Moisture gradient silicone hydrogel contact lenses

Abstract

The present invention provides moisture gradient contact lenses that are easily removable. Such moisture gradient contact lenses can be manufactured according to a cost-effective method that includes creating defects (grooves and / or gaps) in the anterior outer hydrogel layer and partially or completely masking reactive functional groups in selected regions of the anterior surface of the contact lens to be coated before grafting a non-silicone hydrogel material layer. Due to the defects in the anterior outer hydrogel layer, the surface lubricity of the anterior surface is inferior to that of the posterior surface. By adjusting the shape, size, density, and rotational distribution of the defects, the surface lubricity of the anterior surface of the moisture gradient contact lens can be selectively tuned and optimized, thereby improving lens handling while maintaining other desirable properties.

Description

[Technical Field]

[0001] The present invention relates to easily removable moisture gradient silicone hydrogel contact lenses and a method for making such moisture gradient silicone hydrogel contact lenses. [Background technology]

[0002] A new type of soft contact lens, the water gradient silicone hydrogel contact lens (e.g., DAILIES®, TOTAL 1® (Alcon), PRECISION 1® (Alcon), and TOTAL 30® (Alcon)), has been developed and successfully introduced to the market. This new class of soft contact lens has a water gradient structure, characterized by an increasing water content from 33% to over 80% from the core to the surface (see, e.g., U.S. Pat. Nos. 8,480,227, 11,061,168, and 11,256,003). This unique design provides a very smooth and very flexible lens surface that retains a lot of water, thus providing an excellent wearing comfort to the patient.

[0003] Newly developed water gradient silicone hydrogel contact lenses are very flexible, have a high water content, and have a relatively thick and smooth hydrogel coating, which allows for excellent wear comfort for patients. However, one of the main challenges with water gradient contact lenses is lens removal. Because these contact lenses are so smooth, patients, especially first-time patients, may have a steep learning curve in removing the lenses from their eyes. Therefore, water gradient contact lenses that improve lens handling ("ease of insertion / removal") while maintaining other desirable properties are desirable.

[0004] Therefore, there remains a need for moisture gradient contact lenses that are easily removable. Summary of the Invention [Means for solving the problem]

[0005] In one aspect, the present invention provides a coated contact lens comprising: a front surface and an opposite posterior surface; and a layered structural configuration comprising, in a direction from the front surface to the posterior surface, a front outer hydrogel layer, an inner layer, and a posterior outer hydrogel layer, wherein the inner layer is made from a lens bulk material; the posterior outer hydrogel layer is a layer of a first non-silicone hydrogel material having defects (e.g., grooves and / or crevices) distributed therein such that the front outer hydrogel layer has a surface lubricity that is greater than the surface lubricity of the front outer hydrogel layer; and wherein the coated contact lens, when fully hydrated, has a water content of about 10% to about 70% by weight, an oxygen permeability of at least about 50 barrers, and a water breakup time of at least about 10 seconds as measured on the front and posterior surfaces of the coated contact lens.

[0006] In another aspect, the present invention is a method for producing a coated contact lens, the method comprising the steps of: (1) obtaining a preformed contact lens having a convex surface and an opposite concave surface, the preformed contact lens being composed of a lens bulk material and including first reactive functional groups on and near the convex and concave surfaces of the preformed contact lens, each of the first reactive functional groups being capable of reacting with a thermally crosslinkable group at a temperature of from about 60°C to about 140°C, the first reactive functional groups being selected from the group consisting of carboxylic acid groups, primary amino groups, secondary amino groups, thiol groups, and combinations thereof; (2) coating a plurality of regions on the convex surface with a second non-silicone hydrogel material to prevent the first reactive functional groups behind the plurality of regions from reacting with the thermally crosslinkable group, the second non-silicone hydrogel material being free of the first reactive functional groups and the thermally crosslinkable group; and (3) coating a plurality of regions on the convex surface with a second non-silicone hydrogel material at a temperature of from about 6.5 to about 9.a step of directly heating the preformed contact lens obtained in step (2) at a temperature of about 60°C to about 140°C in an aqueous solution having a pH of 5 and containing at least one water-soluble, thermally crosslinkable hydrophilic polymer material to graft a first non-silicone hydrogel material onto each of the anterior and posterior surfaces of the preformed contact lens obtained in step (2), thereby forming a coated contact lens having an anterior surface, an opposite posterior surface, an anterior outer hydrogel layer, and a posterior outer hydrogel layer, wherein the at least one water-soluble, thermally crosslinkable hydrophilic polymer material comprises a second reactive functional group and a third reactive functional group, the second reactive functional group being a thermally crosslinkable group selected from the group consisting of an azetidinium group, an epoxy group, and combinations thereof, and each of the second reactive functional groups being a thermally crosslinkable group selected from the group consisting of an azetidinium group, an epoxy group, and combinations thereof, and each of the second reactive functional groups being a thermally crosslinkable group selected from the group consisting of one of the first or third reactive functional groups; wherein the third reactive functional group is capable of reacting with the first non-silicone hydrogel material to form crosslinks, and the third reactive functional group is selected from the group consisting of a carboxylic acid group, a primary amino group, a secondary amino group, a thiol group, and combinations thereof; the second non-silicone hydrogel material is a crosslinked product of said at least one thermally crosslinkable hydrophilic polymeric material; the posterior outer hydrogel layer is a layer of the first non-silicone hydrogel material, the anterior outer hydrogel layer being a layer of the first non-silicone hydrogel material having defects (e.g., grooves and / or crevices) distributed therein so as to impart a surface lubricity to the posterior surface that is greater than the surface lubricity of the anterior surface of the coated contact lens; wherein the coated contact lens in a fully hydrated state has a water break-up time of at least about 10 seconds measured on the anterior and posterior surfaces of the coated contact lens.

[0007] In a further aspect, the present invention provides a method for producing a coated contact lens, comprising the steps of: (1) obtaining a female mold half and a male mold half, wherein the female mold half has a first molding surface defining an anterior surface of the contact lens to be molded, and the male mold half has a second molding surface defining a posterior surface of the contact lens to be molded, the male mold half and the female mold half being configured to receive each other such that when the female mold half is closed with the male mold half, a lens molding cavity is formed between the first molding surface and the second molding surface; and (2) applying a hydrogel-forming composition to a plurality of regions on the first molding surface, the hydrogel-forming composition comprising at least one crosslinkable polymer having hydroxyl groups and / or ethylenically unsaturated groups, and optionally at least one hydrophobic hydrogel selected from the group consisting of methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, methyl (meth)acrylate, and combinations thereof. (3) optionally, partially curing the hydrogel-forming composition on the first molding surface; and (4) introducing a polymerizable composition into the negative mold half obtained in step (2) or (3), wherein the polymerizable composition contains at least one reactive vinyl monomer having at least one first reactive functional group selected from the group consisting of a carboxylic acid group, a primary amino group, a secondary amino group, and a combination thereof, in an amount of about 1:1 based on the total amount of all polymerizable components.(5) closing the female mold half from step (4) with a male mold half to form a mold assembly containing the polymerizable composition within a lens-forming cavity; (6) curing the polymerizable composition within the mold assembly thermally or with actinic radiation to form a contact lens precursor having a convex surface and an opposing concave surface, the contact lens precursor comprising a lens bulk material having first reactive functional groups, wherein the convex surface of the contact lens precursor is partially coated with a second non-silicone hydrogel material formed from the hydrogel-forming composition in a plurality of regions on the convex surface, such that (7) optionally, hydrating the contact lens precursor obtained in step (6) in water or an aqueous solution to obtain a hydrated contact lens precursor; and (8) heating the contact lens precursor obtained in step (6) or the hydrated contact lens precursor obtained in step (7) at a temperature of about 6.5 to about 9.a step of directly heating the contact lens precursor obtained in step (6) or the hydrated contact lens precursor obtained in step (7) at a temperature of about 60°C to about 140°C in an aqueous solution having a pH of 5 and containing at least one water-soluble, thermally crosslinkable hydrophilic polymer material to graft a first non-silicone hydrogel material onto each of the convex and concave surfaces of the contact lens precursor obtained in step (6) or the hydrated contact lens precursor obtained in step (7), thereby forming a coated contact lens having an anterior surface, an opposite posterior surface, an anterior outer hydrogel layer, and a posterior outer hydrogel layer, wherein the at least one water-soluble, thermally crosslinkable hydrophilic polymer material comprises a second reactive functional group and a third reactive functional group, the second reactive functional group being a thermally crosslinkable group selected from the group consisting of an azetidinium group, an epoxy group, and combinations thereof, and the second reactive functional group is a thermally crosslinkable group selected from the group consisting of an azetidinium group, an epoxy group, and combinations thereof, and the third ... wherein each of the reactive functional groups is capable of reacting with one first or third reactive functional group to form a crosslink, and the third reactive functional group is selected from the group consisting of a carboxylic acid group, a primary amino group, a secondary amino group, a thiol group, and combinations thereof; the posterior outer hydrogel layer is a layer of a first non-silicone hydrogel material, the anterior outer hydrogel layer being a layer of a first non-silicone hydrogel material having defects (e.g., grooves and / or crevices) distributed therein so as to impart a higher surface lubricity to the posterior surface than to the anterior surface of the coated contact lens; and wherein the coated contact lens has a water break-up time of at least about 10 seconds measured on the anterior and posterior surfaces of the coated contact lens. [Brief explanation of the drawings]

[0008] [Figure 1] 1A-E show five printing patterns (A-E) used to apply a hydrogel-forming composition to the anterior surface of a preformed silicone hydrogel contact lens, according to a preferred embodiment of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0009] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Generally, the nomenclature and laboratory procedures used herein are well known and commonly used in the art. Conventional methods are used for these procedures, such as those provided in the art and various general references. Where a term is given in the singular, the inventors also contemplate the plural of that term. The nomenclature used herein and the laboratory procedures described below are well known and commonly used in the art.

[0010] "About" as used herein in this application means that the number referred to as "about" includes the recited number, plus or minus 1 to 10% of the recited number.

[0011] "Contact lens" refers to a structure that can be placed on or in the eye of a wearer. A contact lens can, but need not, correct, improve, or alter the user's vision. A contact lens can be of any suitable material known in the art or later developed, and can be a hard lens, a rigid gas permeable lens, a soft lens, or a hybrid lens.

[0012] As used in this application, the terms "front surface," "front surface," "front curve," or "FC surface" in reference to a contact lens mean interchangeably the surface of the contact lens that faces away from the eye during wear. The front surface (FC surface) is typically substantially convex.

[0013] The terms "posterior surface," "back surface," "base curve surface," or "BC surface," as used herein, in reference to a contact lens, mean interchangeably the surface of the contact lens that faces the eye during wear. The posterior surface (BC surface) is typically substantially concave.

[0014] As used in this application, "central axis" in reference to a contact lens means an imaginary reference line passing through the geometric centers of the anterior and posterior surfaces of the contact lens.

[0015] As used in this application, "central axis" with respect to a mold half means an imaginary reference line that passes perpendicularly through the geometric center of the molding surface of the mold half (ie, perpendicular to the molding surface at the geometric center).

[0016] "Hard contact lens" refers to a contact lens that includes a hard plastic (eg, polymethyl methacrylate) as the lens bulk (or so-called "core") material.

[0017] "Rigid gas permeable contact lens" refers to a contact lens that includes a gas permeable material (eg, a material made from fluorosilicone acrylate) as the bulk material of the lens.

[0018] A hybrid contact lens includes a lens bulk material consisting essentially of a central optic made of a gas-permeable lens material and a peripheral portion made of a silicone hydrogel or conventional hydrogel lens material, extending outward from and surrounding the central optic.

[0019] The implantable contact lens comprises a three-dimensional implantable article and a lens bulk material consisting essentially of a non-silicone hydrogel material or a silicone hydrogel material, the three-dimensional implantable article having a three-dimensional size smaller than a contact lens such that it is partially or preferably completely embedded within the non-silicone hydrogel material or the silicone hydrogel material.

[0020] "Hydrogel contact lens" refers to a contact lens that includes a hydrogel bulk (core) material. The hydrogel bulk material can be a non-silicone hydrogel material, or preferably a silicone hydrogel material.

[0021] "Hydrogel" or "hydrogel material" refers to a crosslinked polymeric material that has a three-dimensional polymer network (i.e., a polymeric matrix) and is insoluble in water but can retain at least 10% by weight of water within its polymeric matrix when fully hydrated (or equilibrated).

[0022] "Silicone hydrogel" or "SiHy" refers to a silicone-containing hydrogel obtained by copolymerization of a polymerizable composition comprising at least one silicone-containing vinyl monomer having an ethylenically unsaturated group, or at least one silicone-containing vinyl macromer, or at least one crosslinkable silicone-containing prepolymer.

[0023] Siloxane, often also referred to as silicone, refers to a molecule having at least one moiety of -Si-O-Si-, where each Si atom has two organic groups as substituents.

[0024] As used in this application, the terms "non-silicone hydrogel" or "non-silicone hydrogel material" are interchangeable and refer to hydrogels that are theoretically silicon-free.

[0025] "Hydrophilic," as used herein, describes a material or portion thereof that associates more readily with water than with lipids.

[0026] The term "room temperature" refers to a temperature of about 17°C to about 26°C.

[0027] The term "soluble" with respect to a compound or substance in a solvent means that the compound or substance can be dissolved in the solvent to provide a solution having a concentration of at least about 0.5% by weight at room temperature (i.e., about 17°C to about 26°C).

[0028] The term "insoluble," in reference to a compound or material in a solvent, means that the compound or material can be dissolved in the solvent at room temperature (as defined above) to provide a solution with a concentration of less than about 0.01% by weight.

[0029] "Vinyl monomer" refers to a compound that has one and only one ethylenically unsaturated group, is soluble in a solvent, and can be polymerized actinically or thermally.

[0030] The terms "olefinically unsaturated group" or "ethylenically unsaturated group" are used broadly herein and are intended to encompass any group containing at least one >C=CH group. Exemplary ethylenically unsaturated groups include, but are not limited to, (meth)acryloyl [ka] , allyl, vinyl, styrenyl, or other C=CH2 containing groups.

[0031] "Acrylic monomer" refers to a vinyl monomer having one and only one (meth)acryloyl group. Examples of acrylic monomers include (meth)acryloxy [or (meth)acryloyloxy] monomers and (meth)acrylamide monomers.

[0032] "(Meth)acryloxy monomer" or "(meth)acryloyloxy monomer" means [ka] refers to a vinyl monomer having one and only one group.

[0033] "(Meth)acrylamide monomer" is [ka] where R o is H or C1-C4 alkyl.

[0034] The term "(meth)acrylamide" refers to methacrylamide and / or acrylamide.

[0035] The term "(meth)acrylate" refers to methacrylate and / or acrylate.

[0036] "N-vinyl amide monomer" refers to an amide compound having a vinyl group (-CH=CH2) attached directly to the nitrogen atom of the amide group.

[0037] "Ene monomer" refers to a vinyl monomer having one and only one ene group.

[0038] "Hydrophilic vinyl monomer," "hydrophilic acrylic monomer," "hydrophilic (meth)acryloxy monomer," or "hydrophilic (meth)acrylamide monomer," as used herein, refers to a vinyl monomer, an acrylic monomer, a (meth)acryloxy monomer, or a (meth)acrylamide monomer, respectively, which typically results in a homopolymer that is water-soluble or can absorb at least 10 weight percent water.

[0039] "Hydrophobic vinyl monomer," "hydrophobic acrylic monomer," "hydrophobic (meth)acryloxy monomer," or "hydrophobic (meth)acrylamide monomer," as used herein, refers to a vinyl monomer, an acrylic monomer, a (meth)acryloxy monomer, or a (meth)acrylamide monomer, respectively, which typically results in a homopolymer that is insoluble in water and can absorb less than 10% by weight of water.

[0040] "Blending vinyl monomer" refers to a vinyl monomer that is capable of dissolving both the hydrophilic and hydrophobic polymerizable components of the polymerizable composition to form a solution.

[0041] As used in this application, the term "vinyl crosslinker" refers to an organic compound having at least two ethylenically unsaturated groups. "Vinyl crosslinker" refers to a vinyl crosslinker having a molecular weight of 700 Daltons or less.

[0042] "Acrylic crosslinker" refers to a vinyl crosslinker having at least two (meth)acryloyl groups.

[0043] The term "acrylic repeat unit" refers to a repeat unit of a polymeric material, each of which is derived from an acrylic monomer or crosslinker in a free radical polymerization to form the polymeric material.

[0044] The term "terminal (meth)acryloyl group" refers to one (meth)acryloyl group at one of the two ends of the main chain (or backbone) of an organic compound.

[0045] As used herein, "actinically" in reference to curing, crosslinking, or polymerization of a polymerizable composition, prepolymer, or material means that the curing (e.g., crosslinking and / or polymerization) is effected by actinic radiation, such as, for example, UV / visible radiation, ionizing radiation (e.g., gamma or X-ray radiation), microwave radiation, etc. Thermal curing or actinic curing methods are well known to those skilled in the art.

[0046] As used in this application, the term "polymer" means a material formed by polymerizing / crosslinking monomers, macromers, prepolymers, or combinations thereof.

[0047] "Macromer" or "prepolymer" refers to a compound or polymer that contains ethylenically unsaturated groups and has a number average molecular weight greater than 700 Daltons.

[0048] As used in this application, the term "molecular weight" of a polymeric material (including a monomeric or macromeric material) refers to number average molecular weight unless otherwise specified or unless the test conditions dictate otherwise. Those skilled in the art will recognize that molecular weight can be measured by known methods, such as GPC (gel permeation chromatography) equipped with one or more of a refractive index detector, a low-angle laser light scattering detector, a multi-angle laser light scattering detector, a differential viscometry detector, a UV detector, and an infrared (IR) detector; MALDI-TOF MS (matrix-assisted desorption / ionization time-of-flight mass spectrometry);1 Recognize methods for determining the molecular weight of polymers, such as by H NMR (proton nuclear magnetic resonance) spectroscopy.

[0049] "Polysiloxane segment" or "polydiorganosiloxane segment" means [ka] where SN is an integer greater than or equal to 3 and R S1 and R S2 Each of these is 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 Fluoroether;Aryl;Aryl C1-C 18 Alkyl;-alk-(OC2H4) γ1 -OR o (wherein alk is a C1-C6 alkylene diradical, and R o is H or C1-C4 alkyl, and γ1 is an integer from 1 to 10; a hydroxyl group (—OH), a carboxyl group (i.e., a carboxylic acid group) (—COOH), an amino group (—NR N1 R N1 '), -NR N1 -amino bond, -CONR N1 -amide bond, -CONR N1 R N1 C2-C alkoxy group having at least one functional group selected from the group consisting of an amide of -OCONH-, a urethane bond of -OCONH-, and a C1-C4 alkoxy group 40 an organic radical; or a linear hydrophilic polymer chain; N1 and R N1 ' are each independently hydrogen or C1-C 15 It is alkyl.

[0050] "Polysiloxane vinyl monomer" refers to a compound containing at least one polysiloxane segment and one single ethylenically unsaturated group.

[0051] "Polydiorganosiloxane vinyl crosslinker" or "polysiloxane vinyl crosslinker" refer interchangeably to a compound containing at least one polysiloxane segment and at least two ethylenically unsaturated groups.

[0052] "Linear polydiorganosiloxane vinyl crosslinker" or "linear polysiloxane vinyl crosslinker" interchangeably refer to a compound comprising a backbone that includes at least one polysiloxane segment and is terminated at each of the two ends of the backbone with one ethylenically unsaturated group.

[0053] The terms "chain-extended polydiorganosiloxane vinyl crosslinker" or "chain-extended polysiloxane vinyl crosslinker" refer interchangeably to a compound containing at least two ethylenically unsaturated groups and at least two polysiloxane segments, each pair of which is linked by a divalent radical.

[0054] The term "fluid" as used herein indicates that the material is capable of flowing like a liquid.

[0055] As used in this application, the term "optically transparent" with respect to a polymerizable composition means that the polymerizable composition is a clear solution or liquid mixture (i.e., has a light transmittance of 85% or more, preferably 90% or more, in the range of 400-700 nm).

[0056] The term "monovalent radical" refers to an organic radical obtained by removing a hydrogen atom from an organic compound and forming one bond with one other group in the organic compound. Examples include, without limitation, alkyl (by removing a hydrogen atom from an alkane), alkoxy (or alkoxyl) (by removing one hydrogen atom from the hydroxyl group of an alkyl alcohol), thiyl (by removing one hydrogen atom from the thiol group of an alkylthiol), cycloalkyl (by removing a hydrogen atom from a cycloalkane), cycloheteroalkyl (by removing a hydrogen atom from a cycloheteroalkane), aryl (by removing a hydrogen atom from the aromatic ring of an aromatic hydrocarbon), heteroaryl (by removing a hydrogen atom from any ring atom), amino (by removing one hydrogen atom from an amine), and the like.

[0057] The term "divalent radical" refers to an organic radical obtained by removing two hydrogen atoms from an organic compound and that forms two bonds with two other groups in the organic compound. For example, an alkylene divalent radical (i.e., alkylenyl) is obtained by removing two hydrogen atoms from an alkane, and a cycloalkylene divalent radical (i.e., cycloalkylenyl) is obtained by removing two hydrogen atoms from a cyclic ring.

[0058] In this application, the term "substituted" with reference to an alkyl or alkylenyl means that the alkyl or alkylenyl replaces one hydrogen atom of the alkyl or alkylenyl and includes at least one substituent selected from the group consisting of hydroxyl (-OH), carboxyl (-COOH), -NH, sulfhydryl (-SH), C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkylthio (alkylsulfido), C1-C4 acylamino, C1-C4 alkylamino, di-C1-C4 alkylamino, and combinations thereof.

[0059] In this application, "oxazoline" means [ka] refers to a compound of the formula: ox1 is hydrogen, methyl, ethyl, N-pyrrolidonylmethyl, N-pyrrolidonylethyl, N-pyrrolidonylpropyl, or -alk-(OC2H4) m3 -OR ” where alk is a C1-C6 alkyl diradical; R″ is a C1-C4 alkyl (preferably methyl); and m3 is an integer from 1 to 10 (preferably 1 to 5).

[0060] In this application, the term "polyoxazoline" refers to [ka] where R ox1 is hydrogen, methyl, ethyl, N-pyrrolidonylmethyl, N-pyrrolidonylethyl, N-pyrrolidonylpropyl, or -alk-(OC2H4) m3 -OR ” where alk is a C1-C6 alkyl diradical; R″ is a C1-C4 alkyl (preferably methyl); m3 is an integer from 1 to 10 (preferably 1 to 5); and x is an integer from 5 to 500.

[0061] In this application, the term "poly(2-oxazoline-co-ethyleneimine)" means [ka] refers to a statistical copolymer or polymer segment thereof having the formula: ox1 is hydrogen, methyl, ethyl, N-pyrrolidonylmethyl, N-pyrrolidonylethyl, N-pyrrolidonylpropyl, or -alk-(OC2H4) m3 -OR ”where alk is a C1-C6 alkyl diradical; R″ is a C1-C4 alkyl (preferably methyl); m3 is an integer from 1 to 10 (preferably 1 to 5); x is an integer from 5 to 500; and z is an integer equal to or less than x. Poly(2-oxazoline-co-ethyleneimine) can be obtained by hydrolyzing polyoxazoline.

[0062] In this application, the term "poly(2-oxazoline-co-ethyleneimine)-epichlorohydrin" refers to a polymer obtained by reacting poly(2-oxazoline-co-ethyleneimine) with epichlorohydrin to convert all or a significant percentage (≧90%) of the secondary amine groups of the poly(2-oxazoline-co-ethyleneimine) to azetidinium groups. Examples of poly(2-oxazoline-co-ethyleneimine)-epichlorohydrin are disclosed in U.S. Patent Application Publication No. 2016 / 0061995 A1.

[0063] "Epichlorohydrin-functionalized polyamine" or "epichlorohydrin-functionalized polyamidoamine" refers to a polymer obtained by reacting a polyamine or polyamidoamine with epichlorohydrin to convert all or a significant percentage of the secondary amine groups of the polyamine or polyamidoamine to azetidinium groups.

[0064] The term "polyamidoamine-epichlorohydrin" refers to an adipic acid-diethylenetriamine copolymer functionalized with epichlorohydrin.

[0065] In this application, the term "azetidinium" or "3-hydroxyazetidinium" means [ka] refers to a positively charged (i.e., cationic), divalent radical (or group or moiety) of

[0066] The term "thermally crosslinkable" with respect to a polymeric material or functional group means that the polymeric material or functional group is capable of undergoing a crosslinking reaction (or coupling reaction) with another material or functional group at relatively high temperatures (about 40°C to about 140°C), but that the polymeric material or functional group is not capable of undergoing 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 20°C in about 1 hour.

[0067] The term "azlactone" refers to a compound of the formula [ka] where p is 0 or 1; 3 R and 4 R are each independently C1 to C8 alkyl (preferably methyl).

