Water gradient siloxane hydrogel contact lenses

Abstract

The invention provides a water gradient contact lens easy to move out. Such water gradient contact lenses contain die marks (trenches and / or gaps) in the front outer hydrogel layer and may be made according to a cost effective method involving the step of partially or completely shielding reactive functional groups in selected regions on the front surface of the contact lens to be coated prior to grafting a layer of non-siloxane hydrogel material. The surface lubricity of the front surface is lower than the surface lubricity of the rear surface in the presence of a mold mark in the front outer hydrogel layer. By adjusting the shape, size, density, and rotational distribution of the die marks, the surface lubricity of the front surface of the water gradient contact lens may also be selectively adjusted and optimized to have improved lens ease of handling while maintaining other desired characteristics.

Description

Technical Field

[0001] The present invention relates to a water-gradient silicone hydrogel contact lens (contact lens) that is easy to remove and a method for producing such a water-gradient silicone hydrogel contact lens. Background Art

[0002] A new class of soft contact lenses (water-gradient polysiloxane hydrogel contact lenses, e.g., (Alcon), (Alcon) and (Alcon)) have been developed and successfully introduced into the market. Such new soft contact lenses are characterized by a water-gradient structure configuration, with the water content increasing from 33% to over 80% from the core to the surface (see, e.g., U.S. Patent Nos. 8480227, 11061168, and 11256003). This unique design can provide a highly lubricated, extremely soft, water-rich lens surface, thus providing superior wearing comfort for patients.

[0003] The newly developed water-gradient (poly)siloxane hydrogel contact lenses can provide superior wearing comfort for patients due to their extremely soft, water-rich, relatively thick, and lubricated hydrogel coating. However, one of the main challenges of water-gradient contact lenses is lens removal. Since these contact lenses are highly lubricated, patients, especially new patients, may have a steep learning curve when removing the lenses from their eyes. Therefore, there is a desire for water-gradient contact lenses with improved lens manipulability ("easy to insert / remove") while maintaining other desired properties.

[0004] Therefore, there is still a need for water-gradient contact lenses that are easy to remove. Summary of the Invention

[0006] In one aspect, the present invention provides a coated contact lens comprising: a front surface and an opposing rear surface; and a layered structure configuration that includes a front outer hydrogel layer, an inner layer, and a rear outer hydrogel layer in a direction from the front surface to the rear surface, wherein the inner layer is made of a lens body material, wherein the rear outer hydrogel layer is a first non-(poly)siloxane hydrogel material layer, wherein the front outer hydrogel layer is the first non-siloxane hydrogel material layer in which imperfections (e.g., grooves and / or gaps) are distributed such that the rear outer hydrogel layer has a higher surface lubricity than the front outer hydrogel layer, wherein the coated contact lens in a fully hydrated state has a water content of about 10 - 70% by weight or less, an oxygen permeability of at least about 50 barrers, and a water break-up time of at least about 10 seconds as measured on the front and rear surfaces of the coated contact lens.

[0007] In another aspect, the present invention provides a method for producing a coated contact lens, which comprises the following steps: (1) obtaining a preformed contact lens having a convex surface and an opposite concave surface, wherein the preformed contact lens is made of a lens body material and includes first reactive functional groups on and near the convex surface and the concave surface of the preformed contact lens, and each of the first reactive functional groups is capable of reacting with a thermally crosslinkable group at a temperature of about 60 - 140 °C and is selected from the group consisting of carboxylic acid groups, primary amino groups, secondary amino groups, thiol groups, and combinations thereof; (2) covering a plurality of regions on the convex surface with a second non-(poly)siloxane hydrogel material to prevent the first reactive functional groups behind the plurality of regions from reacting with the thermally crosslinkable group, wherein the second non-siloxane hydrogel material does not contain any first reactive functional groups and does not contain any thermally crosslinkable groups; (3) directly heating the preformed contact lens obtained in step (b) in an aqueous solution having a pH of about 6.5 - 9.5 and containing at least one water-soluble thermally crosslinkable hydrophilic polymer material at a temperature of about 60 - 140 °C to graft a first non-siloxane hydrogel material onto each of the front surface and the back surface of the preformed contact lens obtained in step (b) to form a coated contact lens having a front surface, an opposite back surface, a front outer hydrogel layer, and a back outer hydrogel layer, wherein the at least one water-soluble thermally crosslinkable hydrophilic polymer material includes a second reactive functional group and a third reactive functional group, wherein the second reactive functional group is a thermally crosslinkable group selected from the group consisting of azetidinium groups, epoxy groups, and combinations thereof, and each of the second reactive functional groups is capable of reacting with a first or third reactive functional group to form a crosslink, wherein the third reactive functional group is selected from the group consisting of carboxylic acid groups, primary amino groups, secondary amino groups, thiol groups, and combinations thereof, wherein the second non-siloxane hydrogel material is a crosslinked product of the at least one thermally crosslinkable hydrophilic polymer material, wherein the back outer hydrogel layer is the first non-siloxane hydrogel material layer, and wherein the front outer hydrogel layer is the first non-siloxane hydrogel material layer in which mold marks (e.g., grooves and / or gaps) are distributed, such that the back surface of the coated contact lens has a higher surface lubricity than the front surface, and 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 front surface and the back surface of the coated contact lens.

[0008] In another aspect, the present invention provides a method for producing a coated contact lens, comprising the steps of: (1) obtaining a female half-mold and a male half-mold, wherein the female half-mold has a first molding surface defining a front surface of the contact lens to be molded, wherein the male half-mold has a second molding surface defining a rear surface of the contact lens to be molded, wherein the male half-mold and the female half-mold are configured to receive each other such that when the female half-mold is closed with the male half-mold, 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 zones on the first molding surface, wherein the hydrogel-forming composition comprises at least one crosslinkable polymer having hydroxyl and / or ethylenically unsaturated groups and optionally at least one hydrophobic ethylenic monomer selected from the group consisting of methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, methyl (meth)acrylate, and combinations thereof, wherein, if the at least one crosslinkable polymer does not contain any ethylenically unsaturated groups, the hydrogel-forming composition further comprises at least one hydroxyl-containing ethylenic monomer and at least one compound having two or more isocyanate groups, wherein 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, partially curing the hydrogel-forming composition on the first molding surface; (4) introducing a polymerizable composition into the female half-mold obtained in step (2) or (3), wherein the polymerizable composition comprises about 1.0-10% by weight, based on the total amount of all polymerizable components, of at least one reactive ethylenic monomer having at least one first reactive functional group selected from the group consisting of carboxylic acid groups, primary amino groups, secondary amino groups, and combinations thereof; (5) closing the female half-mold obtained in step (4) with the male half-mold to form a molded assembly containing the polymerizable composition in the lens-forming cavity; (6) thermally curing or photocuring the polymerizable composition in the molded assembly to form a contact lens precursor having a convex surface and an opposing concave surface and comprising a lens body material having a first reactive functional group, wherein the convex surface of the contact lens precursor is partially covered in the plurality of zones on the convex surface with a second non-silicone hydrogel material formed from the hydrogel-forming composition to prevent the first reactive functional group behind the plurality of zones from reacting with a thermally crosslinkable group that is an azetidinium group and / or an epoxy group at a temperature of about 60-140°C, wherein the second non-silicone hydrogel material does not contain any 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 to obtain a hydrated contact lens precursor; and (8) at a temperature of about 60-140°C in a medium having a pH of about 6.5-9.Directly heating the contact lens precursor obtained in step (6) or the hydrated contact lens precursor obtained in step (7) in an aqueous solution having a pH of 5 and comprising 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) to form a coated contact lens having a front surface, an opposing rear surface, a front outer hydrogel layer, and a rear 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, wherein the second reactive functional group is a thermally crosslinkable group selected from the group consisting of azetidinium groups, epoxy groups, and combinations thereof, wherein each of the second reactive functional groups is capable of reacting with a first or third reactive functional group to form a crosslink, wherein the third reactive functional group is selected from the group consisting of carboxylic acid groups, primary amines, secondary amines, thiols, and combinations thereof, wherein the rear outer hydrogel layer is the first non-silicone hydrogel material layer, wherein the front outer hydrogel layer is the first non-silicone hydrogel material layer in which mold marks (e.g., grooves and / or gaps) are distributed such that the rear surface of the coated contact lens has a higher surface lubricity than the front surface, wherein the coated contact lens has a water break-up time of at least about 10 seconds measured on the front and rear surfaces of the coated contact lens.

[0009] Brief Description of the Drawings

[0010] Figure 1 Shows five printed patterns (A - E) for applying a hydrogel-forming composition to the front surface of a preformed silicone hydrogel contact lens according to a preferred embodiment of the present invention. Summary of the Invention

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

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

[0013] "Contact lens" refers to a structure that can be placed on or within the eye of a wearer. A contact lens can correct, improve, or alter the vision of the user, but this is not required. A contact lens can be made of any suitable material known in the art or developed later, and can be a hard lens, a rigid gas-permeable lens, a soft lens, or a hybrid lens.

[0014] As used in this application, the terms "front surface", "front face", "front curve surface", or "FC surface" with respect to a contact lens interchangeably mean the surface of the contact lens that faces away from the eye during wear. The front surface (FC surface) is typically substantially convex.

[0015] As used in this application, the terms "rear surface", "back surface", "base curve surface", or "BC surface" with respect to a contact lens interchangeably mean the surface of the contact lens that faces the eye during wear. The rear surface (BC surface) is typically substantially concave.

[0016] As used in this application, the "central axis" with respect to a contact lens means an imaginary reference line passing through the geometric centers of the front and rear surfaces of the contact lens.

[0017] As used in this application, the "central axis" with respect to a half-mold means an imaginary reference line passing orthogonally (i.e., at the geometric center, orthogonal to the molding surface) through the geometric center of the molding surface of the half-mold.

[0018] "Hard contact lens" refers to a contact lens that contains a hard plastic (e.g., polymethyl methacrylate) as the lens body (or so-called "core") material.

[0019] "Rigid gas-permeable contact lens" refers to a contact lens that contains a gas-permeable material (e.g., a material made of fluorosilicone acrylate) as the lens body material.

[0020] A hybrid contact lens includes a lens body material that is substantially composed of a central optical zone and a peripheral zone. The central optical zone is made of a gas-permeable lens material, and the peripheral zone is made of a silicone hydrogel or a conventional hydrogel lens material and extends outward from the central optical zone and surrounds the central optical zone.

