wt%, and still more preferably from 0.08 wt% to about 1.0 wt%) of a hydrophilicity enhancer having at least one reactive functional group (carboxyl, primary amino, secondary amino group), and the concentration ratio of the azetidinium-containing polymer to the hydrophilicity enhancer is from about 1000:1 to 1:1000 (preferably from about 500:1 to about 1:500, more preferably from about 250:1 to about 250:1, and still more preferably from about 100:1 to about 1:100).

[0136] In a preferred embodiment, the water-soluble, thermally crosslinkable polymer material comprises (i) a first polymer chain derived from about 20 wt% to about 95 wt% of polyamidoamine-epichlorohydrin or poly(2-oxazoline-co-ethyleneimine)-epichlorohydrin, and (ii) a hydrophilic moiety or a second polymer chain derived from at least one hydrophilic 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), wherein the hydrophilic moiety or the second polymer chain is covalently bonded to the first polymer chain through one or more covalent bonds each formed between one azetidinium group of the polyamidoamine-epichlorohydrin or poly(2-oxazoline-co-ethyleneimine)-epichlorohydrin and one amino, carboxyl or thiol group of the hydrophilic enhancer, and (iii) an azetidinium group that is part of the first polymer chain or 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 of the reaction mixture (based on the total weight of the reactants) used for such polymers according to the crosslinking reaction shown in Scheme I above. For example, if the reaction mixture contains about 75 wt% of polyamidoamine-epichlorohydrin and about 25 wt% of at least one hydrophilic 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 wt% of polyamioamine-epichlorohydrin and a hydrophilic moiety or a second polymer chain derived from about 25 wt% of the at least one hydrophilic enhancer.

[0137] According to the present invention, the heating step is preferably carried out by autoclaving a silicone hydrogel lens precursor immersed in a packaging solution (i.e., a buffered aqueous solution) within a sealed lens package at a temperature of about 115°C to about 125°C for approximately 20 to 90 minutes. According to this embodiment of the present invention, the packaging solution is a buffered aqueous solution that is ophthalmically safe after autoclaving.

[0138] Lens packages (or containers) are well known to those skilled in the art with respect to autoclaving and storing soft contact lenses. Any lens package can be used in the present invention. Preferably, the lens package is a blister package including a base and a cover; here, the cover is sealed to be detachable from the base, and here, the base includes a cavity for receiving a sterilizing packaging solution and a contact lens.

[0139] The lenses are packaged, sealed in individual packages, and sterilized (e.g., by autoclaving at at least 120°C for at least 30 minutes under pressure) before being dispensed to the user. Those skilled in the art will well understand the methods of sealing and sterilizing the lens packages.

[0140] 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, tonicity agents, surfactants, antibacterial agents, preservatives, and lubricants (e.g., cellulose derivatives, polyvinyl alcohol, polyvinyl pyrrolidone).

[0141] The packaging solution contains a buffer in an amount sufficient to maintain the pH of the packaging solution within a desired range, for example, preferably from about 6.8 to about 8.5, more preferably from about 7.0 to 8.2, and even more preferably from about 7.2 to about 8.0. A higher pH has been found to be 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 can be dimensionally stable and have improved lubricity in the packaging solution during autoclaving and storage.

[0142] Any known buffer that is physiologically compatible 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, the phosphate buffer (monobasic sodium dihydrogen phosphate (e.g., NaH 2 PO 4 、KH 2 PO 4 、or a mixture thereof) and dibasic sodium hydrogen phosphate (e.g., Na 2 HPO 4 、K 2 HPO 4 、or a mixture thereof) is used to maintain the pH of the packaging solution. In various preferred embodiments, the total concentration of monobasic sodium dihydrogen phosphate and dibasic sodium hydrogen 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).

[0143] The solutions according to the present invention are preferably formulated to be isotonic with tears. Solutions that are isotonic with tears are generally understood to be solutions whose concentration corresponds to that of a 0.9% sodium chloride solution (308 mOsm / kg). Deviations from this concentration are possible throughout.

[0144] Isotonicity with tears, or yet another desired tonicity, can be adjusted by adding organic or inorganic substances that affect tonicity. Suitable ophthalmically acceptable tonicity 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 be from about 200 to about 450 milliosmoles (mOsm), preferably from about 250 to 350 mOsm.

[0145] In preferred embodiments, one or more organic tonicity agents (e.g., glycerol, propylene glycol, polyethylene glycol having a number average molecular weight of 200 to 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, even more preferably at least 130 mM) to adjust the tonicity of the packaging solution. It has been found that the resulting silicone hydrogel contact lens can have improved lubricity when the ionic strength of the packaging solution is reduced (e.g., by replacing a portion of the NaCl with an organic tonicity agent, such as propylene glycol).

[0146] In preferred embodiments, the packaging solution preferably contains a water-soluble, thermally crosslinkable hydrophilic polymer material having azetidinium groups in an amount of from about 0.01 wt% to about 2 wt%, more preferably from about 0.05 wt% to about 1.5 wt%, even more preferably from about 0.1 wt% to about 1 wt%, and most preferably from about 0.2 wt% to about 0.5 wt%.

[0147] In another aspect, the present invention provides a coated silicone hydrogel contact lens comprising a bulk silicone hydrogel material and a layer of a non-silicone hydrogel material (i.e., a crosslinked hydrophilic polymer material) thereon, wherein the bulk silicone hydrogel material comprises (a) repeating units of at least one hydrophilic polysiloxane vinyl crosslinking agent, (b) repeating units of hydroxyethyl methacrylate, (c) at least one C 1 ~C 2 repeating units of alkoxyethyl (meth)acrylate, (d) carboxyl-containing repeating units of at least one carboxyl-containing (meth)acryloxy monomer, and (e) optionally, repeating units of at least one polymerizable component selected from the group consisting of non-silicone vinyl crosslinking agents, UV-absorbing vinyl monomers, polymerizable UV / high-energy violet light-absorbing compounds, polymerizable photochromic compounds, polymerizable colorants, and combinations thereof (provided that the amount of component (e) is less than 10% by weight based on the total weight of the bulk silicone hydrogel material in the dry state), the layer of the non-silicone hydrogel material is covalently bonded to the bulk silicone hydrogel material through the carboxyl groups of the carboxyl-containing repeating units, and the silicone hydrogel contact lens has a water break-up time (WBUT) of at least about 5 seconds (preferably at least about 10 seconds, more preferably at least about 15 seconds, even more preferably at least about 20 seconds), an oxygen permeability (Dk) of at least about 50 barrers (preferably at least about 60 barrers, more preferably at least about 70 barrers, and even more preferably at least 80 barrers), and a modulus of elasticity of 0.2 MPa to about 1.8 MPa (preferably about 0.2 MPa to about 1.5 MPa, more preferably about 0.3 MPa to about 1.2 MPa, even more preferably about 0.4 MPa to about 1.0 MPa).

[0148] The amount of component (e) relative to the total weight of the bulk silicone hydrogel material in the dry state can be calculated based on the weight percentage of component (e) relative to the total weight of all polymerizable components in the polymerizable composition for forming the bulk silicone hydrogel material.

[0149] In various preferred embodiments, the bulk silicone hydrogel material further comprises repeating units of at least one non-silicone vinyl crosslinking agent, repeating units of at least one UV-absorbing vinyl monomer, repeating units of at least one polymerizable UV / HEVL-absorbing compound, repeating units of at least a polymerizable photochromic compound, or combinations thereof.