[0068] The term "aziridine group" refers to a group of the formula [ka] where R 1 is hydrogen, methyl, or ethyl.

[0069] The term "phosphorylcholine" as used in this application means [ka] where n is an integer from 1 to 5, and R 2 , R 3 , and R 4 are each independently C1 to C8 alkyl or C1 to C8 hydroxyalkyl.

[0070] As used in this application, the term "reactive vinyl monomer" refers to any vinyl monomer having at least one reactive functional group selected from the group consisting of a carboxyl group, a primary amino group, and a secondary amino group.

[0071] As used in this application, the term "non-reactive vinyl monomer" refers to any vinyl monomer (either hydrophilic or hydrophobic) that does not contain a carboxyl group, a primary amino group, a secondary amino group, an epoxide group, an isocyanate group, an azlactone group, or an aziridine group.

[0072] A free radical initiator can be either a photoinitiator or a thermal initiator. A "photoinitiator" refers to a chemical that initiates a free radical crosslinking / polymerization reaction through the use of light. A "thermal initiator" refers to a chemical that initiates a free radical crosslinking / polymerization reaction through the use of thermal energy.

[0073] The material's intrinsic "oxygen permeability coefficient," Dk i is the rate at which oxygen passes through the material. As used in this application, the term "oxygen permeability (Dk)" in reference to a hydrogel (silicone or non-silicone) or contact lens refers to the corrected oxygen permeability (Dk c ), which is measured at approximately 34-35°C and corrected for the surface resistance to oxygen flux caused by boundary layer effects, according to the procedure described in ISO 18369-4. Oxygen permeability is usually expressed in units of barrer, where "barrer" is the unit of [(cm 3 oxygen)(mm) / (cm 2 )(sec)(mmHg)]×10 -9 is defined as:

[0074] The "oxygen permeability" of an insert or material, Dk / t, is the rate at which oxygen passes through a particular insert or material of average thickness t [in mm] over the area being measured. Oxygen permeability is usually expressed in units of barrer / mm, where "barrer / mm" is the number of times the oxygen passes through the insert or material. 3 oxygen) / (cm 2 )(sec)(mmHg)]×10 -9 is defined as:

[0075] The term "modulus" or "elastic modulus" in relation to contact lenses or materials refers to the tensile modulus or Young's modulus, which is a measure of the stiffness of a contact lens or material under tension. Those skilled in the art know how to measure the elastic modulus of a SiHy material or contact lens. For example, all commercially available contact lenses have a reported elastic modulus value.

[0076] "Coating" in relation to a contact lens means that the contact lens has on its surface a thin layer of a material that is different from the bulk material of the contact lens and that is obtained by subjecting the contact lens to a surface treatment.

[0077] "Average water contact angle" refers to the water contact angle (measured by the Sessile Drop Method) obtained by averaging measurements of at least three individual contact lens or silicone hydrogel material samples.

[0078] The term "water gradient" as used in this application in connection with contact lenses means that there is an increase in water content observed as the contact lens passes from the core to the surface, reaching a highest water content in regions near and including the surface of the contact lens. It is understood that the increase in water content from the core to the surface of the contact lens can be continuous and / or stepwise, so long as the water content is highest in regions near and including the surface of the contact lens.

[0079] The terms "inner layer" or "lens bulk material" as used in this application in connection with the contact lenses of the present invention mean interchangeably a layer that has the three-dimensional shape of the contact lens and that includes a central curved surface (which divides the contact lens into two portions, one portion containing a convex surface and the other portion containing a convex surface), and that has a variable thickness.

[0080] The term "external hydrogel layer" as used in this application in connection with contact lenses means the outermost hydrogel layer on the surface of a contact lens, consisting of a front outer hydrogel layer and a back outer hydrogel layer, which completely or partially covers the inner layer (or lens bulk material).

[0081] The term "front outer hydrogel layer" as used in this application with respect to contact lenses means a hydrogel layer that comprises the front surface of a contact lens, is made from one or more non-silicone hydrogel materials, and completely or partially covers the concave surface of the inner layer (or lens bulk material).

[0082] The term "posterior outer hydrogel layer" as used in this application with respect to contact lenses means a hydrogel layer that comprises the posterior surface of a contact lens, is made from one or more non-silicone hydrogel materials, and completely or partially covers the concave surface of the inner layer (or lens bulk material).

[0083] As used herein, the terms "crosslinked coating" or "hydrogel coating" or "hydrogel layer" on a contact lens are used interchangeably to describe a crosslinked polymeric material having a three-dimensional network that can contain water when fully hydrated. The three-dimensional network of the crosslinked polymeric material can be formed by the crosslinking of two or more linear or branched polymers through crosslinking bonds.

[0084] As used herein, "surface modification" or "surface treatment" means that the article has been treated, before or after its formation, with a surface treatment process (or surface modification process) in which (1) a coating is provided on the surface of the article, (2) a chemical species is adsorbed onto the surface of the article, (3) the chemical nature (e.g., electrostatic charge) of chemical groups on the surface of the article is altered, or (4) the surface properties of the article are otherwise altered. Exemplary surface treatment processes include, but are not limited to, surface treatment with energy (e.g., plasma, electrostatic charge, irradiation, or other energy source), chemical treatment, grafting of hydrophilic vinyl monomers or macromers onto the surface of the article, the mold transfer coating process disclosed in U.S. Pat. No. 6,719,929, the incorporation of wetting agents into lens formulations for producing contact lenses as proposed in U.S. Pat. Nos. 6,367,929 and 6,822,016, reinforced mold transfer coating as disclosed in U.S. Pat. No. 7,858,000, and hydrophilic coatings comprised of covalently or physically depositing one or more layers of one or more hydrophilic polymers onto the surface of a contact lens as disclosed in U.S. Pat. Nos. 8,147,897 and 8,409,599 and U.S. Patent Publication Nos. 2011 / 0134387, 2012 / 0026457, and 2013 / 0118127.

[0085] "Post-cure surface treatment" in relation to lens bulk material or contact lenses refers to a surface treatment process that occurs after the lens bulk material or contact lens has been formed by curing (i.e., polymerizing thermally or by actinic radiation) the lens formulation. "Lens formulation" refers to a polymerizable composition that contains all of the polymerizable components necessary to produce a contact lens or lens bulk material, as is well known to those skilled in the art.

[0086] The present invention generally relates to water gradient contact lenses that provide improved lens handling (ease of insertion / removal) while maintaining other desirable properties provided by water gradient contact lenses. The present invention is based, in part, on the discovery that the surface lubricity of the anterior surface of a water gradient contact lens can be controllably reduced by introducing defects (e.g., grooves and / or crevices) into the anterior outer hydrogel layer of the water gradient contact lens in accordance with the cost-effective method of the present invention. Typically, the manufacture of water gradient contact lenses involves grafting (covalently bonding) a non-silicone hydrogel onto the contact lens to be coated. Such a grafting process requires the presence of reactive functional groups (e.g., carboxylic acid groups, primary / secondary amino groups, thiol groups) on the surface of the contact lens to be coated as anchor sites for grafting. It has been discovered that reactive functional groups can be completely or substantially blocked by applying a non-silicone hydrogel material that does not contain reactive functional groups to specific regions of the anterior surface of the contact lens to be coated. The resulting coated contact lens has a non-uniform distribution of reactive functional groups on the anterior surface of the coated contact lens, with no or few reactive functional groups present in these areas, while sufficient reactive functional groups are present in the remaining areas of the anterior surface. As a result, no or little grafting of the non-silicone hydrogel material occurs in these areas of the anterior surface, while grafting of the non-silicone hydrogel material occurs in the remaining areas, resulting in the formation of in situ defects (e.g., grooves and / or gaps) in the anterior outer hydrogel layer of the resulting water gradient contact lens. The presence of such defects (e.g., grooves and / or gaps) in the anterior outer hydrogel layer can reduce the surface lubricity of the anterior surface of the water gradient contact lens. The surface lubricity of the anterior surface of the water gradient contact lens can also be adjusted and optimized by controlling the shape, size, density, and rotational distribution of the defects on the anterior outer hydrogel layer.

[0087] In one aspect, the present invention is a method for producing a coated silicone hydrogel contact lens, the method comprising the steps of: (1) obtaining a preformed contact lens having a convex surface and an opposite concave surface and comprising a lens bulk material, the preformed contact lens being composed of the lens bulk material and comprising first reactive functional groups on and near the convex and concave surfaces of the preformed contact lens, each of the first reactive functional groups being capable of reacting with a thermally crosslinkable group at a temperature of from about 60°C to about 140°C, the first reactive functional groups being selected from the group consisting of carboxylic acid groups, primary amino groups, secondary amino groups, thiol groups, and combinations thereof; (2) coating a plurality of regions on the convex surface with a second non-silicone hydrogel material to prevent the first reactive functional groups behind the plurality of regions from reacting with the thermally crosslinkable group, the second non-silicone hydrogel material being free of the first reactive functional groups and the thermally crosslinkable group; and (3) coating a plurality of regions on the convex surface with a second non-silicone hydrogel material at a temperature of from about 6.5 to about 9.a step of directly heating the preformed contact lens obtained in step (2) at a temperature of about 60°C to about 140°C in an aqueous solution having a pH of 5 and containing at least one water-soluble, thermally crosslinkable hydrophilic polymer material to graft a first non-silicone hydrogel material onto each of the anterior and posterior surfaces of the preformed contact lens obtained in step (2), thereby forming a coated contact lens having a front surface, an opposite posterior surface, a front outer hydrogel layer, and a posterior outer hydrogel layer, wherein the at least one water-soluble, thermally crosslinkable hydrophilic polymer material comprises a second reactive functional group and a third reactive functional group, the second reactive functional group being a thermally crosslinkable group selected from the group consisting of an azetidinium group, an epoxy group, and combinations thereof, and each of the second reactive functional groups being a thermally crosslinkable group selected from the group consisting of an azetidinium group, an epoxy group, and combinations thereof, and each of the second reactive functional groups being a thermally crosslinkable group selected from the group consisting of one of the first or third reactive functional groups; the third reactive functional group is capable of reacting with the at least one thermally crosslinkable hydrophilic polymeric material to form crosslinks, and the third reactive functional group is selected from the group consisting of a carboxylic acid group, a primary amino group, a secondary amino group, a thiol group, and combinations thereof; the second non-silicone hydrogel material is a crosslinked product of said at least one thermally crosslinkable hydrophilic polymeric material; the posterior outer hydrogel layer is a layer of the first non-silicone hydrogel material, the anterior outer hydrogel layer being a layer of the first non-silicone hydrogel material having defects (e.g., grooves and / or crevices) distributed therein so as to impart a surface lubricity to the posterior surface that is greater than the surface lubricity of the anterior surface of the coated contact lens; and the coated contact lens has a water break-up time of at least about 10 seconds measured on the anterior and posterior surfaces of the coated contact lens.

[0088] A preformed contact lens can be any contact lens that has not undergone any surface treatment after being manufactured according to any lens manufacturing process, any contact lens that has been plasma-treated or treated with chemical or physical surface modification, or any commercially available contact lens, as long as there is no hydrogel coating on the surface of the preformed contact lens.Those skilled in the art are very familiar with how to manufacture preformed contact lenses.Those skilled in the art are very familiar with how to manufacture preformed contact lenses.For example, preformed contact lenses can be manufactured in a conventional "spin-casting mold," as described in U.S. Pat. No. 3,408,429, or by a static full-cast molding process, as described in U.S. Pat. Nos. 4,347,198, 5,508,317, 5,583,463, 5,789,464, and 5,849,810, or by lathe cutting of a button of polymer material, as used to manufacture customized contact lenses. In cast molding, a polymerizable composition (i.e., lens formulation) is typically dispensed into a mold and allowed to cure (i.e., polymerize and / or crosslink) within the mold to produce a contact lens.

[0089] Lens molds for producing contact lenses are well known to those skilled in the art and are used, for example, for cast molding or spin casting. For example, a mold (for cast molding) generally includes at least two mold pieces (or portions) or mold halves, i.e., a first and a second mold half. The first mold half defines a first molding (or optical) surface, and the second mold half defines a second molding (or optical) surface. The first and second mold halves are configured to receive each other such that a lens-forming cavity is formed between the first and second molding surfaces. The molding surfaces of the mold halves are the cavity-forming surfaces of the mold and are in direct contact with the polymerizable composition.

[0090] Methods for manufacturing mold sections for cast molding contact lenses are generally well known to those skilled in the art. The method of the present invention is 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 lathing. Examples of suitable processes for forming mold halves are disclosed in U.S. Patent Nos. 4,444,711, 4,460,534, 5,843,346, and 5,894,002.

[0091] Virtually any material known in the art for producing molds can be used to produce molds for producing contact lenses. For example, polymeric materials such as polyethylene, polypropylene, polystyrene, PMMA, Topas® COC grade 8007-S10 (a transparent amorphous copolymer of ethylene and norbornene, manufactured by Ticona GmbH, Frankfurt, Germany and Summit, New Jersey) can be used. Other materials that allow UV light transmission, such as quartz glass and sapphire, could also be used.

[0092] In accordance with the present invention, the polymerizable composition can be introduced (dispensed) into the cavity formed by the mold by any known method.

[0093] After the polymerizable composition is dispensed into the mold, it is polymerized to produce the contact lens. Crosslinking can be initiated thermally or, preferably, by actinic radiation by exposing the polymerizable composition in the mold to spatial confinement of actinic radiation to crosslink the polymerizable components in the polymerizable composition.

[0094] Opening the mould so that the moulded article can be removed from the mould can be done in a manner known per se.

[0095] The molded contact lenses can be subjected to lens extraction to remove unpolymerized polymerizable components. The extraction solvent can be any solvent known to those skilled in the art. Examples of suitable extraction solvents are described below.

[0096] In a preferred embodiment, the preformed contact lens is a hard contact lens comprising a hard plastic material as the bulk material of the lens. Preferably, the hard plastic material is crosslinked polymethyl acrylate. Those skilled in the art are familiar with methods for producing hard plastic materials, such as crosslinked polymethyl methacrylate.

[0097] In another preferred embodiment, the preformed contact lens is a rigid gas permeable contact lens that includes a rigid gas permeable material as the lens bulk material. Those skilled in the art know how to make rigid gas permeable contact lenses.

[0098] In another preferred embodiment, the preformed contact lens is a hybrid contact lens and includes a lens bulk material consisting essentially of a central optic made of a gas permeable lens material and a peripheral portion made of a silicone hydrogel or conventional hydrogel lens material, extending outward from and surrounding the central optic.

[0099] In another preferred embodiment, the preformed contact lenses are non-silicone hydrogel contact lenses (ie, so-called conventional hydrogel contact lenses) that include a non-silicone hydrogel material as the lens bulk material.

[0100] Preformed non-silicone hydrogel contact lenses can be any commercially available non-silicone hydrogel contact lens or can be made according to any known method. For example, for the production of preformed non-silicone hydrogel contact lenses, a non-silicone hydrogel lens formulation (polymerizable composition) for making rods for cast molding or spin casting or for use in lathe cutting of contact lenses typically comprises (1) (a) at least one hydrophilic vinyl monomer (e.g., hydroxyethyl methacrylate, glycerol methacrylate, N-vinylpyrrolidone, or a combination thereof), and (b) a crosslinker, a hydrophobic vinyl monomer, a lubricant (or a so-called internal wetting agent incorporated into the lens formulation), a free radical initiator (photoinitiator or thermal initiator), a UV-absorbing vinyl monomer, a high-energy violet light ("HEVL")-absorbing vinyl monomer, a visible colorant (e.g., a reactive or (2) an aqueous solution comprising one or more water-soluble prepolymers and at least one component selected from the group consisting of a hydrophilic vinyl monomer, a crosslinker, a hydrophobic vinyl monomer, a lubricant (or a so-called internal wetting agent incorporated into the lens formulation), a free-radical initiator (photoinitiator or thermal initiator), a UV-absorbing vinyl monomer, an HEVL-absorbing vinyl monomer, a visible colorant (e.g., a reactive dye, a polymerizable dye, a pigment, or a mixture thereof), an antimicrobial agent (e.g., preferably silver nanoparticles), a bioactive agent, and combinations thereof. The resulting preformed hydrogel contact lens can then be subjected to extraction with an extraction solvent to remove unpolymerized components from the resulting lens and a hydration process, as known to those skilled in the art. It is understood that the presence of a lubricant in a hydrogel lens formulation can improve the lubricity of a preformed hydrogel contact lens compared to the lubricity of a control preformed hydrogel contact lens obtained from a control hydrogel lens formulation without the lubricant.

[0101] Preferred examples of water-soluble prepolymers include, but are not limited to, the water-soluble cross-linkable poly(vinyl alcohol) prepolymers described in U.S. Pat. Nos. 5,583,163 and 6,303,687.

[0102] Numerous non-silicone hydrogel lens formulations have been described in numerous patents and patent applications published as of the filing date of this application and have been used to produce commercially available non-silicone hydrogel contact lenses. Examples of commercially available non-silicone hydrogel contact lenses include, without limitation, alphafilcon A, acofilcon A, deltafilcon A, etafilcon A, focofilcon A, herfilcon A, herfilcon B, hylafilcon B, hyoxifilcon A, hyoxifilcon B, hyoxifilcon D, metafilcon A, metafilcon B, nelfilcon A, nesofilcon A, ocfilcon A, ocfilcon B, ocfilcon C, ocfilcon D, omafilcon A, femfilcon A, polymacon, sanfilcon A, terfilcon A, tetrafilcon A, and bifilcon A.

[0103] In a preferred embodiment, the lens bulk material is comprised of a non-silicone hydrogel material containing at least 50 mole percent repeat units of at least one hydroxyl-containing vinyl monomer, preferably selected from the group consisting of hydroxyethyl (meth)acrylate, glycerol (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-amino-2-hydroxypropyl (meth)acrylate, N-2-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, vinyl alcohol, allyl alcohol, and combinations thereof, more preferably selected from the group consisting of hydroxyethyl (meth)acrylate, glycerol (meth)acrylate, and vinyl alcohol. The mole percentage of repeat units can be calculated based on the non-silicone hydrogel lens formulation for producing the non-silicone hydrogel contact lens.

[0104] In another preferred embodiment, the preformed contact lens is a silicone hydrogel contact lens that includes a silicone hydrogel material as the lens bulk material.

[0105] Preformed silicone hydrogel contact lenses can be any commercially available silicone hydrogel contact lens or can be produced according to any known method. For example, in the production of preformed silicone hydrogel (SiHy) contact lenses, the SiHy lens formulation for making SiHy rods used in casting or spin-casting or lathe-cutting contact lenses typically contains at least one component selected from the group consisting of silicone-containing vinyl monomers, polysiloxane vinyl crosslinkers, silicone-containing prepolymers, hydrophilic vinyl monomers, hydrophobic vinyl monomers, non-silicone vinyl crosslinkers, free-radical initiators (photoinitiators or thermal initiators), silicone-containing prepolymers, and combinations thereof, as known to those skilled in the art. The resulting preformed SiHy contact lens can then be extracted with an extraction solvent to remove unpolymerized components from the resulting lens and subjected to a hydration process, as known to those skilled in the art.

[0106] According to the present invention, the silicone-containing (for example, siloxane-containing) vinyl monomer can be any silicone-containing vinyl monomer known to those skilled in the art.Examples of preferred silicone-containing vinyl monomers include, but are not limited to, vinyl monomers having bis(trialkylsilyloxy) alkylsilyl groups (preferably bis(trimethylsilyloxy) alkylsilyl groups) or tris(trialkylsilyloxy) silyl groups (preferably tris(trimethylsilyloxy) silyl groups), polysiloxane vinyl monomers, 3-methacryloxypropylpentamethyldisiloxane, t-butyldimethylsiloxyethyl vinyl carbonate, trimethylsilylethyl vinyl carbonate, trimethylsilylmethyl vinyl carbonate, and combinations thereof.

[0107] Examples of preferred siloxane-containing vinyl monomers having a bis(trialkylsilyloxy)alkylsilyl group or a tris(trialkylsilyloxy)silyl group, respectively, include, but are not limited to, tris(trimethylsilyloxy)-silylpropyl(meth)acrylate, [3-(meth)acryloxy-2-hydroxypropyloxy]propyl-bis(trimethylsiloxy)-methylsilane, [3-(meth)acryloxy-2-hydroxypropyloxy]propyl-bis(trimethylsiloxy)butylsilane, 3-(meth)acryloyl ... Oxy-2-(2-hydroxyethoxy)-propyloxy)propyl-bis(trimethylsiloxy)methylsilane, 3-(meth)acryloxy-2-hydroxypropyloxy)propyltris(trimethylsiloxy)silane, N-[tris(trimethylsiloxy)-silylpropyl]-(meth)acrylamide, N-(2-hydroxy-3-(3-(bis(trimethylsilyloxy)methylsilyl)propyloxy)-propyl)-2-methyl(meth)acrylamide, N-(2-hydroxy-3-(3-(bis(trimethylsilyloxy)methylsilyl)propyloxy)-propyl)-2-methyl(meth)acrylamide N-(2-hydroxy-3-(3-(tris(trimethylsilyloxy)silyl)propyloxy)propyl)-2-methylacrylamide, N-(2-hydroxy-3-(3-(tris(trimethylsilyloxy)silyl)propyloxy)propyl)(meth)acrylamide, N-[tris(dimethylpropylsiloxy)silylpropyl](meth)acrylamide, N-[tris(dimethylphenylsiloxy)silylpropyl](meth)acrylamide, N-[tris(di N,N-bis[2-hydroxy-3-(3-(bis(trimethylsilyloxy)methylsilyl)propyloxy)propyl]-2-methyl(meth)acrylamide, N,N-bis[2-hydroxy-3-(3-(bis(trimethylsilyloxy)methylsilyl)propyloxy)propyl](meth)acrylamide, N,N-bis[2-hydroxy-3-(3-(tris(trimethylsilyloxy)silyl)propyloxy)propyl]-2-methyl(meth)acrylamide, N,N-bis[2-hydroxy-3-(3-(tris(trimethylsilyloxy)silyl)propyloxy)propyl](meth)acrylamide, N-[2-hydroxy-3-(3-(t-butyldimethylsilyl)propyloxy)propyl]-2-methyl(meth)acrylamide, N-[2-hydroxy-3-(3-(t-butyldimethylsilyl)propyloxy)propyl](meth)acrylamide, N,N-bis[2-hydroxy-3-(3-(t-butyldimethylsilyl)propyloxy)propyl]-2-methyl(meth)acrylamide, N-2-(meth)acryloxyethyl-O-(methyl-bis 3-(trimethylsiloxy-3-propyl)silyl carbamate, 3-(trimethylsilyl)propyl vinyl carbonate, 3-(vinyloxycarbonylthio)propyl-tris(trimethylsiloxy)silane, 3-[tris(trimethylsiloxy)silyl]propyl vinyl carbamate, 3-[tris(trimethylsiloxy)silyl]propyl allyl carbamate, 3-[tris(trimethylsiloxy)silyl]propyl vinyl carbonate, those disclosed in U.S. Pat. Nos. 9,097,840, 9,103,965, and 9,475,827, and mixtures thereof. The preferred silicone-containing vinyl monomers can be obtained from commercial sources or prepared according to the procedures described in U.S. Pat. Nos. 5,070,215, 6,166,236, 6,867,245, 7,214,809, 8,415,405, 8,475,529, 8,614,261, 8,658,748, 9,097,840, 9,103,965, 9,217,813, 9,315,669, and 9,475,827.

