Coated silicone hydrogel contact lens and preparation method thereof

Abstract

The present invention provides a method for producing a coated silicone hydrogel contact lens in a cost effective manner. The method comprises: obtaining a preformed silicone hydrogel contact lens, the preformed silicone hydrogel contact lens comprising a bulk silicone hydrogel material, the bulk silicone hydrogel material comprising repeating units of at least one vinyl monomer containing a carboxyl group and at least one vinyl monomer containing an aryl dihydroxy boron group; and a polymer composition comprising a water-soluble and thermally crosslinkable polymer material having an azetidinium group or an epoxy group and a polymer material having 1, 2-or 1, 2, 3, 3, 3, 3-tetrafluoropropene, heating the preformed silicone hydrogel contact lens in an aqueous coating solution of a glycol-containing hydrophilic polymer having a 1, 3-diol moiety to form a coated silicone hydrogel contact lens comprising a bulk silicone hydrogel material and a hydrogel coating, the hydrogel coating comprises a cross-linked polymeric material covalently attached to the bulk silicone hydrogel material and a grafted glycol-containing hydrophilic polymer covalently attached to the bulk silicone hydrogel material and distributed in the cross-linked polymeric material.

Description

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

[0002] A new class of soft contact lenses (water gradient silicone hydrogel contact lenses, e.g., DAILIES® TOTAL1® (Alcon), PRECISION1® (Alcon), and TOTAL30® (Alcon)) has been developed and successfully introduced into the market. This new class of soft contact lenses is characterized by having a water gradient configuration with water content increasing from 33% to over 80% from the core to the surface (see, e.g., U.S. Patent Nos. 8480227, 11061168, and 11256003). Such water gradient silicone hydrogel contact lenses can provide superior wear comfort to patients due to their extremely soft, water-rich, relatively thick, and lubricious hydrogel coating.

[0003] As described in US 8480227 and US 11256003, the methods for making water gradient contact lenses generally involve forming a non-silicone hydrogel coating on the contact lens, which is either a base coating with reactive functional groups (e.g., carboxylic acid groups) or made from a silicone hydrogel material with reactive functional groups (e.g., carboxylic acid groups). In the case where a reactive base coating is needed, the method for producing water gradient contact lenses can require an additional step for forming the reactive base coating. In the case where the silicone hydrogel material of the contact lens has reactive functional groups (e.g., carboxylic acid groups), such silicone hydrogel contact lenses can be prone to degradation due to the presence of higher amounts of carboxylic acid groups in the silicone hydrogel contact lenses. However, reducing the carboxylic acid content can improve the service life of the lenses, while coating uniformity can be compromised.

[0004] Therefore, it is desirable to develop a new method for forming a uniform non-silicone hydrogel coating while maintaining low acid content in the silicone hydrogel lens material in the production of water gradient contact lenses. SUMMARY

[0005] In one aspect, the present application provides a method for producing a coated silicone hydrogel contact lens, the method comprising the steps of: (1) obtaining a preformed silicone hydrogel contact lens, wherein the preformed hydrogel contact lens comprises a bulk silicone hydrogel material comprising (a) repeat units of at least one polysiloxane vinylic crosslinker and / or at least one siloxane-containing vinylic monomer, (b) about 0.5% to about 3.5% by weight, relative to the total amount of all polymerizable components, of repeat units of at least one carboxyl-containing vinylic monomer, (c) repeat units of at least one hydrophilic vinylic monomer, (d) about 2.5% to about 12.5% by weight of repeat units of at least one arylboronate-containing vinylic monomer having an arylboronate dihydroxy group; (e) optionally but preferably at least one non-silicone vinylic crosslinker, and (2) heating the preformed silicone hydrogel contact lens in an aqueous coating solution at a temperature of about 60 °C to about 140 °C to form a coated silicone hydrogel contact lens comprising the bulk silicone hydrogel material and a non-silicone hydrogel coating thereon, wherein the aqueous coating solution comprises (a) at least one glycol-containing hydrophilic polymer having 1,2- and / or 1,3-diol moieties and (b) at least one water-soluble, thermally crosslinkable hydrophilic polymeric material that is branched or lightly crosslinked and comprises thermally crosslinkable groups and optionally reactive functional groups, wherein the thermally crosslinkable groups are azetidinium groups and / or epoxy groups, wherein the reactive functional groups are primary amino groups, secondary amino groups, carboxylic acid groups, thiol groups, or combinations thereof, wherein the non-silicone hydrogel coating comprises crosslinked polymeric material and grafted hydrophilic polymers, wherein the crosslinked hydrophilic polymeric material is derived from the at least one water-soluble, thermally crosslinkable hydrophilic polymeric material and is covalently attached to the bulk silicone hydrogel material by first linkages each formed between one carboxylic acid group and one azetidinium or epoxy group, and wherein the grafted hydrophilic polymers are derived from the at least one glycol-containing hydrophilic polymer and are covalently attached to the bulk silicone hydrogel material by second linkages each formed between one arylboronate dihydroxy group and one 1,2- or 1,3-diol moiety.

[0006] In another aspect, the present application provides a coated silicone hydrogel contact lens comprising a bulk silicone hydrogel material and a non-silicone hydrogel coating thereon, wherein the bulk silicone hydrogel material comprises (a) repeat units of at least one polysiloxane vinylic crosslinker and / or at least one siloxane-containing vinylic monomer, (b) repeat units of at least one carboxyl-containing vinylic monomer relative to the total amount of all polymerizable components, (c) repeat units of at least one hydrophilic vinylic monomer, (d) repeat units of at least one arylboronate-containing vinylic monomer having an arylboronate group; (e) optionally but preferably repeat units of at least one non-silicone vinylic crosslinker, wherein the non-silicone hydrogel coating comprises a crosslinked polymeric material and a grafted glycol-containing hydrophilic polymer distributed in the crosslinked polymeric material but not covalently bonded to the crosslinked polymeric material, wherein the crosslinked hydrophilic polymeric material is covalently attached to the bulk silicone hydrogel material through first linkages each formed between one carboxylic acid group and one azetidinium or epoxy group, wherein the grafted glycol-containing hydrophilic polymer comprises 1,2- and / or 1,3-diol moieties and is covalently attached to the bulk silicone hydrogel material through second linkages each formed between one arylboronate group and one 1,2- or 1,3-diol moiety, wherein the coated silicone hydrogel contact lens in a fully hydrated state exhibits a coating integrity of about 90% or more and a friction rating of about 2.0 or less. DETAILED DESCRIPTION

[0007] Unless defined otherwise, all technical and scientific terms used herein have the same meaning as is commonly understood by one of ordinary skill in the art to which this application belongs. Generally, the nomenclature used herein and the laboratory procedures are well-known and commonly employed in the art. Conventional methods are used for these procedures, as provided in the art and various general references. When terms are provided in a singular form, a plural of that term is also contemplated by the inventors unless otherwise stated. The nomenclature used herein and the laboratory procedures described below are those well-known and commonly employed in the art.

[0008] In this application, as used herein, "about" means plus or minus 1-10% of the stated numerical value.

[0009] "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 the user, but is not necessarily so.

[0010] "Hydrogel contact lens" refers to a contact lens comprising a hydrogel bulk (core) material. The hydrogel bulk material can be a non-silicone hydrogel material or, preferably, a silicone hydrogel material.

[0011] "Hydrogel" or "hydrogel material" means a crosslinked polymeric material having a three-dimensional polymeric network (i.e., a polymeric matrix) that is insoluble in water, but can hold at least 10% water by weight in its polymeric matrix when fully hydrated (or equilibrated).

[0012] "Silicone hydrogel" or "SiHy" means a silicone-containing hydrogel obtained by copolymerization of a polymerizable composition comprising at least one silicone-containing monomer or at least one silicone-containing macromer or at least one crosslinkable silicone-containing pre-polymer.

[0013] Siloxane, also commonly described as silicone, means a molecule having at least one -Si-O-Si- moiety, wherein each Si atom carries two organic groups as substituents.

[0014] As used in this application, the term "non-silicone hydrogel" or "non-silicone hydrogel material" means interchangeably a hydrogel that is theoretically free of silicon.

[0015] As used herein, "hydrophilic" describes a material or a portion thereof that will more readily associate with water than with lipids.

[0016] The term "room temperature" means a temperature of about 17 °C to about 26 °C.

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

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

[0019] "Vinyl monomer" means a compound having one unique ethylenically unsaturated group, is soluble in a solvent, and can be photopolymerized or thermally polymerized.

[0020] The term "ethylenically unsaturated group" or "ethylenically unsaturated group" is used herein in a broad sense and is intended to include any group containing at least one >C=CH2 group. Exemplary ethylenically unsaturated groups include, but are not limited to, (meth)acryloyl and / or ), allyl, vinyl, styryl, or other C=CH2-containing groups.

[0021] "Acrylic monomer" means an ethylenic monomer having one unique (meth)acryloyl group. Examples of acrylic monomers include (meth)acryloxy (or (meth)acryloyloxy) monomers and (meth)acrylamido monomers.

[0022] "(Meth)acryloxy (or (meth)acryloyloxy) monomer" means an ethylenic monomer having one unique group or (wherein R o is H or C1-C4 alkyl).

[0023] "(Meth)acrylamido monomer" means an ethylenic monomer having one unique group or (wherein R o is H or C1-C4 alkyl).

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

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

[0026] "N-vinyl amide monomer" means an amide compound having a vinyl group directly attached to the nitrogen atom of the amide group.

[0027] "Alkenemonomer" means an ethylenic monomer having one unique alkenyl group.

[0028] As used herein, "hydrophilic ethylenic monomer," "hydrophilic acrylic monomer," "hydrophilic (meth)acryloxy monomer," or "hydrophilic (meth)acrylamido monomer" means, respectively, an ethylenic monomer, an acrylic monomer, a (meth)acryloxy monomer, or a (meth)acrylamido monomer that typically yields a homopolymer that is water soluble or can absorb at least 10% water by weight.

[0029] As used herein, "hydrophobic ethylenic monomer," "hydrophobic acrylic monomer," "hydrophobic (meth)acryloxy monomer," or "hydrophobic (meth)acrylamido monomer" means, respectively, an ethylenic monomer, an acrylic monomer, a (meth)acryloxy monomer, or a (meth)acrylamido monomer that typically yields a homopolymer that is not water soluble and can absorb less than 10% water by weight.

[0030] In the present application, "arylboronate-containing vinylic monomer" means a vinylic monomer that contains one unique arylboronate group attached to its unique ethylenically unsaturated group by one linkage.

[0031] In the present application, "aryldihydroxyboronyl" means a monovalent radical of the formula B is a monovalent radical (preferably H, N02, F, CI, Br, CF3, CH2OH, or CH2NR o R o ', wherein R o and R o are, independently of each other, H or C1-C4 alkyl). It is understood that when R B is CH2OH or CH2NR o R o ', it is located in the ortho position of the boronic acid and can form an intramolecular B-O or B-N coordination to lower the pKa of the boronic acid.

[0032] As used in the present application, the term "vinylic crosslinker" means an organic compound having at least two ethylenically unsaturated groups. "Vinylic crosslinker" means a vinylic crosslinker having a molecular weight of 700 Daltons or less.

[0033] "Acrylic crosslinker" means a vinylic crosslinker having at least two (meth)acryloyl groups.

[0034] The term "acrylic repeat unit" means a repeat unit of a polymeric material, each of which is derived from an acrylic monomer or crosslinker that forms the polymeric material by free radical polymerization.

[0035] The term "terminal (meth)acryloyl group" means one (meth)acryloyl group at one of the two terminal ends of the main chain (or backbone) of an organic compound.

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

[0037] As used in the present application, the term "polymer" means a material formed by the polymerization or crosslinking of one or more monomers or macromonomers or prepolymers or combinations thereof.

[0038] "Macromonomer" or "prepolymer" means a compound or polymer having ethylenically unsaturated groups and having a number average molecular weight of greater than 700 Daltons.

[0039] ​As used in this application, the term "molecular weight" for polymeric materials (including monomeric or macromonomeric materials) is exponential average molecular weight, unless otherwise specified or unless the test conditions indicate otherwise. Those skilled in the art know how to determine the molecular weight of a polymer using known methods, such as GPC (gel permeation chromatography) having one or more of the following: a refractive index detector, a small-angle laser light scattering detector, a multi-angle laser light scattering detector, a differential viscometry detector, a UV detector, and an infrared (IR) detector; or MALDI-TOF MS (matrix-assisted desorption / ionization time-of-flight mass spectrometry). 1 1H NMR (proton nuclear magnetic resonance) spectroscopy, etc.

[0040] "Polysiloxane segment" or "polydiorganosiloxane segment" can be used interchangeably to refer to... The polymer chain segments (i.e., divalent groups), where SN is an integer of 3 or greater, and R S1 and R S2 Each of the following groups is selected independently: C1-C 10 Alkyl; phenyl; C1-C4-alkyl-substituted phenyl; C1-C4-alkoxy-substituted phenyl; phenyl-C1-C6-alkyl; C1-C 10 Fluoroalkyl; C1-C 10 Fluoroethers; aryl; aryl C1-C 18 Alkyl group; -alk-(OC2H4) γ1 -OR o (where alk is a C1-C6 alkylene diester, R) o (is H or C1-C4 alkyl and γ1 is an integer from 1 to 10); C2-C 40 An organic group having at least one selected from a hydroxyl group (-OH), a carboxyl group (-COOH), or an amino group (-NR). N1 R N1 '), amino linker -NR N1 - Amide linker -CONR N1 - Amide-CONR N1 R N1 ', a functional group consisting of a urethane linker -OCONH- and a C1-C4 alkoxy group, or a straight-chain hydrophilic polymer chain, wherein R N1 and R N1 'Independently hydrogen or C1-C 15 alkyl.

[0041] "Polysiloxane ethylene monomers" refer to compounds that contain at least one polysiloxane segment and a unique olefinic unsaturated group.

[0042] "Polydiorganosiloxane vinylic crosslinker" or "polysiloxane vinylic crosslinker" interchangeably means a compound comprising at least one polysiloxane segment and at least two ethylenically unsaturated groups.

[0043] "Linear polydiorganosiloxane vinylic crosslinker" or "linear polysiloxane vinylic crosslinker" interchangeably means a compound comprising a backbone comprising at least one polysiloxane segment and terminated at each of the two ends of the backbone by one ethylenically unsaturated group.

[0044] "Chain-extended polydiorganosiloxane vinylic crosslinker" or "chain-extended polysiloxane vinylic crosslinker" interchangeably means a compound comprising at least two ethylenically unsaturated groups and at least two polysiloxane segments, each pair of polysiloxane segments being connected by one divalent group.

[0045] As used herein, the term "fluid" indicates that a material is capable of flowing like a liquid.

[0046] As used in the present application, the term "optically clear" in relation to a polymerizable composition means that the polymerizable composition is a transparent solution or liquid mixture (i.e. having an optical transmittance of 85% or more, preferably 90% or more, in the range between 400 and 700 nm).

[0047] The term "monovalent group" means an organic group obtained by removing a hydrogen atom from an organic compound and forming one bond with one other group in the organic compound. Examples include, but are not limited to, alkyl (obtained by removing a hydrogen atom from an alkane), alkoxy (or alkoxyl) (obtained by removing a hydrogen atom from the hydroxyl group of an alkyl alcohol), thiyl (obtained by removing a hydrogen atom from the mercapto group of an alkyl mercaptan), cycloalkyl (obtained by removing hydrogen atoms from a cyclic alkane), cycloheteroalkyl (obtained by removing hydrogen atoms from a cyclic heteroalkane), aryl (obtained by removing a hydrogen atom from an aromatic ring of an aromatic hydrocarbon), heteroaryl (obtained by removing a hydrogen atom from any ring atom), amino (obtained by removing a hydrogen atom from an amine), and the like.

[0048] The term "divalent group" means an organic group 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 (or alkylenyl) divalent group is obtained by removing two hydrogen atoms from an alkane, a cycloalkylene (or cycloalkylenyl) divalent group is obtained by removing two hydrogen atoms from a cyclic ring.

[0049] In the present application, the term "substituted" in relation to an alkyl or alkylene group means that the alkyl or alkylene group comprises at least one substituent which replaces one hydrogen atom of the alkyl or alkylene group and is selected from the group consisting of hydroxyl (-OH), carboxyl (-COOH), -NH2, mercapto (-SH), C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkylthio (alkyl sulfide), C1-C4 acylamino, C1-C4 alkylamino, di-C1-C4 alkylamino, and combinations thereof.

[0050] In the present application, the term "polyoxazoline" means a polymer or polymer segment of formula wherein: R ox1 is hydrogen, methyl, ethyl, N-pyrrolidinylmethyl, N-pyrrolidinylethyl, N-pyrrolidinylpropyl, or -alk-(OC2H4) m3 -OR ” is a monovalent group of formula -alk-(OC2H4) ox1 wherein alk is a C1-C4 alkyldiyl; R" is C1-C4 alkyl (preferably methyl); m3 is an integer from 1 to 10 (preferably 1 to 5); x is an integer from 5 to 500.

[0051] In the present application, the term "poly(2-oxazoline-co-vinylimine)" means a statistical copolymer of formula wherein: R ox1 is hydrogen, methyl, ethyl, N-pyrrolidinylmethyl, N-pyrrolidinylethyl, N-pyrrolidinylpropyl, or -alk-(OC2H4) m3 -OR ” is a monovalent group of formula -alk-(OC2H4) ox1 wherein alk is a C1-C6 alkyldiyl; R" is C1-C4 alkyl (preferably methyl); m3 is an integer from 1 to 10 (preferably 1 to 5); x is an integer from 5 to 500; z is an integer equal to or less than x. Poly(2-oxazoline-co-vinylimine) is obtained by hydrolysis of polyoxazoline.

[0052] In the present application, the term "poly(2-oxazoline-co-vinylimine)-epichlorohydrin" means a polymer obtained by reacting poly(2-oxazoline-co-vinylimine) with epichlorohydrin to convert all or a major percentage (>90%) of the secondary amine groups of the poly(2-oxazoline-co-vinylimine) to azetidinium groups. Examples of poly(2-oxazoline-co-vinylimine)-epichlorohydrin are disclosed in U.S. Patent Application No. 2016 / 0061995 Al.

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

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

[0055] In the present application, the term "azetidinium" or "3-hydroxyazetidinium" refers to a positively charged (i.e., cationic) divalent group (or radical or moiety) of formula

[0056] The term "heat-crosslinkable" with respect to a polymeric material or functional group means that the polymeric material or functional group can undergo a crosslinking (or coupling) reaction with another material or functional group at a relatively elevated temperature (about 40 °C to about 140 °C), whereas the 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 over a period of about one hour.

[0057] As used in the present application, the term "phosphorylcholine" refers to a zwitterionic group wherein n is an integer from 1 to 5, and R 2 , R 3 , and R 4 are each independently of the other C1-C8 alkyl or C1-C8 hydroxyalkyl.

[0058] As used in the present application, the term "reactive vinylic monomer" refers to any vinylic monomer having at least one reactive functional group selected from the group consisting of carboxyl, primary amino, and secondary amino.

[0059] As used in the present application, the term "non-reactive vinylic monomer" refers to any vinylic monomer (hydrophilic or hydrophobic vinylic monomer) that does not contain a carboxyl group, a primary amino group, a secondary amino group, an epoxy group, an isocyanate group, an azlactone group, or an aziridine group.

[0060] The free radical initiator can be a photoinitiator or a thermal initiator. A "photoinitiator" refers to a chemical that initiates a free radical crosslinking / polymerization reaction by utilizing light energy. A "thermal initiator" refers to a chemical that initiates a free radical crosslinking / polymerization reaction by utilizing thermal energy.

[0061] As used in the present application, the term "bulk silicone hydrogel material" with respect to a contact lens interchangeably means a layer of a silicone hydrogel material that substantially has the 3-dimensional shape of the contact lens.

[0062] The intrinsic "oxygen permeability" Dk i of a material is the rate of oxygen passing through the material. Oxygen permeability is conventionally expressed in units of barrers, where a "barrer" is defined as [(cm 3 ​Oxygen) / (cm 2 (s) (mm Hg)] x 10 -10 .

[0063] The "oxygen permeability" Dk / t of an insert or material is the rate at which oxygen will pass through a specific insert or material having an average thickness of t [in mm] over the area measured. Oxygen permeability is conventionally expressed in barrers per millimeter, where "barrers per millimeter" is defined as [(cm 3 Oxygen) / (cm 2 (s) (mm Hg)] x 10 -9 .

[0064] The term "modulus" or "elastic modulus" in relation to a contact lens or material means tensile modulus or Young's modulus as a measure of the stiffness of the contact lens or material.

[0065] The term "dry lens precursor" refers to a cast molded contact lens that is obtained by casting molding a polymerizable composition in a mold and that has not been subjected to post-molding processes of extraction and / or hydration (i.e., has not been in contact with water or any organic solvent or any liquid after molding).

[0066] The term "wettable silicone hydrogel contact lens" means a silicone hydrogel contact lens having a water break-up time ("WBUT") of at least 10 seconds, preferably at least 15 seconds, more preferably at least 20 seconds, even more preferably at least 25 seconds. The WBUT can be measured according to the procedure described in Example 1.

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

[0068] "Average water contact angle" refers to the water contact angle (measured by Sessile Drop) obtained by averaging the measurements of at least 3 separate samples of a contact lens or silicone hydrogel material.

[0069] In general, the present invention relates to a method for producing coated SiHy contact lenses each having a non-silicone hydrogel coating thereon in a cost effective manner. The invention is based in part on the discovery that a preformed SiHy contact lens (or other hydrophobic plastic mold) having two types of reactive functional groups (carboxylic acid groups and arylboronate diol groups) can be coated by packaging it in a packaging brine containing two different types of coating materials and autoclaving it therein. The first type of coating material is a lightly crosslinked (or branched) thermally crosslinkable hydrophilic polymeric material containing thermally crosslinkable groups (azetidinium groups and / or epoxy groups) that can react with the carboxylic acid groups during autoclaving. The other type of coating material is a diol-containing hydrophilic polymer containing 1,2- or 1,3-diol moieties that can react with the arylboronate diol groups. By having two different types of coating materials, a hybrid coating with good integrity can be formed on a preformed SiHy contact lens having a relatively low amount of carboxylic acid. As a result, the resulting coated SiHy contact lens can have reduced sensitivity to carboxylic acid-induced degradation, thereby having increased stability (longer useful life).