[0021] An embedded contact lens includes a lens body material that is substantially composed of a three-dimensional embedded article and a non-silicone hydrogel material or a silicone hydrogel material, where the three-dimensional embedded article has a three-dimensional size smaller than that of the contact lens, so that it is partially or preferably completely embedded in the non-silicone hydrogel material or the silicone hydrogel material.

[0022] "Hydrogel contact lens" refers to a contact lens that includes a hydrogel body (core) material. The hydrogel body material can be a non-silicone hydrogel material or preferably a silicone hydrogel material.

[0023] "Hydrogel" or "hydrogel material" refers to such a crosslinked polymeric material that has a three-dimensional polymer network (i.e., polymer matrix), is insoluble in water, but can retain at least 10% by weight of water in its polymer matrix when it is fully hydrated (or equilibrated).

[0024] "Silicone hydrogel" or "SiHy" refers to a silicone-containing hydrogel obtained by copolymerization of a polymerizable composition that includes at least one silicone-containing vinyl monomer or at least one silicone-containing vinyl macromonomer or at least one crosslinkable silicone-containing prepolymer having an ethylenically unsaturated group.

[0025] Silicone, which is also commonly described as such, refers to a molecule having at least one -Si-O-Si- moiety, where each Si atom bears two organic groups as substituents.

[0026] As used in this application, the term "non-silicone hydrogel" or "non-silicone hydrogel material" interchangeably refers to a hydrogel that is theoretically free of silicon.

[0027] As used herein, "hydrophilic" describes a material or a portion thereof that will more readily associate with water as compared to lipids.

[0028] The term "room temperature" refers to a temperature of about 17 - 26 °C.

[0029] The term "soluble" with respect to a compound or material in a solvent means that the compound or material is soluble in the solvent at room temperature (i.e., about 17 - 26 °C) to give a solution having a concentration of at least about 0.5% by weight.

[0030] The term "insoluble" with respect 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 give a solution having a concentration of less than 0.01% by weight.

[0031] "Vinyl monomer" refers to a compound that has a single ethylenically unsaturated group, is soluble in a solvent, and can be photopolymerized or thermopolymerized.

[0032] The term "ethylenically unsaturated group" or "ethylenically unsaturated bond" is used herein in a broad sense and is intended to include any group containing at least one >C=CH2 group. Exemplary ethylenically unsaturated groups include, but are not limited to, (meth)acryloyl An allyl group, a vinyl group, a styryl group, or other groups containing C=CH2.

[0033] "Acrylic monomer" refers to an ethylenically unsaturated monomer having a single (meth)acryloyl group. Examples of acrylic monomers include (meth)acryloxy monomers and (meth)acrylamide monomers.

[0034] "(Meth)acryloxy ((meth)acryloxy or (meth)acryloyloxy) monomer" refers to an ethylenically unsaturated monomer having a single group of ethylenically unsaturated monomers.

[0035] "(Meth)acrylamide monomer" refers to an ethylenically unsaturated monomer having a single group (wherein R o is H or C1-C4 alkyl) of ethylenically unsaturated monomers.

[0036] The term "(meth)acrylamide" refers to methacrylamide and / or acrylamide.

[0037] The term "(meth)acrylate" refers to methacrylate and / or acrylate.

[0038] "N-Vinylamide monomer" refers to an amide compound having a vinyl group (-CH=CH2) directly attached to the nitrogen atom of the amide group.

[0039] "Olefin monomer" refers to an ethylenically unsaturated monomer having a single olefin group.

[0040] As used herein, "hydrophilic ethylenically unsaturated monomer", "hydrophilic acrylic monomer", "hydrophilic (meth)acryloxy monomer", or "hydrophilic (meth)acrylamide monomer" refers respectively to an ethylenically unsaturated monomer, an acrylic monomer, a (meth)acryloxy monomer, or a (meth)acrylamide monomer that typically produces a water-soluble homopolymer or can absorb at least 10% by weight of water.

[0041] As used herein, "hydrophobic ethylenically unsaturated monomer", "hydrophobic acrylic monomer", "hydrophobic (meth)acryloxy monomer", or "hydrophobic (meth)acrylamide monomer" refers respectively to an ethylenically unsaturated monomer, an acrylic monomer, a (meth)acryloxy monomer, or a (meth)acrylamide monomer that typically produces a water-insoluble homopolymer and can absorb less than 10% by weight of water.

[0042] "Blending ethylenically unsaturated monomer" refers to an ethylenically unsaturated monomer that can dissolve both hydrophilic and hydrophobic polymerizable components of a polymerizable composition to form a solution.

[0043] As used in this application, the term "ethylenic crosslinking agent" refers to an organic compound having at least two ethylenically unsaturated groups. An "ethylenic crosslinking agent" refers to an ethylenic crosslinking agent having a molecular weight of 700 daltons or less.

[0044] An "acrylic crosslinking agent" refers to an ethylenic crosslinking agent having at least two (meth)acryloyl groups.

[0045] The term "acrylic repeating unit" refers to a repeating unit of a polymeric material, each of which is derived from an acrylic monomer or crosslinking agent that forms the polymeric material by free radical polymerization.

[0046] The term "terminal (meth)acryloyl group" refers to a (meth)acryloyl group at one of the two terminals of the main chain (or backbone) of an organic compound.

[0047] As used herein, "photochemically" with respect to the curing, crosslinking, or polymerization of a polymerizable composition, prepolymer, or material means curing (e.g., crosslinking and / or polymerization) by photochemical irradiation, such as UV / visible light irradiation, ionizing radiation (e.g., γ-ray or X-ray irradiation), microwave irradiation, etc. Thermal curing or photochemical curing methods are well known to those skilled in the art.

[0048] As used in this application, the term "polymer" means a material formed by polymerizing / crosslinking monomers, macromonomers, prepolymers, or combinations thereof.

[0049] A "macromonomer" or "prepolymer" is a compound or polymer containing ethylenically unsaturated groups and having a number average molecular weight greater than 700 daltons.

[0050] As used in this application, the term "molecular weight" of a polymeric material (including monomer or macromonomer material) refers to the number average molecular weight, unless otherwise specifically indicated or unless the test conditions otherwise dictate. Those skilled in the art know how to determine the molecular weight of a polymer according to known methods, such as GPC (gel permeation chromatography) having one or more of the following: refractive index detector, small angle laser light scattering detector, multi-angle laser light scattering detector, differential viscometry detector, UV detector, and infrared (IR) detector; MALDI-TOF MS (matrix-assisted desorption / ionization time-of-flight mass spectrometry); 1 1H NMR (proton nuclear magnetic resonance) spectroscopy, etc.

[0051] "Polysiloxane segment" or "polydiorganosiloxane segment" may be used interchangeably to refer to Polymer chain segments (i.e., divalent groups), where SN is an integer of 3 or greater, and R S1 and R S2 Each of which is independently selected from the group consisting of: 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; arylC1-C 18 alkyl; -alk-(OC2H4) γ1 -OR o (where alk is a C1-C6 alkylene diyl group, R o is H or C1-C4 alkyl and γ1 is an integer from 1 to 10); C2-C 40 organic group having at least one functional group selected from the group consisting of hydroxyl (-OH), carboxyl (i.e., carboxylic acid group) (-COOH), amino (-NR N1 R N1 ’), amino linker -NR N1 -, amide linker -CONR N1 -, amide -CONR N1 R N1 ’, carbamate linker -OCONH-, and C1-C4 alkoxy, or a linear hydrophilic polymer chain, where R N1 and R N1 ’ are independently hydrogen or C1-C 15 alkyl.

[0052] "Polysiloxane vinyl monomer" refers to a compound containing at least one polysiloxane segment and a single ethylenically unsaturated group.

[0053] "Polydiorganosiloxane vinyl crosslinker" or "polysiloxane vinyl crosslinker" interchangeably refers to a compound containing at least one polysiloxane segment and at least two ethylenically unsaturated groups.

[0054] "Linear polydiorganosiloxane vinyl crosslinker" or "linear polysiloxane vinyl crosslinker" interchangeably refers to a compound containing a main chain that includes at least one polysiloxane segment and is capped at each of the two ends of the main chain by an ethylenically unsaturated group.

[0055] "Chain-extended polydiorganosiloxane vinyl crosslinker" or "chain-extended polysiloxane vinyl crosslinker" interchangeably refers to a compound containing at least two ethylenically unsaturated groups and at least two polysiloxane segments, each pair of which is connected by a divalent group.

[0056] As used herein, the term "fluid" indicates a material that can flow like a liquid.

[0057] As used in this application, the term "optically transparent" with respect to a polymerizable composition means that the polymerizable composition is a transparent solution or liquid mixture (i.e., having a light transmittance of 85% or greater, preferably 90% or greater, in the range between 400 and 700 nm).

[0058] The term "monovalent group" refers to an organic group obtained by removing a hydrogen atom from an organic compound and forming one bond with one other group in the organic compound. Examples include, but are not limited to, alkyl (by removing a hydrogen atom from an alkane), alkoxy (alkoxy or alkoxyl) (by removing a hydrogen atom from the hydroxyl group of an alkyl alcohol), thiyl (by removing a hydrogen atom from the mercapto group of an alkyl mercaptan), cycloalkyl (by removing a hydrogen atom from a cycloalkane), cycloheteroalkyl (by removing a hydrogen atom from a cycloheteroalkane), aryl (by removing a hydrogen atom from an aromatic ring of an aromatic hydrocarbon), heteroaryl (by removing a hydrogen atom from any ring atom), amino (by removing a hydrogen atom from an amine), etc.

[0059] The term "divalent group" refers to an organic group obtained by removing two hydrogen atoms from an organic compound and forming two bonds with two other groups in the organic compound. For example, an alkylene (alkylenyl) divalent group is obtained by removing two hydrogen atoms from an alkane, and a cycloalkylene (cycloalkylenyl) divalent group is obtained by removing two hydrogen atoms from a ring.

[0060] In this application, the term "substituted" with respect to an alkyl or alkylene means that the alkyl or alkylene contains at least one substituent that replaces one hydrogen atom of the alkyl or alkylene and is selected from the group consisting of hydroxyl (-OH), carboxyl (-COOH), -NH2, mercapto (-SH), C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkylthio (alkyl sulfide), C1-C4 acylamino, C1-C4 alkylamino, di-C1-C4 alkylamino, and combinations thereof.