[0108] Examples of preferred polysiloxane vinyl monomers include, but are not limited to, mono-(meth)acryloyl-terminated, mono-alkyl-terminated polysiloxanes of formula (I), including, but not limited to, α-(meth)acryloylpropyl-terminated, ω-butyl (or ω-methyl)-terminated polydimethylsiloxane, α-(meth)acryloxy-2-hydroxypropyloxypropyl-terminated, ω-butyl (or ω-methyl)-terminated polydimethylsiloxane, α-(2-hydroxy-methacryloxypropyloxypropyl)-ω-butyl- Decamethylpentasiloxane, α-[3-(meth)acryloxyethoxy-2-hydroxypropyloxypropyl]-terminated ω-butyl (or ω-methyl) polydimethylsiloxane, α-[3-(meth)acryloxy-propyloxy-2-hydroxypropyloxypropyl]-terminated ω-butyl (or ω-methyl) polydimethylsiloxane, α-[3-(meth)acryloxyisopropyloxy-2-hydroxypropyloxypropyl]-terminated ω-butyl (or ω-methyl) polydimethylsiloxane, α-[3-(meth)acrylo α-[3-(meth)acryloxy-ethylamino-2-hydroxypropyloxypropyl]-terminated ω-butyl (or ω-methyl) polydimethylsiloxane, α-[3-(meth)acryloxy-ethylamino-2-hydroxypropyloxypropyl]-terminated ω-butyl (or ω-methyl) polydimethylsiloxane, α-[3-(meth)acryloxypropylamino-2-hydroxypropyloxypropyl]-terminated ω-butyl (or ω-methyl) polydimethylsiloxane, α-[3-(meth)acryloxy-butylamino-2-hydroxypropyloxypropyl]-terminated ω-butyl (or ω-methyl) polydimethylsiloxane ]-terminated ω-butyl (or ω-methyl)-terminated polydimethylsiloxane, α-(meth)acryloxy(polyethyleneoxy)-2-hydroxypropyloxypropyl]-terminated ω-butyl (or ω-methyl)-terminated polydimethylsiloxane, α-[(meth)acryloxy-2-hydroxypropyloxyethoxypropyl]-terminated ω-butyl (or ω-methyl)-terminated polydimethylsiloxane, α-[(meth)acryloxy-2-hydroxypropyl-N-ethylaminopropyl]-terminated ω-butyl (or ω-methyl)-terminated polydimethylsiloxane,α-[(meth)acryloxy-2-hydroxypropylaminopropyl]-terminated ω-butyl (or ω-methyl) polydimethylsiloxane, α-[(meth)acryloxy-2-hydroxypropyloxy-(polyethyleneoxy)propyl]-terminated ω-butyl (or ω-methyl) polydimethylsiloxane, α-(meth)acryloylamidopropyloxypropyl-terminated ω-butyl (or ω-methyl) polydimethylsiloxane, α-N-methyl-(meth)acryloylamidopropyloxypropyl-terminated ω-butyl (or ω-methyl) ) terminated polydimethylsiloxane, α-[3-(meth)acrylamidoethoxy-2-hydroxypropyloxypropyl]-terminated ω-butyl (or ω-methyl) terminated polydimethylsiloxane, α-[3-(meth)acrylamidopropyloxy-2-hydroxypropyloxypropyl]-terminated ω-butyl (or ω-methyl) terminated polydimethylsiloxane, α-[3-(meth)acrylamidoisopropyloxy-2-hydroxypropyloxypropyl]-terminated ω-butyl (or ω-methyl) terminated polydimethylsiloxane, α-[3-( [meth)acrylamidobutyloxy-2-hydroxypropyloxypropyl]-terminated ω-butyl (or ω-methyl) polydimethylsiloxane, α-[3-(meth)acryloylamido-2-hydroxypropyloxypropyl]-terminated ω-butyl (or ω-methyl) polydimethylsiloxane, α-[3-[N-methyl-(meth)acryloylamido]-2-hydroxypropyloxypropyl]-terminated ω-butyl (or ω-methyl) polydimethylsiloxane, N-methyl-N'-(propyltetra(dimethylsiloxy)dimethylbutyl) methylsilane)(meth)acrylamide, N-(2,3-dihydroxypropane)-N'-(propyltetra(dimethylsiloxy)dimethylbutylsilane)(meth)acrylamide, (meth)acryloylamide-propyltetra(dimethylsiloxy)dimethylbutylsilane, monovinyl carbonate-terminated monoalkyl-terminated polydimethylsiloxane, monovinyl carbamate-terminated monoalkyl-terminated polydimethylsiloxane, those disclosed in U.S. Pat. Nos. 9,097,840 and 9,103,965, and mixtures thereof. Preferred polysiloxane vinyl monomers include:They can be obtained from commercial sources (e.g., Shin-Etsu Chemical, Gelest, etc.) or can be prepared according to procedures described, for example, in U.S. Patent Application Publication Nos. 6,166,236, 6,867,245, 8,415,405, 8,475,529, 8,614,261, 9,217,813, and 9,315,669, or by coupling hydroxyalkyl (meth)acrylates or (meth)acrylamides or (meth)acrylamides according to coupling reactions well known to those skilled in the art. ) can be prepared by reacting acryloxypolyethylene glycol with monoepoxypropyloxypropyl-terminated polydimethylsiloxane, or by reacting glycidyl (meth)acrylate with monocarbinol-terminated polydimethylsiloxane, monoaminopropyl-terminated polydimethylsiloxane, or monoethylaminopropyl-terminated polydimethylsiloxane, or by reacting isocyanatoethyl (meth)acrylate with monocarbinol-terminated polydimethylsiloxane.

[0109] In accordance with the present invention, any polysiloxane vinyl crosslinker can be used in the present invention. Examples of suitable polysiloxane vinyl crosslinkers include, but are not limited to, α,ω-(meth)acryloxy-terminated polydimethylsiloxanes of various molecular weights; α,ω-(meth)acrylamide-terminated polydimethylsiloxanes of various molecular weights; α,ω-vinyl carbonate-terminated polydimethylsiloxanes of various molecular weights; α,ω-vinyl carbamate-terminated polydimethylsiloxanes of various molecular weights; bis-3-methacryloxy-2-hydroxypropyloxypropyl polydimethylsiloxanes of various molecular weights; N,N,N',N'-tetrakis(3-methacryloxy-2-hydroxypropyl)-alpha,omega-bis-3-aminopropyl-polydimethylsiloxanes of various molecular weights. reaction products of glycidyl methacrylate and diamino-terminated polydimethylsiloxane; reaction products of glycidyl methacrylate and dihydroxy-terminated polydimethylsiloxane; reaction products of an azlactone-containing vinyl monomer (any one of the above) and dihydroxy-terminated polydimethylsiloxane; reaction products of isocyanatoethyl (meth)acrylate and dihydroxyl-terminated polydimethylsiloxane; reaction products of isocyanatoethyl (meth)acrylate and diamino-terminated polydimethylsiloxane; polysiloxane-containing macromers selected from the group consisting of Macromer A, Macromer B, Macromer C, and Macromer D described in U.S. Pat. No. 5,760,100;U.S. Patent Nos. 4,136,250, 4,153,641, 4,182,822, 4,189,546, 4,259,467, 4,260,725, 4,261,875, 4,343,927, 4,254,248, 4,355,147, 4,276,402, 4,327,203, and 4,341,889 Specification No. 4486577, Specification No. 4543398, Specification No. 4605712, Specification No. 4661575, Specification No. 4684538, Specification No. 4703097, Specification No. Specification No. 4833218, Specification No. 4837289, Specification No. 4954586, Specification No. 4954587, Specification No. 5010141, Specification No. 5034461, Specification No. 50701 Specification No. 70, Specification No. 5079319, Specification No. 5039761, Specification No. 5346946, Specification No. 5358995, Specification No. 5387632, Specification No. 5416132 , Specification No. 5449729, Specification No. 5451617, Specification No. 5486579, Specification No. 5962548, Specification No. 5981675, Specification No. 6039913, Specification No. 676 2264, 7423074, 8163206, 8480227, 8529057, 8835525, 8993651, 9187601, 10081697, 10301451, and 10465047;

[0110] One class of preferred polysiloxane vinyl crosslinkers are those prepared by reacting glycidyl (meth)acrylate or (meth)acryloyl chloride with diamino- or dihydroxyl-terminated polydimethylsiloxanes, or by reacting isocyanatoethyl (meth)acrylate with dihydroxyl-terminated polydimethylsiloxanes, or by reacting amino-containing acrylic monomers with dicarboxyl-terminated polydimethylsiloxanes in the presence of a coupling agent (carbodiimide), or by reacting carboxyl-containing acrylic monomers with diamino-terminated polydimethylsiloxanes in the presence of a coupling agent (carbodiimide), or by reacting hydroxyl-containing acrylic monomers with dihydroxyl-terminated polydisiloxanes in the presence of a diisocyanate or diepoxy coupling agent.

[0111] Examples of such preferred polysiloxane vinyl crosslinkers are α,ω-bis[3-(meth)acrylamidopropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acryloxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acryloxy-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acryloxyethoxy-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acryloxy propyloxy-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acryloxy-isopropyloxy-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acryloxybutyloxy-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acrylamidoethoxy-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acrylamide [Acrylamidopropyloxy-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acrylamidoisopropyloxy-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acrylamidobutyloxy-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acrylamidobutyloxy-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acryloxyethylamino-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane, α,ω-bis [3-(meth)acryloxypropylamino-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acryloxybutylamino-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane, α,ω-bis[(meth)acrylamidoethylamino-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acrylamidopropylamino-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acrylamido-butylamino-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane, α,ω-bis[(meth)acryloxy-2-hydroxypropyloxy-ethoxypropyl]-terminated polydimethylsiloxane, α,ω-bis[(meth)acryloxy-2-hydroxypropyl-N-ethylaminopropyl]-terminated polydimethylsiloxane, α,ω-bis[(meth)acryloxy-2-hydroxypropyl-aminopropyl]-polydimethylsiloxane, α,ω-bis[(meth)acryloxy-2-hydroxypropyloxy-(polyethyleneoxy)propyl]-terminated polydimethylsiloxane, α,ω-bis[(meth)acryloxyethylamino-carbonyloxy-ethoxypropyl]-terminated polydimethylsiloxane, α,ω-bis[(meth)acryloxyethylamino-carbonyloxy-(polyethyleneoxy)propyl]-terminated polydimethylsiloxane, and mixtures thereof.

[0112] Another class of preferred polysiloxane vinyl crosslinkers are chain-extended polysiloxane vinyl crosslinkers, each containing at least two polysiloxane segments, which can be prepared according to the procedures described in U.S. Pat. Nos. 5,034,461, 5,416,132, 5,449,729, 5,760,100, 7,423,074, 8,529,057, 8,835,525, 8,993,651, and 10,301,451, and U.S. Patent Application Publication No. 2018-0100038A1.

[0113] A further class of preferred polysiloxane vinyl crosslinkers are hydrophilized polysiloxane vinyl crosslinkers each containing at least about 1.50 (preferably at least about 2.0, more preferably at least about 2.5, and even more preferably at least about 3.0) milliequivalents per gram ("meq / g") of hydrophilic moieties, the hydrophilic moieties preferably being hydroxyl (-OH), carboxyl (-COOH), amino (-NHR) groups, or the like. N1 , R N1is H or C1-C2 alkyl), amide moiety (-CO-NR N1 R N2 , R N1 is H or C1-C2 alkyl, and R N2 represents a covalent bond, H, or C1-C2 alkyl), N-C1-C3 acylamino group, urethane moiety (-NH-CO-O-), urea moiety (-NH-CO-NH-), [ka] (n is an integer of 2 to 20, and T1 is H, methyl, or acetyl), or a phosphorylcholine group, or a combination thereof.

[0114] An example of such a preferred hydrophilized polysiloxane vinyl crosslinker is a compound of formula (1): [ka] is a compound of the formula υ1 is an integer of 30 to 500, and ω1 is an integer of 1 to 75, provided that ω1 / υ1 is about 0.035 to about 0.15 (preferably about 0.040 to about 0.12, and even more preferably about 0.045 to about 0.10); X 01 is O or NR n where R n is hydrogen or C1-C 10 - is alkyl; R o is hydrogen or methyl; R2 and R3 are each independently a substituted or unsubstituted C1-C 10 an alkylene divalent radical or a divalent radical of -R5-O-R6-, where R5 and R6 are each independently a substituted or unsubstituted C1-C 10 is an alkylene divalent radical; R4 is a monovalent radical of any one of formulas (2) to (7), [ka] p1 is zero or 1; m1 is an integer from 2 to 4; m2 is an integer from 1 to 5; m3 is an integer from 3 to 6; m4 is an integer from 2 to 5; R7 is hydrogen or methyl; R8 is a C2-C6 hydrocarbon radical having a valence of (m2+1); R9 is a C2-C6 hydrocarbon radical having a valence of (m4+1); R 10 is ethyl or hydroxymethyl; R 11 is methyl or hydromethyl; R 12 is hydroxyl or methoxy; X3 is a sulfur bond of -S- or -NR 13 - is a tertiary amino bond, where R 13 is C1-C1 alkyl, hydroxyethyl, hydroxypropyl, or 2,3-dihydroxypropyl; X4 is [ka] is an amide bond, and R 14 is hydrogen or C1-C 10 is alkyl, L PC is -CH2-CHR0-R 15 -, C3H6-OR 16 -, [ka] where q1 is an integer from 1 to 20, and R 15 is a straight or branched chain C1 to C 10 is an alkylene divalent radical, R 16 is a straight or branched chain C3 to C 10 is an alkylene divalent radical, R 17 is a direct bond or a straight or branched C1-C4 alkylene divalent radical.

[0115] The hydrophilized polysiloxane vinyl crosslinker of formula (1) can be prepared according to the procedures disclosed in US Patent No. 10,081,697 and US Patent Application Publication No. 2022-0251302 A1.

[0116] Any hydrophilic vinyl monomer can be used in the present invention. Examples of preferred hydrophilic vinyl 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), carboxyl-containing acrylic monomers (as described later in this application), N-vinylamide 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 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 vinyl monomers (as described later in this application), N-2-hydroxyethyl vinyl carbamate, N-carboxyvinyl-β-alanine (VINAL), N-carboxyvinyl-α-alanine, and combinations thereof.

[0117] According to the present invention, any hydrophobic vinyl monomer can be included in the present invention.Examples of preferred hydrophobic vinyl monomers include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl valerate, styrene, chloroprene, vinyl chloride, vinylidene chloride, (meth)acrylonitrile, 1-butene, butadiene, vinyl toluene, vinyl ethyl ether, perfluorohexylethyl-thio-carbonyl-aminoethyl-methacrylate, isobornyl (meth)acrylate, trifluoroethyl (meth)acrylate, hexafluoroisopropyl (meth)acrylate, hexafluorobutyl (meth)acrylate, and combinations thereof.

[0118] In accordance with the present invention, any non-silicone vinyl crosslinker may be within the scope of the present invention. Examples of preferred non-silicone vinyl crosslinkers are described later in this application.

[0119] Any thermal polymerization initiator can be used in the present invention. Suitable thermal polymerization initiators are known to those skilled in the art and include, for example, peroxides, hydroperoxides, azo-bis(alkyl- or cycloalkylnitriles), persulfates, percarbonates, or mixtures thereof.Examples of suitable thermal polymerization initiators include, without limitation, benzoyl peroxide, t-butyl peroxide, t-amyl peroxybenzoate, 2,2-bis(tert-butylperoxy)butane, 1,1-bis(tert-butylperoxy)cyclohexane, 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane, 2,5-bis(tert-butylperoxy)-2,5-dimethyl-3-hexyne, bis(1-(tert-butylperoxy)-1-methylethyl)benzyl, 2,2-bis(tert-butylperoxy)butane, 1,1-bis(tert-butylperoxy)cyclo ...2,2-bis(tert-butylperoxy)butane, 2,2-bis(tert-butylperoxy)butane, 2,2-bis(tert-butylperoxy)butane, 2,2-bis(tert-butylperoxy)butane, 2,2-bis(tert-butylperoxy)butane, 2,2-bis(tert-butylperoxy)butane Benzene, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, di-t-butyl-diperoxyphthalate, t-butyl hydroperoxide, t-butyl peracetate, t-butyl peroxybenzoate, t-butyl peroxyisopropyl carbonate, acetyl peroxide, lauroyl peroxide, decanoyl peroxide, dicetyl peroxydicarbonate, di(4-t-butylcyclohexyl) peroxydicarbonate (Perkadox 16S), 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).

[0120] Suitable photoinitiators are benzoin methyl ether, diethoxyacetophenone, benzoylphosphine oxide, 1-hydroxycyclohexylphenyl ketone, and Darocur and Irgacur types, preferably Darocur 1173® and Darocur 2959®, germanium-based Norrish Type I photoinitiators (e.g., those described in U.S. Pat. No. 7,605,190). Examples of benzoylphosphine initiators include 2,4,6-trimethylbenzoyldiphenylphosphine oxide; bis-(2,6-dichlorobenzoyl)-4-N-propylphenyl-phosphine oxide; and bis-(2,6-dichlorobenzoyl)-4-N-butylphenylphosphine oxide.

[0121] The SiHy contact lens formulations may also include other necessary ingredients known to those skilled in the art, such as, for example, UV-absorbing vinyl monomers, HEVL-absorbing vinyl monomers, visibility colorants (e.g., reactive dyes, polymeric dyes, pigments, or mixtures thereof known to those skilled in the art), antimicrobial agents (e.g., preferably silver nanoparticles), bioactive agents, leachable lubricants (e.g., non-polymeric hydrophilic polymers, etc.), leachable tear stabilizing agents (e.g., phospholipids, monoglycerides, diglycerides, triglycerides, glycolipids, glyceroglycolipids, sphingolipids, glycosphingolipids, etc.), and mixtures thereof.

[0122] The polymerizable composition (SiHy lens formulation), as known to those skilled in the art, can be a solvent-free clear liquid prepared by mixing all of the polymerizable components and other required ingredients, or a solution prepared by dissolving all of the desired components in any suitable solvent, such as a mixture of water and one or more organic solvents miscible with water, an organic solvent, or a mixture of one or more organic solvents. The term "solvent" refers to a chemical that cannot participate in a free-radical polymerization reaction.

[0123] Solvent-free SiHy lens formulations typically include at least one blending vinyl monomer as a reactive solvent to dissolve all other polymerizable components of the solvent-free SiHy lens formulation. Examples of preferred blending vinyl monomers are described later in this application. Preferably, methyl methacrylate is used as the blending vinyl monomer in preparing the solvent-free SiHy lens formulation.

[0124] Any solvent can be used in the present invention. Examples of preferred organic solvents include, but are not limited to, tetrahydrofuran, tripropylene glycol methyl ether, dipropylene glycol methyl ether, ethylene glycol n-butyl ether, ketones (e.g., acetone, methyl ethyl ketone, etc.), diethylene glycol n-butyl ether, diethylene glycol methyl ether, ethylene glycol phenyl ether, propylene glycol methyl ether, propylene glycol methyl ether acetate, dipropylene glycol methyl ether acetate, propylene glycol n-propyl ether, dipropylene glycol n-propyl ether, tripropylene glycol n-butyl ether, propylene glycol n-butyl ether, dipropylene glycol n-butyl ether, tripropylene glycol n-butyl ether, ... phenyl ether, dipropylene glycol dimethyl ether, polyethylene glycol, polypropylene glycol, ethyl acetate, butyl acetate, amyl acetate, methyl lactate, ethyl lactate, i-propyl lactate, methylene chloride, 2-butanol, 1-propanol, 2-propanol, menthol, cyclohexanol, cyclopentanol and exonorborneol, 2-pentanol, 3-pentanol, 2-hexanol, 3-hexanol, 3-methyl-2-butanol, 2-heptanol, 2-octanol, 2-nonanol, 2-decanol, 3-octanol, norborneol, tert-butanol, tert-amyl alcohol, 2-methyl-2-pentanol, 2,3-dimethyl-2-butanol, 3-methyl-3-pentanol, 1-methylcyclohexanol, 2-methyl-2-hexanol, 3,7-Dimethyl-3-octanol, 1-chloro-2-methyl-2-propanol, 2-methyl-2-heptanol, 2-methyl-2-octanol, 2-2-methyl-2-nonanol, 2-methyl-2-decanol, 3-methyl-3-hexanol, 3-methyl-3-heptanol, 4-methyl-4-heptanol, 3-methyl-3-octanol, 4-methyl-4-octanol, 3-methyl-3-nonanol, 4-methyl-4-nonanol, 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 Examples of suitable solvents include ethanol, 1-ethylcyclopentanol, 1-ethylcyclopentanol, 3-hydroxy-3-methyl-1-butene, 4-hydroxy-4-methyl-1-cyclopentanol, 2-phenyl-2-propanol, 2-methoxy-2-methyl-2-propanol, 2,3,4-trimethyl-3-pentanol, 3,7-dimethyl-3-octanol, 2-phenyl-2-butanol, 2-methyl-1-phenyl-2-propanol, and 3-ethyl-3-pentanol, 1-ethoxy-2-propanol, 1-methyl-2-pyrrolidone, N,N-dimethylpropionamide, dimethylformamide, dimethylacetamide, dimethylpropionamide, N-methylpyrrolidone, and mixtures thereof.

[0125] Numerous SiHy lens formulations have been described in numerous patents and patent applications published as of the filing date of this application and have been used in producing commercially available SiHy contact lenses. Examples of commercially available SiHy contact lenses include, without limitation, asmofilcon A, balafilcon A, confilcon A, derefilcon A, eflofilcon A, enfilcon A, funfilcon A, galyfilcon A, lotrafilcon A, lotrafilcon B, narafilcon A, narafilcon B, senofilcon A, senofilcon B, senofilcon C, sumafilcon A, somofilcon A, and stenfilcon A.

[0126] The SiHy lens formulation (i.e., polymerizable composition) can be cured (polymerized) thermally or by actinic radiation as known to those skilled in the art, preferably in a mold for casting contact lenses.

[0127] Thermal polymerization is conveniently carried out at temperatures of, for example, 25 to 120°C, preferably 40 to 100°C. The reaction time may vary within wide limits but is conveniently, for example, 1 to 24 hours, or preferably 2 to 12 hours. It is advantageous to previously degas the components and solvents used in the polymerization reaction and to carry out the copolymerization reaction under an inert atmosphere, for example under a nitrogen or argon atmosphere.

[0128] The actinic polymerization can then be induced by actinic radiation, such as light, in particular UV or visible light of a suitable wavelength, the spectral requirements of which can be suitably controlled, if appropriate, by the addition of suitable photosensitizers.

[0129] In accordance with the present invention, the lens formulation can be introduced (dispensed) into the cavity formed by the mold according to any known method.

[0130] After the lens formulation is dispensed into the mold, it is polymerized to produce a contact lens. Polymerization can be initiated thermally or chemically, preferably by exposing the lens formulation in the mold to spatially confined actinic radiation to crosslink polymerizable components in the lens formulation.

[0131] Opening the mould so that the moulded article can be removed from the mould can be done in a manner known per se.

[0132] The molded contact lenses can be subjected to lens extraction to remove unpolymerized polymerizable components. The extraction solvent can be any solvent known to those skilled in the art. Examples of suitable extraction solvents are described above.

[0133] The preformed contact lenses of the present invention can be obtained according to any method known to or to be developed by those skilled in the art.

[0134] In accordance with the present invention, preformed contact lenses inherently contain or are modified to contain first reactive functional groups on and near their surfaces.

[0135] When a preformed contact lens originally contains first reactive functional groups on or near its surface, they can be obtained by polymerizing a polymerizable composition (i.e., a non-silicone hydrogel lens formulation or a silicone hydrogel lens formulation) containing a reactive vinyl monomer (which further contains at least one first reactive functional group selected from the group consisting of, for example, a carboxyl group, an amino group, a primary amino group, a secondary amino group, and combinations thereof). Examples of carboxyl- and amino-containing vinyl monomers are known in the art and can be obtained from commercial sources or prepared according to known procedures. The lens formulation preferably contains from about 1.0% to about 10% by weight, more preferably from about 2.0% to about 7% by weight, and even more preferably from about 2.0% to about 5% by weight of such a vinyl monomer having at least one first reactive functional group.

[0136] According to the present invention, any carboxyl-containing vinyl monomer can be added to the polymerizable composition. Preferred examples of carboxyl-containing vinyl monomers are carboxyl-containing (meth)acryloxy monomers, which preferably include, but are not limited to, acrylic acid, methacrylic acid, ethylacrylic acid, propyacrylic acid, (meth)acryloxyacetic acid, mono-2-[(meth)acryloxy]ethyl succinate, (meth)acryloxypropanoic acid, (meth)acryloxybutanoic acid, and combinations thereof.

[0137] According to the present invention, any amino-containing vinyl monomer can be added to polymerizable composition.Preferred amino-containing vinyl monomer example is amino-containing (meth)acryloxy monomer, which preferably includes but is not limited to N-2-aminoethyl (meth)acrylamide, N-2-methylaminoethyl (meth)acrylamide, N-2-ethylaminoethyl (meth)acrylamide, N-3-aminopropyl (meth)acrylamide, N-3-methylaminopropyl (meth)acrylamide, 2-aminoethyl (meth)acrylate, 2-methylaminoethyl (meth)acrylate, 2-ethylaminoethyl (meth)acrylate, 3-aminopropyl (meth)acrylate, 3-methylaminopropyl (meth)acrylate, 3-ethylaminopropyl (meth)acrylate, 3-amino-2-hydroxypropyl (meth)acrylate and combinations thereof.

[0138] If a preformed contact lens naturally contains amino groups on and near its surface, it can be chemically modified by reacting it with a thiolactone to covalently bond a thiol group through the amino group.

[0139] Examples of preferred commercially available thiolactones include, but are not limited to, 4-butyrothiolactone (or dihydro-2(3H)-thiophenone), 3-methyldihydro-2(3H)-thiophenone, 3-ethyldihydro-2(3H)-thiophenone, 3-(1-methylethyl)dihydro-2(3H)-thiophenone, 3,3-dimethyldihydro-2(3H)-thiophenone, 3-ethyl-3-methyldihydro-2(3H)-thiophenone, 3-acetyldihydro-2(3H)-thiophenone, N-acetylhomocysteine ​​thiolactone, N-propionylhomocysteine ​​thiolactone, N-butyrylhomocysteine ​​thiolactone, and N-carboxybutyrylhomocysteine ​​thiolactone (or 4-oxo-4-[(tetrahydro-2-oxo-3-thienyl)amino]-butanoic acid).