[0070] A method for producing a coated silicone hydrogel contact lens, the method comprising the steps of: (1) obtaining a preformed silicone hydrogel contact lens, wherein the preformed hydrogel contact lens comprises a bulk silicone hydrogel material comprising (a) repeat units of at least one polysiloxane vinylic crosslinker and / or at least one siloxane-containing vinylic monomer, (b) about 0.5% to about 3.5% by weight, relative to the total amount of all polymerizable components, of repeat units of at least one carboxyl-containing vinylic monomer, (c) repeat units of at least one hydrophilic vinylic monomer, (d) about 2.5% to about 12.5% by weight of repeat units of at least one arylboronate-containing vinylic monomer having an arylboronate group; (e) optionally but preferably at least one non-silicone vinylic crosslinker, and (2) heating the preformed silicone hydrogel contact lens in an aqueous coating solution at a temperature of about 60 °C to about 140 °C to form a coated silicone hydrogel contact lens comprising the bulk silicone hydrogel material and a non-silicone hydrogel coating thereon, wherein the aqueous coating solution comprises (a) at least one glycol-containing hydrophilic polymer having 1,2- and / or 1,3-diol moieties and (b) at least one water-soluble, thermally crosslinkable hydrophilic polymeric material that is branched or lightly crosslinked and comprises thermally crosslinkable groups and optionally reactive functional groups, wherein the thermally crosslinkable groups are azetidinium groups and / or epoxy groups, wherein the reactive functional groups are primary amino groups, secondary amino groups, carboxylic acid groups, thiol groups, or combinations thereof, wherein the non-silicone hydrogel coating comprises crosslinked polymeric material and grafted glycol-containing hydrophilic polymer, wherein the crosslinked hydrophilic polymeric material is derived from the at least one water-soluble, thermally crosslinkable hydrophilic polymeric material and is covalently attached to the bulk silicone hydrogel material by first linkages each formed between one carboxylic acid group and one azetidinium or epoxy group, wherein the grafted glycol-containing hydrophilic polymer is derived from the at least one glycol-containing hydrophilic polymer and is covalently attached to the bulk silicone hydrogel material by second linkages each formed between one arylboronate group and one 1,2- or 1,3-diol moiety.

[0071] A preformed SiHy contact lens can be any SiHy contact lens that has not been subjected to any surface treatment after production according to any lens manufacturing process, any contact lens that has been plasma treated or treated with any chemical or physical surface modification, or any commercial contact lens, as long as the surface of the preformed SiHy contact lens is free of a hydrogel coating. It is well known to those skilled in the art how to make a preformed contact lens. It is well known to those skilled in the art how to make a preformed contact lens. For example, a preformed contact lens can be produced in a conventional "spin-cast molding" as described, for example, in US 3408429, or in a static form by a full cast molding process as described in US Patent Nos. 4347198; 5508317; 5583463; 5789464; and 5849810, or by lathe-type cutting of polymer material buttons as used in the preparation of custom contact lenses. In cast molding, a polymerizable composition (i.e., a lens formulation) is typically dispensed into a mold and cured (i.e., polymerized and / or crosslinked) in the mold for making a contact lens.

[0072] Lens molds for making contact lenses, including hydrogel 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 mold (for cast molding) typically includes at least two mold regions (or portions), or mold halves, i.e., a first mold half and a second mold half. The first mold half has a first molding (or optical) surface that is in direct contact with a polymerizable composition used to cast a contact lens and defines a back (or concave) surface of the molded contact lens; and the second mold half has a second molding (or optical) surface that is in direct contact with the polymerizable composition and defines a front (or convex) surface of the molded contact lens. The first mold half and the second mold 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.

[0073] Methods of making mold regions for cast molding contact lenses are generally well known to those of ordinary skill in the art. The methods of the present invention are not limited to any particular method of forming a mold. In fact, any method of forming a mold can be used in the present invention.

[0074] The mold halves can be formed by a variety of different techniques, such as injection molding. Methods of making mold halves for cast molding contact lenses are generally well known to those of ordinary skill in the art. The methods of the present invention are not limited to any particular method of forming a mold. In fact, any method of forming a mold can be used in the present invention. The first and second mold halves can be formed by a variety of techniques, such as injection molding or lathe machining. Examples of suitable methods for forming mold halves are disclosed in US Patent Nos. 4444711; 4460534; 5843346; and 5894002.

[0075] Almost all materials known in the art for making molds for making molds for making contact lenses can be used to make molds for making contact lenses. For example, polymeric materials such as polyethylene, polypropylene, polystyrene, PMMA, Topas ® COC grade 8007-S10 (a transparent amorphous copolymer of ethylene with norbornene from Ticona GmbH, Frankfurt, Germany and Summit, New Jersey, USA), and the like. Other materials that allow transmission of UV light can be used, such as quartz glass and sapphire.

[0076] According to the present application, the preformed SiHy contact lens can be produced from a polymerizable composition comprising: (a) at least one polysiloxane vinylic crosslinker and / or at least one siloxane-containing vinylic monomer, (b) about 0.5% to about 3.5% (preferably about 0.7% to about 3.5%, more preferably about 0.9% to about 3.0%, even more preferably about 1.0% to about 2.8%) by weight of at least one carboxyl-containing vinylic monomer relative to the total amount of all polymerizable components, (c) at least one hydrophilic vinylic monomer, (d) about 2.5% to about 12.5% (preferably about 2.5% to about 10%, more preferably about 3.0% to about 8.0%, even more preferably about 3.5% to about 7.0%) by weight of at least one arylboronate-containing vinylic monomer having an arylboronate group; (e) optionally but preferably at least one non-silicone vinylic crosslinker, and (f) at least one free radical initiator.

[0077] According to the present application, the silicone-containing (or siloxane-containing) vinylic monomer can be any silicone-containing vinylic monomer known to those skilled in the art. Examples of preferred silicone-containing vinylic monomers include, but are not limited to, vinylic monomers each having a bis(trialkylsiloxy)alkylsilyl group (preferably a bis(trimethylsiloxy)-alkylsilyl group) or a tris(trialkylsiloxy)silyl group (preferably a tris(trimethylsiloxy)silyl group), polysiloxane vinylic monomers, 3-methacryloyloxypropylpentamethyldisiloxane, t-butyldimethyl-siloxyethylvinyl carbonate, trimethylsilyl ethyl vinyl carbonate, and trimethylsilylmethyl vinyl carbonate, and combinations thereof.

[0078] Preferred examples of siloxane-containing ethylene monomers, each having a bis(trialkylsilyloxy)alkylsilyl or tri(trialkylsilyloxy)silyl group, include, but are not limited to, tri(trimethylsilyloxy)-propyl methacrylate, [3-(meth)acryloyloxy-2-hydroxypropoxy]propyl-bis(trimethylsiloxy)-methylsilane, [3-(meth)acryloyloxy-2-hydroxypropoxy]propylbis(trimethylsiloxy)butylsilane, 3-(meth)acryloyloxy-2-(2-hydroxyethoxy)-propoxy)propylbis(trimethylsiloxy)-methylsilane, 3-(meth)acryloyloxy-2-(2-hydroxyethoxy)-propoxy)propylbis(trimethylsiloxy)-methylsilane, 3-(meth)propene Acyloxy-2-hydroxypropoxy)propyl-tris(trimethylsilyloxy)silane, N-[tris(trimethylsilyloxy)-silylpropyl]-(methyl)acrylamide, N-(2-hydroxy-3-(3-(bis(trimethylsilyloxy)-methylsilyl)propoxy)propyl)-2-methyl(methyl)acrylamide, N-(2-hydroxy-3-(3-(bis(trimethylsilyloxy)-methylsilyl)propoxy)propyl)(methyl)acrylamide, N-(2-hydroxy-3-(3-(tris(trimethylsilyloxy)-silyl)propoxy)propyl)-2-methylacrylamide, N-(2-hydroxy) -3-(3-(tris(trimethylsilyloxy)-silyl)propoxy)propyl)(methyl)acrylamide, N-[tris(dimethylpropylsilyloxy)-silylpropyl]-(methyl)acrylamide, N-[tris(dimethylphenylsilyloxy)silylpropyl](methyl)acrylamide, N-[tris(dimethyl-ethylsilyloxy)silylpropyl](methyl)acrylamide, N,N-bis[2-hydroxy-3-(3-(bis(trimethyl-silyloxy)methyl-silyl)propoxy)propyl]-2-methyl(methyl)acrylamide, N,N-bis[2-hydroxy-3-(3-(bis(trimethyl-silyloxy)methyl-silyl)propoxy)propyl]-2-methyl(methyl)acrylamide, N,N-bis[2-hydroxy-3-(3-(bis(trimethylsilyloxy)methyl-silyl)propoxy)propyl]-2-methyl(methyl)acrylamide [2-hydroxy-3-(3-(tris(trimethylsilyloxy)propoxy)propyl](methyl)acrylamide, N,N-bis[2-hydroxy-3-(3-(tris(trimethylsilyloxy)propoxy)propyl]-2-methyl(methyl)acrylamide, N,N-bis[2-hydroxy-3-(3-(tris(trimethylsilyloxy)propoxy)propyl](methyl)acrylamide, N-[2-hydroxy-3-(3-(tert-butyldimethylsilyl)propoxy)propyl]-2-methyl(methyl)acrylamide, N-[2-hydroxy-3-(3-(tert-butyldimethylsilyl)propoxy)propyl](methyl)acrylamide, N,N-bis[2-hydroxy-3-(3-(tert-butyldimethyl-silyl)propoxy)propyl]-2-methyl(meth)acrylamide, N-2-(meth)acryloyloxyethyl-O-(methyl-bis-trimethylsiloxy-3-propyl)silylcarbamate, 3-(trimethylsilyl)propyl vinyl carbamate, 3-(vinlyloxy-carbonylthio)propyl-tris(trimethyl-siloxy)silane, 3-[tris(trimethylsiloxy)silyl]propyl vinyl carbamate, 3-[tris(trimethylsiloxy)silyl]propyl allyl carbamate, 3-[tris(trimethylsiloxy)silyl]propyl vinyl carbonate, those disclosed in U.S. Patent Nos. 9097840, 9103965, and 9475827, and mixtures thereof. The above preferred silicone-containing vinylic monomers can be obtained from commercial suppliers or can be prepared according to the procedures described in U.S. Patent Nos. 5070215, 6166236, 6867245, 7214809, 8415405, 8475529, 8614261, 8658748, 9097840, 9103965, 9217813, 9315669, and 9475827.

[0079] Examples of preferred polysiloxane vinylic monomers include, but are not limited to, mono-(meth)acryloyl-terminated, monoalkyl-terminated polysiloxanes having the formula (I) including, but not limited to, a-(meth)acryloxypropyl-terminated, co-butyl (or co-methyl) terminated polydimethylsiloxane, a-(meth)acryloxy-2-hydroxypropyloxypropyl-terminated, co-butyl (or co-methyl) terminated polydimethylsiloxane, a-(2-hydroxy-methacryloxypropoxypropyl)-co-butyl-decamethylpentasiloxane, a-[3-(meth)acryloxyethoxy-2-hydroxypropoxypropyl]-terminated, co-butyl (or co-methyl) terminated polydimethylsiloxane, a-[3-(meth)acryloxy-propoxy-2-hydroxypropoxypropyl]-terminated, co-butyl (or co-methyl) terminated polydimethylsiloxane, a-[3-(meth)acryloxy-isopropoxy-2-hydroxypropoxypropyl]-terminated, co-butyl (or co-methyl) terminated polydimethylsiloxane, a-[3-(meth)acryloxy-butoxy-2-hydroxypropoxypropyl]-terminated, co-butyl (or co-methyl) terminated polydimethylsiloxane, a-[3-(meth)acryloxy-ethylamino-2-hydroxypropoxypropyl]-terminated, co-butyl (or co-methyl) terminated polydimethylsiloxane, a-[3-(meth)acryloxypropylamino-2-hydroxypropoxypropyl]-terminated, co-butyl (or co-methyl) terminated polydimethylsiloxane, a-[3-(meth)acryloxy-butylamino-2-hydroxypropoxypropyl]-terminated, co-butyl (or co-methyl) terminated polydimethylsiloxane, a-(meth)acryloxy(polyethyleneoxy)-2-hydroxypropoxypropyl]-terminated, co-butyl (or co-methyl) terminated polydimethylsiloxane, a-[ (meth)acryloxy-2-hydroxypropoxy-ethoxypropyl]-terminated, co-butyl (or co-methyl) terminated polydimethylsiloxane, a-[ (meth)acryloxy-2-hydroxypropyl-N-ethylaminopropyl]-terminated, co-butyl (or co-methyl) terminated polydimethylsiloxane, a-[ (meth)acryloxy-2-hydroxypropyl-aminopropyl]-terminated, co-butyl (or co-methyl) terminated polydimethylsiloxane, a-[ (meth)acryloxy-2-hydroxypropoxy-(polyethyleneoxy)propyl]-terminated, co-butyl (or co-methyl) terminated polydimethylsiloxane, a-(meth)acrylamidopropoxypropyl-terminated, co-butyl (or co-methyl) terminated polydimethylsiloxane, a-N-methyl-(meth)acrylamidopropoxypropyl-terminated, co-butyl (or co-methyl) terminated polydimethylsiloxane, a-[3-(meth)acrylamidoethoxy-2-hydroxypropoxy-propyl]-terminated, co-butyl (or co-methyl) polydimethylsiloxane,alpha-[3-(Meth)acrylamido-isopropoxy-2-hydroxypropoxypropyl]- terminated omega-butyl (or omega-methyl) terminated polydimethylsiloxane, alpha-[3-(Meth)acrylamido-2-hydroxypropoxypropyl] terminated omega-butyl (or omega-methyl) polydimethylsiloxane, alpha-[3-[N-methyl-(meth)acrylamido]-2-hydroxypropoxy-propyl] terminated omega-butyl (or omega-methyl) terminated polydimethylsiloxane, N-methyl-N'-(propyltetra(dimethylsiloxy)dimethylbutylsilane) (meth)acrylamide, N-(2,3-dihydroxypropane)-N'-(propyltetra(dimethylsiloxy)dimethylbutylsilane) (meth)acrylamide, (meth)acrylamido-propyltetra(dimethylsiloxy)dimethylbutylsilane, mono-vinyl carbonate-terminated mono-alkyl-terminated polydimethylsiloxane, mono-vinyl carbamate-terminated mono-alkyl-terminated polydimethylsiloxane, those disclosed in U.S. Patent Nos. 9097840 and 9103965, and mixtures thereof. The above preferred polysiloxane vinylic monomers can be obtained from commercial suppliers (e.g., Shin-Etsu, Gelest, etc.) or prepared according to procedures described in the patents, for example, U.S. Patent Application Publication Nos. 6166236, 6867245, 8415405, 8475529, 8614261, 9217813, and 9315669, or prepared by reacting a hydroxyalkyl (meth)acrylate or (meth)acrylamide or (meth)acryloyloxy polyethylene glycol with mono-glycidoxypropyl terminated polydimethylsiloxane, by reacting glycidyl (meth)acrylate with mono-methanol terminated polydimethylsiloxane, mono-aminopropyl terminated polydimethylsiloxane, or mono-ethylaminopropyl terminated polydimethylsiloxane, or by reacting isocyanatoethyl (meth)acrylate with mono-methanol terminated polydimethylsiloxane, according to procedures well known to those skilled in the art.

[0080] According to the present application, any polysiloxane vinylic crosslinker can be used in the present application. Examples of preferred polysiloxane vinylic crosslinkers include, but are not limited to, alpha, omega- (meth)acryloxy-terminated polydimethylsiloxanes having different molecular weights; alpha, omega- (meth)acrylamido-terminated polydimethylsiloxanes having different molecular weights; alpha, omega- vinylcarbonate-terminated polydimethylsiloxanes having different molecular weights; alpha, omega- vinylcarbamate-terminated polydimethylsiloxanes having different molecular weights; bis-3-methacryloxy-2-hydroxy-propyl- oxypropyl polydimethylsiloxanes of different molecular weights; N,N,N',N'-tetra(3- methacryloxy-2-hydroxypropyl)-alpha, omega-bis-3-aminopropyl-polydimethylsiloxanes having different molecular weights; reaction products of glycidyl methacrylate with di-amino-terminated polydimethylsiloxanes; reaction products of glycidyl methacrylate with di-hydroxy-terminated polydimethylsiloxanes; reaction products of azlactone-containing vinylic monomers (any of those described above) with di-hydroxy-terminated polydimethylsiloxanes; reaction products of isocyanatoethyl (meth)acrylate with di-hydroxy-terminated polydimethylsiloxanes; reaction products of isocyanatoethyl (meth)acrylate with di-amino-terminated polydimethylsiloxanes; polysiloxane vinylic crosslinkers disclosed in U.S. Patent Nos. 5760100, 4136250, 4153641, 4182822, 4189546, 4259467, 4260725, 4261875, 4343927, 4254248, 4355147, 4276402, 4327203, 4341889, 4486577, 4543398, 4605712, 4661575, 4684538, 4703097, 4833218, 4837289, 4954586, 4954587, 5010141, 5034461, 5070170, 5079319, 5039761, 5346946, 5358995, 5387632, 5416132, 5449729, 5451617, 5486579, 5962548, 5981675, 6039913, 6762264, 7423074, 8163206, 8480227, 8529057, 8835525, 8993651, 9187601, 10081697, 10301451, and 10465047.

[0081] A preferred class of polysiloxane vinylic crosslinkers is prepared by reacting (meth)acrylic acid glycidyl ester or (meth)acryloyl chloride with di-amino-terminated polydimethylsiloxane or di-hydroxy-terminated polydimethylsiloxane; reacting (meth)acrylic acid isocyanatoethyl ester with di-hydroxy-terminated polydimethylsiloxane; reacting amino-containing acrylic monomer with di-carboxy-terminated polydimethylsiloxane in the presence of a coupling agent (a carbodiimide); reacting carboxy-containing acrylic monomer with di-amino-terminated polydimethylsiloxane in the presence of a coupling agent (a carbodiimide); or reacting hydroxyl-containing acrylic monomer with di-hydroxy-terminated polydimethylsiloxane in the presence of a di-isocyanate or di-epoxy coupling agent.

[0082] Examples of such preferred polysiloxane-ethylene crosslinking agents are α,ω-bis[3-(meth)acrylamidopropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acryloyloxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acryloyloxy-2-hydroxypropoxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acryloyloxyethoxy-2-hydroxypropoxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acryloyloxypropoxy-2-hydroxypropoxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acryloyloxy-iso ... [Oxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acryloyloxybutoxy-2-hydroxypropoxy-propyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acrylamidoethoxy-2-hydroxypropoxy-propyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acrylamidopropoxy-2-hydroxypropoxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acrylamidoisopropoxy-2-hydroxypropoxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acrylamidobutoxy-2-hydroxypropoxypropyl]-terminated polydimethylsiloxane, α, ω-bis[3-(meth)acryloyloxyethyl-amino-2-hydroxypropoxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acryloyloxypropylamino-2-hydroxypropoxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acryloyloxybutylamino-2-hydroxypropoxypropyl]-terminated polydimethylsiloxane, α,ω-bis[(meth)acrylamidoethylamino-2-hydroxypropoxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acrylamidopropylamino-2-hydroxypropoxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acrylamidobutyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acrylamidobutyl]-terminated polydimethylsiloxane, [Amino-2-hydroxypropoxypropyl]-terminated polydimethylsiloxane, α,ω-bis[(meth)acryloyloxy-2-hydroxypropoxy-ethoxypropyl]-terminated polydimethylsiloxane, α,ω-bis[(meth)acryloyloxy-2-hydroxypropyl-N-ethylaminopropyl]-terminated polydimethylsiloxane, α,ω-bis[(meth)acryloyloxy-2-hydroxypropyl-aminopropyl]-polydimethylsiloxane, α,ω-bis[(meth)acryloyloxy-2-hydroxypropoxy-(polyvinyloxy)propyl]-terminated polydimethylsiloxane, α,ω-bis[(meth)acryloyloxyethylamino-carbonyloxy-ethoxypropyl]-terminated polydimethylsiloxane, α,omega-bis[(meth)acryloyloxyethylamino-carbonyloxy-(polyethyleneoxy)propyl]- terminated polydimethylsiloxanes, and combinations thereof.

[0083] Another class of preferred polysiloxane vinylic crosslinkers are chain-extended polysiloxane vinylic crosslinkers each comprising at least two polysiloxane segments and can be prepared according to the procedures described in U.S. Patent Nos. 5034461, 5416132, 5449729, 5760100, 7423074, 8529057, 8835525, 8993651, and 10301451, and U.S. Patent Application Publication No. 2018-0100038 Al.

[0084] Another class of preferred polysiloxane vinylic crosslinkers are hydrophilic polysiloxane vinylic crosslinkers each comprising 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 per gram (“meq / g”) of hydrophilic moieties, which are preferably hydroxyl (-OH), carboxyl (-COOH), amino (-NHR N1 wherein R N1 is H or C1-C2 alkyl), amide moieties (-CO-NR N1 R N2 wherein R N1 is H or C1-C2 alkyl and R N2 is a covalent bond, H, or C1-C2 alkyl), N-C1-C3 acylamino, carbamate moieties (-NH-CO-O-), urea moieties (-NH-CO-NH-), polyethylene glycol chains (wherein n is an integer from 2 to 20 and T1 is H, methyl, or acetyl or phosphorylcholine group), or combinations thereof.

[0085] Examples of such preferred hydrophilic polysiloxane vinylic crosslinkers are those compounds of Formula (1)

[0086]

[0087] wherein:

[0088] u1 is an integer from 30 to 500 and w1 is an integer from 1 to 75, provided that w1 / u1 is from about 0.035 to about 0.15 (preferably from about 0.040 to about 0.12, even more preferably from about 0.045 to about 0.10);

[0089] X 01 is O or NR n wherein R n is hydrogen or C1-C 10 -alkyl;

[0090] R o is hydrogen or methyl;

[0091] R2and R3are independently of each other a substituted or unsubstituted C1-C 10 alkylene divalent radical or a divalent radical of -R5-O-R6-, wherein R5and R6are independently of each other a substituted or unsubstituted C1-C 10 alkylene divalent radical;

[0092] R4is a monovalent radical of any one of formulae (2) to (7)

[0093]

[0094]

[0095]

[0096]

[0097]

[0098]

[0099] p1is 0 or 1 ; m1is an integer from 2 to 4; m2is an integer from 1 to 5; m3is an integer from 3 to 6; m4is an integer from 2 to 5;

[0100] R7is hydrogen or methyl;

[0101] R8is a C2-C6hydrocarbon group having a valence of (m2+1);

[0102] R9is a C2-C6hydrocarbon group having a valence of (m4+1);

[0103] R 10 is ethyl or hydroxymethyl;

[0104] R 11 is methyl or hydroxymethyl;

[0105] R 12 is hydroxyl or methoxy;

[0106] X3is a sulfur linker -S- or a tertiary amino linker -NR 13 -, wherein R 13 is C1-C1alkyl, hydroxyethyl, hydroxypropyl, or 2,3-dihydroxypropyl;

[0107] X4is an amide linker or wherein R 14 is hydrogen or C1-C 10 alkyl;

[0108] L PC is a divalent group 、 、 、 、 , or wherein q1 is an integer from 1 to 20, R 15 is a linear or branched C1-C 10 alkylene divalent group, R 16 is a linear or branched C3-C 10 alkylene divalent group, and R 17 is a direct bond or a linear or branched C1-C4 alkylene divalent group.