[0061] In this application, "oxazoline" refers to a compound of, where: R ox1 is hydrogen, methyl, ethyl, N-pyrrolidinylmethyl, N-pyrrolidinylethyl, N-pyrrolidinylpropyl, or -alk-(OC2H4) m3 -OR ”a monovalent group, where alk is a C1-C6 alkyl diyl; R” is a C1-C4 alkyl (preferably methyl); and m3 is an integer from 1 to 10 (preferably 1 to 5).

[0062] In the present application, the term "polyoxazoline" refers to a polymer or polymer segment, where: R ox1 is hydrogen, methyl, ethyl, N-pyrrolidinylmethyl, N-pyrrolidinylethyl, N-pyrrolidinylpropyl, or -alk-(OC2H4) m3 -OR ” a monovalent group, where alk is a C1-C6 alkyl diyl; 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.

[0063] In the present application, the term "poly(2-oxazoline-co-ethyleneimine)" refers to a statistical copolymer having the formula or its polymer segment, where: R ox1 is hydrogen, methyl, ethyl, N-pyrrolidinylmethyl, N-pyrrolidinylethyl, N-pyrrolidinylpropyl, or -alk-(OC2H4) m3 -OR ” a monovalent group, where alk is a C1-C6 alkyl diyl; 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; z is an integer equal to or less than x. Poly(2-oxazoline-co-ethyleneimine) is obtained by hydrolyzing polyoxazoline.

[0064] In the present 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 large percentage (≥90%) of the secondary amine groups of poly(2-oxazoline-co-ethyleneimine) into azetidinium groups. Examples of poly(2-oxazoline-co-ethyleneimine)-epichlorohydrin are disclosed in U.S. Patent Application Publication No. 2016 / 0061995A1.

[0065] "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 large percentage of the secondary amine groups of the polyamine or polyamidoamine into azetidinium groups.

[0066] The term "polyamidoamine-epichlorohydrin" refers to an epichlorohydrin-functionalized adipic acid-diethylenetriamine copolymer.

[0067] In the present application, the term "azetidinium" or "3-hydroxyazetidinium" refers to A positively charged (i.e., cationic) divalent group (or moiety or portion).

[0068] The term "thermally crosslinkable" with respect to a polymeric material or functional group means that the polymeric material or functional group can undergo a crosslinking (or coupling) reaction with another material or functional group at a relatively elevated temperature (40 °C to 140 °C), whereas the polymeric material or functional group cannot undergo the same crosslinking reaction (or coupling reaction) with another material or functional group to a detectable extent within about one hour at a temperature of about 5 - 20 °C.

[0069] The term "azlactone" refers to a monovalent group of the formula where p is 0 or 1; 3 R and 4 R are each independently a C1 - C8 alkyl group (preferably methyl).

[0070] The term "aziridinyl group" refers to a monovalent group having the formula where R 1 is hydrogen, methyl or ethyl.

[0071] As used in the present application, the term "phosphorylcholine" refers to the zwitterionic group where n is an integer from 1 to 5, and R 2 R 3 and R 4 are each independently a C1 - C8 alkyl group or a C1 - C8 hydroxyalkyl group.

[0072] As used in the present application, the term "reactive vinyl monomer" refers to any vinyl monomer having at least one reactive functional group selected from the group consisting of: carboxyl group, primary amino group and secondary amino group.

[0073] As used in the present application, the term "non - reactive vinyl monomer" refers to any vinyl monomer (hydrophilic or hydrophobic) that does not contain a carboxyl group, a primary amino group, a secondary amino group, an epoxy group, an isocyanate group, an azlactone group, or an aziridinyl group.

[0074] The radical initiator can be a photoinitiator or a thermal initiator. A "photoinitiator" refers to a chemical that initiates a radical crosslinking / polymerization reaction by utilizing light. A "thermal initiator" refers to a chemical that initiates a radical crosslinking / polymerization reaction by utilizing heat.

[0075] The intrinsic "oxygen permeability" Dk of a material i is the rate of oxygen passing through the material. As used in the present application, the term "oxygen permeability (Dk)" with respect to a hydrogel (siloxane or non - siloxane) or a contact lens means the corrected oxygen permeability (Dk c), which is measured according to the procedure described in ISO 18369-4 at about 34°C-35°C and corrected for surface resistance to oxygen flux due to boundary layer effects. Oxygen permeability is conventionally expressed in barrers, where "barrer" is defined as [(cm 3 Oxygen)(cm) / (cm 2 )(s)(mm Hg)]×10 -9 .

[0076] The "oxygen transmission rate" Dk / t of an insert or material is the rate at which oxygen will pass through a particular insert or material having an average thickness t in mm over the measured area. Oxygen transmission rate is conventionally expressed in units of barrers / mm, where "barrers / mm" is defined as [(cm 3 Oxygen) / (cm 2 )(s)(mm Hg)]×10 -9 .

[0077] The term "modulus" or "elastic modulus" with respect to a contact lens or material 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 are familiar with how to determine the elastic modulus of a SiHy material or contact lens. For example, all commercial contact lenses have a reported elastic modulus value.

[0078] "Coating" with respect to a contact lens means that the contact lens has on its surface a thin layer of 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.

[0079] "Average water contact angle" refers to the water contact angle (measured by the Sessile Drop method) obtained by averaging the measurements of at least 3 separate contact lenses or samples of silicone hydrogel material.

[0080] As used herein, the term "water gradient" with respect to a contact lens means the increase in water content observed from the core to the surface of the contact lens, reaching a maximum water content in the region of the contact lens near and including the surface. It should be 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 the region of the contact lens near and including the surface.

[0081] As used in this application, the terms "inner layer" or "lens body material" with respect to the contact lenses of the present invention interchangeably refer to a layer having the 3-dimensional shape of the contact lens and including a central curved plane (which divides the contact lens into two parts, one containing a convex surface and the other containing a concave surface) and having a variable thickness.

[0082] As used in this application, the term "outer surface hydrogel layer" with respect to a contact lens means the outermost hydrogel layer on the surface of the contact lens, which consists of a front outer hydrogel layer and a rear outer hydrogel layer and which completely or partially covers the inner layer (or lens body material).

[0083] As used in this application, the term "front outer hydrogel layer" with respect to a contact lens means a hydrogel layer that includes the front surface of the contact lens, is made of one or more non-silicone hydrogel materials, and completely or partially covers the concave surface of the inner layer (or lens body material).

[0084] As used in this application, the term "rear outer hydrogel layer" with respect to a contact lens means a hydrogel layer that includes the rear surface of the contact lens, is made of one or more non-silicone hydrogel materials, and completely or partially covers the concave surface of the inner layer (or lens body material).

[0085] As used in this application, the terms "crosslinked coating" or "hydrogel coating" or "hydrogel layer" on a contact lens may be used interchangeably to describe a crosslinked polymeric material having a three-dimensional network that can accommodate water when fully hydrated. The three-dimensional network of the crosslinked polymeric material can be formed by crosslinking two or more linear or branched polymers.

[0086] As used herein, "surface modification" or "surface treatment" means that an article has been treated in a surface treatment process (or surface modification process) before or after the formation of the article, where (1) a coating is applied to the surface of the article, (2) a chemical substance is adsorbed onto the surface of the article, (3) the chemical nature of chemical groups on the surface of the article is changed (e.g., static charge), or (4) the surface characteristics of the article are otherwise modified. Exemplary surface treatment processes include, but are not limited to, surface treatment by energy (e.g., plasma, static charge, radiation, or other energy sources), chemical treatment, grafting of hydrophilic vinyl monomers or macromonomers onto the surface of the article, the mold transfer coating process disclosed in U.S. Patent No. 6,719,929, incorporation of wetting agents into the lens formulation for preparing contact lenses as proposed in U.S. Patent Nos. 6,367,929 and 6,822,016, enhanced mold transfer coating disclosed in U.S. Patent No. 7,858,000, and hydrophilic coatings consisting of covalent attachment or physical deposition of one or more layers of one or more hydrophilic polymers on the surface of a contact lens as disclosed in U.S. Patent Nos. 8,147,897 and 8,409,599 and U.S. Patent Application Publication Nos. 2011 / 0134387, 2012 / 0026457, and 2013 / 0118127.

[0087] "Post-cure surface treatment" of the lens body material or contact lens means a surface treatment process carried out after forming the lens body material or contact lens by curing (i.e., thermal polymerization or photopolymerization) a lens formulation. A "lens formulation" is a polymerizable composition comprising all necessary polymerizable components known to those skilled in the art for producing a contact lens or lens body material.

[0088] The present invention generally relates to a water gradient contact lens having improved lens handleability ("easy insertion / removal") while maintaining other desired properties provided by the water gradient contact lens. The present invention is partly based on the discovery that, according to a cost-effective method of the present invention, the surface lubricity of the front surface of a water gradient contact lens can be controllably reduced by introducing imperfections (e.g., grooves and / or gaps) into the front external hydrogel layer of the water gradient contact lens. Typically, the production of a water gradient contact lens involves a step of grafting (covalently attaching) a non-silicone hydrogel to the contact lens to be coated. Such a grafting step requires the presence of reactive functional groups (e.g., carboxylic acid groups, primary / secondary amino groups, and thiol groups) on the surface of the contact lens to be coated as anchor sites for grafting. It has been found that by applying a non-silicone hydrogel material free of reactive functional groups to regions on the front surface of the contact lens to be coated, the reactive functional groups can be completely or substantially shielded in these regions. The resulting contact lens to be coated will have a non-uniform distribution of reactive functional groups on the front surface of the contact lens to be coated: there are no or very few reactive functional groups in these regions, while there are sufficient reactive functional groups in the remaining regions of the front surface. Therefore, when grafting the non-silicone hydrogel material to the remaining regions occurs, little or no grafting of the non-silicone hydrogel material to these regions on the front surface may occur, thereby in-situ generating imperfections (e.g., grooves and / or gaps) in the front external hydrogel layer of the resulting water gradient contact lens. In the case of having such imperfections (e.g., grooves and / or gaps) in the front external hydrogel layer, the surface lubricity of the front surface of the water gradient contact lens can be reduced. By adjusting the shape, size, density, and rotational distribution of the imperfections on the front external hydrogel layer, the surface lubricity of the front surface of the water gradient contact lens can also be adjusted and optimized.