[0140] The preformed contact lens can also be subjected to a surface treatment to have first reactive functional groups on or near its surface. Any suitable surface treatment can be used in the present invention. Examples of surface treatments include, but are not limited to, plasma treatment; chemical treatment; chemical vapor deposition; grafting (covalent bonding) of a compound having at least one reactive functional group onto the surface of the article (modified or unmodified); graft polymerization of a vinyl monomer having at least one first reactive functional group onto the surface of the article (modified or unmodified); or combinations thereof.

[0141] Plasma treatment refers to a process in which contact lenses are exposed to plasma to chemically modify their surfaces. The term "plasma" refers to an ionized gas (e.g., produced by an electrical glow discharge, which may consist of electrons, ions of either polarity, gas atoms and molecules in their ground state or any higher state of any form of excitation, and photons). The excited species interact with the solid surface of an article placed in the plasma, resulting in chemical and physical modification of the material surface. When plasma is generated by subjecting a gas to an electric charge, typically at radio frequency (rf) (or microwave or other frequencies), in a vacuum chamber, it is often referred to as "low-temperature plasma." When plasma is generated by an atmospheric discharge (e.g., an arc discharge) and sustained at ambient atmospheric pressure, it is a "high-temperature plasma" or "atmospheric plasma." Atmospheric pressure plasma can be generated by atmospheric pressure discharge.

[0142] For reviews of plasma treatment and its uses, see R. Hartmann, "Plasma polymerisation: Grundlagen, Technik und Anwendung, Jahrb. Oberflaechentechnik (1993) 49, pp. 283-296, Battelle-Inst. eV Frankfurt / Main Germany; H. Yasuda, "Glow Discharge Polymerisation", Journal of Polymer Science: Macromolecular Reviews, vol. 16 (1981), pp. 199-293; H. Yasuda, "Plasma Polymerisation", Academic Press, Inc. (1985); Frank Jansen, "Plasma Deposition Processes", in "Plasma Deposited Thin Films", ed. by T. Mort and F. Jansen, CRC Press Boca Raton (1994); O. Auciello et al. (ed.) "Plasma-Surface Interactions and Processing of Materials", publ. by Kluwer Academic Publishers in NATO ASI Series; Series E: Applied Sciences, vol. 176 (1990), pp. 377-399; and N. Dilsiz and G. Akovali, "Plasma Polymerization of Selected Organic Compounds," Polymer, vol. 37 (1996), pp. 333-341.

[0143] Known plasma treatments under low pressure include plasma deposition, plasma-induced polymerization, plasma grafting, plasma oxidation, etc. Plasma treatment under low pressure has been used in commercial products such as Focus NIGHT & DAY® and AIR OPTIX® (Alcon), and PUREVISION® (Bausch & Lomb). Advantages of plasma coatings, such as those found on Focus NIGHT & DAY®, are their durability, relatively high hydrophilicity / wettability, and low susceptibility to lipid and protein deposition and adsorption. Examples of plasma treatments are those disclosed in U.S. Pat. Nos. 4,143,949; 4,312,575; 5,464,667; 6,881,269; and 7,078,074. It is understood that preformed contact lenses typically must be dried before plasma treatment under low pressure.

[0144] Those skilled in the art are well aware that a plasma (i.e., an electric glow discharge plasma) is a partially ionized gas consisting of a high concentration of excited atomic, molecular, ionic, and free radical species and is produced by subjecting the gas in a vacuum chamber to an electric field, typically at radio frequency (rf) (or at microwave or other frequencies).

[0145] In an illustrative example of low-pressure plasma treatment of silicone hydrogel contact lenses, one or more preformed silicone hydrogel contact lenses are placed in a reactor chamber between opposing electrodes. The chamber is then sealed and depressurized by a vacuum system. A significant amount of time is required to pump the system up to operating pressure. When a suitable pressure is achieved within the chamber, a process gas is introduced into the chamber interior and the electrodes are activated. The resulting plasma cloud may apply a thin layer of polymer (or polymer coating) to the lens and / or alter the chemical composition of the top layer of the lens surface, depending on the process gas used. After a suitable time, the electrodes are turned off and the reactor chamber is returned to atmospheric pressure so that the lens can be removed.

[0146] Low-pressure plasma processing systems are known to those skilled in the art and are disclosed in patents and papers. For example, Peng Ho and Yasuda, in their paper "Ultrathin Coating of Plasma Polymer of Methane Applied on the Surface of Silicone Contact Lenses," Journal of Biomedical Materials Research, Vol. 22, pp. 919-937 (1988)), describe a batch-type low-pressure plasma processing system (or rotary plasma system) including a bell-shaped vacuum chamber in which opposing aluminum electrodes are arranged, with a rotatable aluminum plate disposed between the electrodes and driven by an induction motor within the system. Matsuzawa and Winterton disclose a linear low-pressure plasma system in U.S. Pat. No. 6,881,269.

[0147] In accordance with the present invention, a dry, preformed contact lens is treated with a low pressure plasma generated in a plasma gas (i.e., atmosphere) comprising air, N2, O2, CO2, or a C1-C6 hydrocarbon and air, N2, O2, CO2, or combinations thereof (preferably a mixture of CO2 or a C1-C4 hydrocarbon and a secondary gas selected from the group consisting of air, CO2, N2, and combinations thereof, more preferably a mixture of CO2 or methane and a secondary gas selected from the group consisting of air, CO2, N2, and combinations thereof, even more preferably a mixture of CO2 or methane and CO2).

[0148] The atmospheric plasma surface treatment disclosed in US Patent No. 9,156,213 is preferably used in the present invention. For atmospheric plasma surface treatment, the contact lens can be in a fully hydrated state.

[0149] Those skilled in the art are familiar with methods for grafting (covalently bonding) compounds having at least one first reactive functional group (carboxyl group, amino group, azetidinium group, epoxide group, aziridine group, vinyl sulfone group, thiol group, and combinations thereof) to the surface of a contact lens according to known coupling reactions.

[0150] The graft polymerization of one or more vinyl monomers having at least one first reactive functional group (e.g., carboxyl, amino, azetidinium, epoxide, aziridine groups, and combinations thereof) in the presence or absence of a vinyl crosslinking agent to form a hydrophilic polymer coating has been described in many patents, such as U.S. Pat. Nos. 6,099,122, 6,436,481, 6,440,571, 6,447,920, 6,465,056, 6,521,352, 6,586,038, 6,730,366, 6,734,321, 6,835,410, and 6,878,399, and JP2001075060A. For example, a dry, preformed contact lens is first subjected to plasma treatment in a plasma atmosphere of a compound having at least one reactive functional group (e.g., a primary or secondary amino group, a carboxyl group, an epoxy group, an azlactone group, an aziridine group, or an isocyanate group) to form a plasma coating having reactive functional groups. The plasma-treated contact lens is then reacted with a compound having a free radical initiator site (e.g., a thermal initiator or a photoinitiator) or preferably a living polymerization initiator site (e.g., an atom transfer radical polymerization (ATRP) initiator or a reversible addition-fragmentation chain transfer (RAFT) initiator) and a functional group that co-reacts with the functional groups of the plasma coating on the contact lens, with or without a coupling agent, under coupling reaction conditions known to those skilled in the art. The resulting contact lens having free radical initiator sites thereon is then immersed in a solution of one or more vinyl monomers having at least one first functional group and exposed to conditions that initiate free radical polymerization of the vinyl monomers to form a layer of grafted polymer containing the first reactive functional group.

[0151] Any non-silicone hydrogel material can be used to coat the regions on the convex surface of a preformed contact lens, as long as it does not contain a first reactive functional group (any of those described above) and a thermally crosslinkable group (e.g., an azetidinium group and / or an epoxy group). Those skilled in the art will appreciate that coating these regions on the convex surface of a preformed contact lens is well understood.

[0152] In a preferred embodiment, the hydrogel-forming composition can be applied to multiple areas on the convex surface of a preformed contact lens by pad transfer printing and / or inkjet printing techniques, and the hydrogel-forming composition applied to the areas on the convex surface of the preformed contact lens is then cured thermally or by actinic radiation to form a non-silicone hydrogel material covering those areas.

[0153] Any hydrogel-forming composition can be used to form the non-silicone hydrogel material, so long as the resulting non-silicone hydrogel material does not contain a first reactive functional group (as described above) and a thermally crosslinkable group (azetidinium group and / or epoxy group).

[0154] Preferably, the hydrogel-forming composition comprises at least one crosslinkable polymer having a hydroxyl group and / or an ethylenically unsaturated group, and optionally at least one hydrophobic vinyl monomer selected from the group consisting of methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, methyl (meth)acrylate, and combinations thereof; if the at least one crosslinkable polymer does not contain an ethylenically unsaturated group, the hydrogel-forming composition additionally comprises at least one hydroxyl-containing vinyl monomer and at least one compound having two or more isocyanato groups; and all polymerizable components in the hydrogel-forming composition do not contain a first reactive functional group (as described above) and a thermally crosslinkable group (azetidinium group and / or epoxy group).

[0155] One class of crosslinkable polymers having hydroxyl groups and ethylenically unsaturated groups includes, but is not limited to, water-soluble crosslinkable poly(vinyl alcohol) prepolymers containing repeating units of -CH-CHOH- and repeating units each having one ethylenically unsaturated group, such as those described in U.S. Pat. Nos. 5,583,163 and 6,303,687.

[0156] A preferred crosslinkable polymer having hydroxyl groups but no ethylenically unsaturated groups can be prepared by polymerizing a polymerizable composition containing at least one hydroxyl-containing vinyl monomer, at least one vinyl monomer selected from the group consisting of vinyl pyrrolidone, vinyl chloride, (meth)acrylamide, N,N-dimethyl(meth)acrylamide, methoxyethylethoxyethyl(meth)acrylate, methyl methacrylate, ethyl methacrylate, and combinations thereof, a chain transfer agent (e.g., 2-mercaptoethanol), and a free radical initiator.

[0157] Examples of preferred hydroxyl group-containing vinyl monomers include, but are not limited to, hydroxyethyl (meth)acrylate, glycerol (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-amino-2-hydroxypropyl (meth)acrylate, N-2-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, vinyl alcohol, allyl alcohol, and combinations thereof. More preferably, hydroxyethyl (meth)acrylate, glycerol (meth)acrylate, and vinyl alcohol are used.

[0158] Pad transfer printing is well known in the art (see, for example, U.S. Pat. Nos. 3,536,386, 4,582,402, 4,704,017, and 5,034,166). A typical example of this printing process is as follows: An image is etched into metal to form a cliche. The cliche is placed in a printer. Once placed in the printer, the cliche is inked by either an open inkwell doctor blade system or a closed ink cup that slides across the image. A silicone pad then picks up the ink image from the cliche and transfers the image to the contact lens. The silicone pad is made of a material that includes silicone with variable elasticity. The properties of the silicone material allow the ink (here, a hydrogel-forming composition) to temporarily adhere to the pad and then completely peel off from the pad upon contact with the contact lens or mold. Suitable pad transfer printing structures include, but are not limited to, tampo type printing structures (Tampo vario 90 / 130), rubber stamps, thimbles, doctor blades, direct printing, or transfer printing, as known in the art.

[0159] Any known suitable silicone pad can be used in the present invention. Silicone pads are commercially available. However, different pads may provide different print qualities. Those skilled in the art will know how to select an appropriate pad for a particular hydrogel-forming composition.

[0160] Cliches can be made from ceramic, polymer, or metal (e.g., steel). If the cliche is made from steel, it is desirable to neutralize the pH of the aqueous ink (e.g., adjust the pH to 6.8-7.8) by adding a buffer (e.g., phosphate). Images can be etched into the cliche by any method known to those skilled in the art, such as chemical etching or laser ablation. After use, the cliche is desirably cleaned by standard cleaning techniques known to those skilled in the art, such as immersion in a solvent, ultrasonic treatment, or mechanical abrasion.

[0161] Printing lenses using an inkjet printing process is described in U.S. Patent Application Publication Nos. 2001 / 0050753, 2001 / 0085934, 2003 / 0119943, and 2003 / 0184710.

[0162] According to the present invention, the multiple regions can have any shape. Examples of preferred shapes include, but are not limited to, a circle, a triangle, a square, a rectangle, a hexagon, a polygon, a star, an annular ring, a curve, a straight line, and combinations thereof. The multiple regions can have any two dimensional size. Preferably, one of the two dimensional sizes of the multiple regions is about 0.40 mm or less (preferably about 0.30 mm or less, more preferably about 0.25 mm or less, and even more preferably about 0.05 mm to about 0.20 mm).

[0163] According to one embodiment of the present invention, the regions are arranged in any pattern, preferably a pattern that is rotationally symmetric about the central axis of the preformed contact lens or female mold half, on the convex surface of the preformed contact lens or the molding surface of the female mold half. Preferably, the regions are arranged in an annular region having an inner diameter of about 6.0 mm to about 9.0 mm and an outer diameter of about 11.5 mm to about 14.5 mm, and that is concentric about the central axis of the preformed contact lens or female mold half.

[0164] In one embodiment, the plurality of regions comprises at least three annular rings.

[0165] In another embodiment, the plurality of regions includes at least eight curved or straight lines having a diameter of about 6.0 mm to about 9.0 mm and extending radiating outward from a circle concentric with the central axis of the preformed contact lens or female mold half.

[0166] In another embodiment, the plurality of regions comprises circular dots (preferably having a diameter of about 0.25 mm or less, more preferably about 0.05 mm to about 0.20 mm) arranged on the convex surface of the preformed contact lens or the molding surface of the female mold half in a pattern that is rotationally symmetrical about the central axis of the preformed contact lens or female mold half. Preferably, the circular dots are arranged in annular rings concentric with the central axis of the preformed contact lens or female mold half.

[0167] It is understood that the shape of the regions determines the shape of the defects in the anterior outer hydrogel layer of the coated contact lens of the present invention: regions having annular rings, curves, and / or straight lines will form grooves in the anterior outer hydrogel layer of the coated contact lens, while regions having circular, triangular, square, rectangular, hexagonal, polygonal, and / or star shapes will form gaps in the anterior outer hydrogel layer of the coated contact lens.

[0168] According to the present invention, the water-soluble, thermally crosslinkable hydrophilic polymer material preferably comprises an azetidinium group or an epoxy group or a combination thereof. Preferably, the water-soluble, crosslinkable hydrophilic polymer material is a partially crosslinked polymer material comprising a three-dimensional network and thermally crosslinkable groups, preferably azetidinium groups, within or connected to the network. The term "partially crosslinked" with respect to a polymer material means that the crosslinkable groups of the starting materials for making the polymer material are not completely consumed in the crosslinking reaction. For example, such a thermally crosslinkable hydrophilic polymer material comprises an azetidinium group and is represented by Scheme I: [ka] Scheme I (X1 is -S-*, -OC(=O)-*, or -NR'-*, where R' is hydrogen or a C1-C 20where * represents an organic radical).

[0169] Examples of preferred water-soluble, thermally crosslinkable hydrophilic polymeric materials comprising epoxy groups include, but are not limited to, one or more multi-armed polyethylene glycols each having a terminal epoxy group; a mixture of a multi-armed polyethylene glycol having a terminal epoxy group and one or more polyethylene glycols each having a terminal functional group selected from the group consisting of a primary amine group, a secondary amine group, a carboxyl group, a thiol group, and combinations thereof; a partial reaction product of a multi-armed polyethylene having epoxy groups with 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 (such as disclosed in U.S. Pat. No. 9,505,184, the hydrophilic polymers disclosed in U.S. Pat. No. 6,440,571), or combinations thereof.

[0170] Examples of preferred water-soluble, thermally crosslinkable hydrophilic polymeric materials comprising azetidinium groups include, but are not limited to, poly(2-oxazoline-co-ethyleneimine)-epichlorohydrin copolymers (disclosed in U.S. Pat. No. 9,720,138), chemically modified poly(2-oxazoline-co-ethyleneimine)-epichlorohydrin copolymers (disclosed in U.S. Pat. No. 9,720,138), chemically modified polyamidoamine-epichlorohydrin (disclosed in U.S. Pat. No. 8,529,057), copolymers of azetidinium-containing vinyl monomers and one or more hydrophilic vinyl monomers (disclosed in U.S. Pat. No. 9,422,447), chemically modified copolymers of azetidinium-containing vinyl monomers and one or more hydrophilic vinyl monomers (disclosed in U.S. Pat. No. 9,422,447), or combinations thereof.

[0171] According to the present invention, the term "chemically modified" with respect to a water-soluble, thermally crosslinkable, hydrophilic polymeric material having azetidinium groups means that the poly(2-oxazoline-co-ethyleneimine)-epichlorohydrin copolymer, polyamidoamine-epichlorohydrin, or copolymer of an azetidinium-containing vinyl monomer has been partially reacted (i.e., not all of the azetidinium groups have been consumed) 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 thiol group, and combinations thereof. The chemically modified poly(2-oxazoline-co-ethyleneimine)-epichlorohydrin copolymer or copolymer of a polyamidoamine-epichlorohydrin or azetidinium-containing vinyl monomer may be particularly useful for forming relatively thick and soft non-silicone hydrogel coatings on silicone hydrogel contact lenses.

[0172] Any suitable hydrophilicity enhancing agent can be used in the present invention so long as it contains at least one amino group, at least one carboxyl group, and / or at least one thiol group.

[0173] Preferred classes of hydrophilicity enhancers include, but are not limited to, primary amino, secondary amino, carboxyl, or thiol-containing monosaccharides (e.g., 3-amino-1,2-propanediol, 1-thiolglycerol, 5-keto-D-gluconic acid, galactamine, glucosamine, galacturonic acid, gluconic acid, glucosamine acid, mannosamine, saccharic acid 1,4-lactone, saccharide acids, ketodeoxynonulosonic acid, N-methyl-D-glucamine, 1-ino-1-deoxy-β-D-galactose, 1-amino-1-deoxysorbitol, , 1-methylamino-1-deoxysorbitol, N-aminoethyl gluconamide); primary amino, secondary amino, carboxyl or thiol-containing disaccharides (e.g., chondroitin disaccharide sodium salt, di(β-D-xylopyranosyl)amine, digalacturonic acid, heparin disaccharide, hyaluronic acid disaccharide, lactobionic acid); and primary amino, secondary amino, carboxyl or thiol-containing oligosaccharides (e.g., carboxymethyl-β-cyclodextrin sodium salt, trigalacturonic acid); and combinations thereof.

[0174] Another preferred class of hydrophilic enhancers is hydrophilic polymers having one or more (primary or secondary) amino, carboxyl, and / or thiol groups. More preferably, the content of amino (-NHR' with R' as defined above), carboxyl (-COOH), and / or thiol (-SH) groups in the hydrophilic polymer as hydrophilic enhancer is less than about 40 wt%, preferably less than about 30 wt%, more preferably less than about 20 wt%, and even more preferably less than about 10 wt%, based on the total weight of the hydrophilic polymer.

[0175] One preferred class of hydrophilic polymers as hydrophilicity enhancers are (primary or secondary) amino- or carboxyl-containing polysaccharides, such as carboxymethylcellulose (repeating unit, -[CH 10~m O5(CH2CO2H) m]- (where m is 1 to 3), carboxyethyl cellulose (repeating unit, -[CH 10~m O5(C2H4CO2H) m ]- (where m is 1 to 3), carboxypropyl cellulose (repeating unit, -[CH 10~m O5(C3H6CO2H) m ]- (where m is 1 to 3), hyaluronic acid (repeating unit, -(C 13 H 20 chondroitin sulfate (with an estimated carboxyl content of approximately 11% based on the repeating unit, -(C 12 H 18 O 13 NSCO2H)-), or combinations thereof.

[0176] Another preferred class of hydrophilic polymers as hydrophilicity enhancers includes, but is not limited to, poly(ethylene glycol)s (PEG) having mono-amino (primary or secondary amino), carboxyl, or thiol groups (e.g., PEG-NH, PEG-SH, PEG-COOH); HN-PEG-NH; ​​HOOC-PEG-COOH; HS-PEG-SH; HN-PEG-COOH; HOOC-PEG-SH; HN-PEG-SH; multi-armed PEGs having one or more amino (primary or secondary), carboxyl, or thiol groups; and poly(ethylene glycol)s having one or more amino (primary or secondary), carboxyl, or thiol groups. These include PEG dendrimers having PEG-14 groups, diamino- (primary or secondary) or dicarboxyl-terminated homo- or copolymers of non-reactive hydrophilic vinyl monomers, monoamino- (primary or secondary) or monocarboxyl-terminated homo- or copolymers of non-reactive hydrophilic vinyl monomers, copolymers that are the polymerization product of a composition comprising (1) up to about 60% by weight, preferably about 0.1% to about 30% by weight, more preferably about 0.5% to about 20% by weight, and even more preferably about 1% to about 15% by weight, of one or more reactive vinyl monomers, and (2) at least one non-reactive hydrophilic vinyl monomer, and combinations thereof. The reactive vinyl monomers and non-reactive hydrophilic vinyl monomers are as previously described.

[0177] According to the present invention, the reactive vinyl monomer for preparing the hydrophilicity enhancer can be a carboxyl-containing vinyl monomer, a primary amino-containing vinyl monomer, or a secondary amino-containing vinyl monomer. Examples of preferred carboxyl-containing vinyl monomers include, but are not limited to, acrylic acid, methacrylic ethyl acrylate, N-2-(meth)acrylamidoglycolic acid, and combinations thereof. Examples of preferred primary and secondary amino-containing vinyl monomers include, but are not limited to, N-2-aminoethyl(meth)acrylamide, N-2-methylaminoethyl(meth)acrylamide, N-2-ethylaminoethyl(meth)acrylamide, N-3-aminopropyl(meth)acrylamide, N-3-methylaminopropyl(meth)acrylamide, 2-aminoethyl(meth)acrylate, 2-methylaminoethyl(meth)acrylate, 2-ethylaminoethyl(meth)acrylate, 3-aminopropyl(meth)acrylate, 3-methylaminopropyl(meth)acrylate, 3-ethylaminopropyl(meth)acrylate, 3-amino-2-hydroxypropyl(meth)acrylate, and combinations thereof.

[0178] According to the present invention, the non-reactive vinyl monomer for preparing the hydrophilic enhancer is a vinyl monomer that does not contain any carboxyl group, primary amino group, secondary amino group, epoxide group, isocyanate group, azlactone group, or aziridine group. The non-reactive vinyl monomer is preferably an uncharged hydrophilic vinyl monomer that does not contain a carboxyl or amino group (any of the above may be used herein), a phosphorylcholine-containing vinyl monomer (any of the above may be used herein), or a combination thereof.

[0179] More preferably, the hydrophilic polymer as the hydrophilicity enhancer is Poly(ethylene glycol) having one single functional group of -NH2, -SH or -COOH; poly(ethylene glycol) having two terminal functional groups selected from the group consisting of -NH2, -COOH, -SH, and combinations thereof; multi-arm poly(ethylene glycol) having one or more functional groups selected from the group consisting of -NH2, -COOH, -SH, and combinations thereof; monoamino, monocarboxyl, diamino, or dicarboxyl terminated homo- or copolymers of non-reactive hydrophilic vinyl monomers; A copolymer that is the polymerization product of a composition comprising: (1) from about 0.1% to about 30% by weight, preferably from about 0.5% to about 20% by weight, and more preferably from about 1% to about 15% by weight, of a reactive vinyl monomer; and (2) at least one non-reactive vinyl monomer.

[0180] Examples of preferred reactive vinyl monomers include, but are not limited to, acrylic acid, methacrylic acid, ethyl acrylic acid, 2-(meth)acrylamidoglycolic acid, N-2-aminoethyl(meth)acrylamide, N-2-methylaminoethyl(meth)acrylamide, N-2-ethylaminoethyl(meth)acrylamide, N-3-aminopropyl(meth)acrylamide, N-3-methylaminopropyl(meth)acrylamide, 2-aminoethyl(meth)acrylate, 2-methylaminoethyl(meth)acrylate, 2-ethylaminoethyl(meth)acrylate, 3-aminopropyl(meth)acrylate, 3-methylaminopropyl(meth)acrylate, 3-amino-2-hydroxypropyl(meth)acrylate, and combinations thereof.

[0181] Examples of preferred non-reactive hydrophilic vinyl monomers include, but are not limited to, alkyl(meth)acrylamides (any one of the above), N-2-dimethylaminoethyl(meth)acrylamide, dimethylaminoethyl(meth)acrylate, hydroxyl-containing acrylic monomers (any one of the above), N-vinylamide monomers (any one of the above), methylene-containing pyrrolidone monomers (i.e., pyrrolidone derivatives having a methylene group linked to the pyrrolidone ring at the 3- or 5-position, respectively) (any one of the above), acrylic monomers having a C1-C4 alkoxyethoxy group (any one of the above), vinyl ether monomers (any one of the above), allyl ether monomers (any one of the above), phosphorylcholine-containing vinyl monomers (any one of the above), and combinations thereof.