[0109] The procedure for preparing the polysiloxane vinylic crosslinker of Formula (1) has been described in detail in US 10,081,697 and U.S. Patent Application Publication No. 2022 / 0251302 Al.

[0110] According to the present application, any carboxyl-containing vinylic monomer can be used in the present application. Examples of preferred carboxyl-containing (meth)acryloyloxy monomers include, but are not limited to, acrylic acid, C1-C4 alkyl acrylic acids (e.g., methacrylic acid, ethyl acrylic acid, propyl acrylic acid, butyl acrylic acid), (meth)acryloyloxy-C1-C6 alkanoic acids (e.g., (meth)acryloyloxy-acetic acid, (meth)acryloyloxy-propionic acid, (meth)acryloyloxy butyric acid, (meth)acryloyloxy valeric acid, (meth)acryloyloxy hexanoic acid), succinic acid mono-2-[ (meth)acryloyloxy]-ethyl ester, (meth)acrylamido-C1-C6 alkanoic acids (3-(meth)acrylamidopropionic acid, 4-(meth)acrylamidobutyric acid, 5-(meth)acrylamidovaleric acid, 6-(meth)acrylamidohexanoic acid), 2-acrylamidoglycolic acid, and combinations thereof.

[0111] Any hydrophilic vinylic monomer can be used in the present application. Examples of preferred hydrophilic vinylic monomers are alkyl (meth)acrylamides (as described later in this application), hydroxyl-containing acrylic monomers (as described below), amino-containing acrylic monomers (as described later in this application), N-vinyl amide monomers (as described later in this application), methylene-containing pyrrolidone monomers (i.e., pyrrolidone derivatives each having a methylene group attached to the pyrrolidone ring at either the 3- or 5-position) (as described later in this application), acrylic monomers having C1-C4 alkoxyethoxy groups (as described later in this application), vinyl ether monomers (as described later in this application), allyl ether monomers (as described later in this application), phosphorylcholine-containing vinylic monomers (as described later in this application), N-2-hydroxyethyl vinylcarbamate, N-carboxyvinyl- -alanine (VINAL), N-carboxyvinyl- -alanine, and combinations thereof.

[0112] 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.

[0113] 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, glyceryl 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.

[0114] Examples of preferred N-vinyl amide monomers include, but are not limited to, N-vinyl pyrrolidone (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-vinyl piperidone (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-vinyl caprolactam (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-methyl acetamide, N-vinyl formamide, N-vinyl acetamide, N-vinyl isopropylamide, N-vinyl-N-ethyl acetamide, N-vinyl-N-ethyl formamide, and mixtures thereof. Preferably, the N-vinyl amide monomer is N-vinyl pyrrolidone, N-vinyl-N-methyl acetamide, or a combination thereof.

[0115] Examples of preferred methylene (=CH2)-containing 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-iso-propyl-3-methylene-2-pyrrolidone, 1-iso-propyl-5-methylene-2-pyrrolidone, 1-n-butyl-3-methylene-2-pyrrolidone, 1-t-butyl-3-methylene-2-pyrrolidone, and combinations thereof.

[0116] Examples of preferred acrylic monomers having C1-C4-alkoxyethyl groups include, but are not limited to, ethylene glycol methylether (meth)acrylate, di(ethylene glycol) methylether (meth)acrylate, tri(ethylene glycol) methylether (meth)acrylate, tetra(ethylene glycol) methylether (meth)acrylate, C1-C4-alkoxy poly(ethylene glycol) ethyl (meth)acrylate having a weight average molecular weight of up to 1500, methoxy-poly(ethylene glycol) ethyl (meth)acrylamide having a number average molecular weight of up to 1500, and combinations thereof.

[0117] Examples of preferred vinyl ether monomers include, but are not limited to, ethylene glycol mono vinyl ether, di(ethylene glycol) mono vinyl ether, tri(ethylene glycol) mono vinyl ether, tetra(ethylene glycol) mono vinyl ether, poly(ethylene glycol) mono vinyl 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.

[0118] Examples of preferred allyl ether monomers include, but are not limited to, allyl alcohol, ethylene glycol mono allyl ether, di(ethylene glycol) mono allyl ether, tri(ethylene glycol) mono allyl ether, tetra(ethylene glycol) mono allyl ether, poly(ethylene glycol) mono allyl 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.

[0119] Examples of preferred phosphocholine-containing vinylic monomers include, but are not limited to, (meth)acryloyloxyethylphosphocholine (also known as MPC), or 2-( (meth)acryloyloxy)ethyl-2'-(trimethylammonio)ethylphosphate, (meth)acryloyloxypropylphosphocholine (also known as 3-( (meth)acryloyloxy)propyl-2'-(trimethylammonio)ethylphosphate), 4-( (meth)acryloyloxy)butyl-2'-(trimethylammonio)ethylphosphate, 2-[ (meth)acryloylamino]ethyl-2'-(trimethylammonio)-ethylphosphate, 3-[ (meth)acryloylamino]propyl-2'-(trimethylammonio)ethylphosphate, 4-[ (meth)acryloylamino]butyl-2'-(trimethylammonio)ethylphosphate, 5-( (meth)acryloyloxy)pentyl-2'-(trimethylammonio)ethylphosphate, 6-( (meth)acryloyloxy)hexyl-2'-(trimethylammonio)-ethylphosphate, 2-( (meth)acryloyloxy)ethyl-2'-(triethylammonio)ethylphosphate, 2-( (meth)acryloyloxy)ethyl-2'-(tripropylammonio)ethylphosphate, 2-( (meth)acryloyloxy)ethyl-2'-(tributylammonio)ethylphosphate, 2-( (meth)acryloyloxy)propyl-2'-(trimethylammonio)-ethylphosphate, 2-( (meth)acryloyloxy)butyl-2'-(trimethylammonio)ethylphosphate, 2-( (meth)acryloyloxy)pentyl-2'-(trimethylammonio)ethylphosphate, 2-( (meth)acryloyloxy)hexyl-2'-(trimethylammonio)ethylphosphate, 2-(vinyloxy)ethyl-2'-(trimethylammonio)ethylphosphate, 2-(allyloxy)ethyl-2'-(trimethylammonio)ethylphosphate, 2-(vinyloxycarbonyl)ethyl-2'-(trimethylammonio)ethylphosphate, 2-(allyloxycarbonyl)ethyl-2'-(trimethylammonio)-ethylphosphate, 2-(vinylcarbonylamino)ethyl-2'-(trimethylammonio)ethylphosphate, 2-(allyloxycarbonylamino)ethyl-2'-(trimethylammonio)ethylphosphate, 2-(butenyl-oxy)ethyl-2'-(trimethylammonio)ethylphosphate, and combinations thereof.

[0120] In preferred embodiments, the arylboronate-containing vinylic monomer is represented by formula (I)

[0121] (I)

[0122] wherein: R B is a monovalent group (preferably H, NO2, F, Cl, Br, CF3, CH2OH, or CH2NR o R o ' (R o and R oa monovalent group of the formula -C(O)N(R1)2, wherein R1is independently H or C1-C4alkyl; Q is 、 、 、 、 、 、 、or a monovalent group of the formula -C(O)N(R1)2, wherein R1is independently H or C1-C4alkyl; Q is B a direct bond, a C1-C4alkylene divalent group, 、 、 、 、 、 、 or a divalent group of the formula -C(O)N(R1)2, wherein R1is independently H or C1-C4alkyl; Q is o a direct bond, a C1-C4alkylene divalent group,

[0123] Examples of preferred aryl-containing dihydroxyboron group-containing vinylic monomers of Formula (I) include, but are not limited to, 3-vinylphenylboronic acid, 4-vinylphenylboronic acid (pKa of about 8.8), 3-(meth)acrylamidophenylboronic acid (pKa of about 8.2), 4-(meth)acrylamidophenylboronic acid, 4-(1,6-dioxo-2,5-diaza-7-carboxamido)phenylboronic acid (pKa of about 7.8), 2-dimethylaminomethyl-5-vinylphenyl-boronic acid (pKa < 7.8), 4-(N-allylsulfamoyl)phenylboronic acid (pKa of about 7.4), 4-(3-butenylsulfonyl)phenylboronic acid (pKa of about 7.1 ), 3-(meth)acrylamido-5-nitrophenylboronic acid, 4-(meth)acrylamido-5-nitrophenylboronic acid, 4-(meth)acrylamido-3-nitrophenylboronic acid, 3-[ (meth)acrylamido-C2-C5-alkylaminocarbonyl]-5-nitrophenylboronic acid, 3-[ (meth)acryloyloxy-C2-C5-alkylaminocarbonyl]-5-nitrophenylboronic acid, 3-(meth)acrylamido-6-hydroxymethyl-phenylboronic acid, 3-(meth)acrylamido-6-dimethylaminomethylphenylboronic acid, 4-(meth)acrylamido-6-hydroxymethylphenylboronic acid, 4-(meth)acrylamido-6-dimethylamino-methylphenylboronic acid, reaction products of amino-containing phenylboronic acid derivatives with (meth)acrylic acid halides or epoxy-containing vinylic monomers or with carboxy-containing vinylic monomers in the presence of carbodiimides (e.g., 1 -ethyl-3-(3-dimethylaminopropyl)carbodiimide (EDC), N,N'-dicyclohexyl-carbodiimide (DCC), 1 -cyclohexyl-3-(2-morpholinoethyl)carbodiimide, diisopropylcarbodiimide, or mixtures thereof) and N-hydroxysuccinimide, reaction products of carboxy-containing phenylboronic acid derivatives with amino-containing vinylic monomers in the presence of carbodiimides (e.g., 1 -ethyl-3-(3-dimethylaminopropyl)carbodiimide (EDC), N,N'-dicyclohexyl-carbodiimide (DCC), 1 -cyclohexyl-3-(2-morpholinoethyl)carbodiimide, diisopropylcarbodiimide, or mixtures thereof) and N-hydroxysuccinimide, and combinations thereof.

[0124] Examples of preferred carboxyl-containing phenyl boronic acid derivatives include, but are not limited to, 3-carboxyphenyl boronic acid, 4-carboxyphenyl boronic acid, 3- dihydroxyborylphenyl-acetic acid, 4-dihydroxyborylphenylacetic acid, 2-(4- dihydroxyborylphenyl)-2-methylpropionic acid, 3-(4-dihydroxyborylphenyl)propionic acid, 3-(3-dihydroxyborylphenyl)propionic acid, 5-(3-dihydroxyborylphenyl)pentanoic acid, 5-(4-dihydroxyborylphenyl)pentanoic acid, 4-(2-carboxyethyl)-3-nitrophenyl boronic acid, 3-carboxy-5-nitrophenyl boronic acid, 4-carboxy-3-chlorophenyl boronic acid, 3-carboxy-4-fluorophenyl boronic acid, 3-(3-carboxypropionylamino)phenyl boronic acid, 3-amino-3-(4-dihydroxyborylphenyl)propionic acid, and combinations thereof.

[0125] Examples of preferred amino-containing phenyl boronic acid derivatives include, but are not limited to, 3-aminophenyl boronic acid, 4-aminophenyl boronic acid, 4-amino-3-nitrophenyl boronic acid, 3-amino-6-hydroxymethylphenyl boronic acid, 3-amino-6- (dimethylaminomethyl)phenyl-boronic acid, 4-amino-2-hydroxymethylphenyl boronic acid, 4-amino-2-(dimethylaminomethyl)phenyl boronic acid, 3-amino-4- fluorophenyl boronic acid, 4-(aminomethyl)-5-nitrophenyl boronic acid, 3- (aminomethyl)-phenyl boronic acid, 3-amino-5-nitrophenyl boronic acid, 3-amino-3- (4-dihydroxyborylphenyl)propionic acid, and combinations thereof.

[0126] Examples of preferred acetal-containing phenyl boronic acid derivatives include, but are not limited to, 2-acetyloxyphenyl boronic acid, 3-acetyloxyphenyl boronic acid, 4- acetyloxyphenyl boronic acid, 2-formylphenyl boronic acid, 3-formylphenyl boronic acid, 4-formylphenyl boronic acid, 5-formyl-2-methoxyphenyl boronic acid, 3-fluoro-4- formylphenyl boronic acid, 4-fluoro-3-formylphenyl boronic acid, and combinations thereof.

[0127] Examples of preferred carboxyl-containing vinylic monomers include, but are not limited to, those described above.

[0128] Examples of preferred amino-containing vinylic monomers include, but are not limited to, (meth)acrylic acid amino-C2-C4alkyl esters (e.g., (meth)acrylic acid 2-aminoethyl ester, (meth)acrylic acid 3-aminopropyl ester, (meth)acrylic acid 3-amino-2-hydroxypropyl ester), C1-C3alkylamino-C2-C4alkyl (meth)acrylates (e.g., (meth)acrylic acid 2-methylaminoethyl ester, (meth)acrylic acid 2-ethylaminoethyl ester, (meth)acrylic acid 3-methylaminopropyl ester, (meth)acrylic acid 3-ethylaminopropyl ester), amino-C2-C4alkyl (meth)acrylamides (e.g., N-2-aminoethyl (meth)acrylamide, N-3-aminopropyl (meth)acrylamide, N-4-aminobutyl (meth)acrylamide), C1-C3alkylamino-C2-C4alkyl (meth)acrylamides (e.g., N-2-methylaminoethyl (meth)acrylamide, N-2-ethylaminoethyl (meth)acrylamide, N-3-methylaminopropyl (meth)acrylamide), vinylamines, allylamines, and combinations thereof.

[0129] Examples of preferred epoxy-containing vinylic monomers include, but are not limited to, glycidyl (meth)acrylamide, hydroxyethyl (meth)acrylamide glycidyl ether, 3-hydroxypropyl (meth)acrylamide glycidyl ether, 4-hydroxybutyl (meth)acrylamide glycidyl ether, (meth)acrylic acid glycidyl ester, (meth)acrylic acid hydroxyethyl glycidyl ether, (meth)acrylic acid 3-hydroxypropyl glycidyl ether, (meth)acrylic acid 4-hydroxybutyl glycidyl ether, and combinations thereof.

[0130] According to the present application, any non-silicone vinylic crosslinker can be used in the present application. Examples of preferred non-silicone vinylic crosslinkers include, but are not limited to, ethylene glycol di-(meth)acrylate, diethylene glycol di-(meth)acrylate, triethylene glycol di-(meth)acrylate, tetraethylene glycol di-(meth)acrylate, polyethylene glycol di-(meth)acrylate having a number average molecular weight of 200 to 10,000 Daltons, glycerol di-(meth)acrylate, 1,3-propanediol di-(meth)acrylate, 1,3-butanediol di-(meth)acrylate, 1,4-butanediol di-(meth)acrylate, glycerol 1,3-diglycidate di-(meth)acrylate, ethylenebis[oxy(2-hydroxypropane-1,3-diyl)] di-(meth)acrylate, bis[2-(meth)acryloyloxyethyl] phosphate, trimethylolpropane di-(meth)acrylate, and 3,4-bis[(meth)acryloyl]tetrahydrofuran, diacrylamide (i.e., N-(1-oxo-2-propenyl)-2-propenamide), dimethylacrylamide (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)acrylamido-propane-2-yl dihydrogen phosphate (i.e., N,N'-2-phosphonooxypropylenebis(meth)acrylamide), piperazine diacrylamide (or 1,4-bis(meth)acryloylpiperazine), triallylisocyanurate, 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.

[0131] According to the present application, the free radical initiator can be a photoinitiator or a thermal initiator. By “photoinitiator” is meant a chemical that initiates a free radical crosslinking / polymerization reaction by utilizing light energy. By “thermal initiator” is meant a chemical that initiates a free radical crosslinking / polymerization reaction by utilizing thermal energy.

[0132] Any thermal polymerization initiator can be used in the present application. Suitable thermal polymerization initiators are known to the skilled person and include, for example, peroxides, hydroperoxides, azo-bis(alkyl- or cycloalkyl nitriles), 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(t-butylperoxy)butane, 1,1 -bis(t-butylperoxy)cyclohexane, 2,5-bis(t-butylperoxy)-2,5-dimethylhexane, 2,5-bis(t-butylperoxy)-2,5-dimethyl-3-hexyne, bis(1-(t-butylperoxy)-1 - methylethyl)benzene, 1,1 -bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, di-t-butyl- diperoxyphthalate, t-butyl hydroperoxide, t-butyl peracetate, t-butyl peroxybenzoate, t-butylperoxy isopropyl 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).

[0133] Suitable photoinitiators are benzoin methyl ether, diethoxyacetophenone, benzoyl phosphine oxide, 1-hydroxycyclohexyl phenyl ketone, and Darocur and Irgacur types, preferably Darocur 1173® and Darocur 2959®, germanium-based Norrish Type I photoinitiators (e.g., those described in US 7,605,190). Examples of benzoyl phosphine initiators include 2,4,6-trimethylbenzoyldiphenylphosphine oxide; bis-(2,6-dichlorobenzoyl)-4-N-propylphenylphosphine oxide; and bis-(2,6-dichlorobenzoyl)-4-N-butylphenylphosphine oxide. Reactive photoinitiators, which can be incorporated into the macromonomer or used as a special monomer, are also suitable, for example. Examples of reactive photoinitiators are those disclosed in EP 632 329.

[0134] The SiHy lens formulation (i.e., the polymerizable composition) can also include other necessary components known to those skilled in the art, such as, for example, one or more non-silicone hydrophobic vinylic monomers, UV-absorbing vinylic monomers, polymerizable UV / high-energy visible light ("HEVL") absorbing compounds (including the UV / HEVL absorbing vinylic monomers described below, and / or the polymerizable Cu(II)-porphyrin-like compounds described in U.S. Patent Application Publication No. 20150316688), polymerizable photochromic compounds, visible colorants (e.g., reactive dyes, polymerizable dyes, pigments, or mixtures thereof, as are well known to those skilled in the art), antimicrobial agents (e.g., preferably silver nanoparticles), biologically active agents, leachable lubricants (e.g., non-polymerizable hydrophilic polymers, etc.), leachable tear stabilizers (e.g., phospholipids, monoglycerides, diglycerides, triglycerides, glycolipids, glycosylglycerides, sphingolipids, sphingoglycolipids, etc.), and mixtures thereof, as are well known to those skilled in the art.

[0135] According to the present application, any non-silicone hydrophobic hydrophobic vinylic crosslinker can be used in the present application. Examples of preferred non-silicone hydrophobic vinylic monomers include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl valerate, styrene, chlorobutadiene, chloroethylene, vinylidene chloride, (meth)acrylonitrile, 1-butene, butadiene, vinyl toluene, vinyl ethyl ether, perfluorohexylethyl-thio-carbonyl- aminoethyl-methacrylate, isobornyl (meth)acrylate, trifluoroethyl (meth)acrylate, hexafluoro-isopropyl (meth)acrylate, hexafluorobutyl (meth)acrylate, and combinations thereof.

[0136] Any suitable UV-absorbing vinylic monomer and UV / HEVL-absorbing vinylic monomer can be used in the polymerizable composition used to make the preformed SiHy contact lenses of the present application. Examples of preferred UV-absorbing vinylic monomers and UV / HEVL-absorbing vinylic monomers include, but are not limited to: 2-(2-hydroxy-5-vinylphenyl)-2H-benzotriazole, 2-(2-hydroxy-5-acryloxyphenyl)-2H-benzotriazole, 2-(2-hydroxy-3-methylacrylamidomethyl-5-tert-octylphenyl)benzotriazole, 2-(2'-hydroxy-5'-methylacrylamidophenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-5'-methylacrylamidophenyl)-5-methoxybenzotriazole, 2-(2'-hydroxy-5'-methylacryloxypropyl-3'-tert-butyl-phenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-5'-methylacryloxypropylphenyl)benzotriazole, 2-hydroxy-5-methoxy-3-(5-(trifluoromethyl)-2H-benzo[d][l,2,3]triazol-2-yl)benzyl methacrylate (WL-1), 2-hydroxy-5-methoxy-3-(5-methoxy-2H-benzo[d][l,2,3]triazol-2-yl)benzyl methacrylate (WL-5), 3-(5-fluoro-2H-benzo[d][l,2,3]triazol-2-yl)-2-hydroxy-5-methoxybenzyl methacrylate (WL-2), 3-(2H-benzo[d][l,2,3]triazol-2-yl)-2-hydroxy-5-methoxybenzyl methacrylate (WL-3), 3-(5-chloro-2H-benzo[d][l,2,3]triazol-2-yl)-2-hydroxy-5-methoxybenzyl methacrylate (WL-4), 2-hydroxy-5-methoxy-3-(5-methyl-2H-benzo[d][l,2,3]triazol-2-yl)benzyl methacrylate (WL-6), 2-hydroxy-5-methyl-3-(5-(trifluoromethyl)-2H-benzo[d][l,2,3]triazol-2-yl)benzyl methacrylate (WL-7), 4-allyl-2-(5-chloro-2H-benzo[d][l,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-(l,l-dimethylethyl)-4-vinyl- (UVAM), 2-[2'-hydroxy-5'-(2-methacryloyloxyethyl)phenyl)]-2H-benzotriazole (2-acrylic acid, 2-methyl-,2-[3-(2H-benzotriazol-2-yl)-4-hydroxyphenyl]ethyl ester, Norbloc), 2-{2'-hydroxy-3'-tert-butyl-5'-[3'-methylacryloyloxypropoxy]phenyl}-2H- benzotriazole, 2-{2'-hydroxy-3'-tert-butyl-5'-[3'-methylacryloyloxypropoxy]phenyl}-5- methoxy-2H-benzotriazole (UV 13), 2-{2'-hydroxy-3'-tert-butyl-5'-[3'- methylacryloyloxypropoxy]phenyl}-5-chloro-2H-benzotriazole (UV 28), 2-[2'-hydroxy-3'- tert-butyl-5'-(3'-acryloyloxypropoxy)phenyl]-5-trifluoromethyl-2H-benzotriazole (UV 23), 2-(2'-hydroxy-5-methylacrylamidophenyl)-5-methoxybenzotriazole (UV 6), 2-(3- allyl-2-hydroxy-5-methylphenyl)-2H-benzotriazole (UV 9), 2-(2-hydroxy-3-methylallyl-5- methylphenyl)-2H-benzotriazole (UV 12), 2-3'-tert-butyl-2'-hydroxy-5'-(3"-dimethylvinylsilyl propoxy)-2'-hydroxy-phenyl)-5-methoxybenzotriazole (UV 15), 2-(2'-hydroxy-5'-methylacryloyl propyl-3'-tert-butyl-phenyl)-5-methoxy-2H-benzotriazole (UV 16), 2-(2'-hydroxy-5'- acryloylpropyl-3'-tert-butyl-phenyl)-5-methoxy-2H-benzotriazole (UV 16A), 2-methylacrylic acid 3-[3-tert-butyl-5-(5-chlorobenzotriazol-2-yl)-4-hydroxyphenyl]-propyl ester (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 methyl acrylate (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-vinyl-2H- benzotriazol-2-yl)-4-methyl-, homopolymer (9CI) (CAS # 83063-87-0). According to the present application, the polymerizable composition comprises about 0.1% to about 3.0%, preferably about 0.2% to about 2.5%, more preferably about 0.3% to about 2.0%, by weight, of one or more UV-absorbing vinylic monomers relative to the amount of all polymerizable components in the polymerizable composition.