[0150] In various preferred embodiments, the non-silicone hydrogel material is (1) a crosslinked polymer material comprising repeating monomer units of at least 25 mol% (preferably at least 35 mol%, more preferably at least 45 mol%, even more preferably at least 55 mol%) of at least one hydrophilic vinyl monomer, wherein at least one hydrophilic vinyl monomer is alkyl (meth)acrylamide (any one of those described below), N-2-dimethylaminoethyl (meth)acrylamide, dimethylaminoethyl (meth)acrylate, a hydroxyl-containing acrylic monomer (any one of those described below), an N-vinylamide monomer (any one of those described below), a methylene-containing pyrrolidone monomer (i.e., a pyrrolidone derivative having a methylene group linked to the pyrrolidone ring at the 3- or 5-position) (any one of those described below), C 1 ~C 4An acrylic monomer having an alkoxyethoxy group (any one described below), a vinyl ether monomer (any one described below), an allyl ether monomer (any one described below), and a combination thereof, preferably (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 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, 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, methoxypoly(ethylene glycol)ethyl(meth)acrylamide having a number average molecular weight of up to 1500, C having a weight average molecular weight of up to 1500 1 ~C 4-Alkoxypolyethylene glycol (meth)acrylate, 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)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), 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, even more preferably (meth)acrylamide, dimethyl(meth)acrylamide, N-2-hydroxyethyl(meth)acrylamide, N,N-bis(hydroxyethyl)(meth)acrylamide, N-2,A crosslinked polymer material selected from the group consisting of 3-dihydroxypropyl (meth)acrylamide, N-tris(hydroxymethyl)methyl (meth)acrylamide, 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, and combinations thereof; (2) A crosslinked polymer material containing repeating monomer units of at least 25 mol% (preferably at least 35 mol%, more preferably at least 45 mol%, even more preferably at least 55 mol%) of at least one phosphorylcholine-containing vinyl monomer (any one described below), wherein the at least one phosphorylcholine-containing vinyl monomer is preferably selected from the group consisting of (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, and combinations thereof, a crosslinked polymer material; (3) A crosslinked polymer material containing a poly(ethylene glycol) chain, wherein the poly(ethylene glycol) chain preferably has (a) a poly(ethylene glycol) having a single functional group of -NH 2 , -SH or -COOH, (b) a poly(ethylene glycol) having two terminal functional groups selected from the group consisting of -NH 2 , -COOH, -SH, and combinations thereof, (c) -NH 2A multi-arm poly(ethylene glycol) having one or more functional groups selected from the group consisting of -COOH, -SH, and combinations thereof, and (d) a crosslinked polymer material directly derived from combinations thereof.

[0151] Examples of alkyl (meth)acrylamides 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, and combinations thereof.

[0152] 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 having a number average molecular weight of up to 1500, poly(ethylene glycol)ethyl(meth)acrylamide having a number average molecular weight of up to 1500, and combinations thereof.

[0153] 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, N-vinyl-6-ethyl-2-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.

[0154] Preferred methylene-containing (=CH 2)Examples of 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.

[0155] C 1 ~C 4 Examples of preferred acrylic monomers having an alkoxyethoxy group 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, C 1 ~C 4 -alkoxypoly(ethylene glycol) (meth)acrylate, methoxy-poly(ethylene glycol) ethyl (meth)acrylamide having a number average molecular weight of up to 1500, and combinations thereof.

[0156] 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.

[0157] Examples of 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.

[0158] Examples of 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)acryloyloxy)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)pentyl-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,2-(Vinylcarbonylamino)ethyl-2'-(trimethylammonio)ethyl phosphate, 2-(allyloxycarbonylamino)ethyl-2'-(trimethylammonio)ethyl phosphate, 2-(butenoyloxy)ethyl-2'-(trimethylammonio)ethyl phosphate, and combinations thereof are included.

[0159] Hydrophilic polysiloxane vinyl crosslinking agents, carboxyl-containing (meth)acryloxy monomers, non-silicone vinyl crosslinking agents, UV-absorbing vinyl monomers; polymerizable UV / HEVL absorbing compounds; polymerizable photochromic compounds, free radical initiators, other polymerizable components known to be suitable for making silicone hydrogel contact lenses, various embodiments of water-soluble and thermally crosslinkable hydrophilic polymer materials for forming non-silicone hydrogel coatings on silicone hydrogel contact lenses are described above and can be used in this aspect of the present invention.

[0160] The coated silicone hydrogel contact lenses of the present invention further have an equilibrium water content of about 20 wt% to about 75 wt% (preferably about 25 wt% to about 70 wt%, more preferably about 30 wt% to about 65 wt%) (i.e., when fully hydrated), a friction evaluation of about 3.0 or less (preferably about 2.5 or less, more preferably about 2 or less, even more preferably about 1.5 or less), an average water contact angle of about 90 degrees or less (preferably about 80 degrees or less, more preferably about 70 degrees or less, even more preferably about 60 degrees or less) by the droplet method, or combinations thereof.