[0182] Preferably, the non-reactive hydrophilic vinyl monomer is (meth)acryloyloxyethyl phosphorylcholine, (meth)acryloyloxypropyl phosphorylcholine, 4-((meth)acryloyloxy)butyl-2'-(trimethylammonio)ethyl phosphate, 2-[(meth)acryloylamino]ethyl-2'-(trimethylammonio)ethyl phosphate, 3-[(meth)acryloylamino]propyl-2'-(trimethylammonio)ethyl phosphate, 4-[(meth)acryloylamino]butyl-2'-(trimethylammonio)ethyl phosphate, (meth)acrylamide, dimethyl(meth)acrylamide, N-2-hydroxyethyl(meth)acrylamide, N,N-bis(hydroxyethyl)(meth)acrylamide, N-2,3-Dihydroxypropyl (meth)acrylamide, N-tris(hydroxymethyl)methyl (meth)acrylamide, 2-hydroxyethyl (meth)acrylate, glycerol methacrylate (GMA), tetra(ethylene glycol) (meth)acrylate, poly(ethylene glycol) ethyl (meth)acrylamide having a number average molecular weight of up to 1500, poly(ethylene glycol) (meth)acrylate having a number average molecular weight of up to 1500, N-vinylpyrrolidone, N-vinyl-N-methylacetamide, N-vinylformamide , N-vinylacetamide, 1-methyl-3-methylene-2-pyrrolidone, 1-methyl-5-methylene-2-pyrrolidone, 5-methyl-3-methylene-2-pyrrolidone, tetra(ethylene glycol) methyl ether (meth)acrylate, methoxypoly(ethylene glycol)ethyl (meth)acrylamide having a number average molecular weight of up to 1500, C1-C4 alkoxypolyethylene glycol (meth)acrylate having a weight average molecular weight of up to 1500, tetra(ethylene glycol) monovinyl ether, poly(ethylene glycol) monovinyl ether, tetra(ethylene glycol) methyl vinyl ether, poly(ethylene glycol) methyl vinyl ether, tetra(ethylene glycol) monoallyl ether, poly(ethylene glycol) monoallyl ether, tetra(ethylene glycol) methyl allyl ether, poly(ethylene glycol) methyl allyl ether, vinyl alcohol, allyl alcohol, and combinations thereof, more preferably (meth)acryloyloxyethyl phosphorylcholine, (meth)acryloyloxypropyl ... Folic acid, 4-((meth)acryloyloxy)butyl-2'-(trimethylammonio)ethyl phosphate, 2-[(meth)acryloylamino]ethyl-2'-(trimethylammonio)ethyl phosphate, 3-[(meth)acryloylamino]propyl-2'-(trimethylammonio)ethyl phosphate, 4-[(meth)acryloylamino]butyl-2'-(trimethylammonio)ethyl phosphate, (meth)acrylamide, dimethyl(meth)acrylamide, N-2-hydroxyethyl(meth)acrylamide, N,

[0023] The copolymer is selected from the group consisting of N-bis(hydroxyethyl)(meth)acrylamide, N-2,3-dihydroxypropyl(meth)acrylamide, N-tris(hydroxymethyl)methyl(meth)acrylamide, 2-hydroxyethyl(meth)acrylate, glycerol methacrylate (GMA), poly(ethylene glycol)ethyl(meth)acrylamide having a number average molecular weight of up to 1500, poly(ethylene glycol)(meth)acrylate having a number average molecular weight of up to 1500, N-vinylpyrrolidone, N-vinyl-N-methylacetamide, methoxypoly(ethylene glycol)ethyl(meth)acrylamide having a number average molecular weight of up to 1500, methoxypolyethylene glycol(meth)acrylate having a weight average molecular weight of up to 1500, poly(ethylene glycol)monovinyl ether, poly(ethylene glycol)methylvinyl ether, poly(ethylene glycol)monoallyl ether, poly(ethylene glycol)methylallyl ether, vinyl alcohol, allyl alcohol, and combinations thereof, and more preferably (meth)acryloyloxyethyl phosphonic acid. lylcholine, (meth)acryloyloxypropylphosphorylcholine, 2-[(meth)acryloylamino]ethyl-2'-(trimethylammonio)ethyl phosphate, 3-[(meth)acryloylamino]propyl-2'-(trimethylammonio)ethyl phosphate, (meth)acrylamide, dimethyl(meth)acrylamide, N-2-hydroxyethyl(meth)acrylamide, N,N-bis(hydroxyethyl)(meth)acrylamide, N-2,3-dihydroxypropyl(meth)acrylamide, N-tris(hydroxymethyl )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.

[0183] Functionalized PEGs and functionalized multi-armed PEGs can be obtained from a variety of commercial sources, such as Polyscience and Shearwater Polymers, Inc.

[0184] Monoamino-, monocarboxyl-, diamino-, or dicarboxyl-terminated homopolymers or copolymers of one or more nonreactive hydrophilic vinyl monomers or phosphorylcholine-containing vinyl monomers can be prepared according to the procedures described in U.S. Patent No. 6,218,508. For example, to prepare diamino- or dicarboxyl-terminated homopolymers or copolymers of nonreactive hydrophilic vinyl monomers, the nonreactive vinyl monomer, a chain transfer agent having an amino or carboxyl group (e.g., 2-aminoethanethiol, 2-mercaptopropionic acid, thioglycolic acid, thiobutyric acid, or other hydroxymercaptones, aminomercaptones, or carboxyl-containing mercaptones), and optionally other vinyl monomers are polymerized (thermally or by actinic radiation) with a reactive vinyl monomer (having an amino or carboxyl group) in the presence of a free radical initiator. Typically, the molar ratio of the chain transfer agent to all vinyl monomers other than the reactive vinyl monomer is about 1:5 to about 1:100, while the molar ratio of the chain transfer agent to the reactive vinyl monomer is 1:1. In such preparations, a chain transfer agent having an amino or carboxyl group is used to control the molecular weight of the resulting hydrophilic polymer, terminating the resulting hydrophilic polymer to provide the resulting hydrophilic polymer with one terminal amino or carboxyl group, while a reactive vinyl monomer provides the other terminal carboxyl or amino group. Similarly, to prepare monoamino- or monocarboxyl-terminated homo- or copolymers of non-reactive hydrophilic vinyl monomers, the non-reactive vinyl monomer, a chain transfer agent having an amino or carboxyl group (e.g., 2-aminoethanethiol, 2-mercaptopropionic acid, thioglycolic acid, thiobutyric acid, or other hydroxymercaptones, aminomercaptones, or carboxyl-containing mercaptones), and optionally, other vinyl monomers are polymerized (thermally or by actinic radiation) in the absence of any reactive vinyl monomer.

[0185] Copolymers containing non-reactive hydrophilic vinyl monomers and reactive vinyl monomers (e.g., carboxyl-containing vinyl monomers, primary amino-group-containing vinyl monomers, or secondary amino-group-containing vinyl monomers) can be prepared according to any well-known radical polymerization method or obtained from commercial sources. Copolymers containing methacryloyloxyethyl phosphorylcholine and carboxyl-containing vinyl monomers (or amino-containing vinyl monomers) can be obtained from NOP Corporation (e.g., LIPIDURE®-AC01, and AE).

[0186] The weight average molecular weight M of a hydrophilic polymer (as a hydrophilic enhancer) having at least one amino, carboxyl or thiol group w is preferably about 500 to about 2,000,000, more preferably about 1,000 to about 500,000, and even more preferably about 5,000 to about 250,000 daltons.

[0187] Water-soluble, thermally crosslinkable hydrophilic polymeric materials are those disclosed in US Pat. Nos. 8,529,057, 9,422,447, 9,720,138 and 11,256,003.

[0188] In a preferred embodiment, the water-soluble, thermally crosslinkable polymeric material can be obtained by heating a reactive aqueous solution containing 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 amino, carboxyl, thiol, and combinations thereof, to a temperature of about 35°C to about 85°C and maintaining that temperature for a sufficient period of time (about 8 hours or less, preferably about 5 hours, more preferably about 2 hours to about 4 hours). The reactive aqueous solution preferably contains one or more ionic components at about 70 mM to about 170 mM (preferably about 90 mM to about 150 mM, more preferably about 100 mM to about 130 mM) and has a pH of at least 8.0 (preferably at least 8.5, more preferably at least 9.0, and even more preferably 9.5). It should be understood that the reaction time should be long enough to covalently bond the hydrophilic enhancing agent onto the polymer chain of the azetidinium-containing polymer, but short enough not to consume all of the azetidinium groups on the azetidinium-containing polymer and not form a gel (i.e., not water-soluble) due to too many crosslinks formed between the azetidinium-containing polymer and the hydrophilic enhancing agent. The resulting polymeric material has a highly branched structure and is a lightly crosslinked polymeric material that still contains thermally crosslinkable azetidinium groups.

[0189] Those skilled in the art will understand well 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., HCl, H2SO4, H3PO4, citric acid, acetic acid, boric acid, or mixtures thereof).

[0190] According to the present invention, any ionic compound can be used in the reactive mixture. Preferably, the ionic compound is one used as an ionic tonicity adjuster and an ionic buffer in an ophthalmic solution. Examples of preferred ionic tonicity adjusters include, but are not limited to, sodium chloride, potassium chloride, and combinations thereof. Examples of preferred ionic buffers include various salts of phosphoric acid (e.g., NaH2PO4, Na2HPO4, Na3PO4, KH2PO4, K2HPO4, K3PO4, or mixtures thereof), various salts of boric acid (e.g., sodium borate, potassium borate, or mixtures thereof), various salts of citric acid (e.g., monosodium citrate, disodium citrate, trisodium citrate, monopotassium citrate, dipotassium citrate, tripotassium citrate, or mixtures thereof), various salts of carboxylic acids (e.g., Na2CO3, NaHCO3, K2CO3, KHCO3, or mixtures thereof).

[0191] A reactive aqueous solution for preparing a water-soluble, thermally crosslinkable polymeric material can be prepared by dissolving a desired amount of an azetidinium-containing polymer, a desired amount of a hydrophilicity enhancing agent having at least one reactive functional group, and a desired amount of other components (e.g., an ionic buffer, an ionic tonicity adjuster, etc.) in water (or in a mixture of water and a small amount of a water-soluble organic solvent) to form an aqueous solution, and then adjusting the pH of the aqueous solution, if necessary.

[0192] According to the present invention, the concentration ratio of hydrophilicity enhancer to azetidinium-containing polymer in the aqueous reactive solution should be selected so as not to render the resulting water-soluble, thermally crosslinkable polymeric material water-insoluble (i.e., solubility of less than 0.005 g per 100 ml of water at room temperature) and so as not to consume more than about 99%, preferably about 98%, more preferably about 97%, and even more preferably about 96% of the azetidinium groups of the azetidinium-containing polymer.

[0193] In a preferred embodiment, the reactive aqueous solution contains 0.01 wt % to about 10 wt % (preferably 0.05 wt % to about 5 wt %, more preferably 0.08 wt % to about 1 wt %, and even more preferably 0.1 wt % to about 0.4 wt %) of the azetidinium-containing polymer and about 0.01 wt % to about 10 wt % (preferably 0.02 wt % to about 5 wt %, more preferably 0.05 wt % to about 2 wt %, and even more preferably 0.08 wt % to about 1.0 wt %) of a hydrophilicity enhancer having at least one reactive functional group (carboxyl, primary amino, secondary amino group), and the concentration ratio of the azetidinium-containing polymer to the hydrophilicity enhancer is about 1000:1 to 1:1000 (preferably about 500:1 to about 1:500, more preferably about 250:1 to about 250:1, and even more preferably about 100:1 to about 1:100).

[0194] In a preferred embodiment, the water-soluble, thermally crosslinkable polymeric material comprises (i) about 20% to about 95% by weight of first polymer chains derived from polyamidoamine-epichlorohydrin or poly(2-oxazoline-co-ethyleneimine)-epichlorohydrin, and (ii) about 5% to about 80% by weight of hydrophilic portions or second polymer chains 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 thiol group, and combinations thereof (preferably a carboxyl or thiol group). wherein the hydrophilic portion or second polymer chain is covalently attached to the first polymer chain through 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 thiol group of the hydrophilic enhancer, respectively; and (iii) an azetidinium group that is part of the first polymer chain or is a pendant or terminal group covalently attached to the first polymer chain. The composition of the chemically modified poly(2-oxazoline-co-ethyleneimine)-epichlorohydrin or chemically modified polyamidoamine-epichlorohydrin is determined by the composition (based on the total weight of the reactants) of the reaction mixture used for such polymers according to the crosslinking reaction shown in Scheme I above. For example, if the reaction mixture includes about 75 weight percent polyamidoamine-epichlorohydrin and about 25 weight percent at least one hydrophilic enhancing agent, based on the total weight of the reactants, the resulting chemically modified polyamidoamine-epichlorohydrin will include about 75 weight percent first polymer chains derived from the polyamioamine-epichlorohydrin and about 25 weight percent hydrophilic portions or second polymer chains derived from the at least one hydrophilic enhancing agent.

[0195] According to the present invention, the heating step is preferably carried out by autoclaving the preformed contact lens (obtained in step (2)) immersed in a packaging solution (i.e., a buffered aqueous solution) in a sealed lens package for about 20 to 90 minutes at a temperature of about 115° C. to about 125° C. According to this embodiment of the present invention, the packaging solution is a buffered aqueous solution that is ophthalmically safe after autoclaving.

[0196] Lens packages (or containers) are well known to those skilled in the art for autoclaving and storing soft contact lenses. Any lens package can be used in the present invention. Preferably, the lens package is a blister package comprising a base and a cover, wherein the cover is removably sealed to the base, and wherein the base comprises a cavity for receiving a sterile packaging solution and a contact lens.

[0197] The lenses are packaged in individual packages, sealed, and sterilized (e.g., by autoclaving at about 120°C or higher under pressure for at least 30 minutes) before being distributed to users. Those skilled in the art will be familiar with methods for sealing and sterilizing lens packages.

[0198] According to the present invention, the packaging solution contains at least one buffer and one or more other ingredients known to those skilled in the art, including, but not limited to, tonicity agents, surfactants, antibacterial agents, preservatives, and lubricants (e.g., cellulose derivatives, polyvinyl alcohol, polyvinylpyrrolidone).

[0199] The packaging solution contains a buffer in an amount sufficient to maintain the pH of the packaging solution in a desired range, e.g., preferably from about 6.8 to about 8.5, more preferably from about 7.0 to 8.2, and even more preferably from about 7.2 to about 8.0. A higher pH has been found to be desirable to ensure that all or a substantial portion of the carboxyl groups on the lens bulk material are ionized. As a result, the resulting coated contact lens may be dimensionally stable in the packaging solution during autoclaving and storage and may have improved lubricity.

[0200] Any known physiologically compatible buffering agent can be used. Suitable buffering agents for use as components of contact lens care compositions according to the present invention are known to those skilled in the art. Preferably, a phosphate buffer (consisting essentially of a mixture of monobasic dihydrogen phosphate (e.g., NaH2PO4, KH2PO4, or a mixture thereof) and dibasic monohydrogen phosphate (e.g., Na2HPO4, K2HPO4, or a mixture thereof)) is used to maintain the pH of the packaging solution. In various preferred embodiments, the total concentration of monobasic dihydrogen phosphate and dibasic monohydrogen phosphate is at least 30 mM (preferably at least 35 mM, more preferably at least 40 mM, and even more preferably at least 45 mM).

[0201] The solutions according to the invention are preferably formulated so that they are isotonic with tear fluid. A solution is usually understood to be a solution whose concentration corresponds to that of a 0.9% sodium chloride solution (308 mOsm / kg). Deviations from this concentration are possible throughout.

[0202] Isotonicity with tear fluid, or another desired tonicity, can be adjusted by adding organic or inorganic substances that affect tonicity. Suitable ophthalmically acceptable tonicity agents include, but are not limited to, sodium chloride, potassium chloride, glycerol, propylene glycol, polyols, mannitol, sorbitol, xylitol, and mixtures thereof. The tonicity of the packaging solution is typically adjusted to about 200 to about 450 milliosmoles (mOsm), preferably about 250 to 350 mOsm.

[0203] In preferred embodiments, one or more organic tonicity agents (e.g., glycerol, propylene glycol, polyethylene glycol having a number average molecular weight of 200-800 Daltons, mannitol, sorbitol, xylitol, and mixtures thereof) are present in an amount of at least 70 mM (preferably at least 90 mM, more preferably at least 110 mM, and even more preferably at least 130 mM) to adjust the tonicity of the packaging solution. It has been found that when the ionic strength of the packaging solution is reduced (e.g., by replacing a portion of the NaCl with an organic tonicity agent, such as propylene glycol), the resulting coated contact lens may have improved lubricity.

[0204] In a preferred embodiment, the packaging solution preferably comprises from about 0.01% to about 2% by weight, more preferably from about 0.05% to about 1.5% by weight, even more preferably from about 0.1% to about 1% by weight, and most preferably from about 0.2% to about 0.5% by weight of a water-soluble, thermally crosslinkable, hydrophilic polymeric material having an azetidinium group.

[0205] In another aspect, the present invention is a method for making a coated contact lens, comprising the steps of: (1) obtaining a female mold half and a male mold half, wherein the female mold half has a first molding surface that defines the anterior surface of the contact lens to be molded, and the male mold half has a second molding surface that defines the posterior surface of the contact lens to be molded, the male mold half and the female mold half being configured to receive each other such that when the female mold half is closed with the male mold half, a lens molding cavity is formed between the first molding surface and the second molding surface; (2) applying a hydrogel-forming composition to a plurality of regions on the first molding surface, the hydrogel-forming composition comprising at least one crosslinkable polymer having hydroxyl groups and / or ethylenically unsaturated groups, and optionally at least one hydrophobic vinyl monoacrylate selected from the group consisting of methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, methyl (meth)acrylate, and combinations thereof. and a hydroxyl-containing vinyl monomer, and if the at least one crosslinkable polymer does not contain an ethylenically unsaturated group, the hydrogel-forming composition additionally contains at least one hydroxyl-containing vinyl monomer and at least one compound having two or more isocyanato groups, and none of the polymerizable components in the hydrogel-forming composition contains a reactive functional group selected from the group consisting of a carboxylic acid group, a primary amino group, a secondary amino group, an azetidinium group, an epoxy group, and combinations thereof; (3) an optional but preferably a step of partially curing the hydrogel-forming composition on the first molding surface; and (4) a step of introducing a polymerizable composition into the negative mold half obtained in step (2) or (3), wherein the polymerizable composition contains at least one reactive vinyl monomer having at least one first reactive functional group selected from the group consisting of a carboxylic acid group, a primary amino group, a secondary amino group, and combinations thereof in an amount of about 1:1 based on the total amount of all polymerizable components.(5) closing the female mold half from step (4) with a male mold half to form a mold assembly containing the polymerizable composition within a lens-forming cavity; (6) curing the polymerizable composition within the mold assembly thermally or with actinic radiation to form a contact lens precursor having a convex surface and an opposing concave surface, the contact lens precursor comprising a lens bulk material having first reactive functional groups, wherein the convex surface of the contact lens precursor is partially coated with a second hydrogel material formed from the hydrogel-forming composition in a plurality of regions on the convex surface, resulting in the formation of an azeotropic hydrogel. (7) optionally, hydrating the contact lens precursor obtained in step (6) in water or an aqueous solution to obtain a hydrated contact lens precursor; and (8) heating the contact lens precursor obtained in step (6) or the hydrated contact lens precursor obtained in step (7) at a temperature of about 6.5 to about 9.a step of directly heating the contact lens precursor obtained in step (6) or the hydrated contact lens precursor obtained in step (7) at a temperature of about 60°C to about 140°C in an aqueous solution having a pH of 5 and containing at least one water-soluble, thermally crosslinkable hydrophilic polymer material to graft a first non-silicone hydrogel material onto each of the convex and concave surfaces of the contact lens precursor obtained in step (6) or the hydrated contact lens precursor obtained in step (7), thereby forming a coated contact lens having an anterior surface, an opposite posterior surface, an anterior outer hydrogel layer, and a posterior outer hydrogel layer, wherein the at least one water-soluble, thermally crosslinkable hydrophilic polymer material comprises a second reactive functional group and a third reactive functional group, the second reactive functional group being a thermally crosslinkable group selected from the group consisting of an azetidinium group, an epoxy group, and combinations thereof, and the second reactive functional group is a thermally crosslinkable group selected from the group consisting of an azetidinium group, an epoxy group, and combinations thereof, and the third ... wherein each of the reactive functional groups is capable of reacting with one first or third reactive functional group to form a crosslink, and the third reactive functional group is selected from the group consisting of a carboxylic acid group, a primary amino group, a secondary amino group, a thiol group, and combinations thereof; the posterior outer hydrogel layer is a layer of a first non-silicone hydrogel material, the anterior outer hydrogel layer being a layer of a first non-silicone hydrogel material having defects (e.g., grooves and / or crevices) distributed therein so as to impart a higher surface lubricity to the posterior surface than to the anterior surface of the coated contact lens; and wherein the coated contact lens has a water break-up time of at least about 10 seconds measured on the anterior and posterior surfaces of the coated contact lens.

[0206] Various embodiments are described above and can be used in this aspect of the invention, including preferred embodiments of the mold halves, the hydrogel-forming composition, the technique for applying the hydrogel-forming composition onto the molding surface of the female mold half, the shape, size and distribution of the regions on the molding surface of the female mold half (rather than on the convex surface of the preformed contact lens described above), the curing of the hydrogel-forming composition or polymerizable composition, the polymerizable composition, the water-soluble thermally crosslinkable hydrophilic polymeric material, and the heating step to form the coated contact lens.

[0207] In a further aspect, the present invention provides a coated contact lens comprising: a front surface and an opposite posterior surface; and a layered structural configuration comprising, in a direction from the front surface to the posterior surface, a front outer hydrogel layer, an inner layer, and a posterior outer hydrogel layer, wherein the inner layer is fabricated from lens bulk material; the posterior outer hydrogel layer is a layer of a first non-silicone hydrogel material having defects (e.g., grooves and / or crevices) distributed therein such that the front outer hydrogel layer has a surface lubricity that is greater than the surface lubricity of the front outer hydrogel layer; and wherein the coated contact lens, when fully hydrated, has a water content of about 10% to about 70% by weight, an oxygen permeability of at least about 50 barrers, and a water breakup time of at least about 10 seconds as measured on the front and posterior surfaces of the coated contact lens.

[0208] Various embodiments, including preferred embodiments of lens bulk materials, are described above and may be incorporated into this aspect of the invention.