[0137] Examples of preferred photochromic vinylic monomers include polymerizable naphthopyrans, polymerizable benzopyrans, polymerizable indenonaphthopyrans, polymerizable phenanthropyrans, polymerizable spiro(benzindolin)-naphthopyrans, polymerizable spiro(indolin)benzopyrans, polymerizable spiro(indolin)-naphthopyrans, polymerizable spiro(indolin)quinopyrans, polymerizable spiro(indolin)-pyrans, polymerizable phenoxazines, polymerizable spirobenzopyrans; polymerizable spirobenzopyrans, polymerizable spirobenzothiopyrans, polymerizable naphtho naphthalimides, polymerizable spirooxazines, polymerizable spiro(indolin)phenoxazines, polymerizable spiro(indolin)-pyridobenzoxazines, polymerizable spiro(benzindolin)pyridobenzoxazines, polymerizable spiro(benzindolin)phenoxazines, polymerizable spiro(indolin)-benzoxazines, polymerizable diarylethylene, and combinations thereof, 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.

[0138] The polymerizable composition (SiHy lens formulation) can be a solvent-free, clear liquid prepared by mixing all the polymerizable components and other necessary components; or a solution prepared by dissolving all the desired components in any suitable solvent such as a mixture of water and one or more water-miscible organic solvents, an organic solvent, or a mixture of one or more organic solvents, as known to those skilled in the art. The term "solvent" refers to a chemical that does not participate in the free radical polymerization reaction.

[0139] The solvent-free lens SiHy lens formulation typically contains at least one blended vinylic monomer as a reactive solvent for dissolving all the other polymerizable components of the solvent-free SiHy lens formulation. Examples of preferred blended vinylic monomers are described later in this application. Preferably, methyl methacrylate is used as a blended vinylic monomer in the preparation of the solvent-free SiHy lens formulation.

[0140] Any solvent can be used in the present application. Examples of preferred organic solvents include, but are not limited to, tetrahydrofuran, tripropyleneglycol methyl ether, dipropyleneglycol methyl ether, ethyleneglycol n-butyl ether, ketones (e.g., acetone, methyl ethyl ketone, etc.), diethyleneglycol n-butyl ether, diethyleneglycol methyl ether, ethyleneglycol phenyl ether, propyleneglycol methyl ether, propyleneglycol methyl ether acetate, dipropyleneglycol methyl ether acetate, propyleneglycol n-propyl ether, dipropyleneglycol n-propyl ether, tripropyleneglycol n-butyl ether, propyleneglycol n-butyl ether, dipropyleneglycol n-butyl ether, tripropyleneglycol n-butyl ether, propyleneglycol phenyl ether, dipropyleneglycol dimethyl ether, polyethyleneglycol, polypropyleneglycol, ethyl acetate, butyl acetate, amyl acetate, methyl lactate, ethyl lactate, isopropyl lactate, dichloromethane, 2-butanol, 1-propanol, 2-propanol, menthol, cyclohexanol, cyclopentanol and exonorborneol, 2-pentanol, 3-pentanol, 2-hexanol, 3-hexanol, 3-methyl-2-butanol, 2-heptanol, 2-octanol, 2-nonyl alcohol, 2-decanol, 3-octanol, norborneol, t-butyl alcohol, t-amyl alcohol, 2-methyl-2-pentanol, 2,3-dimethyl-2-butanol, 3-methyl-3-pentanol, 1-methylcyclohexanol, 2-methyl-2-hexanol, 3,7-dimethyl-3-octanol, 1-chloro-2-methyl-2-propanol, 2-methyl-2-heptanol, 2-methyl-2-octanol, 2-2-methyl-2-nonyl alcohol, 2-methyl-2-decanol, 3-methyl-3-hexanol, 3-methyl-3-heptanol, 4-methyl-4-heptanol, 3-methyl-3-octanol, 4-methyl-4-octanol, 3-methyl-3-nonyl alcohol, 4-methyl-4-nonyl alcohol, 3-methyl-3-octanol, 3-ethyl-3-hexanol, 3-methyl-3-heptanol, 4-ethyl-4-heptanol, 4-propyl-4-heptanol, 4-isopropyl-4-heptanol, 2,4-dimethyl-2-pentanol, 1-methylcyclopentanol, 1-ethylcyclopentanol, 1-ethylcyclopentanol, 3-hydroxy-3-methyl-1-butene, 4-hydroxy-4-methyl-1-cyclopentanol, 2-phenyl-2-propanol, 2-methoxy-2-methyl-2-propanol, 2,3,4-trimethyl-3-pentanol, 3,7-dimethyl-3-octanol, 2-phenyl-2-butanol, 2-methyl-1-phenyl-2-propanol, and 3-ethyl-3-pentanol, 1-ethoxy-2-propanol, 1-methyl-2-pyrrolidinone, N,N-dimethylpropionamide, dimethylformamide, dimethylacetamide, dimethylpropionamide, N-methylpyrrolidinone, and mixtures thereof.

[0141] In a preferred embodiment, the polymerizable composition comprises: (i) at least one hydrophilic polysiloxane vinylic crosslinker, (ii) optionally but preferably hydroxyethyl methacrylate, (iii) at least one C1-C2alkoxyethyl (meth)acrylate, (iv) about 0.5% to about 3.5% by weight (preferably about 0.7% to about 3.5%, more preferably about 0.9% to about 3.0%, even more preferably about 1.0% to about 2.8%) relative to the total amount of all polymerizable components of at least one carboxyl-containing vinylic monomer, (v) about 2.5% to about 12.5% by weight (preferably about 2.5% to about 10%, more preferably about 3.0% to about 8.0%, even more preferably about 3.5% to about 7.0%) of at least one arylboronate-containing vinylic monomer having an arylboronate group, (vi) at least one non-silicone vinylic crosslinker, (vii) at least one free radical initiator, and (viii) optionally at least one solvent selected from the group consisting of water, propylene glycol, polyethylene glycol having a molecular weight of about 400 Daltons or less, and combinations thereof. The sum of the amounts of components (i) to (vii) is at least about 90% by weight, preferably at least about 92% by weight, more preferably at least about 94% by weight, even more preferably at least about 96% by weight relative to the total amount of all polymerizable components in the polymerizable composition. It is understood that the polymerizable composition according to this preferred embodiment of the present application can further comprise one or more additional polymerizable components (in addition to components (i) to (v) known to those skilled in the art) as long as the sum of the amounts of those 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, even more preferably about 4% by weight or less relative to the total amount of all polymerizable components in the polymerizable composition. The polymerizable composition can be prepared by blending all the desired components as known to those skilled in the art.

[0142] According to the present application, the polymerizable composition can be dispensed into the lens mold according to any known technique. For example, a specific amount of the polymerizable composition is typically dispensed into the female mold half by means of a dispensing device, and then the male mold half is placed on, and the mold is closed. Upon mold closure, any excess polymerizable composition is pressed into an overflow area provided on the female mold half (or alternatively on the male mold half).

[0143] As known to those skilled in the art, the molded assembly (i.e., the closed mold containing the polymerizable composition) is subsequently heat or actinically cured to form a preformed silicone hydrogel lens comprising a bulk silicone hydrogel material containing carboxyl and arylboronate diol groups. It will be appreciated that the carboxyl groups on and / or near the surface of the bulk silicone hydrogel material can serve as reactive sites to which a covalently attached layer of a crosslinked hydrophilic polymeric material can be attached, while the arylboronate diol groups on and / or near the surface of the bulk silicone hydrogel material can serve as reactive sites to which a covalently attached diol-containing hydrophilic polymer having 1,2- or 1,3-diol moieties can be attached.

[0144] After curing, the mold can be opened according to any technique known to those skilled in the art. After the mold halves are separated, the preformed silicone hydrogel lens adheres to one of the lens-adhered mold halves.

[0145] The preformed silicone hydrogel lens adhered to the lens-adhered mold half can be removed from the lens-adhered mold half and then subjected to one or more post-molding processes.

[0146] According to the present invention, the aqueous coating solution of the present invention must comprise two different types of coating materials.

[0147] The first type of coating material is a water-soluble and heat-crosslinkable hydrophilic polymeric material that is branched or lightly crosslinked and comprises heat-crosslinkable groups (azetidinium groups and / or epoxy groups) and, optionally but preferably, reactive functional groups (primary amino groups, secondary amino groups, carboxylic acid groups, mercapto groups, or combinations thereof).

[0148] The term "lightly crosslinked" with respect to a polymeric material means that the number of crosslinks between polymer chains in the polymeric material is so low that the polymeric material is still water-soluble.

[0149] In preferred embodiments, the water-soluble heat-crosslinkable hydrophilic polymeric material is a partially crosslinked polymeric material that comprises a three-dimensional network and heat-crosslinkable groups, preferably azetidinium groups, within or attached to the network. The term "partially crosslinked" with respect to a polymeric material means that the crosslinkable groups of the starting materials used to make the polymeric material in a crosslinking reaction have not been completely consumed. For example, such a heat-crosslinkable hydrophilic polymeric material comprises azetidinium groups and is a partial reaction product of at least one azetidinium- or epoxy-containing polymer with at least one hydrophilic reinforcing agent (i.e., wetting agent) having at least one carboxyl, primary amine group, secondary amine group, or mercapto group according to the crosslinking reaction shown in Scheme I

[0150]

[0151]

[0152] Scheme I

[0153] wherein X1is -S- , -OC(=0)- , or -NR'- wherein R' is hydrogen or C1-C 20 unsubstituted or substituted alkyl, and represents an organic group.

[0154] Examples of preferred water-soluble and thermally crosslinkable hydrophilic polymeric materials comprising epoxy groups include, but are not limited to: one or more multi-arm polyethylene glycols each having terminal epoxy groups (i.e., epoxide groups); a partial reaction product of a multi-arm polyethylene glycol having terminal epoxy groups with 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 mercaptan group, and combinations thereof; a partial reaction product of a multi-arm polyethylene having terminal epoxy groups with a hydrophilic reinforcing agent having at least one reactive functional group selected from the group consisting of an amino group, a carboxyl group, a mercaptan group, and combinations thereof (as disclosed in U.S. Patent No. 9505184, the hydrophilic polymer disclosed in U.S. Patent No. 6440571); a copolymer of an epoxy-containing vinylic monomer (any of those described above) and one or more hydrophilic vinylic monomers with a partial reaction product of a hydrophilic reinforcing agent (any of those described later) having at least one reactive functional group selected from the group consisting of an amino group, a carboxyl group, a mercaptan group, and combinations thereof; a copolymer of an epoxy-containing vinylic monomer (any of those described above), a hydrophilic vinylic monomer, a C1-C4-alkoxy poly(ethylene glycol) ethyl (meth)acrylate having a number average molecular weight of up to 2500 Daltons, a poly(ethylene glycol) ethyl (meth)acrylate having a number average molecular weight of up to 2500 Daltons, a C1-C4-alkoxy poly(ethylene glycol) ethyl (meth)acrylamide, or a poly(ethylene glycol) ethyl (meth)acrylamide having a number average molecular weight of up to 2500 Daltons; or combinations thereof.

[0155] Examples of preferred water-soluble and heat-crosslinkable hydrophilic polymeric materials comprising azetidinium groups include, but are not limited to, poly(2-oxazoline-co-vinyl imine)-epichlorohydrin copolymers disclosed in U.S. Patent No. 9720138, chemically modified poly(2-oxazoline-co-vinylimine)-epichlorohydrin copolymers disclosed in U.S. Patent No. 9720138, chemically modified polyamidoamine-epichlorohydrin as disclosed in U.S. Patent No. 8529057, copolymers of azetidinium-containing vinylic monomers with one or more hydrophilic vinylic monomers disclosed in U.S. Patent No. 9422447, chemically modified copolymers of azetidinium-containing vinylic monomers with one or more hydrophilic vinylic monomers disclosed in U.S. Patent No. 9422447, or combinations thereof.

[0156] According to the present invention, the term "chemically modified" with respect to water-soluble and heat-crosslinkable hydrophilic polymeric materials having azetidinium groups means that the poly(2-oxazoline-co-vinylimine)-epichlorohydrin copolymer, polyamidoamine-epichlorohydrin, or copolymers of azetidinium-containing vinylic monomers are partially reacted with a hydrophilicity-enhancing agent having at least one reactive functional group selected from the group consisting of an amino group, a carboxyl group, a mercapto group, and combinations thereof (i.e., not all of these azetidinium groups are consumed). Chemically modified poly(2-oxazoline-co-vinylimine)-epichlorohydrin copolymers or polyamidoamine-epichlorohydrin, or copolymers of azetidinium-containing vinylic monomers can be useful, inter alia, for forming relatively thick and soft non-silicone hydrogel coatings on silicone hydrogel contact lenses.

[0157] Any suitable hydrophilicity-enhancing agent can be used in the present invention, so long as they contain at least one amino group, at least one carboxyl group, and / or at least one mercapto group.

[0158] One class of preferred hydrophilicity-enhancing agents includes, but is not limited to, monosaccharides containing primary amino groups, secondary amino groups, carboxyl groups, or mercapto groups (e.g., 3-amino-1,2-propanediol, 1-mercapto glycerol, 5-keto-D-gluconic acid, galactosamine, glucosamine, galacturonic acid, gluconic acid, glucosaminic acid, mannoseamine, glucaric acid 1,4-lactone, saccharic acid, Ketodeoxynonulosonic acid, N-methyl-D-glucamine, 1-amino-1-deoxy-beta-D-galactose, 1-amino-1-deoxy sorbitol, 1-methylamino-1-deoxy sorbitol, N-aminoethyl gluconamide); disaccharides containing primary amino groups, secondary amino groups, carboxyl groups, or mercapto groups (e.g., chondroitin disaccharide sodium salt, di(beta-D-xylopyranosyl)amine, digalacturonic acid, heparin disaccharide, hyaluronan disaccharide, lactobionic acid); and oligosaccharides containing primary amino groups, secondary amino groups, carboxyl groups, or mercapto groups (e.g., carboxymethyl-beta-cyclodextrin sodium salt, trigalacturonic acid); and combinations thereof.

[0159] Another class of preferred hydrophilicity-enhancing agents is a hydrophilic polymer having one or more (primary or secondary) amino groups, carboxyl groups, and / or thiol groups. More preferably, the content of amino groups (-NHR', where R' is as defined above), carboxyl groups (-COOH), and / or thiol groups (-SH) in the hydrophilic polymer as the hydrophilicity-enhancing agent is less than about 40%, preferably less than about 30%, more preferably less than about 20%, even more preferably less than about 10%, by weight based on the total weight of the hydrophilic polymer.

[0160] A preferred class of hydrophilic polymers as the hydrophilicity-enhancing agent is a (primary or secondary) amino group- or carboxyl group-containing polysaccharide, such as, for example, carboxymethylcellulose (having a carboxyl group content of about 40% or less, estimated based on the composition of the repeating unit -[C6H 10-m O5(CH2CO2H) m ] -, where m is 1 to 3), carboxyethylcellulose (having a carboxyl group content of about 36% or less, estimated based on the composition of the repeating unit -[C6H 10-m O5(C2H4CO2H) m ] -, where m is 1 to 3), carboxypropylcellulose (having a carboxyl group content of about 32% or less, estimated based on the composition of the repeating unit -[C6H 10-m O5(C3H6CO2H) m ] -, where m is 1 to 3), hyaluronic acid (having a carboxyl group content of about 11%, estimated based on the composition of the repeating unit -(C 13 H 20 O9NCO2H) -, chondroitin sulfate (having a carboxyl group content of about 9.8%, estimated based on the composition of the repeating unit -(C 12 H 18 O 13 NS CO2H) -, or a combination thereof.

[0161] Another preferred class of hydrophilic polymers as hydrophilicity enhancers includes, but is not limited to: poly(ethylene glycol)s (PEGs) having a single-amino (primary or secondary), carboxyl, or thiol group (e.g., PEG-NH2, PEG-SH, PEG-COOH); H2N-PEG-NH2; HOOC-PEG-COOH; HS-PEG-SH; H2N-PEG-COOH; HOOC-PEG-SH; H2N-PEG-SH; multi-armed 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; di-amino- (primary or secondary) or di-carboxyl-terminated homopolymers or copolymers of non-reactive hydrophilic vinylic monomers; mono-amino- (primary or secondary) or mono-carboxyl-terminated homopolymers or copolymers of non-reactive hydrophilic vinylic monomers; copolymers that are the polymerization product of a composition comprising: (1) about 60% or less by weight, preferably about 0.1% to about 30%, more preferably about 0.5% to about 20%, even more preferably about 1% to about 15% by weight of one or more reactive vinylic monomers, and (2) at least one non-reactive hydrophilic vinylic monomer; and combinations thereof. The one or more reactive vinylic monomers and the one or more non-reactive hydrophilic vinylic monomers are those described previously.

[0162] According to the present application, the reactive vinylic monomers used to make the hydrophilicity enhancer can be carboxyl-containing vinylic monomers (those described above), primary and secondary amino-containing vinylic monomers (those described above).

[0163] According to the present application, the non-reactive vinylic monomers used to make the hydrophilicity enhancer are vinylic monomers that do not contain any carboxyl, primary amino, secondary amino, epoxy, isocyanate, azlactone, or aziridine groups. The non-reactive vinylic monomers are preferably uncharged hydrophilic vinylic monomers that do not contain carboxyl or amino groups (any of those described above can be used here), phosphorylcholine-containing vinylic monomers (any of those described above can be used here), or combinations thereof.

[0164] More preferably, the hydrophilic polymer as the hydrophilicity enhancer is:

[0165] poly(ethylene glycol) having one unique -NH2, -SH, or -COOH functional group;

[0166] poly(ethylene glycol) having two terminal functional groups selected from the group consisting of -NH2, -COOH, -SH, and combinations thereof;

[0167] a multi-arm poly(ethylene glycol) having one or more functional groups selected from the group consisting of -NH2, -COOH, -SH, and combinations thereof;

[0168] a monoamino, monocarboxy, diamino, or dicarboxy terminated homopolymer or copolymer of a non-reactive hydrophilic vinylic monomer;

[0169] a copolymer that is the polymerization product of a composition comprising (1) about 0.1% to about 30%, preferably about 0.5% to about 20%, more preferably about 1% to about 15% by weight of a reactive vinylic monomer, and (2) at least one non-reactive vinylic monomer,

[0170] Examples of preferred reactive vinylic monomers include those described above.

[0171] Examples of preferred non-reactive hydrophilic vinylic monomers include, but are not limited to, (meth)acrylamide, N,N-dimethyl (meth)acrylamide, N-ethyl (meth)acrylamide, N,N-diethyl (meth)acrylamide, N-propyl (meth)acrylamide, N-isopropyl (meth)acrylamide, N-3-methoxypropyl (meth)acrylamide, N-2-dimethylaminoethyl (meth)acrylamide, dimethylaminoethyl (meth)acrylate, a hydroxyl-containing acrylic monomer (any of those described above), an N-vinyl amide monomer (any of those described above), a methylene-containing pyrrolidone monomer (i.e., a pyrrolidone derivative each having a methylene group attached to the pyrrolidone ring at the 3- or 5-position) (any of those described above), an acrylic monomer having a C1-C4 alkoxyethoxy group (any of those described above), a vinyl ether monomer (any of those described above), an allyl ether monomer (any of those described above), a phosphorylcholine-containing vinylic monomer (any of those described above), and combinations thereof.

[0172] Preferably, the non-reactive hydrophilic vinylic monomer is selected from the group consisting of (meth)acryloyloxyethylphosphoylcholine, (meth)acryloyloxypropylphosphoylcholine, 4-( (meth)acryloyloxy)butyl-2'-(trimethylammonio)ethylphosphate, 2-[ (meth)acryloylamino]ethyl-2'-(trimethylammonio)ethylphosphate, 3-[ (meth)acryloylamino]propyl-2'-(trimethylammonio)-ethylphosphate, 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, glyceryl 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, methoxy poly(ethylene glycol)ethyl(meth)acrylamide having a number average molecular weight of up to 1500, C1-C4-alkoxy polyethylene glycol(meth)acrylate having a weight average molecular weight of up to 1500, tetra(ethylene glycol) monovinyl ether, poly(ethylene glycol) monovinyl ether, tetra(ethylene glycol) methylvinyl ether, poly(ethylene glycol) methylvinyl ether, tetra(ethylene glycol) monoallyl ether, poly(ethylene glycol) monoallyl ether, tetra(ethylene glycol) methylallyl ether, poly(ethylene glycol) methylallyl ether, vinyl alcohol, allyl alcohol, and combinations thereof, more preferably selected from the group consisting of (meth)acryloyloxyethylphosphoylcholine, (meth)acryloyloxypropylphosphoylcholine, 4-( (meth)acryloyloxy)butyl-2'-(trimethylammonio)ethylphosphate, 2-[ (meth)acryloylamino]ethyl-2'-(trimethylammonio)ethyl-phosphate, 3-[ (meth)acryloylamino]propyl-2'-(trimethylammonio)-ethylphosphate, 4-[ (meth)acryloylamino]butyl-2'-(trimethylammonio)ethylphosphate, (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, and combinations thereof, even more preferably selected from the group consisting of (meth)acryloyloxyethylphosphoylcholine, (meth)acryloyloxypropylphosphoylcholine, 4-( (meth)acryloyloxy)butyl-2'-(trimethylammonio)ethylphosphate, 2-[ (meth)acryloylamino]ethyl-2'-(trimethylammonio)ethyl-phosphate, 3-[ (meth)acryloylamino]propyl-2'-(trimethylammonio)-ethylphosphate, 4-[ (meth)acryloylamino]butyl-2'-(trimethylammonio)ethylphosphate, (meth)acrylamide, dimethyl(meth)acrylamide, N-2-hydroxyethyl(meth)acrylamide, N,N-bis(hydroxyethyl)(meth)acrylamide, and combinations thereof.3-dihydroxypropyl (meth)acrylamide, N-tris(hydroxymethyl)methyl (meth)acrylamide, 2-hydroxyethyl (meth)acrylate, glyceryl 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) methylvinyl ether, poly(ethylene glycol) monoallyl ether, poly(ethylene glycol) methylallyl ether, vinyl alcohol, allyl alcohol, and combinations thereof, and even more preferably selected from the group consisting of: (meth)acryloyloxyethyl phosphocholine, (meth)acryloyloxypropyl phosphocholine, 2-[ (meth)acryloylamido]ethyl-2'-(trimethylammonio)ethyl phosphate, 3-[ (meth)acryloylamido]propyl-2'-(trimethylammonio)-ethyl phosphate, (meth)acrylamide, dimethyl (meth)acrylamide, N-2-hydroxyethyl (meth)acrylamide, N,N-bis(hydroxyethyl) (meth)acrylamide, N-2,3-dihydroxypropyl (meth)acrylamide, N-tris(hydroxymethyl)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.