[0089] In one aspect, the present invention provides a method for producing a coated silicone hydrogel contact lens, which comprises the following steps: (1) obtaining a preformed contact lens having a convex surface and an opposing concave surface and comprising a lens body material, wherein the preformed contact lens is composed of the lens body material and comprises first reactive functional groups on and near the convex surface and the concave surface of the preformed contact lens, wherein each of the first reactive functional groups is capable of reacting with a thermally crosslinkable group at a temperature of about 60 - 140 °C and is selected from the group consisting of carboxylic acid groups, primary amino groups, secondary amino groups, thiol groups, and combinations thereof; (2) covering 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 groups, wherein the second non-silicone hydrogel material does not contain any first reactive functional groups and does not contain any thermally crosslinkable groups; and (3) directly heating the preformed contact lens obtained in step (2) in an aqueous solution having a pH of about 6.5 - 9.5 and comprising at least one water-soluble thermally crosslinkable hydrophilic polymer material at a temperature of about 60 - 140 °C to graft the first non-silicone hydrogel material onto each of the front surface and the back surface of the preformed contact lens obtained in step (2) to form a coated contact lens having a front surface, an opposing back surface, a front outer hydrogel layer, and a back 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, wherein the second reactive functional group is a thermally crosslinkable group selected from the group consisting of azetidinium groups, epoxy groups, and combinations thereof, wherein each of the second reactive functional groups is capable of reacting with a first or third reactive functional group to form a crosslink, wherein the third reactive functional group is selected from the group consisting of carboxylic acid groups, primary amino groups, secondary amino groups, thiol groups, and combinations thereof, wherein the second non-silicone hydrogel material is a crosslinked product of the at least one thermally crosslinkable hydrophilic polymer material, wherein the back outer hydrogel layer is the first non-silicone hydrogel material layer, wherein the front outer hydrogel layer is the first non-silicone hydrogel material layer in which mold marks (e.g., grooves and / or gaps) are distributed, such that the back surface of the coated contact lens has a higher surface lubricity than the front surface, wherein the coated contact lens has a water break-up time of at least about 10 seconds measured on the front surface and the back surface of the coated contact lens.

[0090] A preformed contact lens can be any contact lens that has not undergone any surface treatment after being produced according to any lens manufacturing process, any contact lens that has been plasma-treated or treated with any chemical or physical surface modification, or any commercial contact lens, provided that there is no hydrogel coating on the surface of the preformed contact lens. Those skilled in the art are well aware of how to prepare preformed contact lenses. Those skilled in the art are well aware of how to prepare preformed contact lenses. For example, preformed contact lenses can be produced by conventional "rotary casting molding" as described, for example, in US 3408429, or produced in a static form by a full casting molding process as described in U.S. Patent Nos. 4347198; 5508317; 5583463; 5789464; and 5849810, or produced by lathe cutting of polymer material buttons as used in the manufacture of custom contact lenses. In casting molding, typically a polymerizable composition (i.e., a lens formulation) is dispensed into a mold and cured (i.e., polymerized and / or crosslinked) in the mold used to prepare the contact lens.

[0091] Lens molds for preparing contact lenses are well known to those skilled in the art and are used, for example, in casting molding or rotary casting. For example, a mold (for injection molding) typically includes at least two mold regions (or parts) or half-molds, i.e., a first and a second half-mold. The first half-mold defines a first molding (or optical) surface, and the second half-mold defines a second molding (or optical) surface. The first half-mold and the second half-mold are configured to receive each other such that a lens-forming cavity is formed between the first molding surface and the second molding surface. The molding surfaces of the half-molds are the cavity-forming surfaces of the mold and are in direct contact with the polymerizable composition.

[0092] Methods for manufacturing mold sections for casting-molded 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 the mold. In fact, any method of forming the mold can be used in the present invention. The first and second half-molds can be formed by various techniques such as injection molding or lathe machining. Examples of suitable methods for forming the half-molds are disclosed in U.S. Patent Nos. 4444711; 4460534; 5843346; and 5894002.

[0093] Nearly all materials known in the art for manufacturing molds can be used to manufacture molds for preparing contact lenses. For example, polymer materials such as polyethylene, polypropylene, polystyrene, PMMA, COC grade 8007-S10 (a transparent amorphous copolymer of ethylene and norbornene from Ticona GmbH, Frankfurt, Germany and Summit, New Jersey, USA), etc. Other materials that allow UV light transmission, such as fused quartz and sapphire, can be used.

[0094] According to the present invention, the polymerizable composition can be introduced (dispensed) into the cavity formed by the mold according to any known method.

[0095] After the polymerizable composition is dispensed into the mold, it is polymerized to produce a contact lens. Crosslinking can preferably be thermally or photochemically initiated by subjecting the polymerizable composition in the mold to spatially restricted actinic radiation to crosslink the polymerizable components in the polymerizable composition.

[0096] Opening the mold to allow removal of the molded article from the mold can occur in a manner known per se.

[0097] The molded contact lens 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 those described below.

[0098] In a preferred embodiment, the preformed contact lens is a rigid contact lens comprising a rigid plastic material as the lens body material. Preferably, the rigid plastic material is a crosslinked polymethacrylate. Those skilled in the art are well aware of how to prepare rigid plastic materials, including crosslinked polymethyl methacrylate.

[0099] In another preferred embodiment, the preformed contact lens is a rigid gas-permeable contact lens comprising a rigid gas-permeable material as the lens body material. Those skilled in the art are well aware of how to prepare rigid gas-permeable contact lenses.

[0100] In another preferred embodiment, the preformed contact lens is a hybrid contact lens that includes a lens body material that consists essentially of a central optical zone and a peripheral zone, the central optical zone being made of a gas-permeable lens material, and the peripheral zone being made of a silicone hydrogel or a conventional hydrogel lens material and extending outward from the central optical zone and surrounding the central optical zone.

[0101] In another preferred embodiment, the preformed contact lens is a non-silicone hydrogel contact lens (or so-called conventional hydrogel contact lens) that includes a non-silicone hydrogel material as the lens body material.

[0102] The preformed non-silicone hydrogel contact lens can be any commercially available non-silicone hydrogel contact lens or can be produced according to any known method. For example, to produce a preformed non-silicone hydrogel contact lens, a non-silicone hydrogel lens formulation (polymerizable composition) for casting molding or spin casting molding or for preparing a rod used in lathe cutting of contact lenses typically is: (1) a monomer mixture that includes (a) at least one hydrophilic vinyl monomer (e.g., hydroxyethyl methacrylate, glycerol methacrylate, N-vinylpyrrolidone, or a combination thereof) and (b) at least one component selected from the group consisting of: a crosslinker, a hydrophobic vinyl monomer, a lubricant (or 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 visibility 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; or (2) an aqueous solution that includes 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 so-called internal wetting agent incorporated into the lens formulation), a free radical initiator (photoinitiator or thermal initiator), a UV-absorbing vinyl monomer, a HEVL-absorbing vinyl monomer, a visibility 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. Then, the resulting preformed hydrogel contact lens can be subjected to extraction 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. It should be understood that the lubricant present in the hydrogel lens formulation can improve the lubricity of the preformed hydrogel contact lens as compared to a control preformed hydrogel contact lens obtained from a control hydrogel lens formulation that does not contain a lubricant.

[0103] Preferred examples of the water-soluble prepolymers include, but are not limited to: the water-soluble crosslinkable poly(vinyl alcohol) prepolymers described in US 5583163 and US 6303687.

[0104] A variety of non-silicone hydrogel lens formulations have been described in many patents and patent applications published as of the filing date of the present application and have been used to produce commercial non-silicone hydrogel contact lenses. Examples of commercial non-silicone hydrogel contact lenses include, but are not limited to, alfafilcon A, acofilcon A, deltafilcon A, etafilcon A, focofilcon A, helfilcon A, helfilcon B, hilafilcon B, hioxifilcon A, hioxifilcon B, hioxifilcon D, methafilcon A, methafilcon B, nelfilcon A, nesofilcon A, ocufilcon A, ocufilcon B, ocufilcon C, ocufilcon D, omafilcon A, phemfilcon A, polymacon, samfilcon A, telfilcon A, tetrafilcon A, and vifilcon A.

[0105] In a preferred embodiment, the lens body material is composed of a non-silicone hydrogel material, the non-silicone hydrogel material comprising repeating units of at least one hydroxy-containing vinyl monomer in an amount of at least 50 mol%, preferably selected from the group consisting of: 2-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: 2-hydroxyethyl (meth)acrylate, glycerol (meth)acrylate, and vinyl alcohol. The mole percentage of the repeating units can be calculated based on the non-silicone hydrogel lens formulation used to prepare the non-silicone hydrogel contact lenses.

[0106] In another preferred embodiment, the preformed contact lens is a silicone hydrogel contact lens comprising a silicone hydrogel material as the lens body material.

[0107] The preformed silicone hydrogel contact lens can be any commercially available silicone hydrogel contact lens or can be produced according to any known method. For example, to produce a preformed silicone hydrogel (SiHy) contact lens, the SiHy lens formulation for cast molding or rotational cast molding or for manufacturing a SiHy rod used in lathe cutting of contact lenses generally comprises at least one component selected from the group consisting of: siloxane-containing vinyl monomers, polysiloxane vinyl crosslinkers, siloxane-containing prepolymers, hydrophilic vinyl monomers, hydrophobic vinyl monomers, non-siloxane vinyl crosslinkers, free radical initiators (photoinitiators or thermal initiators), siloxane-containing prepolymers and combinations thereof, as are well known to those skilled in the art. Then, the resulting preformed SiHy contact lens can be subjected to extraction with an extraction solvent to remove unpolymerized components from the resulting lens and subjected to a hydration process, as is known to those skilled in the art.

[0108] According to the present invention, the siloxane (or siloxane-containing) vinyl monomer can be any siloxane-containing vinyl monomer known to those skilled in the art. Examples of preferred siloxane-containing vinyl monomers include, but are not limited to, vinyl monomers each having bis(trialkylsiloxy)alkylsilyl (preferably bis(trimethylsiloxy)-alkylsilyl) or tris(trialkylsiloxy)silyl (preferably tris(trimethylsiloxy)silyl), polysiloxane vinyl monomers, 3-methacryloxypropylpentamethyldisiloxane, tert-butyldimethyl-siloxyethyl vinyl carbonate, trimethylsilylethyl vinyl carbonate, and trimethylsilylmethyl vinyl carbonate and combinations thereof.