[0209] In various preferred embodiments, the first non-silicone hydrogel material (which comprises the outer hydrogel layers on the front and back surfaces) is (1) A crosslinked polymeric material comprising at least 25 mol % (preferably at least 35 mol %, more preferably at least 45 mol %, and even more preferably at least 55 mol %) of repeating monomer units of at least one hydrophilic vinyl monomer, wherein the at least one hydrophilic vinyl monomer is selected from the group consisting of (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, 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)acrylamide, 2-hydroxyethyl(meth)acrylate, 2-hydroxypropyl(meth)acrylamide ... Hydroxypropyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, glycerol methacrylate (GMA), di(ethylene glycol) (meth)acrylate, tri(ethylene glycol) (meth)acrylate, tetra(ethylene glycol) (meth)acrylate, poly(ethylene glycol) (meth)acrylate having a number average molecular weight of up to 1500, poly(ethylene glycol) ethyl (meth)acrylamide having a number average molecular weight of up to 1500, N-vinylpyrrolidone, N-vinyl-N-methylacetamide, N -vinylformamide, N-vinylacetamide, N-vinylisopropylamide, N-vinyl-N-ethylacetamide, N-vinyl-N-ethylformamide, 1-methyl-3-methylene-2-pyrrolidone, 1-ethyl-3-methylene-2-pyrrolidone, 1-methyl-5-methylene-2-pyrrolidone, 1-ethyl-5-methylene-2-pyrrolidone, 5-methyl-3-methylene-2-pyrrolidone, 5-ethyl-3-methylene-2-pyrrolidone, 1-n-propyl-3-methylene-2-pyrrolidone, 1-n-propyl-5-methylene-2-pyrrolidone,1-Isopropyl-3-methylene-2-pyrrolidone, 1-isopropyl-5-methylene-2-pyrrolidone, 1-n-butyl-3-methylene-2-pyrrolidone, 1-tert-butyl-3-methylene-2-pyrrolidone, ethylene glycol methyl ether (meth)acrylate, di(ethylene glycol) methyl ether (meth)acrylate, tri(ethylene glycol) methyl ether (meth)acrylate, tetra(ethylene glycol) methyl ether (meth)acrylate, C1 to C4 alkoxy poly(ethylene glycol) having a weight average molecular weight of up to 1500 (ethylene glycol) (meth)acrylate, methoxypoly(ethylene glycol)ethyl (meth)acrylamide with a number average molecular weight of up to 1500, allyl alcohol, ethylene glycol monoallyl ether, di(ethylene glycol) monoallyl ether, tri(ethylene glycol) monoallyl ether, tetra(ethylene glycol) monoallyl ether, poly(ethylene glycol) monoallyl ether, ethylene glycol methyl allyl ether, di(ethylene glycol) methyl allyl ether, tri(ethylene glycol) methyl allyl ether, tetra(ethylene glycol) methyl allyl ether, poly(ethylene glycol) methyl allyl ether, ethylene glycol monovinyl ether, di(ethylene glycol) monovinyl ether, tri(ethylene glycol) monovinyl ether, tetra(ethylene glycol) monovinyl ether, poly(ethylene glycol) monovinyl ether, ethylene glycol methyl vinyl ether, di(ethylene glycol) methyl vinyl ether, tri(ethylene glycol) methyl vinyl ether, tetra(ethylene glycol) methyl vinyl ether, poly(ethylene glycol) methyl vinyl ether, and combinations thereof, preferably (meth)acrylamide, dimethyl(meth)acrylamide, N-2-hydroxyethyl(meth)acrylamide, N,N-bis(hydroxyethyl)(meth)acrylamide, N-2,3-dihydroxypropyl(meth)acrylamide, N-tris(hydroxymethyl)methyl(meth)acrylamide, N-2-dimethylaminoethyl(meth)acrylamide, dimethylaminoethyl(meth)acrylate;2-hydroxyethyl (meth)acrylate, glycerol methacrylate (GMA), tetra(ethylene glycol) (meth)acrylate, poly(ethylene glycol) ethyl (meth)acrylamide having a number average molecular weight of up to 1500, poly(ethylene glycol) (meth)acrylate having a number average molecular weight of up to 1500, N-vinylpyrrolidone, N-vinyl-N-methylacetamide, N-vinylformamide, N-vinylacetamide, 1-methyl-3-methylene-2-pyrrolidone, 1-methyl-5-methylene-2-pyrrolidone , 5-methyl-3-methylene-2-pyrrolidone, tetra(ethylene glycol) methyl ether (meth)acrylate, methoxypoly(ethylene glycol)ethyl (meth)acrylamide having a number average molecular weight of up to 1500, C1-C4 alkoxypolyethylene glycol (meth)acrylate having a weight average molecular weight of up to 1500, tetra(ethylene glycol) monovinyl ether, poly(ethylene glycol) monovinyl ether, tetra(ethylene glycol) methyl vinyl ether, poly(ethylene glycol) methyl vinyl ether ether, tetra(ethylene glycol) monoallyl ether, poly(ethylene glycol) monoallyl ether, tetra(ethylene glycol) methyl allyl ether, poly(ethylene glycol) methyl allyl ether, vinyl alcohol, allyl alcohol, and combinations thereof, more preferably (meth)acrylamide, dimethyl(meth)acrylamide, N-2-hydroxyethyl(meth)acrylamide, N,N-bis(hydroxyethyl)(meth)acrylamide, N-2,3-dihydroxypropyl(meth)acrylamide, N-tris(hydroxymethyl)methyl(meth)acrylamide, 2-hydroxyethyl(meth)acrylate, glycerol methacrylate (GMA), poly(ethylene glycol) ethyl(meth)acrylamide having a number average molecular weight of up to 1500, poly(ethylene glycol) (meth)acrylate having a number average molecular weight of up to 1500, N-vinylpyrrolidone, N-vinyl-N-methylacetamide, methoxypoly(ethylene glycol)ethyl(meth)acrylamide having a number average molecular weight of up to 1500,and mixtures thereof, and even more preferably selected from the group consisting of methoxypolyethylene glycol (meth)acrylate having a weight average molecular weight of up to 1500, poly(ethylene glycol) monovinyl ether, poly(ethylene glycol) methyl vinyl ether, poly(ethylene glycol) monoallyl ether, poly(ethylene glycol) methyl allyl ether, vinyl alcohol, allyl alcohol, and combinations thereof; and even more preferably (meth)acrylamide, dimethyl(meth)acrylamide, N-2-hydroxyethyl(meth)acrylamide, N,N-bis(hydroxyethyl)(meth)acrylamide, N-2,3-dihydroxypropyl a crosslinked polymeric material selected from the group consisting of (meth)acrylamide, N-tris(hydroxymethyl)methyl(meth)acrylamide, poly(ethylene glycol)ethyl(meth)acrylamide having a number average molecular weight of up to 1500, poly(ethylene glycol)(meth)acrylate having a number average molecular weight of up to 1500, N-vinylpyrrolidone, N-vinyl-N-methylacetamide, methoxypoly(ethylene glycol)ethyl(meth)acrylamide having a number average molecular weight of up to 1500, methoxypolyethylene glycol(meth)acrylate having a weight average molecular weight of up to 1500, and combinations thereof; (2) A crosslinked polymeric material comprising at least 25 mol % (preferably at least 35 mol %, more preferably at least 45 mol %, and even more preferably at least 55 mol %) of repeating monomer units of at least one phosphorylcholine-containing vinyl monomer (any one of those described below), wherein the at least one phosphorylcholine-containing vinyl monomer is preferably selected from the group consisting of (meth)acryloyloxyethyl phosphorylcholine, (meth)acryloyloxypropyl phosphorylcholine, 4-((meth)acryloyloxy)butyl-2'-(trimethylammonio)ethyl phosphate, 2-[(meth)acryloylamino]ethyl-2'-(trimethylammonio)ethyl phosphate, 3-[(meth)acryloylamino]propyl-2'-(trimethylammonio)ethyl phosphate, 4-[(meth)acryloylamino]butyl-2'-(trimethylammonio)ethyl phosphate, and combinations thereof; (3) Crosslinked polymeric materials comprising poly(ethylene glycol) chains, wherein the poly(ethylene glycol) chains are preferably derived directly from (a) poly(ethylene glycol) having one single functional group selected from -NH, -SH, or -COOH; (b) poly(ethylene glycol) having two terminal functional groups selected from the group consisting of -NH, -COOH, -SH, and combinations thereof; (c) multi-arm poly(ethylene glycol) having one or more functional groups selected from the group consisting of -NH, -COOH, -SH, and combinations thereof; and (d) combinations thereof; is.

[0210] Examples of preferred phosphorylcholine-containing vinyl monomers include, but are not limited to, (meth)acryloyloxyethyl phosphorylcholine (also known as MPC or 2-((meth)acryloyloxy)ethyl-2'-(trimethylammonio)ethyl phosphate), (meth)acryloyloxypropyl phosphorylcholine (also known as 3-((meth)acryloyloxy)propyl-2'-(trimethylammonio)ethyl phosphate), 4-((meth)acryloyloxy)butyl-2'-(trimethylammonio)ethyl phosphate, 2-[(meth)acryloylamino]ethyl-2'-(trimethylammonio)-ethyl phosphate, 3-[(meth)acryloylamino]propyl-2'-(trimethylammonio)ethyl phosphate, 4-[(meth)acryloylamino]butyl-2'-(trimethylammonio)ethyl phosphate, 5-((meth)acryloyloxy)pentyl-2'-(trimethylammonio)ethyl phosphate, 6-((meth)acryloyloxy)hexyl-2'-(trimethylammonio)-ethyl phosphate, 2-((meth)acryloyl 2-((meth)acryloyloxy)ethyl-2'-(triethylammonio)ethyl phosphate, 2-((meth)acryloyloxy)ethyl-2'-(tripropylammonio)ethyl phosphate, 2-((meth)acryloyloxy)ethyl-2'-(tributylammonio)ethyl phosphate, 2-((meth)acryloyloxy)propyl-2'-(trimethylammonio)-ethyl phosphate, 2-((meth)acryloyloxy)butyl-2'-(trimethylammonio)ethyl phosphate, 2-((meth)acryloyloxy)phenyl butyl-2'-(trimethylammonio)ethyl phosphate, 2-((meth)acryloyloxy)hexyl-2'-(trimethylammonio)ethyl phosphate, 2-(vinyloxy)ethyl-2'-(trimethylammonio)ethyl phosphate, 2-(allyloxy)ethyl-2'-(trimethylammonio)ethyl phosphate, 2-(vinyloxycarbonyl)ethyl-2'-(trimethylammonio)ethyl phosphate, 2-(allyloxycarbonyl)ethyl-2'-(trimethylammonio)ethyl phosphate,Examples include 2-(vinylcarbonylamino)ethyl-2'-(trimethylammonio)ethyl phosphate, 2-(allyloxycarbonylamino)ethyl-2'-(trimethylammonio)ethyl phosphate, 2-(butenoyloxy)ethyl-2'-(trimethylammonio)ethyl phosphate, and combinations thereof.

[0211] In various preferred embodiments, the defects in the front outer hydrogel layer include (1) ring-shaped, curved, and / or linear grooves, (2) circular, triangular, square, rectangular, hexagonal, polygonal, and / or star-shaped gaps, or (3) combinations thereof, with the understanding that these defect shapes are shown in plan view.

[0212] The defect can have any two dimensional sizes in a plan view, and preferably, one of the two dimensional sizes of the defect is about 0.40 mm or less (preferably about 0.30 mm or less, more preferably about 0.25 mm or less, and even more preferably about 0.05 mm to about 0.20 mm).

[0213] According to one embodiment of the present invention, the defects are arranged on the anterior surface of the coated contact lens in any pattern, preferably a pattern that is rotationally symmetric about the central axis of the coated contact lens. Preferably, the defects have an inner diameter of about 6.0 mm to about 9.0 mm and an outer diameter of about 11.5 mm to about 14.5 mm, and are arranged in annular regions concentric with the central axis of the coated contact lens.

[0214] In one embodiment, the defect comprises at least three ring-shaped grooves.

[0215] In another embodiment, the defects comprise at least eight curved or linear grooves having a diameter of about 6.0 mm to about 9.0 mm and extending radially outward from a circle concentric with the central axis of the coated contact lens.

[0216] In another embodiment, the defects comprise circular gaps (preferably having a diameter of about 0.25 mm or less, more preferably having a diameter of about 0.05 mm to about 0.20 mm) arranged in a rotationally symmetric pattern on the anterior surface of the coated contact lens. Preferably, the circular gaps are arranged in a pattern of annular rings concentric with the central axis of the coated contact lens.

[0217] According to the present invention, the surface lubricity of the outer hydrogel layers on the anterior and posterior surfaces can preferably be evaluated using a fingertip lubricity test. This test qualitatively characterizes the slipperiness of the lens surface on a friction rating scale of 0 to 4. The higher the friction rating, the lower the slipperiness (or surface lubricity). The procedure for conducting the fingertip lubricity test is described in Example 1.

[0218] In various preferred embodiments, the anterior surface of the coated contact lens has a friction rating that is at least 0.25 (preferably at least 0.50, more preferably at least 0.75) greater than the friction rating of the posterior surface.

[0219] Preferably, the coated contact lenses of the present invention in a fully hydrated state have a water film breakup time of at least about 15 seconds (preferably at least about 20 seconds, more preferably at least about 25 seconds, and even more preferably at least about 30 seconds) measured on the anterior and posterior surfaces of the coated contact lens.

[0220] It is understood that the water breakup time of the coated contact lenses of the present invention is measured on the anterior and / or posterior surfaces according to the procedure described in Example 1.

[0221] In various preferred embodiments, the coated contact lenses of the present invention, when fully hydrated, further have a water content of about 20% to about 70% by weight (preferably about 25% to about 65% by weight, more preferably about 30% to about 60% by weight), a modulus of about 0.2 MPa to about 2.0 MPa (preferably about 0.25 MPa to about 1.5 MPa, more preferably about 0.3 MPa to about 1.2 MPa, even more preferably about 0.35 MPa to about 1.0 MPa), an oxygen permeability of at least 60 barrer / mm (preferably at least 70 barrer / mm, more preferably at least 80 barrer / mm, even more preferably at least 100 barrer / mm), and an average water contact angle of less than 90 degrees (preferably less than 80 degrees, more preferably less than 70 degrees, even more preferably less than 60 degrees), or a combination thereof.