[0173] PEGs with functional groups and multi-arm PEGs with functional groups can be obtained from different commercial suppliers (e.g., Polyscience, and Shearwater Polymers, inc., etc.).

[0174] One or more monoamino, monocarboxy, diamino, or dicarboxy terminated homopolymers or copolymers of non-reactive hydrophilic vinylic monomers or phosphorylcholine containing vinylic monomers can be prepared according to the procedures described in U.S. Patent No. 6,218,508 (incorporated herein by reference in its entirety). For example, to prepare a diamino or dicarboxy terminated homopolymer or copolymer of non-reactive hydrophilic vinylic monomers, a non-reactive vinylic monomer, a chain transfer agent having an amino or carboxyl group (e.g., 2-aminoethanethiol, 2-mercaptopropionic acid, thioglycolic acid, thiolactic acid, or other hydroxyl, amino, or carboxyl containing mercaptan), and optionally other vinylic monomers, are copolymerized (thermally or photochemically) in the presence of a free radical initiator with a reactive vinylic monomer (having an amino or carboxyl group). Typically, the molar ratio of chain transfer agent to all vinylic monomers other than the reactive vinylic monomer is about 1 : 5 to about 1 : 100, while the molar ratio of chain transfer agent to reactive vinylic monomer is 1 : 1. In this 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 termini of the resulting hydrophilic polymer so as to provide a resulting hydrophilic polymer having one terminal amino or carboxyl group, while the reactive vinylic monomer provides the other terminal carboxyl or amino group to the resulting hydrophilic polymer. Similarly, to prepare a monoamino or monocarboxy terminated homopolymer or copolymer of non-reactive hydrophilic vinylic monomers, a non-reactive vinylic monomer, a chain transfer agent having an amino or carboxyl group (e.g., 2-aminoethanethiol, 2-mercaptopropionic acid, thioglycolic acid, thiolactic acid, or other hydroxyl, amino, or carboxyl containing mercaptan), and optionally other vinylic monomers, are copolymerized (thermally or photochemically) in the absence of any reactive vinylic monomer.

[0175] Copolymers comprising a non-reactive hydrophilic vinylic monomer and a reactive vinylic monomer (e.g., a carboxyl containing vinylic monomer, a primary amino containing vinylic monomer, or a secondary amino containing vinylic monomer) can be prepared according to any well known free radical polymerization method or obtained from commercial suppliers. Copolymers containing methacryloyloxyethyl phosphorylcholine and a carboxyl containing vinylic monomer (or an amino containing vinylic monomer) are available from NOFCorporation (e.g., LIPIDURE® -AC01, and AE).

[0176] The weight average molecular weight Mw of the hydrophilic polymer (as the hydrophilic enhancing agent) having at least one amino, carboxyl, or mercapto group w Preferably is about 500 to about 2,000,000, more preferably about 1,000 to about 500,000, even more preferably about 5,000 to about 250,000 Daltons.

[0177] The water-soluble and heat-crosslinkable hydrophilic polymeric material can be prepared according to the methods disclosed in U.S. Patent Nos. 8529057, 9422447, 9720138, and 11256003, and U.S. Patent Application Serial No. 63 / 371,660.

[0178] In preferred embodiments, the water-soluble heat-crosslinkable polymeric material can be obtained by heating an aqueous reactive solution comprising at least one azetidinium-containing polymer and at least one hydrophilicity-enhancing agent (i.e., wetting agent) having at least one reactive functional group selected from the group consisting of an amino group, a carboxyl group, a mercapto group, and combinations thereof, to a temperature of from about 35 °C to about 85 °C and maintaining the temperature for a sufficient period of time (about 8 hours or less, preferably about 5 hours, more preferably from about 2 hours to about 4 hours). The aqueous reactive solution preferably comprises from about 70 mM to about 170 mM (preferably from about 90 mM to about 150 mM, more preferably from about 100 mM to about 130 mM) of one or more ionic compounds and has a pH of at least 8.0 (preferably at least 8.5, more preferably at least 9.0, even more preferably at least 9.5). It is understood that the reaction time should be long enough to covalently attach the hydrophilicity-enhancing agent to the polymer chains of the azetidinium-containing polymer, but short enough not to consume all of the azetidinium groups of the azetidinium-containing polymer and not to form a gel (i.e., not water-soluble) due to too many crosslinks formed between the azetidinium-containing polymer and the hydrophilicity-enhancing agent. The resulting polymeric material is a lightly crosslinked polymeric material, has a highly branched structure, and still contains heat-crosslinkable azetidinium groups.

[0179] It is well understood by those skilled in the art how to adjust the pH of the reactive mixture, for example, by adding a base (e.g., NaOH, KOH, NH4OH, or mixtures thereof) or an acid (e.g., HC1, H2SO4, H3PO4, citric acid, acetic acid, boric acid, or mixtures thereof).

[0180] According to the present invention, any ionic compound can be used in reactive mixtures. Preferably, the ionic compound is one used as an ion tension modifier and an ion buffer used in ophthalmic solutions. Examples of preferred ion tension modifiers include, but are not limited to, sodium chloride, potassium chloride, and combinations thereof. Examples of preferred ion buffers include various salts of phosphoric acid (e.g., NaH₂PO₄, Na₂HPO₄, Na₃PO₄, KH₂PO₄, K₂HPO₄, K₃PO₄, or mixtures thereof), various salts of boric acid (e.g., sodium borate, potassium borate, or mixtures thereof), various salts of citric acid (e.g., monosodium citrate, disodium citrate, trisodium citrate, monopotassium citrate, dipotassium citrate, tripotassium citrate, or mixtures thereof), and various salts of carbonic acid (e.g., Na₂CO₃, NaHCO₃, K₂CO₃, KHCO₃, or mixtures thereof).

[0181] An aqueous reactive solution for preparing a water-soluble, thermally crosslinkable polymer material can be prepared by dissolving a desired amount of a polymer containing a nitrogen-containing heterocyclic butaneonium, a desired amount of a hydrophilic enhancer having at least one reactive functional group, and a desired amount of other components (e.g., ion buffers, ion tension modifiers, etc.) in water (or a mixture of water and a small amount of water-soluble organic solvent) to form an aqueous solution, and then adjusting the pH of the aqueous solution (if necessary).

[0182] According to the present invention, the concentration ratio of the hydrophilicity enhancer relative to the nitrogen-containing heterocyclic butanetonium polymer in the aqueous reactive solution must be selected such that the resulting water-soluble thermally crosslinkable polymer material is insoluble in water (i.e., less than 0.005 g / 100 ml of water at room temperature) and does not consume more than about 99%, preferably about 98%, more preferably about 97%, or even more preferably about 96% of the nitrogen-containing heterocyclic butanetonium polymer nitrogen-containing butanetonium groups.

[0183] In preferred embodiments, the aqueous reactive solution comprises from 0.01% to about 10% by weight (preferably from 0.05% to about 5% by weight, more preferably from 0.08% to about 1% by weight, even more preferably from 0.1% to about 0.4% by weight) of the azetidinium-containing polymer and from about 0.01% to about 10% by weight (preferably from 0.02% to about 5% by weight, more preferably from 0.05% to about 2% by weight, even more preferably from 0.08% to about 1.0% by weight) of the hydrophilicity-enhancing agent having at least one reactive functional group (carboxyl, primary amino, secondary amino), the concentration ratio of the azetidinium-containing polymer to the hydrophilicity-enhancing agent being from about 1000 : 1 to 1 : 1000 (preferably from about 500 : 1 to about 1 : 500, more preferably from about 250 : 1 to about 1 : 250, even more preferably from about 100 : 1 to about 1 : 100).

[0184] In preferred embodiments, the water-soluble heat-crosslinkable polymeric material comprises (i) from about 20% to about 95% by weight of a first polymeric chain derived from a polyamidoamine-epichlorohydrin or a poly(2-oxazoline-co-ethyleneimine)-epichlorohydrin, (ii) from about 5% to about 80% by weight of a hydrophilic moiety or second polymeric chain derived from at least one hydrophilicity-enhancing agent having at least one reactive functional group selected from the group consisting of an amino group, a carboxyl group, a mercapto group, and combinations thereof (preferably a carboxyl group or a mercapto group), wherein the hydrophilic moiety or second polymeric chain is covalently attached to the first polymeric chain by one or more covalent bonds formed between one azetidinium group of the polyamidoamine-epichlorohydrin or poly(2-oxazoline-co-ethyleneimine)-epichlorohydrin and one amino, carboxyl, or mercapto group of the hydrophilicity-enhancing agent, and (iii) an azetidinium group that is part of the first polymeric chain or is a pendant or terminal group covalently attached to the first polymeric 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 reactant mixture used for such polymer based on the total weight of these reactants according to the crosslinking reaction shown in Scheme I above. For example, if the reactant mixture comprises about 75% by weight of the polyamidoamine-epichlorohydrin and about 25% by weight of at least one hydrophilicity-enhancing agent based on the total weight of these reactants, then the resulting chemically modified polyamidoamine-epichlorohydrin comprises about 75% by weight of the first polymeric chain derived from the polyamidoamine-epichlorohydrin and about 25% by weight of the hydrophilic moiety or second polymeric chain derived from the at least one hydrophilicity-enhancing agent.

[0185] According to the present application, the second type of coating material is a diol- containing hydrophilic polymer comprising a 1,2- or 1,3-diol moiety. Any diol-containing hydrophilic polymer having a 1,2- or 1,3-diol moiety can be used in the present application. Examples of preferred diol-containing hydrophilic polymers having a 1,2- or 1,3-diol moiety include, but are not limited to, polyvinyl alcohol, poly(ethylene glycol)-graft-poly(vinyl alcohol), copolymers of vinyl alcohol and a hydrophilic vinylic monomer, copolymers of glyceryl (meth)acrylate and a hydrophilic vinylic monomer, copolymers of 2,3,4-trihydroxybutyl (meth)acrylate and a hydrophilic vinylic monomer, copolymers of 2,2-dihydroxypropyl (meth)acrylate and a hydrophilic vinylic monomer, copolymers of 2,3-dihydroxybutyl (meth)acrylate and a hydrophilic vinylic monomer, copolymers of glycerol-2 (meth)acrylate and a hydrophilic vinylic monomer, copolymers of N-2,3-dihydroxypropyl (meth)acrylamide and a hydrophilic vinylic monomer, copolymers of 3-allyloxy-1,2-propanediol and a hydrophilic vinylic monomer, and combinations thereof.

[0186] According to the present application, during the heating step, the at least one water-soluble, heat-crosslinkable hydrophilic polymeric material is crosslinked according to intermolecular and intramolecular crosslinking reactions between the azetidinium groups or epoxy groups and the carboxyl groups or amino groups or mercapto groups, and is also covalently attached to the bulk silicone hydrogel material according to reactions between the azetidinium groups or epoxy groups and the carboxyl groups, while the diol-containing hydrophilic polymer is covalently attached to the bulk silicone hydrogel material according to reactions between the aryldihydroxyboron groups and the 1,2- or 1,3-diol moieties.

[0187] Preferably, the heating step is performed by autoclaving the pre-formed SiHy contact lens immersed in the packaging solution (i.e., the buffered aqueous coating solution) in a sealed lens package at a temperature of about 115 °C to about 125 °C for about 20-90 minutes.

[0188] Lens packages (or containers) are well known to those skilled in the art for autoclaving and storing soft contact lenses. Any lens package can be used in the present application. Preferably, the lens package is a blister package comprising a base and a cover, wherein the cover is removably sealed to the base, wherein the base comprises a cavity for receiving the sterile packaging solution and the contact lens.

[0189] The lens package is packaged in a separate package, sealed and sterilized (e.g., by autoclaving at about 120 °C or higher under pressure for at least 30 minutes) prior to dispensing to the user. Those skilled in the art will well understand how to seal and sterilize the lens package.

[0190] According to the present application, the packaging solution contains at least one buffering agent and one or more other ingredients known to those skilled in the art. Examples of other ingredients include, but are not limited to, tonicity agents, surfactants, antimicrobial agents, preservatives, and lubricants (e.g., cellulose derivatives, polyvinyl alcohol, polyvinylpyrrolidone).

[0191] The packaging solution contains a buffering agent in an amount sufficient to maintain the pH of the packaging solution within a desired range (e.g., preferably from about 6.8 to about 8.5, more preferably from about 7.0 to 8.2, even more preferably from about 7.2 to about 8.0). Higher pH is found to be desirable to ensure that all or a significant portion of the carboxyl groups of the bulk silicone hydrogel material are ionized. Thus, the resulting silicone hydrogel contact lens becomes dimensionally stable in the packaging solution during autoclaving and storage and can have improved lubricity.

[0192] Any known physiologically compatible buffering agent can be used. Suitable buffering agents as ingredients of the contact lens care composition according to the present application are known to those skilled in the art. Preferably, a phosphate buffer (consisting essentially of a mixture of a monobasic dihydrogen phosphate (e.g., NaH2PO4, KH2PO4, or mixtures thereof) and a dibasic monohydrogen phosphate (e.g., Na2HPO4, K2HPO4, or mixtures thereof)) is used to maintain the pH of the packaging solution. In various preferred embodiments, the total concentration of monobasic dihydrogen phosphate and dibasic monohydrogen phosphate is at least 30 mM (preferably at least 35 mM, more preferably at least 40 mM, even more preferably at least 45 mM).

[0193] The solutions according to the present application are preferably formulated in a manner such that they are isotonic with tears. A solution that is isotonic with tears is generally understood to be a solution whose concentration corresponds to that of a 0.9% sodium chloride solution (308 mOsm / kg). Deviations from this concentration can be throughout.

[0194] Isotonicity with tears or even another desired tonicity can be adjusted by the addition of organic or inorganic substances that affect tonicity. Suitable ophthalmically acceptable tonicity agents include, but are not limited to, sodium chloride, potassium chloride, glycerin, 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.

[0195] In preferred embodiments, one or more organic tonicity agents (e.g., glycerin, 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) for adjusting the tonicity of the packaging solution. It is found that the resulting silicone hydrogel contact lenses 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 (e.g., propylene glycol)).

[0196] In preferred embodiments, the packaging solution comprises, by weight, preferably from about 0.01% to about 2%, more preferably from about 0.05% to about 1.5%, even more preferably from about 0.1% to about 1%, most preferably from about 0.2% to about 0.5%, of a water-soluble, heat-crosslinkable, hydrophilic polymeric material having an azetidinium group.

[0197] In another aspect, the present application provides a coated silicone hydrogel contact lens comprising a bulk silicone hydrogel material and a non-silicone hydrogel coating thereon, wherein the bulk silicone hydrogel material comprises (a) repeat units of at least one polysiloxane vinylic crosslinker and / or at least one siloxane-containing vinylic monomer, (b) repeat units of at least one carboxyl-containing vinylic monomer relative to the total amount of all polymerizable components, (c) repeat units of at least one hydrophilic vinylic monomer, (d) repeat units of at least one arylboronate-containing vinylic monomer having an arylboronate group; (e) optionally but preferably repeat units of at least one non-silicone vinylic crosslinker, wherein the non-silicone hydrogel coating comprises a crosslinked polymeric material and a grafted hydrophilic polymer distributed in the crosslinked polymeric material but not covalently bonded to the crosslinked polymeric material, wherein the crosslinked hydrophilic polymeric material is covalently attached to the bulk silicone hydrogel material through first linkages each formed between one carboxylic acid group and one azetidinium or epoxy group, wherein the grafted hydrophilic polymer comprises 1,2- and / or 1,3-diol moieties and is covalently attached to the bulk silicone hydrogel material through second linkages each formed between one arylboronate group and one 1,2- or 1,3-diol moiety, wherein the coated silicone hydrogel contact lens in a fully hydrated state exhibits a coating integrity of about 90% or more (preferably about 93% or more, more preferably about 96% or more, even more preferably about 98% or more) and a friction rating of about 2.0 or less (preferably about 1.5 or less, more preferably about 1.0 or less, even more preferably about 0.5 or less).

[0198] Various embodiments (including preferred embodiments) of bulk SiHy materials, polysiloxane vinylic crosslinkers, siloxane-containing vinylic monomers, carboxyl-containing vinylic monomers, hydrophilic vinylic monomers, arylboronate-containing vinylic monomers, non-silicone vinylic crosslinkers, water-soluble and heat-crosslinkable hydrophilic polymeric materials, and hydrophilic polymers having 1,2- or 1,3-diol moieties have been described above and can be used in this aspect of the present application.

[0199] While specific terminology, devices and methods have been described herein for the purpose of describing various embodiments of the present application, such description is not intended to be limiting. The words used are words of description rather than limitation. Many changes and modifications within the scope of the present disclosure can be made by those skilled in the art without departing from the spirit or scope of the disclosure. Moreover, it is to be understood that many aspects of the various embodiments of the present application can be interchanged or combined or can be used together in any manner as is explained below:

[0200] 1. A coated silicone hydrogel contact lens comprising:

[0201] a bulk silicone hydrogel material and a non-silicone hydrogel coating thereon,

[0202] wherein the bulk silicone hydrogel material comprises (a) repeating units of at least one polysiloxane vinylic crosslinker and / or at least one siloxane-containing vinylic monomer, (b) repeating units of at least one carboxyl-containing vinylic monomer relative to the total amount of all polymerizable components, (c) repeating units of at least one hydrophilic vinylic monomer, (d) repeating units of at least one arylboronate-containing vinylic monomer having an arylboronate group, and (e) optionally but preferably repeating units of at least one non-silicone vinylic crosslinker,

[0203] wherein the non-silicone hydrogel coating comprises a crosslinked polymeric material and a grafted hydrophilic polymer distributed in the crosslinked polymeric material but not covalently bonded to the crosslinked polymeric material, wherein the crosslinked hydrophilic polymeric material is covalently attached to the bulk silicone hydrogel material by first linkages each formed between one carboxylic acid group and one azetidinium or epoxy group, wherein the grafted hydrophilic polymer comprises 1,2- and / or 1,3-diol moieties and is covalently attached to the bulk silicone hydrogel material by second linkages each formed between one arylboronate group and one 1,2- or 1,3-diol moiety,

[0204] wherein the coated silicone hydrogel contact lens in a fully hydrated state exhibits a coating integrity of about 90% or more and a friction rating of about 2.0 or less.

[0205] 2. The coated silicone hydrogel contact lens of Example 1, wherein the coated silicone hydrogel contact lens in a fully hydrated state exhibits a coating integrity of about 93% or more.

[0206] 3. The coated silicone hydrogel contact lens of Example 1, wherein the coated silicone hydrogel contact lens in a fully hydrated state exhibits a coating integrity of about 96% or more.

[0207] 4. The coated silicone hydrogel contact lens of Example 1, wherein the coated silicone hydrogel contact lens in a fully hydrated state exhibits a coating integrity of about 98% or more.

[0208] 5. The coated silicone hydrogel contact lens of any one of Examples 1 to 4, wherein the coated silicone hydrogel contact lens in a fully hydrated state exhibits a friction rating of about 1.5 or less.

[0209] 6. The coated silicone hydrogel contact lens of any one of Examples 1 to 4, wherein the coated silicone hydrogel contact lens in a fully hydrated state exhibits a friction rating of about 1.0 or less.

[0210] 7. The coated silicone hydrogel contact lens of any one of Examples 1 to 4, wherein the coated silicone hydrogel contact lens in a fully hydrated state exhibits a friction rating of about 0.5 or less.

[0211] 8. The coated silicone hydrogel contact lens of any one of Examples 1 to 7, wherein the at least one carboxyl-containing vinylic monomer is selected from the group consisting of acrylic acid, C1-C4 alkyl acrylate, (meth)acryloyloxy-C1-C6 alkanoic acid, succinic acid mono-2-[ (meth)acryloyloxy] -ethyl ester, 2-acrylamidoglycolic acid, (meth)acrylamido-C1-C6 alkanoic acid, and combinations thereof.

[0212] 9. The coated silicone hydrogel contact lens of any one of Examples 1 to 8, wherein the at least one arylboronate-containing vinylic monomer is represented by Formula (I)

[0213] (I)

[0214] wherein: R B is a monovalent group (preferably H, NO2, F, Cl, Br, CF3, CH2OH, or CH2NR o R o ’— R o and R oindependently H or C1-C4alkyl); Q is 、 、 、 、 、 、 , or a monovalent group; L B is a direct bond, a C1-C4alkylene divalent group, 、 、 、 、 、 、 or a divalent group wherein Y1is CH(OH) or a C1-C4alkylene divalent group, Y2is a C1-C4alkylene divalent group, p2is an integer from 0 to 3, and R o is H or C1-C4alkyl.

[0215] 10. The coated silicone hydrogel contact lens of any one of Examples 1 to 8, wherein the at least one aryl dihydroxyboron containing vinylic monomer comprises 3-vinylphenylboronic acid, 4-vinylphenylboronic acid, 3-(meth)acrylamidophenylboronic acid, 4-(meth)acrylamido-phenylboronic acid, 4-(1,6-dioxo-2,5-diaza-7-carboxamido)phenylboronic acid, 2-dimethylamino-methyl-5-vinylphenyl-boronic acid, 4-(N-allylsulfamoyl)phenylboronic acid, 4-(3-butenyl-sulfonoyl)phenylboronic acid, 3-(meth)acrylamido-5-nitrophenylboronic acid, 4-(meth)acrylamido-5-nitrophenylboronic acid, 4-(meth)acrylamido-3-nitrophenylboronic acid, 3-[ (meth)acrylamido-C2-C5-alkylaminocarbonyl]-5-nitrophenylboronic acid, 3-[ (meth)acryloyloxy-C2-C5-alkylaminocarbonyl]-5-nitrophenylboronic acid, 3-(meth)acrylamido-6-hydroxymethyl-phenylboronic acid, 3-(meth)acrylamido-6-dimethylaminomethylphenylboronic acid, 4-(meth)acrylamido-6-hydroxymethylphenyl-boronic acid, 4-(meth)acrylamido-6-dimethylamino-methylphenylboronic acid, reaction products of an amino-containing phenylboronic acid derivative with a (meth)acrylic acid halide or an epoxy-containing vinylic monomer in the presence of a carbodiimide and N-hydroxysuccinimide, reaction products of a carboxyl-containing phenylboronic acid derivative with an amino-containing vinylic monomer in the presence of a carbodiimide and N-hydroxysuccinimide, or combinations thereof.