[0109] Examples of the preferred siloxane-containing ethylenic monomers each having a bis(trialkylsilyloxy)alkylsilyl or tris(trialkylsilyloxy)silyl group include, but are not limited to, tris(trimethylsilyloxy)-silylpropyl (meth)acrylate, [3-(meth)acryloyloxy-2-hydroxypropoxy]propyl-bis(trimethylsilyloxy)-methylsilane, [3-(meth)acryloyloxy-2-hydroxypropoxy]propyl-bis(trimethylsilyloxy)butylsilane, 3-(meth)acryloyloxy-2-(2-hydroxyethoxy)-propoxy)propyl-bis(trimethylsilyloxy)methylsilane, 3-(meth)acryloyloxy-2-hydroxypropoxy)propyltris(trimethylsilyloxy)silane, N-[tris(trimethylsilyloxy)-silylpropyl]-(meth)acrylamide, N-(2-hydroxy-3-(3-(bis(trimethylsilyloxy)methylsilyl)propoxy)-propyl)-2-methyl(meth)acrylamide, N-(2-hydroxy-3-(3-(bis(trimethylsilyloxy)methylsilyl)-propoxy)propyl)(meth)acrylamide, N-(2-hydroxy-3-(3-(tris(trimethylsilyloxy)silyl)propoxy)-propyl)-2-methylacrylamide, N-(2-hydroxy-3-(3-(tris(trimethylsilyloxy)silyl)propoxy)propyl)(meth)acrylamide, N-[tris(dimethylpropylsilyloxy)-silylpropyl]-(meth)acrylamide, N-[tris(dimethylphenylsilyloxy)silylpropyl](meth)acrylamide, N-[tris(dimethylethylsilyloxy)silylpropyl](meth)acrylamide, N,N-bis[2-hydroxy-3-(3-(bis(trimethylsilyloxy)methylsilyl)propoxy)propyl]-2-methyl(meth)acrylamide, N,N-bis[2-hydroxy-3-(3-(bis(trimethylsilyloxy)methylsilyl)propoxy)-propyl](meth)acrylamide, N,N-bis[2-hydroxy-3-(3-(tris(trimethylsilyloxy)silyl)propoxy)propyl]-2-methyl(meth)acrylamide, N,N-bis[2-hydroxy-3-(3-(tris(trimethylsilyloxy)silyl)propoxy)propyl](meth)acrylamide, N-[2-hydroxy-3-(3-(tert-butyldimethylsilyl)propoxy)propyl]-2-methyl(meth)acrylamide, N-[2-hydroxy-3-(3-(tert-butyldimethylsilyl)propoxy)propyl](meth)acrylamide, N,N-bis[2-hydroxy-3-(3-(tert-butyldimethylsilyl)propoxy)propyl]-2-methyl(meth)acrylamide, N-2-(meth)acryloyloxyethyl-O-(methyl-bis-trimethylsilyloxy-3-propyl)silylcarbamate, 3-(trimethylsilyl)propyl vinylcarbamate, 3-(vinyloxycarbonylthio)propyl-tris(trimethyl-silyloxy)silane, 3-[tris(trimethylsilyloxy)silyl]propyl vinylcarbamate, 3-[tris(trimethylsilyloxy)silyl]propyl allylcarbamate, 3-[tris(trimethylsilyloxy)silyl]propyl vinyl carbonate, those disclosed in U.S. Patent Nos. 9097840, 9103965 and 9475827, and mixtures thereof. The above-preferred siloxane-containing ethylenically unsaturated monomers are available from commercial suppliers or can be prepared according to the procedures described in U.S. Patent Nos. 5070215, 6166236, 6867245, 7214809, 8415405, 8475529, 8614261, 8658748, 9097840, 910396, 9217813, 9315669 and 9475827.,

[0110] Examples of preferred siloxane-vinyl monomers include, but are not limited to, mono-(meth)acryloyl-capped, mono-alkyl-capped polysiloxanes having the formula (I), including but not limited to α-(meth)acryloyloxypropyl-capped, ω-butyl (or ω-methyl)-capped polydimethylsiloxane, α-(meth)acryloyloxy-2-hydroxypropoxypropyl-capped, ω-butyl (or ω-methyl)-capped polydimethylsiloxane, α-(2-hydroxy-methacryloyloxypropoxypropyl)-ω-butyl-decamethylpentasiloxane, α-[3-(meth)acryloyloxyethoxy-2-hydroxypropoxypropyl]-capped, ω-butyl (or ω-methyl)-capped polydimethylsiloxane, α-[3-(meth)acryloyloxy-propoxy-2-hydroxypropoxypropyl]-capped, ω-butyl (or ω-methyl)-capped polydimethylsiloxane, α-[3-(meth)acryloyloxyisopropoxy-2-hydroxypropoxypropyl]-capped, ω-butyl (or ω-methyl)-capped polydimethylsiloxane, α-[3-(meth)acryloyloxybutoxy-2-hydroxypropoxypropyl]-capped, ω-butyl (or ω-methyl)-capped polydimethylsiloxane, α-[3-(meth)acryloyloxy-ethylamino-2-hydroxypropoxypropyl]-capped, ω-butyl (or ω-methyl)-capped polydimethylsiloxane, α-[3-(meth)acryloyloxypropylamino-2-hydroxypropoxypropyl]-capped, ω-butyl (or ω-methyl)-capped polydimethylsiloxane, α-[3-(meth)acryloyloxy-butylamino-2-hydroxypropoxypropyl]-capped, ω-butyl (or ω-methyl)-capped polydimethylsiloxane, α-(meth)acryloyloxy(polyethyleneoxy)-2-hydroxypropoxypropyl]-capped, ω-butyl (or ω-methyl)-capped polydimethylsiloxane, α-[(meth)acryloyloxy-2-hydroxypropoxy-ethoxypropyl]-capped, ω-butyl (or ω-methyl)-capped polydimethylsiloxane, α-[(meth)acryloyloxy-2-hydroxypropyl-N-ethylaminopropyl]-capped, ω-butyl (or ω-methyl)-capped polydimethylsiloxane, α-[(meth)acryloyloxy-2-hydroxypropyl-aminopropyl]-capped, ω-butyl (or ω-methyl)-capped polydimethylsiloxane, α-[(meth)acryloyloxy-2-hydroxypropoxy-(polyethyleneoxy)propyl]-capped, ω-butyl (or ω-methyl)-capped polydimethylsiloxane, α-(meth)acryloylaminopropoxypropyl-capped, ω-butyl (or ω-methyl)-capped polydimethylsiloxane, α-N-methyl-(meth)acryloylaminopropoxypropyl-capped, ω-butyl (or ω-methyl)-capped polydimethylsiloxane, α-[3-(meth)acrylamideethoxy-2-hydroxypropoxy-propyl]-capped, ω-butyl (or ω-methyl) polydimethylsiloxane,α-[3-(Methacrylamido)-propoxy-2-hydroxypropoxypropyl]-terminated ω-butyl (or ω-methyl)-terminated polydimethylsiloxane, α-[3-(methacrylamido)isopropoxy-2-hydroxypropoxypropyl]-terminated ω-butyl (or ω-methyl)-terminated polydimethylsiloxane, α-[3-(methacrylamido)-butoxy-2-hydroxypropoxypropyl]-terminated ω-butyl (or ω-methyl)-terminated polydimethylsiloxane, α-[3-(methacrylamido)-2-hydroxypropoxypropyl]-terminated ω-butyl (or ω-methyl) polydimethylsiloxane, α-[3-[N-methyl-(methacrylamido)]-2-hydroxypropoxy-propyl]-terminated ω-butyl (or ω-methyl)-terminated polydimethylsiloxane, N-methyl-N'-(propyltetrakis(dimethylsilyloxy)dimethylbutylsilane)(meth)acrylamide, N-(2,3-dihydroxypropane)-N'-(propyltetrakis(dimethylsilyloxy)dimethylbutylsilane)(meth)acrylamide, (meth)acrylamido-propyltetrakis(dimethylsilyloxy)dimethylbutylsilane, mono-vinyl carbonate-terminated mono-alkyl-terminated polydimethylsiloxane, mono-vinyl carbamate-terminated mono-alkyl-terminated polydimethylsiloxane, those disclosed in U.S. Patent Nos. 9,097,840 and 9,103,965, and mixtures thereof. The above-preferred polysiloxane vinyl monomers can be obtained from commercial suppliers (e.g., Shin-Etsu, Gelest, etc.) or prepared according to the procedures described in patents, e.g., 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 reacting a hydroxyalkyl (meth)acrylate or (meth)acrylamide or (meth)acryloxypolyethylene glycol with a mono-glycidoxypropyl-terminated polydimethylsiloxane according to coupling reactions well-known to those skilled in the art, by reacting glycidyl (meth)acrylate with a mono-methoxy-terminated polydimethylsiloxane, a mono-aminopropyl-terminated polydimethylsiloxane, or a mono-ethylaminopropyl-terminated polydimethylsiloxane, or by reacting isocyanatoethyl (meth)acrylate with a mono-methoxy-terminated polydimethylsiloxane.

[0111] According to the present invention, any polysiloxane vinyl crosslinker can be used in the present invention. Examples of preferred polysiloxane vinyl crosslinkers include, but are not limited to, α,ω-(meth)acryloxy-terminated polydimethylsiloxanes of different molecular weights; α,ω-(meth)acrylamide-terminated polydimethylsiloxanes of different molecular weights; α,ω-vinyl carbonate-terminated polydimethylsiloxanes of different molecular weights; α,ω-vinyl carbamate-terminated polydimethylsiloxanes of different molecular weights; bis-3-methacryloxy-2-hydroxypropyloxypropyl polydimethylsiloxanes of different molecular weights; N,N,N',N'-tetrakis(3-methacryloxy-2-hydroxypropyl)-α,ω-bis-3-aminopropyl-polydimethylsiloxanes of different molecular weights; reaction products of glycidyl methacrylate with di-amino-terminated polydimethylsiloxanes; reaction products of glycidyl methacrylate with di-hydroxy-terminated polydimethylsiloxanes; reaction products of vinyl monomers containing azlactone (any of those described above) with di-hydroxy-terminated polydimethylsiloxanes; reaction products of isocyanatoethyl (meth)acrylate with di-hydroxy-terminated polydimethylsiloxanes; reaction products of isocyanatoethyl (meth)acrylate with di-amino-terminated polydimethylsiloxanes; polysiloxane-containing macromonomers selected from the group consisting of macromonomer A, macromonomer B, macromonomer C, and macromonomer D described in U.S. Patent No. 5,760,100; polysiloxane vinyl crosslinkers disclosed in 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, 4,341,889, 4,486,577, 4,543,398, 4,605,712, 4,661,575, 4,684,538, 4,703,097, 4,833,218, 4,837,289, 4,954,586, 4,954,587, 5,010,141, 5,034,461, 5,070,170, 5,079,319, 5,039,761, 5,346,946, 5,358,995, 5,387,632, 5,416,132, 5,449,729, 5,451,617, 5,486,579, 5,96,2548, 5,981,675, 6,039,913, 6,762,264, 7,423,074, 8,163,206, 8,480,227, 8,529,057, 8,835,525, 8,993,651, 9,187,601, 10,081,697, 10,301,451, and 10,465,047.