[0161] Although 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 more explanatory than limiting. 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 the present disclosure. In addition, as shown below, it should be understood that aspects of various embodiments of the present invention can be wholly or partially exchanged, or combined in any manner, and / or used together. 1. A method for manufacturing a coated silicone hydrogel contact lens, comprising: (1) introducing a polymerizable composition into a lens molding mold, wherein the polymerizable composition comprises (a) at least one hydrophilic polysiloxane vinyl-based crosslinking agent, (b) optionally, hydroxyethyl methacrylate, (c) at least one C 1 ~C 2 alkoxyethyl (meth)acrylate, (d) at least one carboxyl-containing (meth)acryloxy monomer in an amount of about 2 wt% to about 10 wt% based on the total amount of all polymerizable components, (e) at least one free radical, and (f) optionally, at least one solvent selected from the group consisting of water, propylene glycol, polyethylene glycol having a molecular weight of 400 daltons or less, and combinations thereof, the step of introducing the polymerizable composition; (2) thermally curing or curing with actinic radiation the polymerizable composition in the lens molding mold to form a silicone hydrogel lens precursor comprising a bulk silicone hydrogel material containing carboxyl groups; (3) optionally, hydrating the silicone hydrogel lens precursor obtained in step (2) in water or an aqueous solution to obtain a hydrated silicone hydrogel contact lens; (4) Heating the silicone hydrogel lens precursor obtained in step (2) or the hydrated silicone hydrogel contact lens obtained in step (3) directly in an aqueous solution having a pH of about 6.8 to about 8.5 and containing at least one water-soluble and thermally crosslinkable hydrophilic polymer material 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 layer of a crosslinked hydrophilic polymer material covalently bonded to the bulk silicone hydrogel material, A method in which the coated silicone hydrogel contact lens exhibits a water break-up time (WBUT) of at least about 5 seconds and an oxygen permeability of at least about 50 barrers. 2. The method according to Embodiment 1, wherein the total amount of components (a) to (e) is at least about 90% by weight based on the total amount of all polymerizable components in the polymerizable composition. 3. The method according to Embodiment 1, wherein the total amount of components (a) to (e) is at least about 92% by weight based on the total amount of all polymerizable components in the polymerizable composition. 4. The method according to Embodiment 1, wherein the total amount of components (a) to (e) is at least about 94% by weight, more preferably at least about 96% by weight based on the total amount of all polymerizable components in the polymerizable composition. 5. The method according to Embodiment 1, wherein the total amount of components (a) to (e) is at least about 96% by weight based on the total amount of all polymerizable components in the polymerizable composition. 6. The method according to any one of Embodiments 1 to 5, wherein the polymerizable composition contains about 30% to about 65% by weight of component (a) based on the total amount of all polymerizable components. 7. The method according to any one of Embodiments 1 to 5, wherein the polymerizable composition contains about 35% to about 60% by weight of component (a) based on the total amount of all polymerizable components. 8. The method according to any one of Embodiments 1 to 5, wherein the polymerizable composition contains about 40% to about 60% by weight of component (a) based on the total amount of all polymerizable components. 9. The method according to any one of Embodiments 1 to 8, wherein the polymerizable composition contains components (b) and (c) in an amount of about 30% to about 65% by weight based on the total amount of all polymerizable components. 10. The method according to any one of Embodiments 1 to 8, wherein the polymerizable composition contains components (b) and (c) in an amount of about 35% to about 60% by weight based on the total amount of all polymerizable components. 11. The method according to any one of Embodiments 1 to 8, wherein the polymerizable composition contains components (b) and (c) in an amount of about 40% to about 60% by weight based on the total amount of all polymerizable components. 12. The method according to any one of Embodiments 1 to 11, wherein the polymerizable composition contains component (d) in an amount of about 2% to about 10% by weight based on the total amount of all polymerizable components. 13. The method according to any one of Embodiments 1 to 11, wherein the polymerizable composition contains component (d) in an amount of about 3% to about 9% by weight based on the total amount of all polymerizable components. 14. The method according to any one of Embodiments 1 to 11, wherein the polymerizable composition contains component (d) in an amount of about 4% to about 8% by weight based on the total amount of all polymerizable components. 15. The method according to any one of Embodiments 1 to 14, wherein the weight ratio of component (c) to component (b) in the polymerizable composition is about 40 to about 20. 16. The method according to any one of Embodiments 1 to 14, wherein the weight ratio of component (c) to component (b) in the polymerizable composition is about 35 to about 15. 17. The method according to any one of Embodiments 1 to 14, wherein the weight ratio of component (c) to component (b) in the polymerizable composition is about 30 to about 15. 18. The method according to any one of Embodiments 1 to 17, wherein the polymerizable composition further contains one or more polymerizable components selected from the group consisting of (g) non-silicone vinyl-based crosslinking agents, (h) UV-absorbing vinyl-based monomers, (i) polymerizable UV / high-energy violet light-absorbing compounds, (j) polymerizable photochromic compounds, (k) polymerizable colorants, and (l) combinations thereof, provided that the total of components (g) to (l) is less than 10% by weight based on the amount of all polymerizable components. 19. The method according to embodiment 18, wherein the curable composition further comprises a non-silicone vinyl-based crosslinking agent 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, 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)acryloxyethyl] phosphate, trimethylolpropane di-(meth)acrylate, and 3,4-bis[(meth)acryloyl]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), piperazine diacrylamide (or 1,4-bis(meth)acryloylpiperazine), triallyl isocyanurate, triallyl cyanurate, and combinations thereof. 20. The method according to embodiment 19, wherein the non-silicone vinyl-based crosslinking agent is 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. 21. The method according to any one of embodiments 1 to 20, wherein the heating step is preferably carried out by autoclaving a silicone hydrogel lens precursor immersed in a packaging solution (i.e., a buffered aqueous solution) in a sealed lens package at a temperature of about 115°C to about 125°C for approximately 20 to 90 minutes. 22. The method according to any one of embodiments 1 to 21, wherein the at least one water-soluble and thermally crosslinkable hydrophilic polymer material contains an azetidinium group, an epoxy group, or a combination thereof. 23. The method according to embodiment 22, wherein the at least one water-soluble and thermally crosslinkable hydrophilic polymer material has a three-dimensional network and thermally crosslinkable groups bonded within or to the network. 24. The method according to embodiment 22, wherein the at least one water-soluble and thermally crosslinkable hydrophilic polymer material is one or more multi-arm polyethylene glycols each having a terminal epoxy group; a mixture of a multi-arm polyethylene glycol having a terminal epoxy 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 epoxy group and a hydrophilic 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. 25. The method according to embodiment 22, wherein the at least one water-soluble and thermally crosslinkable hydrophilic polymer material contains an azetidinium group and is a partial reaction product of an azetidinium-containing polymer with a hydrophilic enhancer having at least one reactive 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. 26. The method according to embodiment 25, 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 combinations thereof. 27. The method according to embodiment 25 or 26, wherein the hydrophilic enhancer is a monosaccharide, disaccharide, or oligosaccharide containing a primary amino, secondary amino, carboxyl, or thiol group, or combinations thereof. 28. The method according to embodiment 25 or 26, wherein the hydrophilic 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 combinations thereof. 29. The method according to embodiment 28, wherein the hydrophilic enhancer is a polysaccharide having a primary amine group, a secondary amine group, a carboxyl group, or combinations thereof. 30. The hydrophilic enhancer is -NH 2 , poly(ethylene glycol) having a single functional group of -SH or -COOH; -NH 2 , poly(ethylene glycol) having two terminal functional groups selected from the group consisting of -COOH, -SH, and combinations thereof; -NH 2 , multi-arm poly(ethylene glycol) having one or more functional groups selected from the group consisting of -COOH, -SH, and combinations thereof; Monoamino, monocarboxyl, diamino or dicarboxyl terminal homo- or copolymers of non-reactive hydrophilic vinyl monomers; (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, which is a copolymer that is a polymerization product of the composition; The 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; The method according to Embodiment 28, wherein 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, azlactone group, or aziridine group. 31. The reactive vinyl monomer is acrylic acid, methacrylic acid, ethylacrylic acid, 2-(meth)acrylamidoglycolic acid, N-2-aminoethyl (meth)acrylamide, N-2-methylaminoethyl (meth)acrylamide, N-2-ethylaminoethyl (meth)acrylamide, N-3-aminopropyl (meth)acrylamide, N-3-methylaminopropyl (meth)acrylamide, 2-aminoethyl (meth)acrylate, 2-methylaminoethyl (meth)acrylate, 2-ethylaminoethyl (meth)acrylate, 3-aminopropyl (meth)acrylate, 3-methylaminopropyl (meth)acrylate, 3-amino-2-hydroxypropyl (meth)acrylate, or a combination thereof; 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 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, 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, methoxypoly(ethylene glycol) ethyl (meth)acrylamide having a number average molecular weight of up to 1500, C having a weight average molecular weight of up to 1500 1 ~C 4The method according to embodiment 30, selected from the group consisting of -alkoxypolyethylene glycol (meth)acrylate, 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. 32. The method according to any one of embodiments 1 to 31, wherein the aqueous solution has a pH of about 7.0 to about 8.2, and the aqueous solution contains about 0.01 wt% to about 2 wt% (preferably about 0.05 wt% to about 1.5 wt%, more preferably about 0.1 wt% to about 1 wt%, even more preferably about 0.2 wt% to about 0.5 wt%) of the at least one water-soluble, thermally crosslinkable hydrophilic polymer material. 33. The method according to any one of embodiments 1 to 31, wherein the aqueous solution has a pH of about 7.2 to about 8.0, and the aqueous solution contains about 0.01 wt% to about 2 wt% (preferably about 0.05 wt% to about 1.5 wt%, more preferably about 0.1 wt% to about 1 wt%, even more preferably about 0.2 wt% to about 0.5 wt%) of the at least one water-soluble, thermally crosslinkable hydrophilic polymer material. 34. The method according to any one of embodiments 1 to 33, wherein the aqueous solution contains a mixture of monobasic sodium phosphate and dibasic sodium phosphate to maintain the pH of the aqueous solution, and the total concentration of monobasic sodium phosphate and dibasic sodium phosphate is at least 30 mM. 35. The method according to embodiment 34, wherein the total concentration of monobasic sodium phosphate and dibasic sodium phosphate is at least 35 mM. 36. The method according to embodiment 34, wherein the total concentration of monobasic sodium phosphate and dibasic sodium phosphate is at least 40 mM. 37. The method according to embodiment 34, wherein the total concentration of monobasic sodium phosphate and dibasic sodium phosphate is at least 45 mM. 38. The tonicity of the aqueous solution is adjusted to about 200 to about 450 milliosmoles (mOsm), and the aqueous solution contains one or more organic tonicity agents selected from the group consisting of glycerol, propylene glycol, polyethylene glycol having a number average molecular weight of 200 to 800 daltons, mannitol, sorbitol, xylitol, and mixtures thereof, and the total concentration of the one or more organic tonicity agents is at least 70 mM, the method according to any one of embodiments 1 to 37. 39. The method according to embodiment 38, wherein the total concentration of the one or more organic tonicity agents is at least 90 mM. 40. The method according to embodiment 38, wherein the total concentration of the one or more organic tonicity agents is at least 110 mM. 41. The method according to embodiment 38, wherein the total concentration of the one or more organic tonicity agents is at least 130 mM. 42. A coated silicone hydrogel contact lens, comprising a bulk silicone hydrogel material and a layer of a non-silicone hydrogel material thereon, wherein the bulk silicone hydrogel material comprises (a) repeating units of at least one hydrophilic polysiloxane vinyl-based crosslinking agent, (b) optionally (but preferably) repeating units of hydroxyethyl methacrylate, (c) at least one C 1 ~C 2 repeating units of alkoxyethyl (meth)acrylate, (d) carboxyl-containing repeating units of at least one carboxyl-containing (meth)acryloxy monomer, and (e) optionally, at least one repeating unit of a polymerizable component selected from the group consisting of non-silicone vinyl-based crosslinking agents, UV-absorbing vinyl-based monomers, polymerizable UV / high-energy violet light-absorbing compounds, polymerizable photochromic compounds, polymerizable colorants, and combinations thereof (provided that the amount of component (e) is less than 10% by weight based on the total weight of the bulk silicone hydrogel material in the dry state), and the layer of non-silicone hydrogel material is covalently bonded to the bulk silicone hydrogel material through carboxyl groups of the carboxyl-containing repeating units. A coated silicone hydrogel contact lens having a water break-up time (WBUT) of at least 5 seconds, an oxygen permeability (Dk) of at least 50 barrers, and a modulus of elasticity of from about 0.2 MPa to about 1.8 MPa. 43. The coated silicone hydrogel contact lens according to embodiment 42 or the method according to any one of embodiments 1 to 41, wherein the coated silicone hydrogel contact lens has a water break-up time (WBUT) of at least about 10 seconds. 44. The coated silicone hydrogel contact lens according to embodiment 42 or the method according to any one of embodiments 1 to 41, wherein the coated silicone hydrogel contact lens has a water break-up time (WBUT) of at least about 15 seconds. 45. The coated silicone hydrogel contact lens according to embodiment 42 or the method according to any one of embodiments 1 to 41, wherein the coated silicone hydrogel contact lens has a water break-up time (WBUT) of at least about 20 seconds. 46. The coated silicone hydrogel contact lens according to any one of embodiments 42 to 45 or the method according to any one of embodiments 1 to 41 and 43 to 45, wherein the coated silicone hydrogel contact lens has an oxygen permeability (Dk) of at least about 60 barrers. 47. The coated silicone hydrogel contact lens according to any one of embodiments 42 to 45 or the method according to any one of embodiments 1 to 41 and 43 to 45, wherein the coated silicone hydrogel contact lens has an oxygen permeability (Dk) of at least about 70 barrers. 48. The coated silicone hydrogel contact lens according to any one of embodiments 42 to 45 or the method according to any one of embodiments 1 to 41 and 43 to 45, wherein the coated silicone hydrogel contact lens has an oxygen permeability (Dk) of at least about 80 barrers. 49. The coated silicone hydrogel contact lens has a modulus of elasticity of from about 0.2 MPa to about 1.5 MPa, the coated silicone hydrogel contact lens according to any one of embodiments 42 to 48 or the method according to any one of embodiments 1 to 41 and 43 to 48. 50. The coated silicone hydrogel contact lens has a modulus of elasticity of from about 0.3 MPa to about 1.2 MPa, the coated silicone hydrogel contact lens according to any one of embodiments 42 to 48 or the method according to any one of embodiments 1 to 41 and 43 to 48. 51. The coated silicone hydrogel contact lens has a modulus of elasticity of from about 0.4 MPa to about 1.0 MPa, the coated silicone hydrogel contact lens according to any one of embodiments 42 to 48 or the method according to any one of embodiments 1 to 41 and 43 to 48. 52. The coated silicone hydrogel contact lens has an equilibrium water content of from about 20 wt% to about 75 wt% (i.e., when fully hydrated), the coated silicone hydrogel contact lens according to any one of embodiments 42 to 51 or the method according to any one of embodiments 1 to 41 and 43 to 51. 53. The coated silicone hydrogel contact lens has an equilibrium water content of from about 25 wt% to about 70 wt% (i.e., when fully hydrated), the coated silicone hydrogel contact lens according to any one of embodiments 42 to 51 or the method according to any one of embodiments 1 to 41 and 43 to 51. 54. The coated silicone hydrogel contact lens has an equilibrium water content of from about 30 wt% to about 65 wt% (i.e., when fully hydrated), the coated silicone hydrogel contact lens according to any one of embodiments 42 to 51 or the method according to any one of embodiments 1 to 41 and 43 to 51. 55. The coated silicone hydrogel contact lens according to any one of embodiments 42 to 54, or the method according to any one of embodiments 1 to 41 and 43 to 54, having a friction evaluation of about 3.0 or less. 56. The coated silicone hydrogel contact lens according to any one of embodiments 42 to 54, or the method according to any one of embodiments 1 to 41 and 43 to 54, having a friction evaluation of about 2.5 or less. 57. The coated silicone hydrogel contact lens according to any one of embodiments 42 to 54, or the method according to any one of embodiments 1 to 41 and 43 to 54, having a friction evaluation of about 2 or less. 58. The coated silicone hydrogel contact lens according to any one of embodiments 42 to 54, or the method according to any one of embodiments 1 to 41 and 43 to 54, having a friction evaluation of about 1.5 or less. 59. The coated silicone hydrogel contact lens according to any one of embodiments 42 to 58, or the method according to any one of embodiments 1 to 41 and 43 to 58, having an average water contact angle of about 90 degrees or less by the droplet method. 60. The coated silicone hydrogel contact lens according to any one of embodiments 42 to 58, or the method according to any one of embodiments 1 to 41 and 43 to 58, having an average water contact angle of about 80 degrees or less by the droplet method. 61. The coated silicone hydrogel contact lens according to any one of Embodiments 42 to 58, or the method according to any one of Embodiments 1 to 41 and 43 to 58, having an average water contact angle of about 70 degrees or less, more preferably about 60 degrees or less, by the droplet method. 62. The coated silicone hydrogel contact lens according to any one of Embodiments 42 to 58, or the method according to any one of Embodiments 1 to 41 and 43 to 58, having an average water contact angle of about 60 degrees or less by the droplet method. 63. The at least one hydrophilic polysiloxane vinyl-based crosslinking agent contains at least about 1.50 milliequivalents / gram ("meq / g") of a hydrophilic moiety, which is preferably a hydroxyl group (-OH), a carboxyl group (-COOH), an amino group (-NHR N1 (wherein R N1 is H or C 1 ~C 2 alkyl)), an amide moiety (-CO-NR N1 R N2 (wherein R N1 is H or C 1 ~C 2 alkyl, and R N2 is a covalent bond, H, or C 1 ~C 2 alkyl)), an N-C 1 ~C 3 acylamino group, a urethane moiety (-NH-CO-O-), a urea moiety (-NH-CO-NH-),