[0216] 11. The coated silicone hydrogel contact lens of Example 10, wherein the amino- containing phenylboronic acid derivative is 3-carboxyphenylboronic acid, 4- carboxyphenylboronic acid, 3-dihydroxyborylphenyl-acetic acid, 4- dihydroxyborylphenylacetic acid, 2-(4-dihydroxyborylphenyl)-2-methylpropionic acid, 3-(4-dihydroxyborylphenyl)propionic acid, 3-(3- dihydroxyborylphenyl)propionic acid, 5-(3-dihydroxyborylphenyl)pentanoic acid, 5-(4-dihydroxyborylphenyl)pentanoic acid, 4-(2- carboxyethyl)-3-nitrophenylboronic acid, 3-carboxy-5-nitrophenylboronic acid, 4-carboxy-3-chlorophenylboronic acid, 3-carboxy-4- fluorophenylboronic acid, 3-(3-carboxypropionyl-amino)phenylboronic acid, or 3-amino-3-(4-dihydroxyborylphenyl)propionic acid, wherein the carboxyl-containing phenylboronic acid derivative is 3- aminophenylboronic acid, 4-aminophenylboronic acid, 4-amino-3- nitrophenylboronic acid, 3-amino-6-hydroxymethyl-phenylboronic acid, 3- amino-6-(dimethylaminomethyl)phenyl-boronic acid, 4-amino-2- hydroxymethylphenylboronic acid, 4-amino-2-(dimethylaminomethyl)- phenylboronic acid, 3-amino-4-fluorophenylboronic acid, 4- (aminomethyl)-5-nitrophenylboronic acid, 3-(aminomethyl)-phenylboronic acid, 3-amino-5-nitrophenylboronic acid, or 3-amino-3-(4- dihydroxyborylphenyl)propionic acid.

[0217] 12. The coated silicone hydrogel contact lens of any one of embodiments 1 to 11, wherein the crosslinked polymeric material comprises: (1) poly(ethylene glycol) chains designated as PEG chains, (2) polymer chains derived from a copolymer that is a polymerization product of a composition comprising: (i) 60% or less by weight of at least one reactive vinylic monomer comprising at least one reactive functional group selected from the group consisting of carboxylic acid, primary amino, secondary amino, epoxy, and combinations thereof, and (ii) at least one non-reactive vinylic monomer selected from the group consisting of acrylamide, methacrylamide, N,N-dimethylacrylamide, N,N-dimethylmethacrylamide, N-vinylpyrrolidone, N,N-dimethylaminoethyl methacrylate, N,N-dimethylaminoethyl acrylate, N,N-dimethylaminopropyl methacrylamide, N,N-dimethylaminopropyl acrylamide, glycerol methacrylate, 3-acryloylamino-1-propanol, N-hydroxyethyl acrylamide, N-[tris(hydroxymethyl)methyl]-acrylamide, N-methyl-3-methylene-2-pyrrolidone, 1-ethyl-3-methylene-2-pyrrolidone, 1-methyl-5-methylene-2-pyrrolidone, 1-ethyl-5-methylene-2-pyrrolidone, 5-methyl-3-methylene-2-pyrrolidone, 5-ethyl-3-methylene-2-pyrrolidone, 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, a phosphorylcholine-containing vinylic monomer, C1-C4-alkoxy poly(ethylene glycol) ethyl (meth)acrylate having a weight average molecular weight of up to 1500 Dalton, C1-C4-alkoxy poly(ethylene glycol) ethyl (meth)acrylamide having a weight average molecular weight of up to 1500 Dalton, poly(ethylene glycol) ethyl (meth)acrylate having a weight average molecular weight of up to 1500 Dalton, poly(ethylene glycol) ethyl (meth)acrylamide having a weight average molecular weight of up to 1500 Dalton, N-vinylformamide, N-vinylacetamide, N-vinylisopropylamide, N-vinyl-N-methylacetamide, allyl alcohol, vinyl alcohol, and combinations thereof.or (3) a combination thereof, wherein the at least one reactive vinylic monomer is selected from the group consisting of amino-C2-C4 alkyl (meth)acrylate, C1-C3 alkylamino-C2-C4 alkyl (meth)acrylate, allylamine, vinylamine, amino-C2-C4 alkyl (meth)acrylamide, C1-C3 alkylamino-C2-C4 alkyl (meth)acrylamide, acrylic acid, C1-C4 alkylacrylic acid, (meth)acryloyloxy-C2-C6 alkanoic acid, 2-acrylamidoglycolic acid, (meth)acrylamido-C2-C6 alkanoic acid, epoxy-containing vinylic monomer, and combinations thereof, wherein the epoxy-containing vinylic monomer is selected from the group consisting of glycidyl (meth)acrylamide, hydroxyethyl (meth)acrylamide glycidyl ether, 3-hydroxypropyl (meth)acrylamide glycidyl ether, 4-hydroxybutyl (meth)acrylamide glycidyl ether, glycidyl (meth)acrylate, hydroxyethyl (meth)acrylate glycidyl ether, 3-hydroxypropyl (meth)acrylate glycidyl ether, 4-hydroxybutyl (meth)acrylate glycidyl ether, and combinations thereof.

[0218] 13. The coated silicone hydrogel contact lens of any one of embodiments 1 to 11, wherein the crosslinked polymeric material comprises polymeric chains derived from a copolymer that is the polymerization product of a composition comprising (i) 0.1% to 30% by weight of at least one reactive vinylic monomer and (ii) at least one non-reactive vinylic monomer selected from the group consisting of acrylamide, methacrylamide, N,N-dimethylacrylamide, N,N-dimethylmethacrylamide, N,N-dimethylaminopropylmethacrylamide, N,N-dimethylaminopropylacrylamide, and combinations thereof, wherein the at least one reactive vinylic monomer is selected from the group consisting of amino-C2-C4 alkyl (meth)acrylate, C1-C3 alkylamino-C2-C4 alkyl (meth)acrylate, allylamine, vinylamine, amino-C2-C4 alkyl (meth)acrylamide, C1-C3 alkylamino-C2-C4 alkyl (meth)acrylamide, acrylic acid, C1-C4 alkylacrylic acid, (meth)acryloyloxy-C2-C6 alkanoic acid, 2-acrylamidoglycolic acid, (meth)acrylamido-C2-C6 alkanoic acid, epoxy-containing vinylic monomer, and combinations thereof, wherein the epoxy-containing vinylic monomer is selected from the group consisting of glycidyl (meth)acrylamide, hydroxyethyl (meth)acrylamide glycidyl ether, 3-hydroxypropyl (meth)acrylamide glycidyl ether, 4-hydroxybutyl (meth)acrylamide glycidyl ether, glycidyl (meth)acrylate, hydroxyethyl (meth)acrylate glycidyl ether, 3-hydroxypropyl (meth)acrylate glycidyl ether, 4-hydroxybutyl (meth)acrylate glycidyl ether, and combinations thereof.

[0219] 14. The coated silicone hydrogel contact lens of any one of embodiments 1 to 11, wherein the crosslinked polymeric material comprises polymeric chains derived from a copolymer that is the polymerization product of a composition comprising (i) 0.1% to 30% by weight of at least one reactive vinylic monomer and (ii) at least one non-reactive vinylic monomer selected from the group consisting of N,N-dimethylaminoethyl methacrylate, N,N-dimethylaminoethyl acrylate, C1-C4-alkoxypolyethylene glycol (meth)acrylate having a weight average molecular weight of up to 1500 Daltons, and combinations thereof, wherein the at least one reactive vinylic monomer is selected from the group consisting of (meth)acrylic acid amino-C2-C4 alkyl ester, (meth)acrylic acid C1-C3 alkylamino-C2-C4 alkyl ester, allylamine, vinylamine, amino-C2-C4 alkyl (meth)acrylamide, C1-C3 alkylamino-C2-C4 alkyl (meth)acrylamide, acrylic acid, C1-C4 alkyl acrylate, (meth)acryloyloxy-C2-C6 alkanoic acid, 2-acrylamidoglycolic acid, (meth)acrylamido-C2-C6 alkanoic acid, epoxy-containing vinylic monomer, and combinations thereof, wherein the epoxy-containing vinylic monomer is selected from the group consisting of glycidyl (meth)acrylamide, hydroxyethyl (meth)acrylamide glycidyl ether, 3-hydroxypropyl (meth)acrylamide glycidyl ether, 4-hydroxybutyl (meth)acrylamide glycidyl ether, (meth)acrylic acid glycidyl ester, (meth)acrylic acid hydroxyethyl glycidyl ether, (meth)acrylic acid 3-hydroxypropyl glycidyl ether, (meth)acrylic acid 4-hydroxybutyl glycidyl ether, and combinations thereof.

[0220] 15. The coated silicone hydrogel contact lens of any one of embodiments 1 to 11, wherein the crosslinked polymeric material comprises polymeric chains derived from a copolymer that is the polymerization product of a composition comprising (i) 0.1% to 30% by weight of at least one reactive vinylic monomer and (ii) at least one non-reactive vinylic monomer selected from the group consisting of glyceryl methacrylate, 3-acryloylamino-1-propanol, N-hydroxyethyl acrylamide, N-[tris(hydroxymethyl)methyl]-acrylamide, 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, allyl alcohol, vinyl alcohol, and combinations thereof, wherein the at least one reactive vinylic monomer is selected from the group consisting of amino-C2-C4 alkyl (meth)acrylate, C1-C3 alkylamino-C2-C4 alkyl (meth)acrylate, allylamine, vinyl amine, amino-C2-C4 alkyl (meth)acrylamide, C1-C3 alkylamino-C2-C4 alkyl (meth)acrylamide, acrylic acid, C1-C4 alkyl acrylate, (meth)acryloyloxy-C2-C6 alkanoic acid, 2-acrylamidoglycolic acid, (meth)acrylamido-C2-C6 alkanoic acid, epoxy-containing vinylic monomer, and combinations thereof, wherein the epoxy-containing vinylic monomer is selected from the group consisting of glycidyl (meth)acrylamide, hydroxyethyl (meth)acrylamide glycidyl ether, 3-hydroxypropyl (meth)acrylamide glycidyl ether, 4-hydroxybutyl (meth)acrylamide glycidyl ether, glycidyl (meth)acrylate, hydroxyethyl (meth)acrylate glycidyl ether, 3-hydroxypropyl (meth)acrylate glycidyl ether, 4-hydroxybutyl (meth)acrylate glycidyl ether, and combinations thereof.

[0221] 16. The coated silicone hydrogel contact lens of any one of embodiments 1 to 11, wherein the crosslinked polymeric material comprises polymeric chains derived from a copolymer that is the polymerization product of a composition comprising (i) 0.1% to 30% by weight of at least one reactive vinylic monomer and (ii) at least one non-reactive vinylic monomer selected from the group consisting of N-methyl-3-methylene-2-pyrrolidone, 1-ethyl-3-methylene-2-pyrrolidone, 1-methyl-5-methylene-2-pyrrolidone, 1-ethyl-5-methylene-2-pyrrolidone, 5-methyl-3-methylene-2-pyrrolidone, 5-ethyl-3-methylene-2-pyrrolidone, N-vinylpyrrolidone, N-vinylformamide, N-vinylacetamide, N-vinylisopropylamide, N-vinyl-N-methylacetamide, and combinations thereof, wherein the at least one reactive vinylic monomer is selected from the group consisting of (meth)amino-C2-C4 alkyl acrylate, C1-C3 alkylamino-C2-C4 alkyl (meth)acrylate, allylamine, vinylamine, amino-C2-C4 alkyl (meth)acrylamide, C1-C3 alkylamino-C2-C4 alkyl (meth)acrylamide, acrylic acid, C1-C4 alkyl acrylate, (meth)acryloyloxy-C2-C6 alkanoic acid, 2-acrylamidoglycolic acid, (meth)acrylamido-C2-C6 alkanoic acid, epoxy-containing vinylic monomer, and combinations thereof, wherein the epoxy-containing vinylic monomer is selected from the group consisting of glycidyl (meth)acrylamide, hydroxyethyl (meth)acrylamide glycidyl ether, 3-hydroxypropyl (meth)acrylamide glycidyl ether, 4-hydroxybutyl (meth)acrylamide glycidyl ether, (meth)acrylic acid glycidyl ester, (meth)acrylic acid hydroxyethyl ester glycidyl ether, (meth)acrylic acid 3-hydroxypropyl ester glycidyl ether, (meth)acrylic acid 4-hydroxybutyl ester glycidyl ether, and combinations thereof.

[0222] 17. The coated silicone hydrogel contact lens of any one of embodiments 1 to 11, wherein the crosslinked polymeric material comprises polymeric chains derived from a copolymer that is the polymerization product of a composition comprising (i) 0.1% to 30% by weight of at least one reactive vinylic monomer and (ii) at least one phosphorylcholine-containing vinylic monomer, wherein the at least one reactive vinylic monomer is selected from the group consisting of (meth)amino-C2-C4 alkyl (meth)acrylate, C1-C3 alkylamino-C2-C4 alkyl (meth)acrylate, allylamine, vinylamine, amino-C2-C4 alkyl (meth)acrylamide, C1-C3 alkylamino-C2-C4 alkyl (meth)acrylamide, acrylic acid, C1-C4 alkylacrylic acid, (meth)acryloyloxy-C2-C6 alkanoic acid, 2-acrylamidoglycolic acid, (meth)acrylamid-C2-C6 alkanoic acid, epoxy-containing vinylic monomer, and combinations thereof, wherein the epoxy-containing vinylic monomer is selected from the group consisting of glycidyl (meth)acrylamide, hydroxyethyl (meth)acrylamide glycidyl ether, 3-hydroxypropyl (meth)acrylamide glycidyl ether, 4-hydroxybutyl (meth)acrylamide glycidyl ether, (meth)acrylic acid glycidyl ester, (meth)acrylic acid hydroxyethyl ester glycidyl ether, (meth)acrylic acid 3-hydroxypropyl ester glycidyl ether, (meth)acrylic acid 4-hydroxybutyl ester glycidyl ether, and combinations thereof.

[0223] 18. The coated silicone hydrogel contact lens of embodiment 17, wherein the phosphorylcholine-containing vinylic monomer is (meth)acryloyloxyethyl phosphorylcholine.

[0224] 19. The coated silicone hydrogel contact lens of any one of embodiments 1 to 11, wherein the crosslinked polymeric material comprises poly(ethylene glycol) chains, designated PEG chains, and derived from at least one member selected from the group consisting of PEG-NH2; H2N-PEG-NH2; H2N-PEG-COOH; multi-armed PEG having one or more amino groups; PEG dendrimers having one or more amino groups; and combinations thereof.

[0225] 20. The coated silicone hydrogel contact lens of any one of embodiments 1 to 11, wherein the crosslinked polymeric material comprises poly(ethylene glycol) chains, designated PEG chains, and derived from at least one member selected from the group consisting of PEG-COOH; HOOC-PEG-COOH; multi-armed PEG having one or more carboxyl groups; PEG dendrimers having one or more carboxyl groups; and combinations thereof.

[0226] 21. The coated silicone hydrogel contact lens of any one of embodiments 1 to 11, wherein the crosslinked polymeric material comprises poly(ethylene glycol) chains designated as PEG chains and derived from at least one member selected from the group consisting of: PEG-SH; HS-PEG-SH; HOOC-PEG-SH; H2N-PEG-SH; a multi-armed PEG having one or more thiol groups; a PEG dendrimer having one or more thiol groups; and combinations thereof.

[0227] 22. The coated silicone hydrogel contact lens of any one of embodiments 1 to 11, wherein the crosslinked polymeric material comprises poly(ethylene glycol) chains designated as PEG chains and derived from at least one member selected from the group consisting of: ; ; ; a multi-armed PEG having one or more epoxy groups; a PEG dendrimer having one or more epoxy groups; and combinations thereof.

[0228] 23. The coated silicone hydrogel contact lens of any one of embodiments 1 to 22, wherein the coated silicone hydrogel contact lens in a fully hydrated state has a water content of about 10% to about 70%, an oxygen permeability of about 50 to 180 barrers, and a water break-up time of at least 10 seconds.

[0229] 24. The coated silicone hydrogel contact lens of any one of embodiments 1 to 23, wherein the grafted hydrophilic polymer is derived from the at least one hydrophilic polymer having 1,2- or 1,3-diol moieties.

[0230] 25. A method for producing a coated silicone hydrogel contact lens, the method comprising the steps of:

[0231] (1) obtaining a preformed silicone hydrogel contact lens, wherein the preformed hydrogel contact lens comprises a bulk silicone hydrogel material, the bulk silicone hydrogel material comprising

[0232] (a) at least one polysiloxane vinylic crosslinker and / or repeating units of at least one siloxane-containing vinylic monomer,

[0233] (b) about 0.5% to about 3.5% by weight of repeating units of at least one carboxyl-containing vinylic monomer,

[0234] (c) repeating units of at least one hydrophilic vinylic monomer,

[0235] (d) about 2.5% to about 12.5% by weight of repeating units of at least one arylboronate-containing vinylic monomer having an arylboronate group, and

[0236] (e) optionally but preferably at least one non-silicone ethylenic crosslinker, and

[0237] (2) heating the preformed silicone hydrogel contact lens in an aqueous coating solution at a temperature of about 60 °C to about 140 °C to form a coated silicone hydrogel contact lens comprising the bulk silicone hydrogel material and a non-silicone hydrogel coating thereon, wherein the aqueous coating solution comprises (a) at least one hydrophilic polymer having 1,2- and / or 1,3-diol moieties and (b) at least one water-soluble, thermally crosslinkable hydrophilic polymeric material that is branched or lightly crosslinked and comprises thermally crosslinkable groups and optionally reactive functional groups, wherein the thermally crosslinkable groups are azetidinium groups and / or epoxy groups, wherein the reactive functional groups are primary amino groups, secondary amino groups, carboxylic acid groups, thiol groups, or combinations thereof, wherein the non-silicone hydrogel coating comprises crosslinked polymeric material and grafted hydrophilic polymers, wherein the crosslinked hydrophilic polymeric material is derived from the at least one water-soluble, thermally crosslinkable hydrophilic polymeric material and is covalently attached to the bulk silicone hydrogel material by first linkages each formed between one carboxylic acid group and one azetidinium or epoxy group, wherein the grafted hydrophilic polymers are derived from the at least one hydrophilic polymer and are covalently attached to the bulk silicone hydrogel material by second linkages each formed between one aryldihydroxyl boron group and one 1,2- or 1,3-diol moiety.

[0238] 26. The method of embodiment 25, wherein the heating step is preferably performed by autoclaving the preformed silicone hydrogel contact lens immersed in the aqueous coating solution in a sealed lens package at a temperature of about 115 °C to about 125 °C for about 20-90 minutes, wherein the aqueous coating solution further comprises a buffer for maintaining a pH of about 6.8 to about 8.5 and one or more tonicity agents.

[0239] 27. The method of embodiment 25 or 26, wherein the aqueous solution has a pH of about 7.0 to about 8.2, wherein the aqueous solution comprises about 0.01% to about 2% (preferably about 0.05% to about 1.5%, more preferably about 0.1% to about 1%, even more preferably about 0.2% to about 0.5%) by weight of the at least one water-soluble thermally crosslinkable hydrophilic polymeric material.

[0240] 28. The method of any one of embodiments 25-27, wherein the aqueous solution comprises a mixture of monobasic dihydrogen phosphate salts and dibasic monohydrogen phosphate salts for maintaining the pH of the aqueous solution, wherein the total concentration of the monobasic dihydrogen phosphate salts and the dibasic monohydrogen phosphate salts is at least 30 mM.

[0241] 29. The coated silicone hydrogel contact lens of embodiment 24 or the method of any one of embodiments 25-28, wherein the at least one diol-containing hydrophilic polymer comprises polyvinyl alcohol, poly(ethylene glycol)-graft-poly(vinyl alcohol), a copolymer of vinyl alcohol and a hydrophilic vinylic monomer, a copolymer of glyceryl (meth)acrylate and a hydrophilic vinylic monomer, a copolymer of 2,3,4-trihydroxybutyl (meth)acrylate and a hydrophilic vinylic monomer, a copolymer of 2,2-dihydroxypropyl (meth)acrylate and a hydrophilic vinylic monomer, a copolymer of 2,3-dihydroxybutyl (meth)acrylate and a hydrophilic vinylic monomer, a copolymer of glycerol-2 (meth)acrylate and a hydrophilic vinylic monomer, a copolymer of N-2,3-dihydroxypropyl (meth)acrylamide and a hydrophilic vinylic monomer, a copolymer of 3-allyloxy-1,2-propanediol and a hydrophilic vinylic monomer, or a combination thereof.

[0242] 30. The method of any one of embodiments 25-29, wherein the bulk silicone hydrogel material comprises about 0.7% to about 3.5% by weight of repeat units of the at least one carboxyl-containing vinylic monomer.

[0243] 31. The method of any one of embodiments 25-29, wherein the bulk silicone hydrogel material comprises about 0.9% to about 3.0% by weight of repeat units of the at least one carboxyl-containing vinylic monomer.

[0244] 32. The method of any one of embodiments 25-29, wherein the bulk silicone hydrogel material comprises about 1.0% to about 2.8% by weight of repeat units of the at least one carboxyl-containing vinylic monomer.

[0245] 33. The method of any one of embodiments 25-32, wherein the at least one carboxyl-containing vinylic monomer is selected from the group consisting of acrylic acid, C1-C4 alkyl acrylic acid, (meth)acryloyloxy-C1-C6 alkanoic acid, succinic acid mono-2-[ (meth)acryloyloxy]-ethyl ester, 2-acrylamidoglycolic acid, (meth)acrylamido-C1-C6 alkanoic acid, and combinations thereof.

[0246] 34. The method of any one of embodiments 25 to 33, wherein the bulk silicone hydrogel material comprises about 2.5% to about 10% by weight of repeat units of the at least one aryl-containing dihydroxyboron-containing vinylic monomer.