[0112] A preferred class of polyorganosiloxane vinyl crosslinkers are vinyl crosslinkers prepared by reacting glycidyl (meth)acrylate or (meth)acryloyl chloride with di - amino - terminated polydimethylsiloxane or di - hydroxy - terminated polydimethylsiloxane; reacting isocyanatoethyl (meth)acrylate with di - hydroxy - terminated polydimethylsiloxane; reacting an amino - containing acrylic monomer with di - carboxy - terminated polydimethylsiloxane in the presence of a coupling agent (carbodiimide); reacting a carboxy - containing acrylic monomer with di - amino - terminated polydimethylsiloxane in the presence of a coupling agent (carbodiimide); or reacting a hydroxy - containing acrylic monomer with di - hydroxy - terminated polysiloxane in the presence of a diisocyanate or a di - epoxy coupling agent.

[0113] 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-hydroxypropoxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acryloxyethoxy-2-hydroxypropoxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acryloxypropoxy-2-hydroxypropoxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acryloxy-isopropoxy-2-hydroxypropoxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acryloxybutoxy-2-hydroxypropoxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acrylamidoethoxy-2-hydroxypropoxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acrylamidopropoxy-2-hydroxypropoxy-propyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acrylamidoisopropoxy-2-hydroxypropoxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acrylamidobutoxy-2-hydroxypropoxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acryloxy-ethylamino-2-hydroxypropoxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acryloxypropylamino-2-hydroxypropoxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acryloxybutylamino-2-hydroxypropoxypropyl]-terminated polydimethylsiloxane, α,ω-bis[(meth)acrylamidoethylamino-2-hydroxypropoxy-propyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acrylamidopropylamino-2-hydroxypropoxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acrylamide-butylamino-2-hydroxypropoxy-propyl]-terminated polydimethylsiloxane, α,ω-bis[(meth)acryloxy-2-hydroxypropoxy-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-hydroxypropoxy-(polyethyleneoxy)propyl]-terminated polydimethylsiloxane, α,ω-bis[(meth)acryloxyethylamino-carbonyl-oxy-ethoxypropyl]-terminated polydimethylsiloxane, α,ω-bis[(meth)acryloxyethylamino-carbonyl-oxy-(polyethyleneoxy)propyl]-terminated polydimethylsiloxane, and mixtures thereof.

[0114] Another class of preferred polysiloxane vinyl crosslinkers are chain-extended polysiloxane vinyl crosslinkers each containing at least two polysiloxane segments and can be prepared according to the procedures described in U.S. Patent Nos. 5,034,461, 5,416,132, 5,449,729, 5,760,100, 7,423,074, 8,529,057, 8,835,525, 8,993,651 and 10,301,451 and U.S. Patent Application Publication No. 2018-0100038A1.

[0115] Another 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, even more preferably at least about 3.0) milliequivalents / gram ("meq / g") of hydrophilic moieties, which are preferably hydroxyl (-OH), carboxyl (-COOH), amino (-NHR N1 , where R N1 is H or C1-C2 alkyl), amide moiety (-CO-NR N1 R N2 , where R N1 is H or C1-C2 alkyl and R N2 is a covalent bond, H, or C1-C2 alkyl), N-C1-C3 acylamino, urethane moiety (-NH-CO-O-), urea moiety (-NH-CO-NH-), polyethylene glycol chain (where n is an integer from 2 to 20 and T1 is H, methyl or acetyl or phosphocholine group), or a combination thereof.

[0116] Examples of such preferred hydrophilized polysiloxane vinyl crosslinkers are those compounds of formula (1):

[0117]

[0118] where:

[0119] υ1 is an integer from 30 to 500 and ω1 is an integer from 1 to 75, provided that ω1 / υ1 is from about 0.035 to about 0.15 (preferably from about 0.040 to about 0.12, even more preferably from about 0.045 to about 0.10);

[0120] X 01 is O or NR n , where R n is hydrogen or C1-C 10 -alkyl;

[0121] R o is hydrogen or methyl;

[0122] R2 and R3 are each independently a substituted or unsubstituted C1-C 10 alkylene divalent group or a divalent group of -R5-O-R6-, where R5 and R6 are each independently a substituted or unsubstituted C1-C 10 alkylene divalent group;

[0123] R4 is a monovalent group of any one of formulas (2) to (7)

[0124]

[0125] p1 is 0 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;

[0126] R7 is hydrogen or methyl;

[0127] R8 is a C2-C6 hydrocarbon group having a valence of (m2 + 1);

[0128] R9 is a C2-C6 hydrocarbon group having a valence of (m4 + 1);

[0129] R 10 is ethyl or hydroxymethyl;

[0130] R 11 is methyl or hydroxymethyl;

[0131] R 12 is hydroxy or methoxy;

[0132] X3 is a sulfur linking group -S- or a tertiary amino linking group -NR 13 -, where R 13 is a C1-C1 alkyl, hydroxyethyl, hydroxypropyl, or 2,3-dihydroxypropyl;

[0133] X4 is an amide linking group where R 14 is hydrogen or C1-C 10 alkyl;

[0134] L PC is a divalent group -CH2-CHR0-R 15 -, -C3H6-O-R 16 -, where q1 is an integer from 1 to 20, R 15 is a straight-chain or branched C1-C 10 alkylene divalent group, R 16 is a straight-chain or branched C3-C 10 alkylene divalent group, and R 17 ]> is a direct bond or a straight-chain or branched C1-C4 alkylene divalent group.

[0135] The hydrophilic polysiloxane vinyl crosslinker of formula (1) can be prepared according to the procedures disclosed in U.S. Patent No. 10081697 and U.S. Patent Application Publication No. 2022 / 0251302A1.

[0136] 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), hydroxy-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 linked to the pyrrolidone ring at the 3-position or 5-position) (as described later in this application), acrylic monomers having a C1-C4 alkoxyethoxy group (as described later in this application), vinyl ether monomers (as described later in this application), allyl ether monomers (as described later in this application), phosphocholine-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.

[0137] According to the present invention, any hydrophobic vinyl monomer can be used 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, vinyltoluene, vinyl ethyl ether, perfluorohexylethyl-thio-carbonyl-aminoethyl-methacrylate, isobornyl (meth)acrylate, trifluoroethyl (meth)acrylate, hexafluoro-isopropyl (meth)acrylate, hexafluorobutyl (meth)acrylate, and combinations thereof.

[0138] According to the present invention, any non-siloxane vinyl crosslinker can be used in the present invention. Examples of preferred non-siloxane vinyl crosslinking reagents are described later in this application.

[0139] 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 cycloalkyl nitriles), persulfates, percarbonates, or mixtures thereof. Examples of preferred thermal polymerization initiators include, but are not limited to, benzoyl peroxide, tert-butyl peroxide, tert-amyl peroxybenzoate, 2,2-bis(tert-butylperoxy)butane, 1,1-bis(tert-butylperoxy)cyclohexane, 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane, 2,5-bis(tert-butylperoxy)-2,5-dimethyl-3-hexyne, bis(1-(tert-butylperoxy)-1-methylethyl)benzene, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, di-tert-butyl diperoxyphthalate, tert-butyl hydroperoxide, tert-butyl peracetate, tert-butyl peroxybenzoate, tert-butyl peroxyisopropyl carbonate, acetyl peroxide, lauroyl peroxide, decanoyl peroxide, dicetyl peroxydicarbonate, di(4-tert-butylcyclohexyl) peroxydicarbonate (Perkadox 16S), di(2-ethylhexyl) peroxydicarbonate, tert-butyl peroxyneopentanoate (Lupersol 11); tert-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).

[0140] Suitable photoinitiators are benzoin methyl ether, diethoxyacetophenone, benzoylphosphine oxide, 1-hydroxycyclohexyl phenyl ketone and the Darocur and Irgacur types, preferably Darocur and Darocur Germanium-based Norrish type I photoinitiators (e.g., those described in US 7,605,190). Examples of benzoylphosphine initiators include 2,4,6-trimethylbenzoyldiphenylphosphine oxide; bis-(2,6-dichlorobenzoyl)-4-N-propylphenyl-oxide phosphine; and bis-(2,6-dichlorobenzoyl)-4-N-butylphenylphosphine oxide.

[0141] The SiHy contact lens formulation may also contain other necessary components known to those skilled in the art, such as UV-absorbing vinyl monomers, HEVL-absorbing vinyl monomers, visibility colorants (e.g., reactive dyes, polymerizable dyes, pigments, or mixtures thereof, as well known to those skilled in the art), antimicrobial agents (e.g., preferably silver nanoparticles), bioactive agents, leachable lubricants (e.g., non-polymerizable hydrophilic polymers, etc.), leachable tear stabilizers (e.g., phospholipids, glycerol monoesters, glycerol diesters, glycerol triesters, glycolipids, glyceroglycolipids, sphingolipids, glycosphingolipids, etc.), and mixtures thereof.

[0142] The polymerizable composition (SiHy lens formulation) can be a solvent-free transparent liquid, which is prepared by mixing all polymerizable components and other necessary components; or a solution, which is prepared by dissolving all desired components in any suitable solvent such as a mixture of water and one or more water-miscible organic solvents, an organic solvent, or a mixture of one or more organic solvents, as known to those skilled in the art. The term "solvent" refers to chemicals that cannot participate in free radical polymerization reactions.

[0143] The solvent-free SiHy lens formulation typically contains at least one blend vinyl monomer as a reactive solvent for dissolving all other polymerizable components of the solvent-free SiHy lens formulation. Examples of preferred blend vinyl monomers are described later in this application. Preferably, methyl methacrylate is used as the blend vinyl monomer in the preparation of the solvent-free SiHy lens formulation.