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[0162] Those skilled in the art will be able to implement the present invention based on the above disclosure. Various modifications, changes, and combinations can be made to the various embodiments described herein. References to the following examples are proposed to make it more possible for the reader to fully understand a particular embodiment and its advantages. The specification and examples are intended to be considered illustrative.

Examples

[0163] Example 1 Measurement of oxygen permeability Unless otherwise specified, the oxygen permeability coefficient (Dk / t), intrinsic (or edge-corrected) oxygen permeability (Dk i or Dk c ) of the lens and lens material is measured according to the procedure described in ISO 18369-4.

[0164] Water break-up time (WBUT) test The surface hydrophilicity of the lens (after autoclave treatment) is evaluated by measuring the time required for the water film to begin to break on the lens surface according to the procedure described in Example 1 of US Patent Application Publication No. 20210181379A1.

[0165] Equilibrium water content The equilibrium water content (EWC) of the contact lens is determined according to the procedure described in Example 1 of US Patent Application Publication No. 20210181379A1.

[0166] Elastic modulus The elastic modulus of the contact lens is determined according to the procedure described in Example 1 of US Patent Application Publication No. 20210181379A1.

[0167] Light transmittance Manually place the contact lens in a specially manufactured sample holder or the like that can maintain the shape of the lens in the same manner as when placed on the eye. Then, immerse this holder in a quartz cell with a 1 cm path length containing phosphate buffered saline (PBS, pH approximately 7.0 - 7.4) as a reference. For this measurement, a UV / Visible spectrophotometer such as a Varian Cary 3E UV-Visible spectrophotometer equipped with a LabSphere DRA-CA-302 beam splitter or the like can be used. The percent transmission spectrum is collected in the wavelength range of 250 - 800 nm, and the %T values are collected at 0.5 nm intervals. The light transmittance of the contact lens is the average transmittance % from 400 nm to 700 nm.

[0168] Measurement of water contact angle (WCA). The measurement of the water contact angle (WCA) is carried out by the droplet method using pure water (Fluka, surface tension 72.5 mN / m at 20 °C) with a DSA 10 droplet formation analysis system from Kruess GmbH, Germany. For the purpose of the measurement, the contact lens is taken out of the storage solution using tweezers and excess storage solution is removed by gently shaking. The contact lens is placed on the male part of the lens forming mold and gently wiped with a dry clean cloth. Then, a water droplet (approximately 1 μl) is placed at the apex of the lens, and the change in the contact angle of this droplet over time (WCA(t), circle fitting mode) is monitored. WCA is calculated by extrapolating the graph WCA(t) to t = 0.

[0169] Determination of the lens diameter of the hydrated contact lens The lens diameter of the hydrated contact lens is determined according to the procedure described in Example 1 of US Patent Application Publication No. 20210181379A1.

[0170] Evaluation of lubricity. The lubricity of the contact lens is evaluated by using a finger-felt lubricity test that qualitatively evaluates the slipperiness of the lens surface on a friction evaluation scale of 0 to 4. The higher the friction evaluation, the lower the slipperiness (or lubricity).

[0171] Friction evaluations of 0, 1, 2, 3, and 4 (hereinafter referred to as "FR") are assigned to commercially available lenses: DAILIES® TOTAL1®; ACUVUE® OASYS™; ACUVUE® ADVANCE PLUS™; DAILIES® Aqua Comfort Plus®; and AIR OPTIX® respectively. They are used as standard lenses to determine the friction evaluation of the lenses to be tested.

[0172] Place the samples in PBS for at least two rinses of 30 minutes each, then transfer to fresh PBS before evaluation. Before evaluation, wash hands with soap solution, rinse thoroughly with DI water, and then wipe with a KimWipe® towel. Touch the sample between the fingers and assign a numerical value to each sample compared to the above-described standard lens. For example, if the lens is determined to be slightly better than the AIR OPTIX® lens, assign a numerical value of 3 to the lens. The value of the friction evaluation is obtained by averaging the results of at least two friction evaluations of the contact lens by two or more people and / or by averaging the friction evaluations of two or more contact lenses (from the same batch of lens production) by one person.

[0173] The finger lubricity (i.e., friction evaluation) of the contact lens can be determined directly out-of-pack (OOP), but can also be determined after immersion in PBS for ≧ 30 minutes following the procedure described above.