[0247] 35. The method of any one of embodiments 25 to 33, wherein the bulk silicone hydrogel material comprises about 3.0% to about 8.0% by weight of repeat units of the at least one aryl-containing dihydroxyboron-containing vinylic monomer.

[0248] 36. The method of any one of embodiments 25 to 33, wherein the bulk silicone hydrogel material comprises about 3.5% to about 7.0% by weight of repeat units of the at least one aryl-containing dihydroxyboron-containing vinylic monomer.

[0249] 37. The method of any one of embodiments 25 to 36, wherein the at least one aryl-containing dihydroxyboron-containing vinylic monomer is represented by Formula (I)

[0250] (I)

[0251] wherein: R B is a monovalent group (preferably H, N02, F, CI, Br, CF3, CH2OH, or CH2NR o R o '— R o and R o ' are independently of each other H or C1-C4 alkyl); Q is 、 、 、 、 、 、 , or a monovalent group; L B is a direct bond, a C1-C4 alkylene divalent group, 、 、 、 、 、 、 or a divalent group, wherein Y1is CH(OH) or a C1-C4 alkylene divalent group, Y2is a C1-C4 alkylene divalent group, p2is an integer from 0 to 3, and R o is H or C1-C4 alkyl.

[0252] 38. The method of any one of embodiments 25 to 36, wherein the at least one aryl- containing dihydroxyboryl-containing vinylic monomer comprises 3-vinylphenylboronic acid, 4-vinylphenylboronic acid, 3-(meth)acrylamidophenylboronic acid, 4-(meth)acrylamidophenylboronic acid, 4-(l,6-dioxo-2,5-diaza-7-oxalyl)phenylboronic acid, 2-dimethylaminomethyl-5-vinylphenyl-boronic acid, 4-(N-allylsulfamoyl)phenylboronic acid, 4-(3-butenylsulfonyl)phenylboronic acid, 3-(meth)acrylamido-5-nitrophenylboronic acid, 4-(meth)acrylamido-5-nitrophenylboronic acid, 4-(meth)acrylamido-3-nitrophenylboronic acid, 3-[ (meth)acrylamido-C2-C5-alkylaminocarbonyl]-5-nitrophenylboronic acid, 3-[ (meth)acryloyloxy-C2-C5-alkylaminocarbonyl]-5-nitrophenylboronic acid, 3-(meth)acrylamido-6-hydroxymethyl-phenylboronic acid, 3-(meth)acrylamido-6-dimethylaminomethylphenylboronic acid, 4-(meth)acrylamido-6-hydroxymethylphenylboronic acid, 4-(meth)acrylamido-6-dimethylamino-methylphenylboronic acid, reaction products of amino-containing phenylboronic acid derivatives with (meth)acrylic acid halides or epoxy-containing vinylic monomers or with carboxylic acid-containing vinylic monomers in the presence of carbodiimides and N-hydroxysuccinimide, reaction products of carboxylic acid-containing phenylboronic acid derivatives with amino-containing vinylic monomers in the presence of carbodiimides and N-hydroxysuccinimide, or combinations thereof.

[0253] 39. The method of embodiment 38, wherein the amino-containing phenyl boronic acid derivative is 3-carboxyphenyl boronic acid, 4-carboxyphenyl boronic acid, 3- dihydroxyborylphenyl-acetic acid, 4-dihydroxyborylphenylacetic acid, 2-(4- dihydroxyborylphenyl)-2-methylpropionic acid, 3-(4-dihydroxyborylphenyl)propionic acid, 3-(3-dihydroxyborylphenyl)propionic acid, 5-(3-dihydroxyborylphenyl)pentanoic acid, 5-(4-dihydroxyborylphenyl)pentanoic acid, 4-(2-carboxyethyl)-3-nitrophenyl boronic acid, 3-carboxy-5-nitrophenyl boronic acid, 4-carboxy-3-chlorophenyl boronic acid, 3-carboxy-4-fluorophenyl boronic acid, 3-(3-carboxypropionylamino)phenyl boronic acid, or 3-amino-3-(4-dihydroxyborylphenyl)propionic acid, wherein the carboxyl-containing phenyl boronic acid derivative is 3-aminophenyl boronic acid, 4- aminophenyl boronic acid, 4-amino-3-nitrophenyl boronic acid, 3-amino-6- hydroxymethylphenyl boronic acid, 3-amino-6-(dimethylaminomethyl)phenyl- boronic acid, 4-amino-2-hydroxymethylphenyl boronic acid, 4-amino-2- (dimethylaminomethyl)-phenyl boronic acid, 3-amino-4-fluorophenyl boronic acid, 4-(aminomethyl)-5-nitrophenyl boronic acid, 3-(aminomethyl)-phenyl boronic acid, 3-amino-5-nitrophenyl boronic acid, or 3-amino-3-(4-dihydroxyborylphenyl)propionic acid.

[0254] 40. The method of any one of embodiments 25 to 39, wherein the at least one water-soluble and heat-crosslinkable hydrophilic polymeric material comprises an epoxy group.

[0255] 41. The method of embodiment 40, wherein the at least one water-soluble and heat-crosslinkable hydrophilic polymeric material comprises: (i) one or more multi-arm polyethylene glycol each having terminal epoxy groups; (ii) a partial reaction product of a multi-arm polyethylene glycol having terminal epoxy groups and one or more polyethylene glycol each having a terminal functional group selected from the group consisting of a primary amine group, a secondary amine group, a carboxyl group, a thiol group, and combinations thereof; (iii) a partial reaction product of a multi-arm polyethylene having terminal epoxy groups and a hydrophilic enhancing agent having at least one reactive functional group selected from the group consisting of an amino group, a carboxyl group, a thiol group, and combinations thereof; (iv) a partial reaction product of a copolymer of an epoxy-containing vinylic monomer and one or more hydrophilic vinylic monomers and a hydrophilic enhancing agent having at least one reactive functional group selected from the group consisting of an amino group, a carboxyl group, a thiol group, and combinations thereof; (v) a copolymer of an epoxy-containing vinylic monomer, a hydrophilic vinylic monomer, and a C1-C4-alkoxy poly(ethylene glycol) ethyl (meth)acrylate having a number average molecular weight of up to 2500 Daltons, a poly(ethylene glycol) ethyl (meth)acrylate having a number average molecular weight of up to 2500 Daltons, a C1-C4-alkoxy poly(ethylene glycol) ethyl (meth)acrylamide, or a poly(ethylene glycol) ethyl (meth)acrylamide having a number average molecular weight of up to 2500 Daltons; or (vi) combinations thereof.

[0256] 42. The method of any one of embodiments 25-39, wherein the at least one water-soluble and heat-crosslinkable hydrophilic polymeric material comprises an azetidinium group.

[0257] 43. The method of embodiment 42, wherein the at least one water-soluble and heat-crosslinkable hydrophilic polymeric material is a three-dimensional network and heat-crosslinkable groups within or attached to the network.

[0258] 44. The method of embodiment 42, wherein the at least one water-soluble and heat-crosslinkable hydrophilic polymeric material is one or more multi-arm polyethylene glycol each having terminal epoxy groups; a mixture of a multi-arm polyethylene glycol having terminal epoxy groups and one or more polyethylene glycol 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 terminal epoxy groups and a hydrophilic enhancing agent having at least one reactive functional group selected from the group consisting of an amino group, a carboxyl group, a thiol group; or combinations thereof.

[0259] 45. The method of embodiment 42, wherein the at least one water-soluble and heat-crosslinkable hydrophilic polymeric material comprises an azetidinium group and is a partial reaction product of a nitrogen-containing azetidinium-containing polymer and a hydrophilicity-enhancing agent 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.

[0260] 46. The method of embodiment 45, wherein the nitrogen-containing azetidinium-containing polymer is a poly(2-oxazoline-co-vinyl imine)-epichlorohydrin copolymer, a polyamidoamine-epichlorohydrin, a copolymer of a nitrogen-containing azetidinium-containing vinylic monomer and one or more hydrophilic vinylic monomers, or combinations thereof.

[0261] 47. The method of embodiment 45 or 46, wherein the hydrophilicity-enhancing agent is: a monosaccharide containing a primary amino group, a secondary amino group, a carboxyl group, or a thiol group; a disaccharide containing a primary amino group, a secondary amino group, a carboxyl group, or a thiol group; an oligosaccharide containing a primary amino group, a secondary amino group, a carboxyl group, or a thiol group; or combinations thereof.

[0262] 48. The method of embodiment 45 or 46, wherein the hydrophilicity-enhancing agent 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.

[0263] 49. The method of embodiment 48, wherein the hydrophilicity-enhancing agent is a polysaccharide having a primary amine group, a secondary amine group, a carboxyl group, or combinations thereof.

[0264] 50. The method of embodiment 48, wherein the hydrophilicity-enhancing agent is:

[0265] a poly(ethylene glycol) having one unique -NH2, -SH, or -COOH functional group;

[0266] a poly(ethylene glycol) having two terminal functional groups selected from the group consisting of -NH2, -COOH, -SH, and combinations thereof;

[0267] a multi-armed poly(ethylene glycol) having one or more functional groups selected from the group consisting of -NH2, -COOH, -SH, and combinations thereof;

[0268] a monoamino-, monocarboxyl-, diamino-, or dicarboxyl-terminated homopolymer or copolymer of a non-reactive hydrophilic vinylic monomer;

[0269] a copolymer that is a polymerization product of a composition comprising: (1) about 0.1% to about 30% (preferably about 0.5% to about 20%, more preferably about 1% to about 15%) of a reactive vinylic monomer, and (2) at least one non-reactive hydrophilic vinylic monomer,

[0270] wherein the at least one reactive vinylic monomer is a vinylic monomer having a functional group selected from the group consisting of a carboxyl group, a primary amine group, and a secondary amine group,

[0271] wherein the non-reactive hydrophilic monomer is a hydrophilic vinylic monomer that does not contain any carboxyl group, primary amine group, secondary amine group, epoxy group, isocyanate group, azlactone group, or aziridine group.

[0272] 51. The method of embodiment 50, wherein the reactive vinylic monomer is an amino-C2-C4 alkyl (meth)acrylate, a C1-C3 alkylamino-C2-C4 alkyl (meth)acrylate, an allylamine, a vinylamine, an amino-C2-C4 alkyl (meth)acrylamide, a C1-C3 alkylamino-C2-C4 alkyl (meth)acrylamide, an acrylic acid, a C1-C4 alkylacrylic acid, a (meth)acryloyloxy-C2-C6 alkanoic acid, a 2-acrylamidoglycolic acid, a (meth)acrylamido-C2-C6 alkanoic acid, and combinations thereof.

[0273] 52. The method of either of embodiments 50 or 51, wherein the non-reactive hydrophilic vinylic monomer is selected from the group consisting of (meth)acryloyloxyethyl phosphoylcholine, (meth)acryloyloxypropyl phosphoylcholine, 4-( (meth)acryloyloxy)butyl-2'-(trimethylammonio)-ethyl-phosphonate, 2-[ (meth)acryloylamido]ethyl-2'-(trimethylammonio)ethylphosphonate, 3-[ (meth)acryloylamido]propyl-2'-(trimethylammonio)ethylphosphonate, 4-[ (meth)acryloylamido]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, glyceryl 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, methoxy poly(ethylene glycol) ethyl (meth)acrylamide having a number average molecular weight of up to 1500, C1-C4-alkoxy polyethylene glycol (meth)acrylate having a weight average molecular weight of up to 1500, tetra(ethylene glycol) monovinyl ether, poly(ethylene glycol) monovinyl ether, tetra(ethylene glycol) methylvinyl ether, poly(ethylene glycol) methylvinyl ether, tetra(ethylene glycol) monoallyl ether, poly(ethylene glycol) monoallyl ether, tetra(ethylene glycol) methylallyl ether, poly(ethylene glycol) methylallyl ether, vinyl alcohol, allyl alcohol, and combinations thereof.

[0274] The above disclosure will enable one of ordinary skill in the art to practice the present application. Various modifications, changes, and combinations of the various embodiments described herein can be made. For example, different specific materials and parameters are contemplated and can be determined in accordance with available resources, desired results, and / or optimal "design choices." It is therefore intended that the disclosure be considered as exemplary.

[0275] Example 1

[0276] Oxygen permeability measurements

[0277] Unless specified, the oxygen permeation rate (Dk / t), intrinsic (or edge corrected) oxygen permeability (Dk ior Dk c ).

[0278] Water Break-up Time (WBUT) Test

[0279] The surface hydrophilicity of the contact lenses was evaluated by determining the time required for a water film to start breaking on the surface of the lens using the Interfacial Dewetting and Drainage Optical Platform (iDDroP) as described in the article by Bhamla et al. entitled Influence of Lipid Coatings on Surface Wettability Characteristics of Silicone Hydrogels published on Langmuir. 2015, 31:3820-3828. During the IDDrop test, the lens was placed on the stage and immersed in PBS. Then, a small surface of the lens was exposed to air. A motorized linear stage and motion controller were used in order to expose the contact lens at a specified depth. A video of the water break-up was taken in order to evaluate the water break-up time and the pattern of water film break-up.

[0280] Equilibrium Water Content

[0281] The equilibrium water content (EWC) of the contact lenses (i.e., the water content of the contact lens in a fully hydrated state) was determined according to the procedure described in Example 1 of U.S. Patent Application Publication No. 20210181379 Al.

[0282] Elastic Modulus

[0283] The elastic modulus of the contact lenses was determined according to the procedure described in Example 1 of U.S. Patent Application Publication No. 20210181379 Al.

[0284] Water Contact Angle (WCA) Measurement. Water contact angle (WCA) measurements were performed by the sessile drop method with pure water (Fluka, surface tension 72.5 mN / m at 20 °C) using a DSA 10 drop shape analysis system from Krüss GmbH, Germany. For the purpose of the measurement, the contact lens was taken from the storage solution with tweezers and excess storage solution was removed by gently shaking. The contact lens was placed on the male part of the lens mold and gently blotted dry with a dry and clean cloth. Then a water drop (approximately 1 µl) was added on the lens vertex and the change in contact angle of the water drop over time (WCA(t), circle fit model) was monitored. The WCA was calculated by extrapolating the plot WCA(t) to t = 0.

[0285] Lubricity Evaluation.

[0286] Lubricity of contact lenses was evaluated by using a Finger Feel Lubricity Test that qualitatively characterizes the slipperiness of the lens surface on a scale of 0 to 4 friction ratings. The higher the friction rating, the lower the slipperiness (or lubricity). During this test procedure, the lens is felt between the thumb and index finger and a rating of 0-4 is given qualitatively based on the level of friction perceived by the tester. The ratings given are compared to 5 commercial lenses that are standards for this test, corresponding to 5 levels of lubricity.

[0287] The levels and standards are as follows: DAILIES® TOTAL1® lenses (Alcon) are the standard at level 0 on the scale, ACUVUE® OASYS TM lenses (Johnson & Johnson) are the standard at level 1, ULTRA® lenses (Bausch & Lamb) are the standard at level 2, DAILIES® Aqua Comfort Plus® lenses (Alcon) are the standard at level 3, and AIR OPTIX® Aqua lenses are the standard at level 4.

[0288] The samples were placed in PBS for rinsing for at least two 30-minute periods and then transferred to fresh PBS prior to evaluation. Prior to evaluation, the hands were rinsed with a soap solution, rinsed thoroughly with DI water and then dried with a KimWipe® towel. When evaluating the lubricity of the front surface, the lens was placed on the index finger with the back surface facing the index finger and the thumb moved against the front surface to feel the slipperiness (or lubricity) of the front surface. When evaluating the lubricity of the back surface, the lens was first inverted and then placed on the index finger with the inverted front surface facing the index finger and then the thumb moved against the inverted back surface to feel the slipperiness (or lubricity) of the back surface.

[0289] Each sample was assigned a friction rating relative to the above standard lenses described above. The value of the friction rating is a value obtained by averaging the results of at least two friction ratings of a contact lens by two or more individuals and / or by averaging the friction ratings of two or more contact lenses (from the same batch of lens production) by one individual.

[0290] The finger lubricity (i.e., friction rating) of a contact lens can be determined directly out-of-pack (OOP) but after immersion in PBS for ≥ 30 min according to the procedure described above.

[0291] Coating integrity test

[0292] The integrity of the coating on the surface of a coated SiHy contact lens can be tested as follows according to the Sudan Black Staining Test. Each SiHy contact lens having a coating thereon is immersed in a Sudan Black dye solution (Sudan Black in a mixture of about 80% mineral oil and about 20% Vitamin E oil). Sudan Black dye is hydrophobic and has a strong tendency to be adsorbed by or to adsorb onto hydrophobic points on the surface of a hydrophobic lens or partially coated surface of a hydrophobic lens (e.g., a silicone hydrogel contact lens). If the coating on the hydrophobic lens is intact, no stains should be observed on or in the lens. All test lenses are fully hydrated. Visible fine lines on the surface of the lens can indicate the presence of cracking of the crosslinked coating.

[0293] Images of the Sudan Black stained contact lenses are recorded by a digital camera and then analyzed with a computer to determine the percentage of stained area on the coated SiHy contact lenses ("SBQ") taken directly out of the package ("OOP") or out of the package and subjected to an aqueous extraction process consisting of (1) a first simulated 1 -day wear extraction cycle involving removal of one ready-to-use SiHy contact lens from a sealed package and blotting, and soaking the blotted ready-to-use SiHy contact lens in 1.0 mL of fresh phosphate buffered saline (PBS) in a vial as the extraction medium at 35 °C under agitation for 24 hours, which has a pH of 7.2 ± 0.2 at 25 °C and contains about 0.077 wt. % NaH2P04-H20, about 0.31 wt. % Na2HP04-2H20, and about 0.77 wt. % NaCl; and (2) second through seventh simulated 1 -day wear extraction cycles, each cycle involving removal of all PBS used in the previous cycle, then adding 1.0 mL of fresh PBS as the extraction medium to the vial, and soaking the ready-to-use SiHy contact lens in the added 1 mL of fresh PBS as the extraction medium at 35 °C under agitation for 24 hours. The coating integrity is (1 - SBQ) when determined directly out of the package.

[0294] As a control, SiHy contact lenses without any coating are also tested. Since these SiHy contact lenses in the control experiment do not have a hydrogel coating thereon, their surfaces are completely stained by Sudan Black.

[0295] Chemicals

[0296] The following abbreviations are used in the following examples: HEMA stands for hydroxyethyl methacrylate; EOEMA stands for ethoxyethyl methacrylate; MAA stands for methacrylic acid; NaMAA stands for the sodium salt of methacrylic acid; AA stands for acrylic acid; TEGDMA is tri(ethylene glycol) dimethacrylate; APBA stands for 3-acrylamidophenylboronic acid (pKa of approximately 8.2); VPBA stands for 4-vinylphenylboronic acid (pKa of approximately 8.8); Vazo 67 stands for 2,2’-azobis(2-methyl-butane nitrile); Nobloc is 2-[3-(2H-benzotriazol-2-yl)-5-hydroxyphenyl]ethyl methacrylate; RB247 is Reactive Blue 247; PBS stands for phosphate buffered saline having a pH of 7.2 ± 0.2 at 25 °C and containing about 0.044 wt.% NaH2PO4·H2O, about 0.388 wt.% Na2HPO4·2H2O, and about 0.79 wt.% NaCl, and wt.% stands for weight percent; PG stands for propylene glycol; EDTA stands for ethylenediaminetetraacetic acid; poly(AAm-co-AA) stands for poly(AAm-co-AA) (90 / 10) partial sodium salt (Mw of approximately 200,000 from Polysciences, Inc.); PAE stands for polyamidoamine-epichlorohydrin; “PEG-PDMS” macromonomer stands for dimethacryloyloxypropyl terminated polysiloxane having the formula (A) (Mn of approximately 13 K g / mol, x is approximately 85, y is approximately 8, z is approximately 12).

[0297]

[0298] Example 2

[0299] Phosphate buffered saline (PBS)

[0300] Phosphate buffered saline was prepared by dissolving NaH2PO4•H2O, Na2HPO4•2H2O, and NaCl in a given volume of purified water (distilled or deionized) to have the following composition: about 0.044 w / w% NaH2PO4•H2O, about 0.388 w / w / % Na2HPO4•2H2O, and about 0.79 w / w% NaCl.

[0301] Preparation of in-package coated saline

[0302] Kymene or PAE solutions of different solid contents were purchased from Solenis as aqueous solutions and used as received.

[0303] Polyvinyl alcohol (PVA) (Mw of approximately 80,000 Daltons) was purchased from Sigma Aldrich and used as received.

[0304] Poly(ethylene glycol)-graft-poly(vinyl alcohol) polymer ("PEG-PVA") (Mw of 45,000 Daltons) was purchased from BASF and used as received.

[0305] Poly(N-vinylpyrrolidone-co-vinyl alcohol) copolymer ("PVP-PVA") was prepared by hydrolysis of poly(N-vinylpyrrolidone-co-vinyl acetate) copolymer ("PVP-PVAc") (Mw of 50,000 Daltons) purchased from Sigma Aldrich.

[0306] An IPC saline (IPC-1) was prepared by dissolving about 0.07% by weight of poly(AAm-co-AA); about 0.05% by weight of PAE; 0.776% by weight of Na2HP04-2H20; 0.044% by weight of NaH2P04-H20; 0.160% by weight of NaCl; and 10 ppm of EDTA in water.

[0307] An IPC saline (IPC-2) was prepared by dissolving about 0.07% by weight of poly(AAm-co-AA); about 0.05% by weight of PAE; about 0.2% by weight of PVA; 0.776% by weight of Na2HP04-2H20; 0.044% by weight of NaH2P04-H20; 0.160% by weight of NaCl; and 10 ppm of EDTA in water.

[0308] An IPC saline (IPC-3) was prepared by dissolving about 0.07% by weight of poly(AAm-co-AA); about 0.05% by weight of PAE; about 0.05% by weight of PVA; 0.776% by weight of Na2HP04-2H20; 0.044% by weight of NaH2P04-H20; 0.160% by weight of NaCl; and 10 ppm of EDTA in water.

[0309] IPC brine (IPC-4) is prepared by dissolving the following: approximately 0.07% poly(AAm-co-AA) by weight; approximately 0.05% PAE by weight; approximately 0.1% PEG-PVA by weight; 0.776% Na2HPO4·2H2O by weight; 0.044% NaH2PO4·H2O by weight; 0.160% NaCl by weight; and 10 ppm EDTA in water.