[0144] 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 (such as acetone, methyl ethyl ketone, etc.), diethylene glycol n-butyl ether, diethylene glycol methyl ether, ethylene glycol phenyl ether, propylene glycol methyl ether, propylene glycol methyl ether acetate, dipropylene glycol methyl ether acetate, propylene glycol n-propyl ether, dipropylene glycol n-propyl ether, tripropylene glycol n-butyl ether, propylene glycol n-butyl ether, dipropylene glycol n-butyl ether, tripropylene glycol n-butyl ether, propylene glycol phenyl ether, dipropylene glycol dimethyl ether, polyethylene glycol, polypropylene glycol, ethyl acetate, butyl acetate, amyl acetate, methyl lactate, ethyl lactate, isopropyl lactate, dichloromethane, 2-butanol, 1-propanol, 2-propanol, menthol, cyclohexanol, cyclopentanol and exonorborneol, 2-pentanol, 3-pentanol, 2-hexanol, 3-hexanol, 3-methyl-2-butanol, 2-heptanol, 2-octanol, 2-nonanol, 2-decanol, 3-octanol, norbornane, tert-butanol, tert-pentanol, 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, 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-dimethyl propionamide, dimethylformamide, dimethylacetamide, dimethyl propionamide, N-methylpyrrolidone, and mixtures thereof.

[0145] A variety of SiHy lens formulations have been described in many patents and patent applications published as of the filing date of the present application and have been used to produce commercial SiHy contact lenses. Examples of commercial SiHy contact lenses include, but are not limited to, asmofilcon A, balafilcon A, comfilcon A, delefilcon A, efrofilcon A, enfilcon A, fanfilcon A, galyfilcon A, lotrafilcon A, lotrafilcon B, narafilcon A, narafilcon B, senofilcon A, senofilcon B, senofilcon C, smafilcon A, somofilcon A, and stenfilcon A.

[0146] The SiHy lens formulation (i.e., the polymerizable composition) can be preferably cured (polymerized) thermally or photochemically in a mold for casting contact lenses as known to those skilled in the art.

[0147] Thermal polymerization is conveniently carried out, for example, at a temperature of 25°C to 120°C and preferably 40°C to 100°C. The reaction time can vary within a wide range, but is conveniently, for example, 1 to 24 hours or preferably 2 to 12 hours. It is advantageous to degas the components and solvents used in the polymerization reaction in advance and to carry out the copolymerization reaction under an inert atmosphere, for example, in a nitrogen or argon atmosphere.

[0148] Then, photochemical polymerization can be initiated by actinic radiation, such as light, especially UV light or visible light of a suitable wavelength. Thus, if appropriate, the spectral requirements can be controlled by adding a suitable photosensitizer.

[0149] According to the present invention, the lens formulation can be introduced (dispensed) into the cavity formed by the mold according to any known method.

[0150] After the lens formulation is dispensed into the mold, it is polymerized to produce a contact lens. The polymerization can preferably be carried out by thermally or photochemically initiating the exposure of the lens formulation in the mold to spatially restricted actinic radiation to crosslink the polymerizable components in the lens formulation.

[0151] Opening the mold to enable removal of the molded article from the mold can occur in a manner known per se.

[0152] The molded contact lens 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 those described above.

[0153] The preformed contact lenses of the present invention can be obtained by any method known to those skilled in the art or to be developed.

[0154] According to the present invention, the preformed contact lenses inherently contain or have been modified to contain first reactive functional groups on and near their surfaces.

[0155] In the case where the preformed contact lenses inherently contain first reactive functional groups on and near their surfaces, they are obtained by polymerizing a polymerizable composition containing a reactive vinyl monomer (i.e., a non-silicone hydrogel lens formulation or a silicone hydrogel lens formulation), the reactive vinyl monomer further containing at least one first reactive functional group, for example, selected from the group consisting of carboxyl groups, primary amino groups, secondary amino groups, and combinations thereof. Examples of carboxyl-containing vinyl monomers 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 contains preferably about 1.0 - 10%, more preferably about 2.0 - 7%, even more preferably about 2.0 - 5% by weight of such vinyl monomers having at least one first reactive functional group.

[0156] According to the present invention, any carboxyl-containing vinyl monomer can be added to the polymerizable composition. Examples of preferred carboxyl-containing vinyl monomers are carboxyl-containing (meth)acryloyloxy monomers, which preferably include but are not limited to acrylic acid, methacrylic acid, ethylacrylic acid, propylacrylic acid, (meth)acryloyloxyacetic acid, succinic acid mono-2-[(meth)acryloyloxy]ethyl ester, (meth)acryloyloxypropionic acid, (meth)acryloyloxybutyric acid, and combinations thereof.

[0157] According to the present invention, any amino-containing vinyl monomer can be added to the polymerizable composition. Examples of preferred amino-containing vinyl monomers are amino-containing (meth)acryloyloxy monomers, which preferably 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.

[0158] In the case where the preformed contact lenses inherently contain amino groups on and near their surfaces, it can be chemically modified by reacting it with a thiolactone to covalently attach a mercapto group through the amino group.

[0159] Examples of preferred commercially available thiolactones include, but are not limited to, 4-butyrylthiolactone (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-acyldihydro-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]-butyric acid).

[0160] The preformed contact lens can also be surface treated to have first reactive functional groups on and 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 (covalently attaching) a compound having at least one reactive functional group to the (modified or unmodified) surface of the article; graft polymerization of an ethylenic monomer having at least one first reactive functional group to the (modified or unmodified) surface of the article; or a combination thereof.

[0161] Plasma treatment refers to a method in which a contact lens is exposed to plasma to chemically modify the surface of the contact lens. The term "plasma" refers to an ionized gas (e.g., generated by an electric glow discharge, which can consist of electrons, ions of either polarity, gas atoms and molecules in the ground state or any higher state of any excited form, and photons). The excited species interacts with the solid surface of the article placed in the plasma, resulting in chemical and physical modification of the material surface. In the case where plasma is generated by subjecting a gas in a vacuum chamber to charge typically at radio frequency (rf) (or at microwave or other frequencies), it is commonly referred to as "low-temperature plasma". In the case where plasma is generated by an atmospheric discharge (e.g., arc discharge) and maintained at ambient atmospheric pressure, it is a "high-temperature plasma" or "atmospheric pressure plasma". Atmospheric pressure plasma can be generated by an atmospheric discharge.

[0162] For a review of plasma treatment and its uses, reference is made to R. Hartmann "Plasma Polymerisation: Grundlagen, Technik und Anwendung, Jahrb. Surface Engineering" (1993) pp. 49,283-296, Battelle-Inst.e.V., Frankfurt / Germany; H. Yasuda, "Glow Discharge Polymerization", Journal of Polymer Science: Macromolecular Reviews, Vol. 16 (1981), pp. 199-293; H. Yasuda, "Plasma Polymerization", Academic Press, Inc. (1985); Frank Jansen, "Plasma Deposition Processes", in "Plasma Deposited Thin Films", edited by T. Mort and F. Jansen, CRC Press Boca Raton (19); O. Auciello et al. (ed.) "Plasma-Surface Interactions and Processing of Materials", published 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) 333-341.

[0163] Known plasma treatments at low pressure include plasma deposition, plasma-induced polymerization, plasma grafting, plasma oxidation, etc. Plasma treatments at low pressure have been used in commercial products, such as Focus NIGHT& and AIR (Alcon, Inc.) and (Bausch & Lomb). The advantages of plasma coatings (such as, for example, with Focus NIGHT& Those discovered are its durability, relatively high hydrophilicity / wettability, and low susceptibility to lipid and protein deposition and adsorption. Examples of plasma treatment are those disclosed in U.S. Patent Nos. 4,143,949; 4,312,575; 5,464,667; 6,881,269; and 7,078,074. It should be understood that preformed contact lenses typically must be dried prior to plasma treatment at low pressure.

[0164] Those skilled in the art well understand that a plasma (i.e., an electric glow discharge plasma) is a partially ionized gas that consists of a high concentration of excited atoms, molecules, ions, and free radical species and is generated by subjecting a gas in a vacuum chamber typically to an electric field at radio frequency (rf) (or at microwave or other frequencies).

[0165] As an illustrative example of plasma treatment of a silicone hydrogel contact lens at low pressure, one or more preformed silicone hydrogel contact lenses are placed in a reactor chamber between opposing electrodes. The chamber is then sealed, and the pressure is reduced by a vacuum system. Considerable time is required to pump the system down to the operating pressure. When the appropriate pressure is reached in the chamber, a process gas is introduced into the interior of the chamber, and the electrodes are energized. Depending on the process gas used, the resulting plasma cloud can apply a thin polymer layer (or polymer coating) to the lens and / or alter the chemical composition of the top layer of the lens surface. After an appropriate time, the power to the electrodes is stopped, and the reactor chamber is returned to atmospheric pressure so that the lens can be removed.

[0166] Low-pressure plasma treatment systems are known to those skilled in the art and have been disclosed in patents and articles. For example, Peng Ho and Yasuda described in their paper ("Ultrathin Coating Of PlasmaPolymer Of Methane Applied On The Surface Of Silicone Contact Lenses", Journal of BiomedicalMaterials Research, Vol. 22, 919-937 (1988)) a batch low-pressure plasma treatment system (or rotary plasma system) that includes a bell-shaped vacuum chamber in which opposing aluminum electrodes are arranged and a rotatable aluminum plate is located between the electrodes and is driven by an induction motor within the system. Matsuzawa and Winterton disclosed a linear low-pressure plasma system in US 6,881,269.

[0167] According to the present invention, a dry preformed contact lens is treated with a low-pressure plasma generated in a plasma gas (i.e., the atmosphere), which is composed of a mixture of air, N2, O2, CO2, or a C1-C6 hydrocarbon and a secondary gas selected from the group consisting of air, N2, O2, CO2, and 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).

[0168] Preferably, the atmospheric pressure plasma surface treatment disclosed in U.S. Patent No. 9,156,213 is used in the present invention. For the atmospheric pressure plasma surface treatment, the contact lens can be in a fully hydrated state.

[0169] Those skilled in the art are familiar with how to graft (covalently attach) a compound having at least one first reactive functional group (carboxyl group, amino group, azetidinium group, epoxy group, aziridinyl group, vinyl sulfone group, mercapto group, and combinations thereof) onto the surface of a contact lens according to known coupling reactions.