[0174] Chemical substance In the following examples, the following abbreviations are used: HEMA represents hydroxyethyl methacrylate; EOEMA represents ethoxyethyl methacrylate; MAA represents methacrylic acid; AA represents acrylic acid; PEG-DA represents poly(ethylene glycol) diacrylate (Mn about 800 g / mol); PG represents propylene glycol; Vazo 52 represents 2,2'-azobis(2,4-dimethylvaleronitrile); Vazo 67 represents 2,2'-azodi(2-methylbutyronic nitrile); Perkadox 16 represents di(4-tert-butylcyclohexyl) peroxydicarbonate; MPC represents 2-methacryloyloxyethyl phosphorylcholine; EGMA represents 2-methoxyethyl methacrylate; AMA represents allyl methacrylate; TEGDMA represents tri(ethylene glycol) di-methacrylate; TEGDVE represents tri(ethylene glycol) divinyl ether; Nobloc represents 2-[3-(2H-benzotriazol-2-yl)-5-hydroxyphenyl]ethyl methacrylate; RB247 represents Reactive Blue 247; PBS represents phosphate buffered saline having a pH of 7.2 ± 0.2 at 25°C and containing about 0.044 wt% NaH 2 PO 4 ·H 2 O, about 0.388 wt% Na 2 HPO 4 ·2H 2 O, and about 0.79 wt% NaCl; wt.% represents weight percent; HO-PDMS-MA represents the reaction product of glycidyl methacrylate and

Chemical formula

Chemical formula

[0175] Example 2 Phosphate Buffered Saline (PBS) Phosphate Buffered Saline is prepared by dissolving a predetermined amount of purified water (distilled or deionized) with NaH 2 PO 4 ·H 2 O, Na 2 HPO 4 ·2H 2 O, and NaCl: about 0.044 w / w% of NaH 2 PO 4 ·H 2 O, about 0.388 w / w / % of Na 2 HPO 4 ·2H 2 O and about 0.79 w / w% of NaCl.

[0176] Preparation of Packaging Saline - Saline - 1 Copolymer 845 is a copolymer of N - vinylpyrrolidone and dimethylaminoethyl methacrylate (GPC M w about 700,000 - 1,200,000 g / mol, M w / M n about 5.7 - 8.5) and is obtained from ISP.

[0177]

Chemical formula

[0178] The packaging saline having the following composition is prepared by dissolving all components in 1 L of water: 0.77 wt% NaCl; 0.076 wt% NaH 2 PO 4 ·H2 O; 0.47 wt% Na 2 HPO 4 ·7H 2 O; 1.0 wt% Copolymer - 845; and 0.015 wt% CH 3 O(EO) 45 (BO) 10 。

[0179] Preparation of In - package Coating Physiological Saline - IPC - 1 IPC physiological saline (IPC - 1) is prepared by mixing an appropriate amount of poly(AAm - co - AA) or other wetting agent with PAE in phosphate - buffered saline and pre - treating at a specific temperature for a desired time. Poly(AAm - co - AA)(90 / 10) partial sodium salt, poly(AAm - co - AA) 90 / 10, Mw 200,000) is purchased from Polysciences, Inc. and used as received. Kymene or PAE solutions with different solids contents are purchased from Solenis as aqueous solutions and used as received. 0.07% PAAm - PAA and approximately 0.1% Kymene are mixed together in PBS and pre - treated at 60 °C for about 6 hours. After pre - treatment by heat, IPC physiological saline is filtered using a 0.22 - micron membrane filter and cooled back to room temperature. To prevent the growth of bioburden, 5 ppm hydrogen peroxide can be added to the final IPC physiological saline, and the IPC physiological saline is filtered using a 0.22 - micron membrane filter.

[0180] Preparation of Polymerizable Composition The polymerizable composition (SiHy lens formulation) is prepared to have the composition as shown in Table 1.

[0181]

Table 1

[0182] The complex is prepared by placing the described components in a clean bottle in their target amounts and mixing at 600 rpm for 30 minutes at room temperature using a stir bar. After all solids have dissolved, the formulation is filtered by using a 2.7 μm glass microfiber filter (GMF).

[0183] Cast silicone hydrogel contact lens The lens formulation is purged with nitrogen at room temperature for 30 - 35 minutes. N 2 The purged lens formulation is placed into a polypropylene mold and thermally cured in an oven under nitrogen under the following curing conditions: heat up from room temperature to 55 °C at a heating rate of about 7 °C / min; hold at 55 °C for about 30 minutes; heat up from 55 °C to 80 °C at a heating rate of about 7 °C / min; hold at 80 °C for about 30 minutes; heat up from 80 °C to 100 °C at a heating rate of about 7 °C / min; hold at 100 °C for about 30 minutes. Open the mold and remove the molded lens from the mold.

[0184] The lens is then hydrated in packaging saline for 30 minutes, inspected, and packaged in glass vials in packaging saline for sterilization (autoclaved at 121 °C for 45 minutes). List the lens properties in Table 2.

[0185]

Table 2

[0186] Example 3 Preparation of polyacrylic acid (PAA) solution A solution of polyacrylic acid (PAA) (Carbopol® 907 polymer from Lubrizol, Mw 82k) is dissolved in propylene glycol to have a concentration of 5 wt%.

[0187] Preparation of packaging saline - saline - 2 Polyvinylpyrrolidone (PVP) (M from Sigma nDissolve it (about 360 K) in the PBS prepared in Example 2 so as to have a concentration of 1% by weight.

[0188] Preparation of Polymerizable Composition Prepare a polymerizable composition (SiHy lens formulation) to have the composition as shown in Table 3.

[0189]

Table 3

[0190] Cast Molded Silicone Hydrogel Contact Lens Cast mold the SiHy lens precursor (dry lens) according to the procedure described in Example 2. After dry demolding / lens removal, hydrate the SiHy lens precursor in physiological saline 2 for about 30 minutes, inspect it, and package it in a glass vial in package physiological saline for sterilization (autoclaving at 121 °C for 45 minutes). List the lens characteristics in Table 4.

[0191]

Table 4

[0192] Example 4 Preparation of Polymerizable Composition Prepare a polymerizable composition (SiHy lens formulation) to have the composition as shown in Table 5.

[0193]

Table 5

[0194] Cast Molded Silicone Hydrogel Contact Lens The SiHy lens precursor (dry lens) is injection molded according to the procedure described in Example 2. After dry demolding / lens removal, the SiHy lens precursor is placed, inspected, and packaged in a glass vial in IPC-1 prepared in Example 2 for sterilization (autoclaving at 121 °C for 45 minutes). The lens properties are listed in Table 6.

[0195] [Table 6]

[0196] Example 5 Preparation of the Polymerizable Composition The polymerizable composition (SiHy lens formulation) is prepared to have the composition as shown in Table 7.

[0197] [Table 7]

[0198] Injection Molded Silicone Hydrogel Contact Lens The SiHy lens precursor (dry lens) is injection molded according to the procedure described in Example 2. After dry demolding / lens removal, the SiHy lens precursor is placed, inspected, and packaged in a glass vial in IPC-1 prepared in Example 2 for sterilization (autoclaving at 121 °C for 45 minutes). The lens properties are listed in Table 8.

[0199] [Table 8]

[0200] Example 6 Preparation of the Polymerizable Composition The polymerizable composition (SiHy lens formulation) is prepared to have the composition as shown in Table 9.

[0201] [Table 9]

[0202] Injection-molded silicone hydrogel contact lens The SiHy lens precursor (dry lens) is injection-molded according to the procedure described in Example 2. After dry demolding / lens removal, the SiHy lens precursor (dry lens) is individually packaged in 0.85 mL of IPC-1 prepared in Example 2 within a duodrop blister shell and subsequently sterilized (autoclaved at 121 °C for 45 minutes). The lens properties are listed in Table 10.

[0203]

Table 10

[0204] Measure the lens diameter data for both lenses immersed in PBS outside the package and for a specific time according to the procedure described in Example 1. As shown in Table 11, the lens diameter for both types of lenses increases over time during PBS immersion.

[0205]

Table 11

[0206] Regarding this increase in diameter, it is considered that the packaged physiological saline (0.85 mL of IPC-1) may not have a sufficiently high pH or may not have sufficient buffering capacity to neutralize the carboxylic acid groups (i.e., methacrylic acid) in the bulk SiHy material. Therefore, when the SiHy lens precursor is placed in PBS, the phosphate in PBS (i.e., more buffer) may hold the deprotonation of the carboxylic acid and cause the lens to swell.