[0310] IPC brine (IPC-5) is prepared by dissolving the following: approximately 0.07% poly(AAm-co-AA) by weight; approximately 0.05% PAE by weight; approximately 0.1% PVP-PVA by weight; 0.776% Na2HPO4·2H2O by weight; 0.044% NaH2PO4·H2O by weight; 0.160% NaCl by weight; and 10 ppm EDTA in water.

[0311] Preparation of polymerizable compositions

[0312] The polymerizable compositions (i.e., SiHy lens formulations) were prepared by adding all components to a clean bottle in their target amounts and mixing with a stir bar at 600 rpm for 30 minutes at room temperature. After all solids were dissolved, the formulations were filtered using a 2.7 µm glass microfiber (GMF) filter. Eight SiHy lens formulations were prepared to have the compositions reported in Table 1.

[0313] Table 1

[0314]

[0315] Preparation of coated SiHy contact lenses

[0316] The prepared lens assembly was purged with nitrogen at room temperature for 30 to 35 minutes. The N2-purged lens assembly was then introduced into a polypropylene mold and heat-cured in an oven under nitrogen at the following conditions: a gradual decrease in temperature from room temperature to 55°C at a ramp rate of approximately 7°C / min; holding at 55°C for approximately 30 minutes; a gradual decrease in temperature from 55°C to 100°C at a ramp rate of approximately 7°C / min; and holding at 100°C for approximately 60 minutes. The molds were then opened, and the molded lens was removed.

[0317] The lenses are then hydrated in the prepared IPC saline solution for >120 minutes, inspected, and packaged in blister packs for sterilization in the IPC saline solution (autoclaving at 121°C for 45 minutes).

[0318] Example 3

[0319] Coated SiHy contact lenses were prepared according to the procedure described in Example 2. In this example, two SiHy lens formulations prepared in Example 2 (SiHy-1 and SiHy-2) and two IPC saline solutions prepared in Example 2 (IPC-1 and IPC-2) were used.

[0320] Table 2 shows characterization results for coated SiHy contact lenses comprising bulk silicone hydrogel material obtained from either SiHy-1 lens formulation or SiHy-2 lens formulation and non-silicone hydrogel coatings obtained from either IPC-1 saline (as a control) or IPC-2 saline.

[0321] Table 2

[0322]

[0323] It can be noted that when the IPC saline contains a hydrophilic polymer having a 1,2- or 1,3-diol moiety (i.e., PVA), the integrity of the coating is improved (IPC-2 vs. IPC-1). This indicates the formation of a non-silicone hydrogel coating ("hybrid coating") on the preformed SiHy contact lens. The non-silicone hydrogel coating is covalently attached to the bulk SiHy material and consists of crosslinked polymeric material and PVA distributed therein.

[0324] Example 4

[0325] Coated SiHy contact lenses were prepared according to the procedure described in Example 2. In this example, two SiHy lens formulations prepared in Example 2 (SiHy-3 and SiHy-4) and four IPC saline solutions prepared in Example 2 (IPC-1, IPC-3, IPC-4, and IPC-5) were used.

[0326] Table 3 shows characterization results for coated SiHy contact lenses comprising bulk silicone hydrogel material obtained from SiHy-3 lens formulation and non-silicone hydrogel coatings obtained from either IPC-1 saline (as a control), IPC-3, IPC-4, or IPC-5 saline.

[0327] Table 3

[0328]

[0329] Table 4 shows characterization results for coated SiHy contact lenses comprising bulk silicone hydrogel material obtained from SiHy-3 lens formulation and non-silicone hydrogel coatings obtained from either IPC-1 saline (as a control), IPC-3, IPC-4, or IPC-5 saline.

[0330] Table 4

[0331]

[0332] It can be noted that when the IPC brine contains a hydrophilic polymer with a 1,2- or 1,3-diol moiety (i.e. PVA, PEG-PVA, or PVP-PVA), the integrity of the coating is improved (compared to IPC-1). This indicates the formation of a non-silicone hydrogel coating ("hybrid coating") on the preformed SiHy contact lens. The non-silicone hydrogel coating is covalently attached to the bulk SiHy material and consists of a crosslinked polymeric material and PVA distributed therein.

[0333] Example 5

[0334] Coated SiHy contact lenses were prepared according to the procedure described in Example 2. In this example, two SiHy lens formulations prepared in Example 2 (SiHy-5 and SiHy-6) and two IPC brines prepared in Example 2 (IPC-1 and IPC-3) were used.

[0335] Table 5 shows the characterization results of coated SiHy contact lenses comprising bulk silicone hydrogel material obtained from SiHy-5 or SiHy-6 lens formulations and a non-silicone hydrogel coating from IPC-1 brine (as a control) or IPC-3 brine.

[0336] Table 5

[0337]

[0338] It can be noted that when the IPC brine contains a hydrophilic polymer with a 1,2- or 1,3-diol moiety (i.e. PVA), the integrity of the coating is improved (IPC-3 relative to IPC-1). This indicates the formation of a non-silicone hydrogel coating ("hybrid coating") on the preformed SiHy contact lens. The non-silicone hydrogel coating is covalently attached to the bulk SiHy material and consists of a crosslinked polymeric material and PVA distributed therein.

[0339] Example 6

[0340] Coated SiHy contact lenses were prepared according to the procedure described in Example 2. In this example, two SiHy lens formulations prepared in Example 2 (SiHy-7 and SiHy-8) and two IPC brines prepared in Example 2 (IPC-1 and IPC-3) were used.

[0341] Table 6 shows the characterization results of coated SiHy contact lenses comprising bulk silicone hydrogel material obtained from SiHy-7 or SiHy-8 lens formulations and a non-silicone hydrogel coating from IPC-1 brine (as a control) or IPC-3 brine.

[0342] Table 6

[0343]

[0344] It can be noted that when the IPC saline contains a hydrophilic polymer having a 1,2- or 1,3-diol moiety (i.e., PVA), the integrity of the coating is improved (IPC-3 vs. IPC-1). This indicates the formation of a non-silicone hydrogel coating ("hybrid coating") on the preformed SiHy contact lens. The non-silicone hydrogel coating is covalently attached to the bulk SiHy material and consists of a crosslinked polymeric material and PVA distributed therein.

[0345] All publications, patents, and patent applications cited hereinabove in this application are hereby incorporated by reference in their entirety.

Claims

1. A coated silicone hydrogel contact lens, comprising: The bulk silicone hydrogel material and the non-silicone hydrogel coating thereon, The bulk silicone hydrogel material comprises (a) a repeating unit of at least one polysiloxane vinyl crosslinking agent and / or at least one siloxane-containing vinyl monomer, (b) a repeating unit of at least one carboxyl-containing vinyl monomer relative to the total amount of all polymerizable components, (c) a repeating unit of at least one hydrophilic vinyl monomer, (d) at least one repeating unit of an aryldihydroxyboron-containing vinyl monomer having an aryldihydroxyboron group, and (e) optionally, but preferably, a repeating unit of at least one non-silicone vinyl crosslinking agent. The non-silicone hydrogel coating comprises a cross-linked polymer material and a grafted hydrophilic polymer distributed within the cross-linked polymer material but not covalently bonded to it. The cross-linked hydrophilic polymer material is covalently attached to the bulk silicone hydrogel material via a first linker bond formed between a carboxylic acid group and an aziridine or epoxy group. The grafted hydrophilic polymer comprises a 1,2- and / or 1,3-diol moiety and is covalently attached to the bulk silicone hydrogel material via a second linker bond formed between an aryldihydroxyboron group and a 1,2- or 1,3-diol moiety. The coated silicone hydrogel contact lens in a fully hydrated state exhibits approximately 90% or higher coating integrity and approximately 2.0 or lower friction rating.

2. The coated silicone hydrogel contact lens as described in claim 1, wherein, The at least one carboxyl-containing ethylene monomer is selected from the group consisting of: acrylic acid, C1-C4 alkyl acrylic acid, (meth)acryloyloxy-C1-C6 alkyl acid, mono-2-[(meth)acryloyloxy]-ethyl succinate, 2-acrylamidoglycolic acid, (meth)acrylamido-C1-C6 alkyl acid, and combinations thereof.

3. The coated silicone hydrogel contact lens as described in claim 1 or 2, wherein, The at least one aryl dihydroxyboronyl ethylene monomer is represented by formula (I). (I) Where: R B It is H, NO2, F, Cl, Br, CF3, CH2OH, or CH2NR. o R o '——of which R o and R o 'Independently, each is H or C1-C4 alkyl; Q is , , , , , , ,or Monovalent groups; L B It is a direct bond, a C1-C4 alkylene divalent group. , , , , , , or The divalent groups, where Y1 is CH(OH) or a C1-C4 alkylene divalent group, Y2 is a C1-C4 alkylene divalent group, p2 is an integer from 0 to 3, and R o It is H or C1-C4 alkyl.

4. The coated silicone hydrogel contact lens according to any one of claims 1 to 3, wherein, The at least one aryl dihydroxyboronic acid-containing vinyl monomer includes 3-vinylphenylboronic acid, 4-vinylphenylboronic acid, 3-(methyl)acrylamidophenylboronic acid, 4-(methyl)acrylamido-phenylboronic acid, 4-(1,6-dioxo-2,5-diaza-7-oxaaminoyl)phenylboronic acid, 2-dimethylamino-methyl-5-vinylphenylboronic acid, 4-(N-allylaminosulfonyl)phenylboronic acid, 4-(3-butenyl-sulfonyl)phenylboronic acid, 3-(methyl)acrylamido-5-nitrophenylboronic acid, 4-(methyl)acrylamido-5-nitrophenylboronic acid, 4-(methyl)acrylamido-3-nitrophenylboronic acid, and 3-[(methyl)acrylamido-C2-C5-alkylaminocarbonyl]-5-nitrobenzene. 3-[(meth)acryloyloxy-C2-C5-alkylaminocarbonyl]-5-nitrophenylboronic acid, 3-(meth)acrylamido-6-hydroxymethyl-phenylboronic acid, 3-(meth)acrylamido-6-dimethylaminomethylphenylboronic acid, 4-(meth)acrylamido-6-hydroxymethylphenylboronic acid, 4-(meth)acrylamido-6-dimethylamino-methylphenylboronic acid, products of the reaction of amino-containing phenylboronic acid derivatives with (meth)acrylic acid halides or epoxy-containing vinyl monomers or with carboxyl-containing vinyl monomers in the presence of carbodiimide and N-hydroxysuccinimide, products of the reaction of carboxyl-containing phenylboronic acid derivatives with amino-containing vinyl monomers in the presence of carbodiimide and N-hydroxysuccinimide, or combinations thereof.

5. The coated silicone hydrogel contact lens as described in claim 4, wherein, The amino-containing phenylboronic acid derivatives are 3-carboxyphenylboronic acid, 4-carboxyphenylboronic acid, 3-dihydroxyboronylphenyl-acetic acid, 4-dihydroxyboronylphenylacetic acid, 2-(4-dihydroxyboronylphenyl)-2-methylpropionic acid, 3-(4-dihydroxyboronylphenyl)propionic acid, 3-(3-dihydroxyboronylphenyl)propionic acid, 5-(3-dihydroxyboronylphenyl)valerate, 5-(4-dihydroxyboronylphenyl)valerate, 4-(2-carboxyethyl)-3-nitrophenylboronic acid, 3-carboxy-5-nitrophenylboronic acid, 4-carboxy-3-chlorophenylboronic acid, 3-carboxy-4-fluorophenylboronic acid, 3-(3-carboxypropionyl-amino)phenylboronic acid, or 3-amino -3-(4-dihydroxyborylphenyl)propionic acid, wherein the carboxyl-containing phenylboronic acid derivative is 3-aminophenylboronic acid, 4-aminophenylboronic acid, 4-amino-3-nitrophenylboronic acid, 3-amino-6-hydroxymethyl-phenylboronic acid, 3-amino-6-(dimethylaminomethyl)phenylboronic acid, 4-amino-2-hydroxymethylphenylboronic acid, 4-amino-2-(dimethylaminomethyl)phenylboronic acid, 3-amino-4-fluorophenylboronic acid, 4-(aminomethyl)-5-nitrophenylboronic acid, 3-(aminomethyl)-phenylboronic acid, 3-amino-5-nitrophenylboronic acid, or 3-amino-3-(4-dihydroxyborylphenyl)propionic acid.

6. The coated silicone hydrogel contact lens according to any one of claims 1 to 5, wherein, The crosslinked polymeric material comprises: (1) a poly(ethylene glycol) chain designated as a PEG chain, and (2) a polymeric chain derived from a copolymer, said copolymer being a polymeric product comprising: (i) 60% or less by weight of at least one reactive vinyl monomer containing at least one reactive functional group selected from carboxylic acids, primary amino groups, secondary amino groups, epoxy groups, and combinations thereof; and (ii) At least one non-reactive vinyl monomer, wherein the at least one non-reactive vinyl monomer is selected from acrylamide, methacrylamide, N,N-dimethylacrylamide, N,N-dimethylmethacrylamide, N-vinylpyrrolidone, N,N-dimethylaminoethyl methacrylate, N,N-dimethylaminoethyl acrylate, N,N-dimethylaminopropyl methacrylamide, N,N-dimethylaminopropyl acrylamide, glyceryl methacrylate, 3-acryloylamino-1-propanol, N-hydroxyethylacrylamide, N-[tris(hydroxymethyl)methyl]acrylamide, N-methyl-3-methylene-2-pyrrolidone, 1-ethyl-3-methylene-2-pyrrolidone, 1-methyl-5-methylene-2-pyrrolidone, 1-ethyl-5-methylene-2-pyrrolidone, 5-methyl-3-methylene-2-pyrrolidone. -Pyrrolidone, 5-ethyl-3-methylene-2-pyrrolidone, 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, phosphorylcholine-containing vinyl monomers, C1-C4-alkoxy poly(ethylene glycol) ethyl (meth)acrylates having a weight average molecular weight of up to 1500 Daltons, C1-C4-alkoxy poly(ethylene glycol) ethyl (meth)acrylamides having a weight average molecular weight of up to 1500 Daltons, poly(ethylene glycol) ethyl (meth)acrylates having a weight average molecular weight of up to 1500 Daltons, poly(ethylene glycol) ethyl (meth)acrylamides having a weight average molecular weight of up to 1500 Daltons, N-vinylformamide, N-vinylacetamide, N-vinylisopropylamide, N-vinyl-N-methylacetamide, allyl alcohol, vinyl alcohol, and combinations thereof;Or (3) combinations thereof, wherein the at least one reactive ethylene monomer is selected from amino-C2-C4 alkyl esters of (meth)acrylate, C1-C3 alkylamino-C2-C4 alkyl esters of (meth)acrylate, allylamine, ethyleneamine, amino-C2-C4 alkyl(meth)acrylamide, C1-C3 alkylamino-C2-C4 alkyl(meth)acrylamide, acrylic acid, C1-C4 alkyl acrylic acid, (meth)acryloyloxy-C2-C6 alkyl acid, 2-acrylamidoglycolic acid, (meth)acrylamido-C2-C6 alkyl acid, The group consisting of epoxy-containing vinyl monomers and combinations thereof, wherein the epoxy-containing vinyl monomers are selected from the group consisting of glycidyl (meth)acrylamide, hydroxyethyl (meth)acrylamide glycidyl ether, 3-hydroxypropyl (meth)acrylamide glycidyl ether, 4-hydroxybutyl (meth)acrylamide glycidyl ether, glycidyl (meth)acrylate, hydroxyethyl (meth)acrylate glycidyl ether, 3-hydroxypropyl (meth)acrylate glycidyl ether, 4-hydroxybutyl (meth)acrylate glycidyl ether, and combinations thereof.

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

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

9. The coated silicone hydrogel contact lens as described in claim 8, wherein, The at least one diol-containing hydrophilic polymer includes polyvinyl alcohol, poly(ethylene glycol)-grafted-poly(vinyl alcohol), copolymers of vinyl alcohol and hydrophilic vinyl monomers, copolymers of glyceryl (meth)acrylate and hydrophilic vinyl monomers, copolymers of 2,3,4-trihydroxybutyl (meth)acrylate and hydrophilic vinyl monomers, copolymers of 2,2-dihydroxypropyl (meth)acrylate and hydrophilic vinyl monomers, copolymers of 2,3-dihydroxybutyl (meth)acrylate and hydrophilic vinyl monomers, copolymers of glycerol-2-(meth)acrylate and hydrophilic vinyl monomers, copolymers of N-2,3-dihydroxypropyl (meth)acrylamide and hydrophilic vinyl monomers, copolymers of 3-allyloxy-1,2-propanediol and hydrophilic vinyl monomers, or combinations thereof.

10. A method for producing coated silicone hydrogel contact lenses, the method comprising the following steps: (1) Obtaining a pre-formed silicone hydrogel contact lens, wherein the pre-formed hydrogel contact lens comprises a bulk silicone hydrogel material, the bulk silicone hydrogel material comprising... (a) at least one polysiloxane ethylene crosslinking agent and / or at least one repeating unit of a siloxane-containing ethylene monomer, (b) a repeating unit of at least one carboxyl-containing ethylene monomer, comprising about 0.5% to about 3.5% by weight. (c) A repeating unit of at least one hydrophilic ethylene monomer, (d) by weight about 2.5% to about 12.5% ​​of at least one repeating unit of an aryldihydroxyboron-containing ethylene monomer having an aryldihydroxyboron group, and (e) Optionally, but preferably, at least one non-silicone vinyl crosslinking agent, and (2) Heating the pre-formed silicone hydrogel contact lens in an aqueous coating solution at a temperature of about 60°C to about 140°C to form a coated silicone hydrogel contact lens comprising the bulk silicone hydrogel material and a non-silicone hydrogel coating thereon, wherein the aqueous coating solution comprises (a) at least one hydrophilic polymer having a 1,2- and / or 1,3-diol moiety and (b) At least one water-soluble, thermally crosslinkable hydrophilic polymer material, which is branched or slightly crosslinked and comprises thermally crosslinkable groups and optionally reactive functional groups, wherein the thermally crosslinkable groups are azirmonium nitride groups and / or epoxy groups, wherein the reactive functional groups are primary amino, secondary amino, carboxylic acid groups, mercapto groups, or combinations thereof, wherein the non-silicone hydrogel coating comprises a crosslinked polymer material and a grafted hydrophilic polymer, wherein the crosslinked hydrophilic polymer material is derived from the at least one water-soluble, thermally crosslinkable hydrophilic polymer material and is covalently attached to the bulk silicone hydrogel material by a first linker bond formed between a carboxylic acid group and an azirmonium nitride or epoxy group, wherein the grafted hydrophilic polymer is derived from the at least one hydrophilic polymer and is covalently attached to the bulk silicone hydrogel material by a second linker bond formed between an aryldihydroxyboron group and a 1,2- or 1,3-diol moiety.

11. The method of claim 10, wherein, The heating step is preferably performed by autoclaving the pre-formed silicone hydrogel contact lens immersed in the aqueous coating solution in the sealed lens package at a temperature of about 115°C to about 125°C for about 20-90 minutes, wherein the aqueous coating solution further comprises a buffer for maintaining a pH of about 6.8 to about 8.5 and one or more tensioning agents.

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

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

14. The method according to any one of claims 10 to 13, wherein, The at least one diol-containing hydrophilic polymer includes polyvinyl alcohol, poly(ethylene glycol)-grafted-poly(vinyl alcohol), copolymers of vinyl alcohol and hydrophilic vinyl monomers, copolymers of glyceryl (meth)acrylate and hydrophilic vinyl monomers, copolymers of 2,3,4-trihydroxybutyl (meth)acrylate and hydrophilic vinyl monomers, copolymers of 2,2-dihydroxypropyl (meth)acrylate and hydrophilic vinyl monomers, copolymers of 2,3-dihydroxybutyl (meth)acrylate and hydrophilic vinyl monomers, copolymers of glycerol-2-(meth)acrylate and hydrophilic vinyl monomers, copolymers of N-2,3-dihydroxypropyl (meth)acrylamide and hydrophilic vinyl monomers, copolymers of 3-allyloxy-1,2-propanediol and hydrophilic vinyl monomers, or combinations thereof.

15. The method according to any one of claims 10 to 14, wherein, The at least one carboxyl-containing ethylene monomer is selected from the group consisting of: acrylic acid, C1-C4 alkyl acrylic acid, (meth)acryloyloxy-C1-C6 alkyl acid, mono-2-[(meth)acryloyloxy]-ethyl succinate, 2-acrylamidoglycolic acid, (meth)acrylamido-C1-C6 alkyl acid, and combinations thereof. The at least one aryl dihydroxyboronyl ethylene monomer is represented by formula (I). (I) Where: R B It is a monovalent group (preferably H, NO2, F, Cl, Br, CF3, CH2OH, or CH2NR). o R o '——R o and R o (Each is independently H or C1-C4 alkyl); Q is , , , , , , ,or Monovalent groups; L B It is a direct bond, a C1-C4 alkylene divalent group. , , , , , , or The divalent groups, where Y1 is CH(OH) or a C1-C4 alkylene divalent group, Y2 is a C1-C4 alkylene divalent group, p2 is an integer from 0 to 3, and R o It is H or C1-C4 alkyl.

16. The method according to any one of claims 10 to 15, wherein, The at least one water-soluble and thermally crosslinkable hydrophilic polymer material contains epoxy groups.

17. The method according to any one of claims 10 to 15, wherein, The at least one water-soluble and thermally crosslinkable hydrophilic polymer material contains a nitrogen-containing heterocyclic butaneonium group.

18. The method according to any one of claims 10 to 17, wherein, The at least one water-soluble and thermally crosslinkable hydrophilic polymer material comprises: (i) one or more multi-arm polyethylene glycols, each having a terminal epoxy group; (ii) a partial reaction product 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 primary amine, secondary amine, carboxyl, thiol, and combinations thereof; (iii) a partial reaction product of a multi-arm polyethylene having a terminal epoxy group and a hydrophilic reinforcing agent having at least one reactive functional group selected from the group consisting of amino, carboxyl, thiol, and combinations thereof; (iv) a partial reaction product of a copolymer of an epoxy-containing vinyl monomer and one or more hydrophilic vinyl monomers and a hydrophilic reinforcing agent having at least one reactive functional group selected from the group consisting of amino, carboxyl, thiol, and combinations thereof; (v) The epoxy-containing vinyl monomers, hydrophilic vinyl monomers, and copolymers of C1-C4-alkoxy poly(ethylene glycol) ethyl (meth) acrylates having a number average molecular weight of up to 2,500 Daltons, poly(ethylene glycol) ethyl (meth) acrylates having a number average molecular weight of up to 2,500 Daltons, C1-C4-alkoxy poly(ethylene glycol) ethyl (meth) acrylamide, or poly(ethylene glycol) ethyl (meth) acrylamide having a number average molecular weight of up to 2,500 Daltons; or (vi) combinations thereof.

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

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