[0222] Although various embodiments of the present invention have been described using specific terms, devices, and methods, such description is for illustrative purposes only. The words used are words of description rather than of limitation. As will be apparent to those skilled in the art, many variations and modifications of the present invention may be made by those skilled in the art without departing from the spirit and scope of the novel concepts of the present disclosure. In addition, it should be understood that aspects of the various embodiments of the present invention may be interchanged in whole or in part, or may be combined in any manner and / or used together, as set forth below. 1. A front surface and an opposite rear surface; a layered structural configuration including, in a direction from the anterior surface to the posterior surface, a front outer hydrogel layer, an inner layer, and a posterior outer hydrogel layer; 1. A coated contact lens, wherein the inner layer is fabricated from a lens bulk material, the posterior outer hydrogel layer is a layer of a first non-silicone hydrogel material, the front outer hydrogel layer being a layer of the first non-silicone hydrogel material having defects (e.g., grooves and / or crevices) distributed therein so as to provide the posterior outer hydrogel layer with a surface lubricity that is greater than the surface lubricity of the front outer hydrogel layer, and wherein the coated contact lens in a fully hydrated state has a water breakup time of at least about 10 seconds measured on the anterior and posterior surfaces of the coated contact lens. 2. A method for producing a coated contact lens, comprising: (1) a process for obtaining a preformed contact lens having a convex surface and an opposite concave surface, the preformed contact lens being composed of a lens bulk material and including first reactive functional groups on and near the convex and concave surfaces of the preformed contact lens, each of the first reactive functional groups being capable of reacting with a thermally crosslinkable group at a temperature of from about 60°C to about 140°C, the first reactive functional groups being selected from the group consisting of a carboxylic acid group, a primary amino group, a secondary amino group, a thiol group, and combinations thereof; (2) coating the plurality of regions on the convex surface with a second non-silicone hydrogel material to prevent the first reactive functional groups at the rear of the plurality of regions from reacting with the thermally crosslinkable groups, wherein the second non-silicone hydrogel material does not contain the first reactive functional groups and the thermally crosslinkable groups; (3) directly heating the preformed contact lens obtained in step (2) at a temperature of about 60°C to about 140°C in an aqueous solution having a pH of about 6.5 to about 9.5 and containing at least one water-soluble, thermally crosslinkable hydrophilic polymer material, to graft a first non-silicone hydrogel material onto each of the anterior and posterior surfaces of the preformed contact lens obtained in step (2), thereby forming a coated contact lens having an anterior surface, an opposite posterior surface, an anterior outer hydrogel layer, and a posterior outer hydrogel layer, wherein the at least one water-soluble, thermally crosslinkable hydrophilic polymer material contains a second reactive functional group and a third reactive functional group, and the second reactive functional group is selected from the group consisting of an azetidinium group, an epoxy group, and combinations thereof. wherein each of the second reactive functional groups is capable of reacting with one of the first or third reactive functional groups to form a crosslink, and the third reactive functional groups are selected from the group consisting of a carboxylic acid group, a primary amino group, a secondary amino group, a thiol group, and combinations thereof; the first non-silicone hydrogel material is a crosslinked product of at least one thermally crosslinkable hydrophilic polymeric material; the posterior outer hydrogel layer is a layer of the first non-silicone hydrogel material, the anterior outer hydrogel layer being a layer of the first non-silicone hydrogel material having defects (e.g., grooves and / or crevices) distributed therein so as to provide the posterior surface with a surface lubricity that is greater than the surface lubricity of the anterior surface of the coated contact lens; Including, A method wherein the coated contact lens in a fully hydrated state has a water break-up time of at least about 10 seconds measured on the anterior and posterior surfaces of the coated contact lens. 3. The method of embodiment 2, wherein step (2) is carried out by applying the hydrogel-forming composition onto a plurality of regions on the convex surface of the preformed contact lens (preferably by pad transfer printing and / or inkjet printing techniques), and then curing the hydrogel-forming composition thermally or with actinic radiation to form a second non-silicone hydrogel material to cover the plurality of regions. 4. A method for producing a coated contact lens, comprising: (1) obtaining a female mold half and a male mold half, the female mold half having a first molding surface that defines the anterior surface of the contact lens to be molded, and the male mold half having a second molding surface that defines the posterior surface of the contact lens to be molded, the male and female mold halves configured to receive each other such that when the female mold half is closed with the male mold half a lens molding cavity is formed between the first and second molding surfaces; (2) applying a hydrogel-forming composition to a plurality of regions on a first molding surface, the hydrogel-forming composition comprising at least one crosslinkable polymer having a hydroxyl group and / or an ethylenically unsaturated group, and optionally at least one hydrophobic vinyl monomer selected from the group consisting of methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, methyl (meth)acrylate, and combinations thereof, and if the at least one crosslinkable polymer does not contain an ethylenically unsaturated group, the hydrogel-forming composition additionally comprises at least one hydroxyl-containing vinyl monomer and at least one compound having two or more isocyanato groups, and all polymerizable components in the hydrogel-forming composition do not contain reactive functional groups selected from the group consisting of carboxylic acid groups, primary amino groups, secondary amino groups, azetidinium groups, epoxy groups, and combinations thereof; (3) optionally but preferably, partially curing the hydrogel-forming composition on the first molding surface; (4) introducing a polymerizable composition into the negative mold half obtained in step (2) or (3), wherein the polymerizable composition contains about 1.0% to about 10% by weight of at least one reactive vinyl monomer having at least one first reactive functional group selected from the group consisting of a carboxylic acid group, a primary amino group, a secondary amino group, and combinations thereof, based on the total amount of all polymerizable components; (5) closing the female mold half obtained in step (4) with the male mold half to form a mold assembly containing the polymerizable composition within the lens-forming cavity; (6) curing the polymerizable composition in the molding assembly thermally or with actinic radiation to form a contact lens precursor having a convex surface and an opposite concave surface, the contact lens precursor comprising a lens bulk material having first reactive functional groups, wherein the convex surface of the contact lens precursor is partially coated with a second non-silicone hydrogel material formed from the hydrogel-forming composition in a plurality of regions on the convex surface, thereby preventing reaction of the first reactive functional groups behind the plurality of regions with the thermally crosslinkable groups, which are azetidinium groups and / or epoxy groups, at a temperature of about 60°C to about 140°C, and the second non-silicone hydrogel material is free of the first reactive functional groups and the thermally crosslinkable groups; (7) optionally hydrating the contact lens precursor obtained in step (6) in water or an aqueous solution; and (8) directly heating the contact lens precursor obtained in step (6) or step (7) at a temperature of about 60°C to about 140°C in an aqueous solution having a pH of about 6.5 to about 9.5 and containing at least one water-soluble, thermally crosslinkable, hydrophilic polymer material, to graft a first non-silicone hydrogel material onto each of the convex and concave surfaces of the contact lens precursor obtained in step (6) or the hydrated contact lens precursor obtained in step (7), thereby forming a coated contact lens having an anterior surface, an opposite posterior surface, an anterior outer hydrogel layer, and a posterior outer hydrogel layer, wherein the at least one water-soluble, thermally crosslinkable, hydrophilic polymer material contains a second reactive functional group and a third reactive functional group, and the second reactive functional group is selected from the group consisting of an azetidinium group, an epoxy group, and a hydroxyl group. the first non-silicone hydrogel material is a crosslinked product of said at least one thermally crosslinkable hydrophilic polymeric material, and the posterior outer hydrogel layer is a layer of a first non-silicone hydrogel material having defects (e.g., grooves and / or crevices) distributed therein so as to provide said posterior surface with a surface lubricity greater than that of the anterior surface of a coated contact lens; Including, A method wherein the coated contact lens has a water breakup time of at least about 10 seconds measured on the anterior and posterior surfaces of the coated contact lens. 5. The method of embodiment 4, wherein the polymerizable composition is a non-silicone hydrogel lens formulation containing from about 1.0% to about 10% by weight (preferably from about 2.0% to about 7% by weight, more preferably from about 2.0% to about 5% by weight) of at least one carboxyl-containing vinyl monomer and / or at least one amino-containing vinyl monomer. 6. The at least one carboxyl-containing vinyl monomer is selected from the group consisting of acrylic acid, methacrylic acid, ethylacrylic acid, propylacrylic acid, (meth)acryloyloxyacetic acid, mono-2-[(meth)acryloyloxy]ethyl succinate, (meth)acryloyloxypropanoic acid, (meth)acryloyloxybutanoic acid, and combinations thereof, and the at least one amino-containing vinyl monomer is selected from the group consisting of N-2-aminoethyl(meth)acrylamide, N-2-methylaminoethyl(meth)acrylamide, N-2-ethyl ... 6. The method of embodiment 5, wherein the alkyl group is selected from the group consisting of N-3-aminopropyl(meth)acrylamide, N-3-aminopropyl(meth)acrylamide, N-3-methylaminopropyl(meth)acrylamide, 2-aminoethyl(meth)acrylate, 2-methylaminoethyl(meth)acrylate, 2-ethylaminoethyl(meth)acrylate, 3-aminopropyl(meth)acrylate, 3-methylaminopropyl(meth)acrylate, 3-ethylaminopropyl(meth)acrylate, 3-amino-2-hydroxypropyl(meth)acrylate, and combinations thereof. 7. The method of any one of embodiments 3-6, wherein the hydrogel-forming composition comprises at least one crosslinkable polymer having a hydroxyl group and / or an ethylenically unsaturated group, and optionally at least one hydrophobic vinyl monomer selected from the group consisting of methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, methyl (meth)acrylate, and combinations thereof, and when the at least one crosslinkable polymer does not contain an ethylenically unsaturated group, the hydrogel-forming composition additionally comprises at least one hydroxyl-containing vinyl monomer and at least one compound having two or more isocyanato groups, and none of the polymerizable components in the hydrogel-forming composition contains a first reactive functional group and a thermally crosslinkable group that is an azetidinium group and / or an epoxy group. 8. The method of any one of embodiments 2 to 7, wherein the heating step is carried out by autoclaving a preformed contact lens or contact lens precursor immersed in a packaging solution (i.e., a buffered aqueous solution) in a sealed lens package at a temperature of about 115°C to about 125°C for about 20 to 90 minutes. 9. The method of any one of embodiments 2-8, wherein the at least one water-soluble, thermally crosslinkable, hydrophilic polymeric material comprises an azetidinium group, an epoxy group, or a combination thereof. 10. The method of embodiment 9, wherein the at least one water-soluble, thermally crosslinkable hydrophilic polymeric material is a three-dimensional network and thermally crosslinkable groups within or connected to the network. 11. The method of embodiment 9, wherein the at least one water-soluble, thermally crosslinkable hydrophilic polymeric material is one or more multi-arm polyethylene glycols, each having a terminal epoxy group; a mixture of multi-arm polyethylene glycols having terminal epoxy groups and one or more polyethylene glycols, each having a terminal functional group selected from the group consisting of a primary amine group, a secondary amine group, a carboxyl group, a thiol group, and combinations thereof; a partial reaction product of a multi-arm polyethylene glycol having an epoxy group and a hydrophilicity enhancing agent having at least one reactive functional group selected from the group consisting of an amino group, a carboxyl group, and a thiol group; or a combination thereof. 12. The method of embodiment 9, wherein the at least one water-soluble, thermally crosslinkable hydrophilic polymeric material comprises an azetidinium group and is the partial reaction product of an 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. 13. The method of embodiment 12, wherein the azetidinium-containing polymer is poly(2-oxazoline-co-ethyleneimine)-epichlorohydrin copolymer, polyamidoamine-epichlorohydrin, a copolymer of an azetidinium-containing vinyl monomer and one or more hydrophilic vinyl monomers, or a combination thereof. 14. The method of embodiment 12 or 13, wherein the hydrophilicity enhancer is a primary amino, secondary amino, carboxyl, or thiol-containing monosaccharide; a primary amino, secondary amino, carboxyl, or thiol-containing disaccharide; a primary amino, secondary amino, carboxyl, or thiol-containing oligosaccharide; or a combination thereof. 15. The method of embodiment 12 or 13, wherein the hydrophilic enhancer is a hydrophilic polymer having one or more primary or secondary amino groups, one or more carboxyl groups, one or more thiol groups, or a combination thereof. 16. The method of embodiment 15, wherein the hydrophilicity enhancer is a polysaccharide having primary amine groups, secondary amine groups, carboxyl groups, or a combination thereof. 17. The method of embodiment 15, wherein the hydrophilicity enhancer is: Poly(ethylene glycol) having one single functional group of -NH2, -SH or -COOH; poly(ethylene glycol) having two terminal functional groups selected from the group consisting of -NH2, -COOH, -SH, and combinations thereof; multi-arm poly(ethylene glycol) having one or more functional groups selected from the group consisting of -NH2, -COOH, -SH, and combinations thereof; monoamino, monocarboxyl, diamino, or dicarboxyl terminated homo- or copolymers of non-reactive hydrophilic vinyl monomers; 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%) of a reactive vinyl monomer; and (2) at least one non-reactive hydrophilic vinyl monomer; the reactive vinyl monomer is a vinyl monomer having a functional group selected from the group consisting of a carboxyl group, a primary amine group, and a secondary amine group; a copolymer in which the non-reactive hydrophilic monomer is a hydrophilic vinyl monomer that does not contain any carboxyl, primary amine, secondary amine, epoxide, isocyanate, azlactone, or aziridine groups; That's the method. 18. The method of embodiment 17, wherein the reactive vinyl monomer is acrylic acid, methacrylic acid, ethyl acrylic acid, 2-(meth)acrylamidoglycolic acid, N-2-aminoethyl(meth)acrylamide, N-2-methylaminoethyl(meth)acrylamide, N-2-ethylaminoethyl(meth)acrylamide, N-3-aminopropyl(meth)acrylamide, N-3-methylaminopropyl(meth)acrylamide, 2-aminoethyl(meth)acrylate, 2-methylaminoethyl(meth)acrylate, 2-ethylaminoethyl(meth)acrylate, 3-aminopropyl(meth)acrylate, 3-methylaminopropyl(meth)acrylate, 3-amino-2-hydroxypropyl(meth)acrylate, or a combination thereof. 19. The non-reactive hydrophilic vinyl monomer is selected from the group consisting of acrylamide, N,N-dimethylacrylamide, N-vinylpyrrolidone, (meth)acryloyloxyethyl phosphorylcholine, N-vinyl-N-methylacetamide, glycerol (meth)acrylate, hydroxyethyl (meth)acrylate, N-hydroxyethyl (meth)acrylamide, C1-C4 alkoxypolyethylene glycol (meth)acrylate having a weight average molecular weight of up to 400 Daltons, vinyl alcohol, and combinations thereof; and the non-reactive hydrophilic vinyl monomer is selected from the group consisting of (meth)acryloyloxyethyl phosphorylcholine, (meth)acryloyloxyethyl phosphorylcholine, N-vinyl-N-methylacetamide, glycerol (meth)acrylate, hydroxyethyl (meth)acrylate, N-hydroxyethyl (meth)acrylamide, C1-C4 alkoxypolyethylene glycol (meth)acrylate having a weight average molecular weight of up to 400 Daltons, vinyl alcohol, and combinations thereof. Iyloxypropylphosphorylcholine, 4-((meth)acryloyloxy)butyl-2'-(trimethylammonio)ethyl phosphate, 2-[(meth)acryloylamino]ethyl-2'-(trimethylammonio)ethyl phosphate, 3-[(meth)acryloylamino]propyl-2'-(trimethylammonio)ethyl phosphate, 4-[(meth)acryloylamino]butyl-2'-(trimethylammonio)ethyl phosphate, (meth)acrylamide, dimethyl(meth)acrylamide, N-2-hydroxyethyl(meth)acrylamide, N,N-bis(hydroxyethyl)(meth)acrylamide, N-2,3-Dihydroxypropyl (meth)acrylamide, N-tris(hydroxymethyl)methyl (meth)acrylamide, 2-hydroxyethyl (meth)acrylate, glycerol methacrylate (GMA), tetra(ethylene glycol) (meth)acrylate, poly(ethylene glycol) ethyl (meth)acrylamide having a number average molecular weight of up to 1500, poly(ethylene glycol) (meth)acrylate having a number average molecular weight of up to 1500, N-vinylpyrrolidone, N-vinyl-N-methylacetamide, N-vinylformamide, N-vinylacetamide, 1-methyl-3-methylene-2-pyrrolidone, 1-methyl-5-methylene-2-pyrrolidone, 5-methyl-3-methylene-2-pyrrolidone, tetra(ethylene glycol) methyl ether (meth)acrylate 19. The method of claim 17 or 18, wherein the hydroxypropyl methyl ether is selected from the group consisting of methyl methyl ether, methoxypoly(ethylene glycol)ethyl (meth)acrylamide having a number average molecular weight of up to 1500, C1-C4 alkoxypolyethylene glycol (meth)acrylate having a weight average molecular weight of up to 1500, tetra(ethylene glycol) monovinyl ether, poly(ethylene glycol) monovinyl ether, tetra(ethylene glycol) methyl vinyl ether, poly(ethylene glycol) methyl vinyl ether, tetra(ethylene glycol) monoallyl ether, poly(ethylene glycol) monoallyl ether, tetra(ethylene glycol) methyl allyl ether, poly(ethylene glycol) methyl allyl ether, vinyl alcohol, allyl alcohol, and combinations thereof. 20. The method of any one of embodiments 2 to 19, wherein the aqueous solution has a pH of about 7.0 to about 8.2, and the aqueous solution comprises about 0.01 wt % to about 2 wt % (preferably about 0.05 wt % to about 1.5 wt %, more preferably about 0.1 wt % to about 1 wt %, and even more preferably about 0.2 wt % to about 0.5 wt %) of the at least one water-soluble, thermally crosslinkable, hydrophilic polymeric material. 21. The method of any one of embodiments 2-20, wherein the aqueous solution comprises a mixture of monobasic dihydrogen phosphate and dibasic monohydrogen phosphate to maintain the pH of the aqueous solution, and the total concentration of monobasic dihydrogen phosphate and dibasic monohydrogen phosphate is at least 30 mM. 22. The method of embodiment 21, wherein the total concentration of monobasic dihydrogen phosphate and dibasic monohydrogen phosphate is at least 35 mM. 23. The method of embodiment 21, wherein the total concentration of monobasic dihydrogen phosphate and dibasic monohydrogen phosphate is at least 40 mM. 24. The method of embodiment 21, wherein the total concentration of monobasic dihydrogen phosphate and dibasic monohydrogen phosphate is at least 45 mM. 25. The method of any one of embodiments 2 to 24, wherein the tonicity of the aqueous solution is adjusted to about 200 to about 450 milliosmoles (mOsm), the aqueous solution comprises one or more organic tonicity agents selected from the group consisting of glycerol, propylene glycol, polyethylene glycol having a number average molecular weight of 200 to 800 daltons, mannitol, sorbitol, xylitol, and mixtures thereof, and the total concentration of the one or more organic tonicity agents is at least 70 mM. 26. The method of embodiment 25, wherein the total concentration of the one or more organic tonicity agents is at least 90 mM. 27. The method of embodiment 25, wherein the total concentration of the one or more organic tonicity agents is at least 110 mM. 28. The method of embodiment 25, wherein the total concentration of the one or more organic tonicity agents is at least 130 mM. 29. The coated contact lens of embodiment 1, or the method of any one of embodiments 2 to 28, wherein the anterior surface of the coated contact lens has a friction rating that is at least 0.25 greater than the friction rating of the posterior surface, as assessed by using a finger-touch lubricity test. 30. The coated contact lens of embodiment 1, or the method of any one of embodiments 2 to 28, wherein the anterior surface of the coated contact lens has a friction rating that is at least 0.50 greater than the friction rating of the posterior surface, as assessed by using a finger-touch lubricity test. 31. The coated contact lens of embodiment 1, or the method of any one of embodiments 2 to 28, wherein the anterior surface of the coated contact lens has a friction rating that is at least 0.75 greater than the friction rating of the posterior surface, as assessed by using a finger-touch lubricity test. 32. The coated contact lens of any one of embodiments 1 and 29-31, or the method of any one of embodiments 2-31, wherein the coated contact lens has a water film breakup time of at least about 15 seconds measured on the anterior and posterior surfaces of the coated contact lens in a fully hydrated state. 33. A coated contact lens according to any one of embodiments 1 and 29-31, or the method according to any one of embodiments 2-31, wherein the coated contact lens has a water film breakup time of at least about 20 seconds measured on the anterior and posterior surfaces of the coated contact lens in a fully hydrated state. 34. A coated contact lens according to any one of embodiments 1 and 29-31, or a method according to any one of embodiments 2-31, wherein the coated contact lens has a water film breakup time of at least about 25 seconds measured on the anterior and posterior surfaces of the coated contact lens in a fully hydrated state. 35. A coated contact lens according to any one of embodiments 1 and 29-31, or a method according to any one of embodiments 2-31, wherein the coated contact lens has a water film breakup time of at least about 30 seconds measured on the anterior and posterior surfaces of the coated contact lens in a fully hydrated state. 36. The coated contact lens of any one of embodiments 1 and 29-35, or the method of any one of embodiments 2-35, wherein the defects include (1) grooves that are ring-shaped, curved, and / or linear in plan view, or (2) gaps that are circular, triangular, square, rectangular, hexagonal, polygonal, and / or star-shaped in plan view. 37. The coated contact lens or method of embodiment 36, wherein one of two dimensions of each of the defects in a plan view is about 0.40 mm or less. 38. The coated contact lens or method of embodiment 36, wherein one of two dimensions of each of the defects in a plan view is about 0.30 mm or less. 39. The coated contact lens or method of embodiment 36, wherein one of two dimensions of each of the defects in a plan view is about 0.25 mm or less. 40. The coated contact lens or method of embodiment 36, wherein one of the two dimensions of each of the defects in a plan view is between about 0.05 mm and about 0.20 mm. 41. The coated contact lens of any one of embodiments 1 and 29-40, or the method of any one of embodiments 2-40, wherein the defects on the anterior surface of the coated contact lens are arranged in a pattern that is rotationally symmetric about the central axis of the coated contact lens. 42. The coated contact lens of any one of embodiments 1 and 29-40, or the method of any one of embodiments 2-40, wherein the defects on the anterior surface of the coated contact lens have an inner diameter of about 6.0 mm to about 9.0 mm and an outer diameter of about 11.5 mm to about 14.5 mm, and are arranged in an annular region concentric with the central axis of the coated contact lens. 43. The coated contact lens of any one of embodiments 1 and 29 to 42, or the method of any one of embodiments 2 to 42, wherein the defect comprises at least three grooves that are ring-shaped in plan view. 44. The coated contact lens of any one of embodiments 1 and 29-43, or the method of any one of embodiments 2-43, wherein the defects comprise at least eight curved or linear grooves having a diameter of about 6.0 mm to about 9.0 mm and extending radially outward from a circle concentric with the central axis of the coated contact lens. 45. The coated contact lens of any one of embodiments 1 and 29 to 44, or the method of any one of embodiments 2 to 44, wherein the defect comprises a circular gap in plan view. 46. ​​The coated contact lens or method of embodiment 45, wherein the circular gaps each have a diameter of about 0.25 mm or less in plan view. 47. The coated contact lens or method of embodiment 45, wherein the circular gaps each have a diameter of about 0.05 mm to about 0.20 mm in plan view. 48. The coated contact lens or method of any one of embodiments 45 to 47, wherein the gaps, each circular in plan view, are arranged in a rotationally symmetric pattern on the anterior surface of the coated contact lens. 49. The coated contact lens or method of embodiment 48, wherein the gaps, which are circular in plan view, are arranged in a pattern of annular rings concentric with the central axis of the coated contact lens. 50. The first non-silicone hydrogel material is selected from the group consisting of (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, N-2-dimethylaminoethyl(meth)acrylamide, dimethylaminoethyl(meth)acrylate, 2-hydroxyethyl(meth)acrylate, glycerol methacrylate ( GMA), tetra(ethylene glycol) (meth)acrylate, poly(ethylene glycol) ethyl (meth)acrylamide having a number average molecular weight of up to 1500, poly(ethylene glycol) (meth)acrylate having a number average molecular weight of up to 1500, N-vinylpyrrolidone, N-vinyl-N-methylacetamide, N-vinylformamide, N-vinylacetamide, 1-methyl-3-methylene-2-pyrrolidone, 1-methyl-5-methylene-2-pyrrolidone, 5-methyl-3-methylene-2-pyrrolidone, tetra(ethylene glycol) (meth)acrylate 45. The coated contact lens of any one of embodiments 1 and 29-44, or the method of any one of embodiments 2-49, wherein the crosslinked polymeric material comprises at least 35 mol % repeating monomer units of at least one hydrophilic vinyl monomer selected from the group consisting of tetra(ethylene glycol) monovinyl ether, poly(ethylene glycol) monovinyl ether, tetra(ethylene glycol) methyl vinyl ether, poly(ethylene glycol) methyl vinyl ether, tetra(ethylene glycol) monoallyl ether, poly(ethylene glycol) monoallyl ether, tetra(ethylene glycol) methyl allyl ether, poly(ethylene glycol) methyl allyl ether, vinyl alcohol, allyl alcohol, and combinations thereof. 51. The first non-silicone hydrogel material is selected from the group consisting of (meth)acrylamide, dimethyl(meth)acrylamide, N-2-hydroxyethyl(meth)acrylamide, N,N-bis(hydroxyethyl)(meth)acrylamide, N-2,3-dihydroxypropyl(meth)acrylamide, N-tris(hydroxymethyl)methyl(meth)acrylamide, 2-hydroxyethyl(meth)acrylate, glycerol methacrylate, 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, and methoxymethyl(meth)acrylamide having a number average molecular weight of up to 1500. The coated contact lens of any one of embodiments 1 and 29-44; or the method of any one of embodiments 2-49, wherein the crosslinked polymeric material comprises at least 45 mole % repeating monomer units of at least one hydrophilic vinyl monomer selected from the group consisting of poly(ethylene glycol) ethyl (meth)acrylamide, methoxypolyethylene glycol (meth)acrylate having a weight average molecular weight of up to 1500, poly(ethylene glycol) monovinyl ether, poly(ethylene glycol) methyl vinyl ether, poly(ethylene glycol) monoallyl ether, poly(ethylene glycol) methyl allyl ether, vinyl alcohol, allyl alcohol, and combinations thereof. 52. The coated contact lens of any one of embodiments 1 and 29-44, or the method of any one of embodiments 2-49, wherein the first non-silicone hydrogel material is a crosslinked polymeric material comprising at least 55 mol % repeating monomer units of at least one hydrophilic vinyl monomer selected from the group consisting of (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. 53. The coated contact lens of any one of embodiments 1 and 29-44, or the method of any one of embodiments 2-49, wherein the first non-silicone hydrogel material is a crosslinked polymeric material comprising at least 25 mol % of repeating monomer units of at least one phosphorylcholine-containing vinyl monomer. 54. The coated contact lens of any one of embodiments 1 and 29-44, or the method of any one of embodiments 2-49, wherein the first non-silicone hydrogel material is a crosslinked polymeric material comprising at least 35 mol % of repeating monomer units of at least one phosphorylcholine-containing vinyl monomer. 55. The coated contact lens of any one of embodiments 1 and 29-44, or the method of any one of embodiments 2-49, wherein the first non-silicone hydrogel material is a crosslinked polymeric material comprising at least 45 mol % of repeating monomer units of at least one phosphorylcholine-containing vinyl monomer. 56. The coated contact lens of any one of embodiments 1 and 29-44, or the method of any one of embodiments 2-49, wherein the first non-silicone hydrogel material is a crosslinked polymeric material comprising at least 55 mol % of repeating monomer units of at least one phosphorylcholine-containing vinyl monomer. 57. The coated contact lens or method of any one of embodiments 53-56, wherein the at least one phosphorylcholine-containing vinyl monomer is selected from the group consisting of (meth)acryloyloxyethyl phosphorylcholine, (meth)acryloyloxypropyl phosphorylcholine, 4-((meth)acryloyloxy)butyl-2'-(trimethylammonio)ethyl phosphate, 2-[(meth)acryloylamino]-ethyl-2'-(trimethylammonio)ethyl phosphate, 3-[(meth)acryloylamino]propyl-2'-(trimethylammonio)-ethyl phosphate, 4-[(meth)acryloylamino]butyl-2'-(trimethylammonio)ethyl phosphate, and combinations thereof. 58. The coated contact lens of any one of embodiments 1 and 29-44, or the method of any one of embodiments 2-49, wherein the first non-silicone hydrogel material is a crosslinked polymeric material comprising poly(ethylene glycol) chains, preferably derived directly from (a) poly(ethylene glycol) having a single functional group selected from one of -NH, -SH, or -COOH; (b) poly(ethylene glycol) having two terminal functional groups selected from the group consisting of -NH, -COOH, -SH, and combinations thereof; (c) multi-arm poly(ethylene glycol) having one or more functional groups selected from the group consisting of -NH, -COOH, -SH, and combinations thereof; and (d) combinations thereof. 59. A coated contact lens according to any one of embodiments 1 and 29 to 58, or a method according to any one of embodiments 2 to 58, wherein the lens bulk material is a hard plastic material (preferably a cross-linked polymethacrylate). 60. A coated contact lens according to any one of embodiments 1 and 29-58, or a method according to any one of embodiments 2-58, wherein the lens bulk material is a rigid gas-permeable material. 61. A coated contact lens according to any one of embodiments 1 and 29 to 58, or a method according to any one of embodiments 2 to 58, wherein the lens bulk material consists essentially of a central optical portion made of a gas-permeable lens material and a peripheral portion made of a silicone hydrogel or a third non-silicone hydrogel lens material, extending outward from the central optical portion and surrounding the central optical portion. 62. A coated contact lens described in any one of embodiments 1 and 29 to 58, or a method described in any one of embodiments 2 to 58, wherein the lens bulk material is a third non-silicone hydrogel material having a water content of about 10% to about 70% by weight when fully hydrated. 63. The lens bulk material has a water content of about 10% to about 70% by weight when fully hydrated, and is preferably selected from the group consisting of hydroxyethyl (meth)acrylate, glycerol (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-amino-2-hydroxypropyl (meth)acrylate, N-2-hydroxyethyl (meth)acrylamide, N-3-hydroxypropyl (meth)acrylamide, N-2-hydroxypropyl (meth)acrylamide, N-2,3-dihydroxypropyl (meth)acrylamide, and N-tris(meth)acrylate. The coated contact lens of any one of embodiments 1 and 29-58, or the method of any one of embodiments 2-58, wherein the third non-silicone hydrogel material comprises at least 50 mol % of repeat units of at least one hydroxyl-containing vinyl monomer selected from the group consisting of (hydroxymethyl)methyl(meth)acrylamide, vinyl alcohol, allyl alcohol, and combinations thereof, more preferably selected from the group consisting of hydroxyethyl(meth)acrylate, glycerol(meth)acrylate, and vinyl alcohol. 64. A coated contact lens according to any one of embodiments 1 and 29 to 58, or a method according to any one of embodiments 2 to 58, wherein the lens bulk material is a silicone hydrogel material having a water content of about 10% to about 70% by weight when fully hydrated and an oxygen permeability coefficient of at least about 50 barrers. 65. The coated contact lens or method of embodiment 64, wherein the coated contact lens has a water content of about 20% to about 70% by weight (preferably about 25% to about 65% by weight, more preferably about 30% to about 60% by weight), a modulus of about 0.2 MPa to about 2.0 MPa (preferably about 0.25 MPa to about 1.5 MPa, more preferably about 0.3 MPa to about 1.2 MPa, even more preferably about 0.35 MPa to about 1.0 MPa), an oxygen permeability of at least 60 barrer / mm (preferably at least 70 barrer / mm, more preferably at least 80 barrer / mm, even more preferably at least 100 barrer / mm), and an average water contact angle of less than 90 degrees (preferably less than 80 degrees, more preferably less than 70 degrees, even more preferably less than 60 degrees). 66. The method of any one of embodiments 2 to 65, wherein the plurality of regions have a circular, triangular, square, rectangular, hexagonal, polygonal, star-shaped, annular ring-shaped, curved, linear, or combination thereof. 67. The method of any one of embodiments 2 to 66, wherein one of two dimensions of the plurality of regions is less than or equal to about 0.40 mm. 68. The method of any one of embodiments 2 to 66, wherein one of two dimensions of the plurality of regions is less than or equal to about 0.30 mm. 69. The method of any one of embodiments 2 to 66, wherein one of two dimensions of the plurality of regions is less than or equal to about 0.25 mm. 70. The method of any one of embodiments 2 to 66, wherein one of the two dimensions of the plurality of regions is between about 0.05 mm and about 0.20 mm. 71. The method of any one of embodiments 2-70, wherein the plurality of regions are arranged in a pattern that is rotationally symmetric about the central axis of the preformed contact lens or female mold half. 72. The method of any one of embodiments 2 to 71, wherein the plurality of regions are arranged in an annular region having an inner diameter of about 6.0 mm to about 9.0 mm and an outer diameter of about 11.5 mm to about 14.5 mm and concentric with the central axis of the preformed contact lens or female mold half. 73. The method of any one of embodiments 2-72, wherein the plurality of regions comprises at least three annular rings. 74. The method of any one of embodiments 2 to 73, wherein the plurality of regions comprises at least eight curved or straight lines extending radially outward from a circle having a diameter of about 6.0 mm to about 9.0 mm and concentric with the central axis of the preformed contact lens or female mold half. 75. The method of any one of embodiments 2 to 74, wherein the plurality of regions comprises circular dots having a diameter of about 0.25 mm or less. 76. The method of any one of embodiments 2 to 74, wherein the plurality of regions comprises circular dots having a diameter of about 0.05 mm to about 0.20 mm. 77. The method of embodiment 75 or 76, wherein the circular dots are arranged on the convex surface of the preformed contact lens or the molding surface of the female mold half in a pattern that is rotationally symmetrical relative to the central axis of the preformed contact lens or female mold half. 78. The method of any one of embodiments 75-77, wherein the circular dots are arranged in an annular ring concentric with the central axis of the preformed contact lens or female mold half.

[0223] The above disclosure will enable those skilled in the art to practice the present invention. Various modifications, variations and combinations can be made to the various embodiments described herein. In order to better enable the reader to understand specific embodiments and their advantages, reference to the following examples is suggested. It is intended that the specification and examples be considered as illustrative. [Example]

[0224] Example 1 Measurement of oxygen permeability coefficient Unless otherwise specified, the oxygen permeability (Dk / t) of the lens and lens material, the intrinsic (or edge-corrected) oxygen permeability coefficient (Dk i or Dk c ) is measured according to the procedure described in ISO 18369-4.

[0225] Water film break-up time (WBUT) test The surface hydrophilicity of the lens is evaluated by measuring the time required for the water film on the lens surface to start breaking using an interfacial de-wetting and drainage optical platform (iDDroP), as described in the paper titled Influence of Lipid Coatings on Surface Wettability Characteristics of Silicone Hydrogels published by Bhamla et al. in Langmuir. 2015, 31: 3820-3828. During the IDDrop test, the lens is placed on the stage and immersed in PBS. Then, a small surface of the lens is exposed to air. An electric linear stage and a motion controller are used to expose the contact lens at a specified depth. A video of the water film break-up is taken to evaluate the water film break-up time and the water film break-up pattern.

[0226] Equilibrium water content The equilibrium water content (EWC) of the contact lens (i.e., the water content of the contact lens in a fully hydrated state) is determined according to the procedure described in Example 1 of US Patent Application Publication No. 20210181379A1.

[0227] Elastic modulus The elastic modulus of the contact lens is determined according to the procedure described in Example 1 of US Patent Application Publication No. 20210181379A1.

[0228] Light transmittance A contact lens is manually placed in a specially fabricated specimen holder, which maintains the lens' shape as it would be on the eye. The holder is then immersed in a 1 cm pathlength quartz cuvette containing phosphate-buffered saline (PBS, pH approximately 7.0-7.4) as a reference. This measurement can be performed using a UV / visible spectrophotometer, such as a Varian Cary 3E UV-Visible spectrophotometer equipped with a LabSphere DRA-CA-302 beamsplitter. Percent transmittance spectra are collected over the wavelength range of 250-800 nm, with %T values ​​collected at 0.5 nm intervals. The optical transmittance of the contact lens is the average % transmittance from 400 nm to 700 nm.

[0229] Measurement of Water Contact Angle (WCA). Water contact angle (WCA) measurements are performed by the sessile drop method on a DSA 10 drop formation analysis system from Krüss GmbH, Germany, using pure water (Fluka, surface tension 72.5 mN / m at 20 °C). For measurement purposes, the contact lens is removed from the storage solution using tweezers and excess storage solution is removed by gentle shaking. The contact lens is placed on the male part of the lens mold and gently wiped with a dry, clean cloth. A water droplet (approximately 1 μl) is then placed on the apex of the lens, and the change in the contact angle of this droplet over time (WCA(t), circle fitting mode) is monitored. WCA is calculated by extrapolating the graph WCA(t) to t = 0.

[0230] Lubricity evaluation. The lubricity of contact lenses is assessed using a finger-touch lubricity test, which qualitatively characterizes the slipperiness of the lens surface on a friction rating scale of 0 to 4. The higher the friction rating, the less slipperiness (i.e., lubricity). In this test, the lens is touched between the thumb and index finger, and a qualitative rating of 0 to 4 is given based on the level of friction perceived by the tester. The given rating is compared to five commercially available lenses corresponding to five levels of lubricity, which serve as benchmarks for this test.

[0231] The levels and standards are as follows: DAILIES® TOTAL 1® lenses (Alcon) are the standard with a grade of 0 on the scale, ACUVUE® OASYS TM The lenses (Johnson & Johnson) are grade 1 standards, the ULTRA® lenses (Bausch & Lamb) are grade 2 standards, the DAILIES® Aqua Comfort Plus® lenses (Alcon) are grade 3 standards, and the AIR OPTIX® Aqua lenses are grade 4 standards.