[0207] To support this hypothesis, the buffering capacity of IPC-1 was calculated, and [Na 2 HPO 4 ·2H 2 O]=21.8 mM; [NaH 2 PO 4·H 2 Assume it has [O]=3.2 mM. Calculate the concentration of carboxyl groups (from MAA or AA) by assuming that 1) the dry lens weight is 20 mg and 2) the package physiological saline volume is 0.85 mL, to be 16.4 mM and 19.6 mM respectively. Based on these calculations, it is clear that the buffering capacity (especially dibasic phosphate for neutralizing carboxylic acid) is very close to the acid concentration for neutralizing all or most of the acid groups.

[0208] Example 7 Phosphate buffer (PB) The aqueous phosphate buffer (PB) is prepared by dissolving a predetermined amount of purified water (distilled or deionized) with NaH 2 PO 4 ·H 2 O, Na 2 HPO 4 ·2H 2 O: about 1.164 w / w% of Na 2 HPO 4 ·2H 2 O, about 0.044 w / w / % of NaH 2 PO 4 ·H 2 O.

[0209] Preparation of in-package coating physiological saline - IPC - 2 IPC physiological saline (IPC - 2) is prepared by blending IPC - 1 prepared in Example 2 and PB prepared above in a 1:1 weight ratio. The composition of IPC - 2 is about 0.05 wt% of PAE; 0.035 wt% of poly(AAm - co - AA) (90 / 10), 0.776 wt% of Na 2 HPO 4 ·2H 2 O, 0.044 wt% of NaH 2 PO 4 ·H 2 O, and 0.395 wt% of NaCl. Compared with IPC - 1, IPC - 2 has twice the concentration of Na 2 HPO 4 ·2H 2It has O, while the concentrations of PAE, poly(AAm-co-AA) and NaCl in IPC-2 are reduced by only half.

[0210] Preparation of the Polymerizable Composition The polymerizable composition (SiHy lens formulation) is prepared to have the composition as shown in Table 12.

[0211]

Table 12

[0212] Cast Molded Silicone Hydrogel Contact Lens The SiHy lens precursor (dry lens) is cast molded according to the procedure described in Example 2. After dry demolding / lens removal, the SiHy lens precursor (dry lens) is individually packaged in 0.85 mL of IPC-1 prepared in Example 2 within a duodrop blister shell and subsequently sterilized (autoclaved at 121 °C for 45 minutes).

[0213] The lens properties are summarized in Tables 13 and 14. It is clear that after replacing IPC-1 with IPC-2 (having a higher dibasic phosphate concentration and a higher pH), the lens diameter becomes much more stable when immersed in PBS, and the finger lubricity also appears to be improved. These property improvements are achieved even though IPC-2 contains half the PAE / poly(AAm-co-AA) concentration compared to IPC-1.

[0214]

Table 13

[0215]

Table 14

[0216] Example 8 Preparation of In-Package Coating Physiological Saline - IPC-3 IPC physiological saline (IPC-3) is prepared by blending the IPC-2 prepared in Example 7, the PB prepared in Example 7, and propylene glycol (PG) in a weight ratio of 50:50:1. The composition of IPC-3 is about 0.05 wt% PAE; 0.035 wt% poly(AAm-co-AA) (90 / 10), 0.768 wt% Na 2 HPO 4 ·2H 2 O, 0.044 wt% NaH 2 PO 4 ·H 2 O, 0.196 wt% NaCl; and 0.99 wt% PG.

[0217] Preparation of the polymerizable composition The polymerizable composition (SiHy lens formulation) is prepared to have the composition as shown in Table 15.

[0218]

Table 15

[0219] Cast silicone hydrogel contact lenses The SiHy lens precursor (dry lens) is cast according to the procedure described in Example 2. After dry demolding / lens removal, the SiHy lens precursor (dry lens) is individually packaged in 0.85 mL of the IPC-2 prepared in Example 7 or the IPC-3 prepared above in a duodrop blister shell and then sterilized (autoclaved at 121 °C for 45 minutes).

[0220] The lens properties (lens diameter and finger lubricity) are summarized in Table 16. As shown in the table, the lens diameter is stable in PBS. Compared with IPC-2, IPC-3 can provide better finger lubricity, which is likely due to its lower NaCl concentration that can further enhance carboxylate-IPC charge complex formation and their subsequent reactions during autoclaving.

[0221]

Table 16

[0222] Example 9 Preparation of In - package Coating Physiological Saline - IPC - 4 Physiological saline IPC - 4 is prepared based on the following composition - about 0.05 wt% of PAE; 0.035 wt% of poly(AAm - co - AA)(90 / 10), 0.776 wt% of Na 2 HPO 4 ·2H 2 O, 0.044 wt% of NaH 2 PO 4 ·H 2 O, 0.198 wt% of NaCl; and 0.0005 wt% of hydrogen peroxide and 1% of glycerol.

[0223] Preparation of Polymerizable Composition The polymerizable composition (SiHy lens formulation) is prepared to have the composition as shown in Table 17.

[0224]

Table 17

[0225] Cast - molded Silicone Hydrogel Contact Lens The SiHy lens precursor (dry lens) is cast - molded according to the procedure described in Example 2. After dry demolding / lens removal, the SiHy lens precursor (dry lens) is individually packaged in 0.85 mL of IPC - 2 prepared in Example 7 or IPC - 4 prepared above in a duodrop blister shell and then sterilized (autoclaved at 121 °C for 45 minutes).

[0226] The lens properties are summarized in Tables 18 and 19. As shown in the tables, the lens diameter shifts slightly in PBS. This may be due to the glycerol diffusion effect.

[0227]

Table 18

[0228]

Table 19

[0229] Example 10 Preparation of In-Package Coating Physiological Saline - IPC-4 The preparation of IPC physiological saline (IPC-4) is the same as that in Example 9.

[0230] Preparation of Polymerizable Composition A polymerizable composition (SiHy lens formulation) is prepared to have the composition as shown in Table 20.

[0231]

Table 20

[0232] Cast-Molded Silicone Hydrogel Contact Lenses The SiHy lens precursor (dry lens) is cast-molded according to the procedure described in Example 2. After dry demolding / lens removal, the SiHy lens precursor (dry lens) is individually packaged in 0.85 mL of IPC-2 prepared in Example 7 or IPC-4 prepared above in a duodrop blister shell and then sterilized (autoclaved at 121 °C for 45 minutes).

[0233] The lens properties are summarized in Tables 21 and 22. As shown in the tables, the lens diameter still shifts slightly in PBS. The presence of other factors such as the AA to HEMA ratio was shown. The composition of 10-5 resulted in an IP value of <1. This means that the formed lens network does not allow ion penetration in the aqueous medium.

[0234]

Table 21

[0235]

Table 22

[0236] Example 11 Preparation of In-Package Coating Physiological Saline - IPC-5 Physiological saline IPC-5 is prepared based on the following composition - approximately 0.05 wt% PAE; 0.035 wt% poly(AAm-co-AA) (90 / 10), 0.776 wt% Na 2 HPO 4 ·2H 2 O, 0.044 wt% NaH 2 PO 4 ·H 2 O, 0.160 wt% NaCl; and an appropriate amount of water to make 100%.

[0237] Preparation of the Polymerizable Composition The polymerizable composition (SiHy lens formulation) is prepared to have the composition as shown in Table 23.

[0238]

Table 23

[0239] Cast-Molded Silicone Hydrogel Contact Lenses The SiHy lens precursor (dry lens) is cast-molded according to the procedure described in Example 2. After dry demolding / lens removal, the SiHy lens precursor (dry lens) is individually packaged in 0.85 mL of the IPC-5 prepared above in a duodrop blister shell and subsequently sterilized (autoclaved at 121 °C for 45 minutes).

[0240] The lens properties are summarized in Tables 24 and 25.

[0241]

Table 24

[0242]

Table 25

[0243] Example 12 Preparation of In - Package Coating Physiological Saline - IPC - 5 The preparation of IPC physiological saline (IPC - 5) is the same as that in Example 11.

[0244] Preparation of Polymerizable Composition The polymerizable composition (SiHy lens formulation) is prepared to have the composition as shown in Table 26.

[0245]

Table 26

[0246] Cast - molded Silicone Hydrogel Contact Lens The SiHy lens precursor (dry lens) is cast - molded according to the procedure described in Example 2. After dry demolding / lens removal, the SiHy lens precursor (dry lens) is packaged in 0.85 mL of IPC - 5 prepared in Example 11 in a duodrop blister shell and then sterilized (autoclaved at 121 °C for 45 minutes).

[0247]

Table 27

[0248] The lens properties are summarized in Tables 27 and 28. As shown in the tables, MPC in the formulation plays a major role in improving lens IP.

[0249]

Table 28

[0250] Example 13 Preparation of In-Package Coating Physiological Saline - IPC-5 The preparation of IPC physiological saline (IPC-5) is the same as that in Example 11.

[0251] Preparation of Polymerizable Composition The polymerizable composition (SiHy lens formulation) is prepared to have the composition as shown in Table 29.

[0252] [Table 29]

[0253] Cast-Molded Silicone Hydrogel Contact Lens The SiHy lens precursor (dry lens) is cast-molded according to the procedure described in Example 2. After dry demolding / lens removal, the SiHy lens precursor (dry lens) is individually packaged in 0.85 mL of the IPC-5 physiological saline prepared above in a duodrop blister shell and then sterilized (autoclaved at 121 °C for 45 minutes).

[0254] [Table 30]

[0255] The lens properties are summarized in Tables 30 and 31. It was demonstrated that the MPC to HEMA ratio is another factor for the lens IP.

[0256] [Table 31]

[0257] Example 15 Preparation of In-Package Coating Physiological Saline - IPC-5 The preparation of IPC physiological saline (IPC-5) is the same as that in Example 11.

[0258] Preparation of Polymerizable Composition Prepare a coincidence composition (SiHy lens formulation) to have a composition as shown in Table 32.

[0259]

Table 32

[0260] Cast-molded silicone hydrogel contact lens Cast-mold the SiHy lens precursor (dry lens) according to the procedure described in Example 2. After dry demolding / lens removal, individually package the SiHy lens precursor (dry lens) in 0.85 mL of the IPC-5 physiological saline prepared above in a duodrop blister shell, and then sterilize it (autoclave treatment at 121 °C for 45 minutes).

[0261]

Table 33

[0262] Summarize the lens characteristics in Table 33. The experiment showed that MPC also improved lens transparency.

[0263] Example 16 Preparation of in-package coating physiological saline - IPC-5 The preparation of IPC physiological saline (IPC-5) is the same as that in Example 11.

[0264] Preparation of polymerizable composition Prepare a polymerizable composition (SiHy lens formulation) to have a composition as shown in Table 34.

[0265]

Table 34

[0266] Cast-molded silicone hydrogel contact lens The SiHy lens precursor (dry lens) is injection molded according to the procedure described in Example 2. After dry demolding / lens removal, the SiHy lens precursor (dry lens) is individually packaged in 0.85 mL of the IPC-5 physiological saline prepared above in a duodrop blister shell and subsequently sterilized (autoclaved at 121 °C for 45 minutes).

[0267]

Table 35

[0268] The lens IP values are listed in Table 35. The experiments showed that small amounts of NVP, AMA, or TEGDVE in the formulation did not improve the lens IP.

[0269] Example 17 Preparation of In-package Coating Physiological Saline - IPC-5 The preparation of IPC physiological saline (IPC-5) is the same as in Example 11.

[0270] Preparation of Polymerizable Composition A polymerizable composition (SiHy lens formulation) is prepared to have the composition as shown in Table 36.

[0271]

Table 36

[0272] Injection Molded Silicone Hydrogel Contact Lens The SiHy lens precursor (dry lens) is injection molded according to the procedure described in Example 2. After dry demolding / lens removal, the SiHy lens precursor (dry lens) is individually packaged in 0.85 mL of the IPC-5 physiological saline prepared above in a duodrop blister shell and subsequently sterilized (autoclaved at 121 °C for 45 minutes).

[0273]

Table 37

[0274] Example 18 Preparation of In-package Coating Physiological Saline - IPC-7 IPC physiological saline (IPC-7) is prepared based on the following composition - about 0.05 wt% PAE; 0.07 wt% poly(AAm-co-AA) (90 / 10), 0.776 wt% Na2HPO4·2H2O, 0.044 wt% NaH2PO4·H2O, 0.160 wt% NaCl; and an appropriate amount of water to make 100%.

[0275] Preparation of In-package Coating Physiological Saline - IPC-7B IPC physiological saline (IPC-7B) is prepared based on the following composition - about 0.05 wt% PAE; 0.07 wt% poly(AAm-co-AA) (90 / 10), 0.776 wt% Na2HPO4·2H2O, 0.044 wt% NaH2PO4·H2O, 0.160 wt% NaCl; 10 ppm EDTA, and an appropriate amount of water to make 100%.

[0276] Preparation of Polymerizable Composition The polymerizable composition (SiHy lens formulation) is prepared to have the composition as shown in Table 38.

[0277]

Table 38

[0278] Cast-molded silicone hydrogel contact lens The SiHy lens precursor (dry lens) is cast-molded from lens formulations 17-1 and 17-3 according to the procedure described in Example 2.

[0279] The SiHy lens precursor (dry lens) is cast-molded from lens formulations 17-2 and 17-4 as follows. The lens formulation is purged with nitrogen at room temperature for 30 - 35 minutes. N 2Place the 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; and hold at 100 °C for about 100 minutes.

[0280] After dry release / lens removal, the SiHy lens precursor (dry lens) is individually packaged in 0.85 mL of the IPC-7 or IPC-7B prepared above in a duodrop blister shell and subsequently sterilized (autoclaved at 121 °C for 45 minutes).

[0281] [Table 39]

[0282] All publications, patents, and published patent applications cited above in this application are hereby incorporated by reference in their entirety into this specification.

Claims

1. A method for manufacturing a coated silicone hydrogel contact lens, comprising: (1) A step of introducing a curable composition into a lens molding die, wherein the curable composition comprises: (a) at least one hydrophilic polysiloxane vinyl crosslinking agent; (b) hydroxyethyl methacrylate; (c) at least one C １ -C ２ alkoxyethyl (meth)acrylate; (d) at least one carboxyl-containing (meth)acryloxy monomer in an amount of 2% to 10% by weight based on the total amount of all polymerizable components; (e) at least one free radical initiator; and (f) at least one solvent selected from the group consisting of water, propylene glycol, polyethylene glycol having a molecular weight of 400 or less, and combinations thereof. (2) thermally curing or radiation curing the polymerizable composition in the lens mold to form a silicone hydrogel lens precursor comprising a bulk silicone hydrogel material containing carboxyl groups; (3) heating the silicone hydrogel lens precursor obtained in step (2) directly at a temperature of 60 °C to 140 °C in an aqueous solution having a pH of 6.8 to 8.5 and containing at least one water-soluble and thermally crosslinkable hydrophilic polymer material to form a coated silicone hydrogel contact lens comprising a bulk silicone hydrogel material and a layer of a crosslinked hydrophilic polymer material covalently bonded to the bulk silicone hydrogel material. The method is characterized in that the coated silicone hydrogel contact lens exhibits a water film break-up time (WBUT) of at least 5 seconds and an oxygen permeability of at least 50 barrers. A method, wherein the coated silicone hydrogel contact lens exhibits a water film break-up time (WBUT) of at least 5 seconds and an oxygen permeability of at least 50 barrers.

2. The method according to claim 1, wherein the total amount of components (a) to (e) is at least 90% by weight based on the total amount of all polymerizable components in the polymerizable composition.

3. The method according to claim 1 or 2, wherein the polymerizable composition comprises 30% to 65% by weight of component (a) and 30% to 65% by weight of components (b) and (c) based on the total amount of all polymerizable components.

4. The method according to claim 1 or 2, wherein the weight ratio of component (c) to component (b) in the polymerizable composition is 40 to 20.

5. The method according to claim 1 or 2, wherein the polymerizable composition further comprises one or more polymerizable components selected from the group consisting of (g) non-silicone vinyl-based crosslinking agents, (h) UV-absorbing vinyl-based monomers, (i) polymerizable UV / high-energy violet light-absorbing compounds, (j) polymerizable photochromic compounds, (k) polymerizable colorants, and (l) combinations thereof, provided that the total of components (g) to (l) is less than 10% by weight based on the amount of all polymerizable components.

6. The method according to claim 1 or 2, wherein the heating step is carried out by autoclaving the silicone hydrogel lens precursor immersed in a packaging solution, which is a buffered aqueous solution, in a sealed lens package at a temperature of 115 °C to 125 °C for 20 to 90 minutes.

7. The method according to claim 1 or 2, wherein the at least one water-soluble and thermally crosslinkable hydrophilic polymer material comprises an azetidinium group, an epoxy group, or a combination thereof.

8. The method according to claim 7, wherein the at least one water-soluble and thermally crosslinkable hydrophilic polymer material is one or more multi-arm polyethylene glycols each having a terminal epoxy group; a multi-arm polyethylene glycol having a terminal epoxy 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 epoxy group and a hydrophilic 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.

9. The method according to claim 7, wherein the at least one water-soluble and thermally crosslinkable hydrophilic polymer material comprises an azetidinium group and is a partial reaction product of an azetidinium-containing polymer and a hydrophilic enhancer having at least one reactive 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.