[0232] The samples are placed in PBS for at least two rinses, each for 30 minutes, and then transferred to fresh PBS before evaluation. Before evaluation, hands are rinsed with soap solution, thoroughly rinsed with deionized water, and then dried with a KimWipe towel. When evaluating the lubricity of the anterior surface, the lens is placed on the index finger with the posterior surface facing the index finger, and the thumb is rubbed against the anterior surface to check the feel of slipperiness (i.e., lubricity) of the anterior surface. When evaluating the lubricity of the posterior surface, the lens is first inverted, then placed on the index finger with the inverted anterior surface facing the index finger, and the thumb is rubbed against the inverted posterior surface to check the feel of smoothness (or lubricity) of the posterior surface.

[0233] Each sample is assigned a friction rating relative to the reference lens described above. The friction rating value is obtained by averaging the results of at least two friction ratings of the contact lenses by two or more people and / or by averaging the friction ratings of two or more contact lenses (from the same batch of lens manufacturing) by one person.

[0234] The finger lubricity (i.e., friction rating) of contact lenses can be determined directly out-of-pack (OOP) or after immersion in PBS for ≥ 30 minutes according to the procedure described above.

[0235] Lens removal evaluation The overall removability of each lens group is measured using a 3D-printed eye model, including a soft cornea, orbital bones, and nasal bones. The inclusion of these details allows for a biologically accurate reproduction of the interactions involved in contact lens insertion and removal. A blinded study is conducted in which two testers determine the number of removal attempts for the test lens. A removal "attempt" is defined as a tear-off motion on the surface of the eye model while the contact lens is placed in the ocular region of the eye. This is performed with minimal downward force applied to the surface of the eye model to simulate the actual lens removal motion. After placing the contact lens in the eye, a drop of artificial tear is also instilled to simulate the moisturizing effect of blinking.

[0236] chemicals In the examples below, the following abbreviations are used: HEMA stands for hydroxyethyl methacrylate; EOEMA stands for ethoxyethyl methacrylate; MAA stands for methacrylic acid; AA stands for acrylic acid; PEG-DA stands for poly(ethylene glycol) diacrylate (Mn approx. 800 g / mol); PG stands for propylene glycol; Vazo 64 stands for azobisisobutyronitrile; Vazo 67 stands for 2,2'-azodi(2-methylbutyronicnitrile); AIBN stands for azobis(isobutyronitrile); Perkadox 16 represents di(4-tert-butylcyclohexyl)peroxydicarbonate; MPC represents 2-methacryloyloxyethyl phosphorylcholine; EGMA represents 2-methoxyethyl methacrylate; AMA represents allyl methacrylate; TEGDVE represents tri(ethylene glycol) divinyl ether; Nobloc represents 2-[3-(2H-benzotriazol-2-yl)-5-hydroxyphenyl]ethyl methacrylate; RB247 represents Reactive Blue 247; HDI represents hexamethylene diisocyanate; ELA represents ethyl lactate; ME represents 2-marcaptoethanol; PBS represents phosphate buffered saline containing about 0.044 wt% NaH2PO4·H2O, about 0.388 wt% Na2HPO4·2H2O, and about 0.79 wt% NaCl (wt% represents percentage by weight) and having a pH of 7.2±0.2 at 25°C; "G2" macromer represents a dimethylacryloyloxypropyl-terminated polysiloxane of formula (A) (molecular weight about 8 kg / mol, OH content about 3.5 meq / g). [ka]

[0237] Example 2 Preparation of polymerizable composition A polymerizable composition (SiHy lens formulation) is prepared having the composition as shown in Table 1.

[0238] [Table 1]

[0239] The formulation is prepared by placing the listed ingredients in their target amounts in a clean bottle and mixing with a stir bar at 600 rpm for 30 minutes at room temperature. After all solids have dissolved, the formulation is filtered using a 2.7 μm glass microfiber filter (GMF).

[0240] Cast-molded silicone hydrogel contact lenses The lens formulation is purged with nitrogen at room temperature for 30-35 minutes. The N2-purged lens formulation is placed into a polypropylene mold and heat cured in an oven under nitrogen under the following cure conditions: room temperature to 55°C at approximately 7°C / min; hold at 55°C for approximately 30 minutes; ramp from 55°C to 80°C at approximately 7°C / min; hold at 80°C for approximately 30 minutes; ramp from 80°C to 100°C at approximately 7°C / min; hold at 100°C for approximately 30 minutes. The mold is then opened. The molded lens remains attached to the male mold half.

[0241] Example 3 Phosphate-buffered saline (PBS) Phosphate buffered saline is prepared by dissolving NaH2PO4·H2O, Na2HPO4·2H2O, and NaCl in a predetermined amount of purified water (distilled or deionized) to have the following composition: approximately 0.044 w / w% NaH2PO4·H2O, approximately 0.388 w / w / % Na2HPO4·2H2O, and approximately 0.79 w / w% NaCl.

[0242] Preparation of In-Package Coated Saline - IPC-1 IPC saline (IPC-1) was prepared by mixing the appropriate amount of poly(AAm-co-AA) with PAE in phosphate-buffered saline and pretreating at a predetermined temperature for a predetermined time. Poly(AAm-co-AA) (90 / 10) partial sodium salt, poly(AAm-co-AA) 90 / 10, Mw 200,000, was produced in-house. Kymene or PAE solutions with different solids contents were purchased as aqueous solutions from Solenis and used as received. The components were approximately 0.05 wt% PAE; 0.035 wt% poly(AAm-co-AA) (90 / 10), 0.776 wt% NaHPO 2H O, 0.044 wt% NaHPO H O, 0.160 wt% NaCl, and the balance to 100% water. The resulting aqueous solution was pretreated at 60°C for approximately 1 hour. After heat pretreatment, the IPC saline is filtered through a 0.22 micron membrane filter and cooled to room temperature. To prevent bioburden growth, 5 ppm hydrogen peroxide can be added to the final IPC saline, which is then filtered through a 0.22 micron membrane filter.

[0243] Preparation of Hydrogel-Forming Compositions A crosslinkable polymer containing hydroxyl groups is prepared by polymerizing a composition containing 38.33% HEMA, 4.20% EOEMA, 0.32% ME, 0.21% AIBN, and 56.93% cyclopentanone according to the method described in U.S. Pat. No. 4,668,240.

[0244] A hydrogel-forming composition is prepared having the following composition by weight: 49.7% crosslinkable polymer prepared above, 16% HEMA, 1.8% EOEMA, 3.2% HDI, 0.1% Vazo64, and 29.2% ELA.

[0245] Making a cliché Image patterns of various dot sizes and densities are engraved into the printing plates to produce metal, polymer, or ceramic cliches for use in pad printers. All patterns are 15 microns deep.

[0246] Figure 1A shows a 0.25 pt. printed pattern (five rings) with each dot having a diameter of 90 μm. The smallest ring has an inner diameter of 7.5 mm.

[0247] Figure 1B shows a 0.50 pt. printed pattern (five rings) with each dot having a diameter of 170 μm. The smallest ring has an inner diameter of 6.4 mm.

[0248] Figure 1C shows a 0.75 pt. printed pattern (five rings) with each dot having a diameter of 90 μm. The smallest ring has an inner diameter of 7.5 mm.

[0249] Figure 1D shows a 1.0 pt. printed pattern (five rings) with each dot having a diameter of 170 μm. The smallest ring has an inner diameter of 6.4 mm.

[0250] Figure 1E shows the printing pattern of a donut ring pt. with an inner diameter of 4.4 mm and an outer diameter of 11.1 mm.

[0251] Manufacturing of moisture gradient contact lenses The hydrogel-forming composition prepared above is applied to the anterior (convex) surface of a preformed SiHy contact lens (a dry lens attached to a male mold half) prepared in Example 2 in the above-described printing pattern according to the pad printing procedure described in Example 4 of U.S. Patent Application Publication No. 2020 / 0376787 A1. The lens can be printed in one pass (one layer) or two passes (two layers) of the hydrogel-forming composition. After pad printing, the lens undergoes a second heat-curing step. This step adheres the printed hydrogel to the lens and imparts different surface properties to the lens. The lens is removed from the mold (lens removal), packaged, and hydrated in IPC saline for 30 minutes, followed by autoclaving at 121°C for 45 minutes.

[0252] Control lenses are not printed with the hydrogel formulation, are packaged in the same IPC saline solution, and are autoclaved.

[0253] The resulting moisture gradient contact lens has a water content of about 47%, an oxygen permeability (Dkc) of about 65 barrers, and a modulus of elasticity of about 0.7 MPa when fully hydrated.

[0254] Lubricity evaluation The moisture gradient contact lenses prepared above are used to conduct a fingertip lubricity test according to the procedure described in Example 1. Lenses with a friction rating of 0-1 are designated as 0.5, and lenses with a friction rating slightly greater than 0 are designated as 0.25. The results are reported in Table 2.

[0255] [Table 2]

[0256] Water film breakdown time by IDDrop The water film burst time of the above prepared moisture gradient contact lenses is determined using IDDrop according to the procedure described in Example 1. The results are reported in Table 3.

[0257] [Table 3]

[0258] During the IDDrop test, the fracture pattern on unprinted lenses is observed to be fairly uniform. However, the water film fracture on printed lenses, especially those with two layers of large dot size printing, is less uniform because water tends to pool around the printed area.

[0259] Lens removal evaluation The lens removability of the water gradient contact lenses prepared above is evaluated according to the procedure described in Example 1. The results are reported in Table 4.

[0260] [Table 4]

[0261] All publications, patents and published patent applications cited herein above in this application are hereby incorporated by reference in their entirety.

Claims

1. a front surface and an opposite rear surface; a layered structural configuration including, in a direction from the anterior surface toward the posterior surface, an anterior outer hydrogel layer, an inner layer, and a posterior outer hydrogel layer, 1. A coated contact lens, wherein the inner layer is a lens bulk material, the posterior outer hydrogel layer is a layer of a first non-silicone hydrogel material, the front outer hydrogel layer having defects distributed therein such that the posterior outer hydrogel layer has a surface lubricity that is greater than the surface lubricity of the front outer hydrogel layer, and wherein the coated contact lens, in a fully hydrated state, has a water breakup time of at least about 10 seconds measured on the anterior and posterior surfaces of the coated contact lens.

2. 1. A method for producing a coated contact lens, comprising: (1) obtaining a preformed contact lens having a convex surface and an opposite concave surface, the preformed contact lens being composed of a lens bulk material and including first reactive functional groups on and adjacent the convex and concave surfaces of the preformed contact lens, each of the first reactive functional groups being capable of reacting with a thermally crosslinkable group at a temperature of from about 60°C to about 140°C, the first reactive functional groups being selected from the group consisting of a carboxylic acid group, a primary amino group, a secondary amino group, a thiol group, and combinations thereof; (2) coating a plurality of regions on the convex surface with a first non-silicone hydrogel material to prevent first reactive functional groups at the rear of the plurality of regions from reacting with thermally crosslinkable groups, wherein the first non-silicone hydrogel material does not contain first reactive functional groups and thermally crosslinkable groups; (3) directly heating the preformed contact lens obtained in step (2) at a temperature of about 60°C to about 140°C in an aqueous solution having a pH of about 6.5 to about 9.5 and containing at least one water-soluble, thermally crosslinkable, hydrophilic polymer material, to graft a second non-silicone hydrogel material onto each of the anterior and posterior surfaces of the preformed contact lens obtained in step (2), thereby forming a coated contact lens having an anterior surface, an opposite posterior surface, an anterior outer hydrogel layer, and a posterior outer hydrogel layer, a polymeric material comprising a second reactive functional group and a third reactive functional group, wherein the second reactive functional groups are thermally crosslinkable groups selected from the group consisting of an azetidinium group, an epoxy group, and combinations thereof, each of the second reactive functional groups being capable of reacting with one of the first or third reactive functional groups to form a crosslink, and the third reactive functional groups being selected from the group consisting of a carboxylic acid group, a primary amino group, a secondary amino group, a thiol group, and combinations thereof, and wherein the second non-silicone hydrogel material is a crosslinked product of the at least one thermally crosslinkable hydrophilic polymeric material; Including, a front outer hydrogel layer having defects (e.g., grooves and / or crevices) distributed therein that impart a surface lubricity to the posterior surface that is greater than the surface lubricity of the front surface of the coated contact lens, and wherein the coated contact lens in a fully hydrated state has a water breakup time of at least about 10 seconds measured on the front and posterior surfaces of the coated contact lens.

3. 3. The method of claim 2, wherein step (2) is carried out by applying a hydrogel-forming composition onto a plurality of regions on the convex surface of the preformed contact lens (preferably by pad transfer printing and / or inkjet printing techniques), and then curing the hydrogel-forming composition thermally or by actinic radiation to form the first non-silicone hydrogel material to cover the plurality of regions.

4. 1. A method for producing a coated contact lens, comprising: (1) obtaining a female mold half and a male mold half, the female mold half having a first molding surface that defines the anterior surface of a contact lens to be molded, the male mold half having a second molding surface that defines the posterior surface of the contact lens to be molded, the male mold half and the female mold half configured to receive each other such that a lens molding cavity is formed between the first molding surface and the second molding surface when the female mold half is closed with the male mold half; (2) applying a hydrogel-forming composition to a plurality of regions on the first molding surface, wherein the hydrogel-forming composition comprises at least one crosslinkable polymer having a hydroxyl group and / or an ethylenically unsaturated group, and optionally at least one hydrophobic vinyl monomer selected from the group consisting of methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, methyl (meth)acrylate, and combinations thereof, and when the at least one crosslinkable polymer does not contain an ethylenically unsaturated group, the hydrogel-forming composition additionally comprises at least one hydroxyl-containing vinyl monomer and at least one compound having two or more isocyanato groups, and all polymerizable components in the hydrogel-forming composition do not contain reactive functional groups selected from the group consisting of carboxylic acid groups, primary amino groups, secondary amino groups, azetidinium groups, epoxy groups, and combinations thereof; (3) optionally but preferably, partially curing the hydrogel-forming composition on the first molding surface; (4) introducing a polymerizable composition into the negative mold half obtained in step (2) or (3), wherein the polymerizable composition comprises about 1.0% to about 10% by weight of at least one reactive vinyl monomer having at least one first reactive functional group selected from the group consisting of a carboxylic acid group, a primary amino group, a secondary amino group, and combinations thereof, based on the total amount of all polymerizable components; (5) closing the female mold half obtained in step (4) with the male mold half to form a mold assembly containing the polymerizable composition within the lens-forming cavity; (6) curing the polymerizable composition in the molding assembly thermally or with actinic radiation to form a contact lens precursor having a convex surface and an opposite concave surface, the contact lens precursor comprising a lens bulk material having first reactive functional groups, wherein the convex surface of the contact lens precursor is partially coated with a first hydrogel material formed from the hydrogel-forming composition in a plurality of regions on the convex surface, thereby preventing reaction of the first reactive functional groups behind the plurality of regions with thermally crosslinkable groups that are azetidinium groups and / or epoxy groups at a temperature of about 60° C. to about 140° C., and the first non-silicone hydrogel material is free of first reactive functional groups and thermally crosslinkable groups; (7) optionally hydrating the contact lens precursor obtained in step (6) in water or an aqueous solution; (8) directly heating the contact lens precursor obtained in step (6) or step (7) at a temperature of about 60°C to about 140°C in an aqueous solution having a pH of about 6.5 to about 9.5 and containing at least one water-soluble, thermally crosslinkable hydrophilic polymer material, and grafting the second non-silicone hydrogel material onto each of the convex and concave surfaces of the contact lens precursor obtained in step (6) or the hydrated contact lens precursor obtained in step (7), thereby producing a coated contact lens precursor having an anterior surface, an opposite posterior surface, an anterior outer hydrogel layer, and a posterior outer hydrogel layer. forming a contact lens, wherein the at least one water-soluble, thermally crosslinkable hydrophilic polymeric material comprises a second reactive functional group and a third reactive functional group, the second reactive functional group being a thermally crosslinkable group selected from the group consisting of an azetidinium group, an epoxy group, and combinations thereof, each of the second reactive functional groups being capable of reacting with one of the first or third reactive functional groups to form a crosslink, and the third reactive functional group being selected from the group consisting of a carboxylic acid group, a primary amino group, a secondary amino group, a thiol group, and combinations thereof; Including, a front outer hydrogel layer having defects (e.g., grooves and / or crevices) distributed therein that impart a surface lubricity to the posterior surface that is greater than the surface lubricity of the front surface of the coated contact lens, and the coated contact lens having a water breakup time of at least about 10 seconds measured on the front and posterior surfaces of the coated contact lens.

5. 5. The method of claim 3 or 4, wherein the hydrogel-forming composition comprises at least one crosslinkable polymer having a hydroxyl group and / or an ethylenically unsaturated group, and optionally at least one hydrophobic vinyl monomer selected from the group consisting of methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, methyl (meth)acrylate, and combinations thereof, and when the at least one crosslinkable polymer does not contain an ethylenically unsaturated group, the hydrogel-forming composition additionally comprises at least one hydroxyl-containing vinyl monomer and at least one compound having two or more isocyanato groups, and all polymerizable components in the hydrogel-forming composition do not contain a first reactive functional group and a thermally crosslinkable group that is an azetidinium group and / or an epoxy group.

6. 6. The method of any one of claims 2 to 5, wherein the heating step is carried out by autoclaving the preformed contact lens or contact lens precursor immersed in a packaging solution (i.e., a buffered aqueous solution) in a sealed lens package at a temperature of about 115°C to about 125°C for about 20 to 90 minutes.

7. The method of any one of claims 2 to 6, wherein the at least one water-soluble, thermally crosslinkable hydrophilic polymeric material comprises an azetidinium group, an epoxy group, or a combination thereof.

8. 8. The method of claim 7, wherein the at least one water-soluble, thermally crosslinkable hydrophilic polymeric material is a three-dimensional network and thermally crosslinkable groups within or connected to the network.

9. 9. The coated contact lens of claim 1 or the method of any one of claims 2 to 8, wherein the defects comprise: (1) grooves that are ring-shaped, curved, and / or linear in plan view; (2) gaps that are circular, triangular, square, rectangular, hexagonal, polygonal, and / or star-shaped in plan view.

10. 10. The coated contact lens of claim 1 or 9 or the method of any one of claims 2 to 9, wherein the defects on the anterior surface of the coated contact lens are arranged in a pattern that is rotationally symmetric about a central axis of the coated contact lens.

11. 10. The coated contact lens of claim 1 or 9 or the method of any one of claims 2 to 9, wherein the defects on the anterior surface of the coated contact lens have an inner diameter of about 6.0 mm to about 9.0 mm and an outer diameter of about 11.5 mm to about 14.5 mm, and are arranged in an annular region concentric with a central axis of the coated contact lens.

12. 12. The coated contact lens of any one of claims 1 and 9 to 11, or the method of any one of claims 2 to 11, wherein the defect comprises at least three grooves that are ring-shaped in plan view.

13. 13. The coated contact lens of any one of claims 1 and 9 to 12, or the method of any one of claims 2 to 12, wherein the defects comprise at least eight curved or linear grooves having a diameter of about 6.0 mm to about 9.0 mm and extending radially outward from a circle concentric with a central axis of the coated contact lens.

14. 14. The coated contact lens of any one of claims 1 and 9 to 13, or the method of any one of claims 2 to 13, wherein the defect comprises a circular gap in plan view.

15. 15. The coated contact lens or method of claim 14, wherein the gaps, which are circular in plan view, are arranged in a rotationally symmetric pattern on the anterior surface of the coated contact lens.

16. 15. The coated contact lens or method of claim 14, wherein the gaps, which are circular in plan view, are arranged in a pattern of annular rings concentric with a central axis of the coated contact lens.

17. the first non-silicone hydrogel material comprising: (1) (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, N-2-hydroxyethyl(meth)acrylamide, N,N-bis(hydroxyethyl)(meth)acrylamide, N-3-hydroxypropyl(meth)acrylamide, N-2-hydroxypropyl(meth)acrylamide, N-2,3-dihydroxypropyl(meth)acrylamide, N-tris(hydroxymethyl)methyl(meth)acrylamide, 2-hydroxyethyl(meth)acrylate, 3-hydroxypropyl(meth)acrylate, 2-hydroxypropyl(meth)acrylate, glycerol methacrylate (GMA), di(ethylene glycol)(meth)acrylate, tri(ethylene glycol)(meth)acrylate, tetra(ethylene glycol)(meth)acrylate, poly(ethylene glycol)(meth)acrylate having a number average molecular weight of up to 1500, poly(ethylene glycol)ethyl(meth)acrylamide having a number average molecular weight of up to 1500, N-vinylpyrrolidone, N-vinyl-N-methylacetamide, N-vinylformamide, N-vinylacetamide, N-vinylisopropylamide, N-vinyl-N-ethylacetamide, N-vinyl-N-ethylformamide, 1-methyl -3-methylene-2-pyrrolidone, 1-ethyl-3-methylene-2-pyrrolidone, 1-methyl-5-methylene-2-pyrrolidone, 1-ethyl-5-methylene-2-pyrrolidone, 5-methyl-3-methylene-2-pyrrolidone, 5-ethyl-3-methylene-2-pyrrolidone, 1-n-propyl-3-methylene-2-pyrrolidone, 1-n-propyl-5-methylene-2-pyrrolidone, 1-isopropyl-3-methylene-2-pyrrolidone, 1-isopropyl-5 -methylene-2-pyrrolidone, 1-n-butyl-3-methylene-2-pyrrolidone, 1-tert-butyl-3-methylene-2-pyrrolidone, ethylene glycol methyl ether (meth)acrylate, di(ethylene glycol) methyl ether (meth)acrylate, tri(ethylene glycol) methyl ether (meth)acrylate, tetra(ethylene glycol) methyl ether (meth)acrylate, C having a weight average molecular weight of up to 1500, １ ~C ４ Alkoxy poly(ethylene glycol) (meth)acrylate, methoxy poly(ethylene glycol) ethyl (meth)acrylamide having a number average molecular weight of up to 1500, allyl alcohol, ethylene glycol monoallyl ether, di(ethylene glycol) monoallyl ether, tri(ethylene glycol) monoallyl ether, tetra(ethylene glycol) monoallyl ether, poly(ethylene glycol) monoallyl ether, ethylene glycol methyl allyl ether, di(ethylene glycol) methyl allyl ether, tri(ethylene glycol) methyl allyl ether, tetra(ethylene glycol) methyl allyl ether, poly(ethylene glycol) methyl allyl ether a crosslinked polymeric material comprising at least 25 mole percent repeating monomer units of at least one hydrophilic vinyl monomer selected from the group consisting of ethylene glycol monovinyl ether, di(ethylene glycol) monovinyl ether, tri(ethylene glycol) monovinyl ether, tetra(ethylene glycol) monovinyl ether, poly(ethylene glycol) monovinyl ether, ethylene glycol methyl vinyl ether, di(ethylene glycol) methyl vinyl ether, tri(ethylene glycol) methyl vinyl ether, tetra(ethylene glycol) methyl vinyl ether, poly(ethylene glycol) methyl vinyl ether, and combinations thereof; or (2) a crosslinked polymeric material containing at least 25 mole percent repeating monomer units of at least one phosfurylcholine-containing vinyl monomer; or (3) A cross-linked polymer material comprising poly(ethylene glycol) chains, the poly(ethylene glycol) chains preferably being: (a) —NH ２ (b) poly(ethylene glycol) having one single functional group of -SH or -COOH; ２ (c) a poly(ethylene glycol) having two terminal functional groups selected from the group consisting of —NH ２ , —COOH, —SH, and combinations thereof; and (d) multi-arm poly(ethylene glycol) having one or more functional groups selected from the group consisting of: —COOH, —SH, and combinations thereof; and (4) A coated contact lens according to any one of claims 1 and 9 to 16, or a method according to any one of claims 2 to 16, which is a combination thereof.

18. 18. The method of any one of claims 2 to 17, wherein the plurality of regions have a circular, triangular, square, rectangular, hexagonal, polygonal, star-shaped, annular ring-shaped, curved, linear, or combinations thereof.

19. 19. The method of any one of claims 2 to 18, wherein the plurality of regions are arranged in a pattern that is rotationally symmetric about a central axis of the preformed contact lens or the female mold half.

20. 20. The method of any one of claims 2 to 19, wherein the plurality of regions are arranged in an annular region having an inner diameter of about 6.0 mm to about 9.0 mm and an outer diameter of about 11.5 mm to about 14.5 mm and concentric with a central axis of the preformed contact lens or female mold half.

21. The method of any one of claims 2 to 20, wherein the plurality of regions comprises at least three annular rings.

22. 22. The method of any one of claims 2 to 21, wherein the plurality of regions comprises at least eight curved or straight lines extending radially outward from circles having a diameter of about 6.0 mm to about 9.0 mm and concentric with a central axis of the preformed contact lens or female mold half.

23. 23. The method of claim 22, wherein the plurality of regions comprise circular dots, the circular dots being arranged on the convex surface of the preformed contact lens or the molding surface of the female mold half in a pattern that is rotationally symmetrical about the central axis of the preformed contact lens or the female mold half.

24. 23. The method of claim 22, wherein the plurality of regions comprise circular dots, the circular dots being arranged in an annular ring concentric with a central axis of the preformed contact lens or the female mold half.

Images