10. 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. The hydrophilic enhancer is (a) a monosaccharide containing a primary amino group, a secondary amino group, a carboxyl group, or a thiol group; (b) a disaccharide containing a primary amino group, a secondary amino group, a carboxyl group, or a thiol group; (c) an oligosaccharide containing a primary amino group, a secondary amino group, a carboxyl group, or a thiol group; (d) a polysaccharide having a primary amine group, a secondary amine group, a carboxyl group, or a combination thereof; (e) -NH ２ , -SH, or a poly(ethylene glycol) having only one functional group of -COOH; (f) -NH ２ , -COOH, -SH, and a poly(ethylene glycol) having two terminal functional groups selected from the group consisting of combinations thereof; (g) -NH ２ , -COOH, -SH, and a multi-arm poly(ethylene glycol) having one or more functional groups selected from the group consisting of combinations thereof; (h) a monoamino, monocarboxyl, diamino, or dicarboxyl terminal homo- or copolymer of a non-reactive hydrophilic vinyl monomer; (i) a copolymer which is a polymerization product of a composition containing (1) 0.1% to 30% of a reactive vinyl monomer and (2) at least one non-reactive hydrophilic vinyl monomer, wherein the 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, and the non-reactive hydrophilic monomer is a hydrophilic vinyl monomer not containing any carboxyl group, primary amine group, secondary amine group, epoxide group, isocyanate group, azlactone group, or aziridine group, or (j) a combination thereof, according to the method of claim 9.

11. The method according to claim 1 or 2, wherein the aqueous solution has a pH of 7.0 to 8.2 and the aqueous solution contains 0.01% to 2% by weight of the at least one water-soluble, thermally crosslinkable hydrophilic polymer material.

12. A coated silicone hydrogel contact lens, comprising a bulk silicone hydrogel material and a layer of a non-silicone hydrogel material thereon. The bulk silicone hydrogel material comprises (a) repeating units of at least one hydrophilic polysiloxane vinyl-based crosslinking agent, (b) repeating units of hydroxyethyl methacrylate, and (c) at least one C １ to C ２ repeating units of alkoxyethyl (meth)acrylate, (d) carboxyl-containing repeating units of at least one carboxyl-containing (meth)acryloxy monomer, and (e) repeating units of at least one polymerizable component selected from the group consisting of non-silicone vinyl-based crosslinking agents, UV-absorbing vinyl-based monomers, polymerizable UV / high-energy violet light-absorbing compounds, polymerizable photochromic compounds, polymerizable colorants, and combinations thereof (provided that the amount of the component (e) is less than 10% by weight based on the total weight of the bulk silicone hydrogel material in the dry state). The layer of the non-silicone hydrogel material is covalently bonded to the bulk silicone hydrogel material through the carboxyl group of the carboxyl-containing repeating unit. The coated silicone hydrogel contact lens has a water break-up time (WBUT) of at least 5 seconds, an oxygen permeability (Dk) of at least 50 barrers, an elastic modulus of 0.2 MPa to 1.8 MPa, an equilibrium water content of 20 wt% to 75 wt% (i.e., when fully hydrated), a friction evaluation of 3.0 or less, and an average water contact angle of 90 degrees or less by the droplet method. A coated silicone hydrogel contact lens.

13. The at least one hydrophilic polysiloxane vinyl-based crosslinking agent contains at least 1.50 milliequivalents / gram ("meq / g") of a hydrophilic moiety, which is a hydroxyl group (-OH), a carboxyl group (-COOH), an amino group (-NHR Ｎ１ (wherein R Ｎ１ is H or C １ ~C ２ alkyl)), an amide moiety (-CO-NR Ｎ１ R Ｎ２ (wherein R Ｎ１ is H or C １ ~C ２ alkyl and R Ｎ２ is a covalent bond, H, or C １ ~C ２ alkyl)), an N-C １ ~C ３ acylamino group, a urethane moiety (-NH-CO-O-), a urea moiety (-NH-CO-NH-), 【Chemical 1】 wherein n is an integer from 2 to 20, and T １ is H, methyl, acetyl or a phosphorylcholine group), a polyethylene glycol chain, or a combination thereof, the coated silicone hydrogel contact lens according to claim 12, or the method according to claim 1 or 2.

14. The at least one hydrophilic polysiloxane vinyl-based crosslinking agent is (1) a polysiloxane segment containing dimethylsiloxane units and hydrophilic siloxane units each having one methyl-substituted group and one monovalent C ４ -C ４０ organic radical-substituted group, and (2) a polysiloxane vinyl-based crosslinking agent containing two terminal (meth)acryloyl groups, the coated silicone hydrogel contact lens according to claim 12 or the method according to claim 1 or 2.

15. The at least one hydrophilic polysiloxane vinyl-based crosslinking agent has the formula (1) 【Chemical Formula 2】 (wherein: υ1 is an integer from 30 to 500 and ω1 is an integer from 1 to 75, provided that ω1 / υ1 is from 0.035 to 0.15; X ０１ is O or NR ｎ where R ｎ is hydrogen or C １ to C １０ -alkyl; R ｏ is hydrogen or methyl; R ２ and R ３ are, independently of each other, a substituted or unsubstituted C １ -C １０ alkylene divalent radical or -R ５ -O-R ６ - divalent radical, where R ５ and R ６ are, independently of each other, a substituted or unsubstituted C １ -C １０ alkylene divalent radical; R ４ is any one monovalent radical among formulas (2) to (7), [Chemical Formula 3] p1 is zero or 1; m1 is an integer from 2 to 4; m2 is an integer from 1 to 5; m3 is an integer from 3 to 6; m4 is an integer from 2 to 5; R ７ is hydrogen or methyl; R ８ is a C having a valence of (m2 + 1) ２ ~C ６ hydrocarbon radical; R ９ is a C having a valence of (m4 + 1) ２ to C ６ hydrocarbon radical; R １０ is ethyl or hydroxymethyl; R １１ is methyl or hydroxymethyl, and R １２ is hydroxyl or methoxy; X ３ is a sulfur bond of -S- or a tertiary amino bond of -NR １３ -, where R １３ is C １ to C １ alkyl, hydroxyethyl, hydroxypropyl, or 2,3-dihydroxypropyl; X ４ is 【Chemical Formula 4】 is an amide bond, where R １４ is hydrogen or C １ to C １０ alkyl, and L ＰＣ is -CH ２ -CHR ０ -R １５ -, -C ３ H ６ -O-R １６ -, 【Chemical Formula 5】 is a divalent radical, where q1 is an integer from 1 to 20, and R １５ is a linear or branched C １ to C １０ alkylene divalent radical, and R １６ is a linear or branched C ３ to C １０ alkylene divalent radical, and R １７ is a direct bond or a linear or branched C １ to C ４ alkylene divalent radical), the coated silicone hydrogel contact lens or method according to claim 14.

16. The non-silicone hydrogel material is a crosslinked polymer material containing repeating monomer units of at least 25 mol% of at least one hydrophilic vinyl monomer, and the at least one hydrophilic vinyl monomer is 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, 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 having a number average molecular weight of up to 1500, poly(ethylene glycol)ethyl(meth)acrylamide having a number average molecular weight of up to 1500, N-vinylpyrrolidone, 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, N-vinyl-3-methyl-2-piperidone, N-vinyl-4-methyl-2-piperidone, N-vinyl-5-methyl-2-piperidone, N-vinyl-6-methyl-2-piperidone, N-vinyl-6-ethyl-2-piperidone, N-vinyl-3,5-dimethyl-2-piperidone, N-vinyl-4,4-Dimethyl-2-piperidone, N-vinylcaprolactam, 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, 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, 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, C having a weight average molecular weight of up to 1500, １ ~C ４ - alkoxypoly(ethylene glycol) (meth)acrylate, methoxy-poly(ethylene glycol) ethyl (meth)acrylamide having a number average molecular weight of up to 1500, 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, the coated silicone hydrogel contact lens according to claim 12.

17. The coated silicone hydrogel contact lens according to claim 12, wherein the non-silicone hydrogel material is a crosslinked polymer material containing repeating monomer units of at least one phosphorylcholine-containing vinyl-based monomer in an amount of at least 25 mol%.

18. The coated silicone hydrogel contact lens according to claim 12, wherein the non-silicone hydrogel material is a crosslinked polymer material containing a poly(ethylene glycol) chain.

19. each of said poly(ethylene glycol) chains being (a) a poly(ethylene glycol) having only one reactive group of —NH ２ , —SH or —COOH, (b) a poly(ethylene glycol) having two terminal functional groups selected from the group consisting of —NH ２ , —COOH, —SH, and combinations thereof, (c) a multi-arm poly(ethylene glycol) having one or more functional groups selected from the group consisting of —NH ２ , —COOH, —SH, and combinations thereof, and (d) a coated silicone hydrogel contact lens according to claim 18 directly derived from combinations thereof.

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