[0170] The graft polymerization of one or more ethylenically unsaturated monomers having at least one first reactive functional group (e.g., carboxyl, amino, azetidinium group, epoxy group, aziridinyl group, and combinations thereof) in the presence or absence of an ethylenically unsaturated crosslinking reagent to form a hydrophilic polymer coating is described in many patents, e.g., U.S. Patent 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, as well as in JP 2001075060. For example, a preformed contact lens in the dry state is first plasma-treated in a plasma atmosphere of a compound having at least one reactive functional group (e.g., an ethylenically unsaturated monomer having a primary or secondary amino group, carboxyl group, epoxy group, azlactone group, aziridinyl group, or isocyanate group) to form a plasma coating having reactive functional groups. The plasma-treated contact lens is reacted with a compound having a free radical initiator moiety (e.g., a thermal initiator or a photoinitiator) or preferably a living polymerization initiator moiety (e.g., an atom transfer radical polymerization (ATRP) initiator or a reversible addition-fragmentation chain transfer polymerization (RAFT) initiator) and a functional group that co-reacts with the functional groups of the plasma coating on the contact lens under coupling reaction conditions known to those skilled in the art in the presence or absence of a coupling agent. The resulting contact lens having a free radical initiator moiety thereon is immersed in a solution of one or more ethylenically unsaturated monomers having at least one first functional group and subjected to conditions that initiate the free radical polymerization of those ethylenically unsaturated monomers, thereby forming a graft layer of a polymer containing the first reactive functional group.

[0171] Any non-silicone hydrogel material can be used to cover the areas on the convex surface of the preformed contact lens, provided that they do not contain the first reactive functional group (any of those described above) and thermally crosslinkable groups (e.g., azetidinium group and / or epoxy group). Those skilled in the art are familiar with covering those areas on the convex surface of the preformed contact lens.

[0172] In a preferred embodiment, the hydrogel-forming composition can be applied to multiple areas on the convex surface of the preformed contact lens according to pad printing and / or inkjet printing techniques, and then the hydrogel-forming composition applied to the areas on the convex surface of the preformed contact lens is thermally cured or photocured to form a non-silicone hydrogel material to cover those areas.

[0173] Any hydrogel-forming composition for forming a non-silicone hydrogel material can be used, provided that the resulting non-silicone hydrogel material does not contain the first reactive functional group (those described above) and thermally crosslinkable groups (azetidinium group and / or epoxy group).

[0174] Preferably, the hydrogel-forming composition comprises at least one crosslinkable polymer having hydroxyl and / or ethylenically unsaturated groups and optionally at least one hydrophobic ethylenically unsaturated monomer selected from the group consisting of methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, methyl (meth)acrylate, and combinations thereof, wherein if the at least one crosslinkable polymer does not contain any ethylenically unsaturated groups, the hydrogel-forming composition further comprises at least one hydroxyl-containing ethylenically unsaturated monomer and at least one compound having two or more isocyanate groups, wherein all polymerizable components in the hydrogel-forming composition do not contain the first reactive functional groups (those described above) and thermally crosslinkable groups (azetidinium groups and / or epoxy groups).

[0175] One class of crosslinkable polymers having hydroxyl and ethylenically unsaturated groups includes, but is not limited to, water-soluble crosslinkable poly(vinyl alcohol) prepolymers comprising repeating units of -CH2-CHOH- and repeating units each having one ethylenically unsaturated group, as described in US 5583163 and US 6303687.

[0176] Preferred crosslinkable polymers having hydroxyl but no ethylenically unsaturated groups can be prepared by polymerizing a polymerizable composition comprising: at least one hydroxyl-containing ethylenically unsaturated monomer, at least one ethylenically unsaturated monomer selected from the group consisting of vinylpyrrolidone, vinyl chloride, (meth)acrylamide, N,N-dimethyl(meth)acrylamide, methoxyethyl ethoxyethyl (meth)acrylate, methyl methacrylate, ethyl methacrylate, and combinations thereof; a chain transfer agent (e.g., 2-mercaptoethanol); and a free radical initiator.

[0177] Examples of preferred hydroxyl-containing ethylenically unsaturated monomers include, but are not limited to, 2-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, 2-hydroxyethyl (meth)acrylate, glycerol (meth)acrylate, and vinyl alcohol are used.

[0178] Pad printing is well known in the art (see, e.g., U.S. Patent Nos. 3,536,386; 4,582,402; 4,704,017; 5,034,166). The following is a typical example of such printing. An image is etched into a metal to form a stereotype. The stereotype is placed in a printing press. Once in the press, the stereotype is inked by scraping it across an open ink fountain system or by sliding a closed ink cup over the image. Then, a silicone pad picks up the inked image from the stereotype and transfers the image to a contact lens. The silicone pad is made of a material that includes a silicone with variable elasticity. The properties of the silicone material allow the ink (here, a hydrogel-forming composition) to temporarily stick to the pad and to be completely released from the pad when it contacts the contact lens or mold. Suitable pad printing structures include, but are not limited to, Tampo-type printing structures (such as Tampo vario 90 / 130), rubber stamps, thimbles, scrapers, direct printing, or transfer printing, as they are known in the art.

[0179] Any known and suitable silicone pad can be used in the present invention. Silicone pads are commercially available. However, different pads can give different printing qualities. A person skilled in the art will know how to select a pad for a given hydrogel-forming composition.

[0180] The stereotype can be made of ceramic, polymer, or metal (e.g., steel). When the stereotype is made of steel, it will be desirable to neutralize the pH of a water-based ink (e.g., adjust the pH to 6.8 - 7.8) by adding a buffering agent (e.g., such as phosphate). The image can be etched into the stereotype according to any method known to a person skilled in the art, such as by chemical etching or laser ablation, etc. It is also desirable to clean the stereotype using standard cleaning techniques known to a person skilled in the art after use, such as, for example, dipping in a solvent, sonication, or mechanical abrasion.

[0181] Printing lenses using an inkjet printing process is described in U.S. Patent Application Nos. 2001 / 0050753, 2001 / 0085934, 2003 / 0119943, and 2003 / 0184710.

[0182] According to the present invention, the plurality of zones can have any shape. Examples of preferred shapes include, but are not limited to, circular shape, triangular shape, square shape, rectangular shape, hexagonal shape, polygonal shape, star shape, annular ring, curve, straight line, and combinations thereof. The plurality of zones can have any two-dimensional size. Preferably, one of the two dimensions of the plurality of zones is about 0.40 mm or less (preferably about 0.30 mm or less, more preferably about 0.25 mm or less, even more preferably about 0.05 - 0.20 mm).

[0183] According to one embodiment of the present invention, a plurality of zones are arranged in any pattern on the convex surface of a preformed contact lens or on the molding surface of a female half-mold, preferably in a rotationally symmetric pattern with respect to the central axis of the preformed contact lens or the female half-mold. Preferably, the plurality of zones are located in an annular zone having an inner diameter of about 6.0 - 9.0 mm and an outer diameter of about 11.5 - 14.5 mm and being concentric with the central axis of the preformed contact lens or the female half-mold.

[0184] In one embodiment, the plurality of zones includes at least three annular rings.

[0185] In another embodiment, the plurality of zones includes at least eight curves or straight lines radiating outward from a circle having a diameter of about 6.0 - 9.0 mm and being concentric with the central axis of the preformed contact lens or the female half-mold.

[0186] In another embodiment, the plurality of zones includes circular dots (preferably having a diameter of about 0.25 mm or less, more preferably having a diameter of about 0.05 - 0.20 mm), which are arranged in a rotationally symmetric pattern on the convex surface of the preformed contact lens or on the molding surface of the female half-mold with respect to the central axis of the preformed contact lens or the female half-mold. Preferably, the circular dots are arranged in an annular ring concentric with the central axis of the preformed contact lens or the female half-mold.

[0187] It should be understood that the shape of the plurality of zones determines the shape of the mold marks in the front external hydrogel layer of the coated contact lens of the present invention. Zones having annular rings, curves, and / or thick lines will result in the formation of grooves in the front external hydrogel layer of the coated contact lens, while zones having circular shapes, triangular shapes, square shapes, rectangular shapes, hexagonal shapes, polygonal shapes, and / or star shapes will result in the formation of gaps in the front external hydrogel layer of the coated contact lens.

[0188] According to the present invention, the water-soluble and thermally crosslinkable hydrophilic polymer material preferably contains azetidinium groups or epoxy groups or a combination thereof. Preferably, the water-soluble and crosslinkable hydrophilic polymer material is a partially crosslinked polymer material that contains a three-dimensional network and thermally crosslinkable groups within the network or attached to the network, preferably azetidinium groups. The term "partially crosslinked" with respect to the polymer material means that the crosslinkable groups of the starting materials used to make the polymer material have not been completely consumed in the crosslinking reaction. For example, such a thermally crosslinkable hydrophilic polymer material contains azetidinium groups and is a partial reaction product of at least one azetidinium-containing polymer and at least one hydrophilic enhancer (i.e., wetting agent) having at least one carboxyl group, primary amine group, secondary amine group, or thiol group according to the crosslinking reaction shown in Scheme I.

[0189]

[0190] wherein X1 is -S-*, -OC(=O)-*, or -NR'-*, wherein R' is hydrogen or an unsubstituted or substituted C1-C 20 alkyl, and * represents an organic group.

[0191] Examples of preferred water-soluble and thermally crosslinkable hydrophilic polymer materials containing epoxy groups include, but are not limited to: one or more multi-arm polyethylene glycols each having terminal epoxy groups; a mixture of a multi-arm polyethylene glycol having terminal epoxy groups and one or more polyethylene glycols each having a terminal functional group selected from the group consisting of primary amine groups, secondary amine groups, carboxyl groups, thiol groups, and combinations thereof; a partial reaction product of a multi-arm polyethylene and a hydrophilic enhancer having at least one reactive functional group selected from the group consisting of amino groups, carboxyl groups, thiol groups, and combinations thereof (such as the hydrophilic polymers disclosed in U.S. Patent No. 9,505,184 and U.S. Patent No. 6,440,571), or combinations thereof.

[0192] Examples of preferred water-soluble and thermally crosslinkable hydrophilic polymer materials containing azetidinium groups include, but are not limited to, the poly(2-oxazoline-co-vinylimine)-epichlorohydrin copolymer disclosed in U.S. Patent No. 9,720,138, the chemically modified poly(2-oxazoline-co-vinylimine)-epichlorohydrin copolymer disclosed in U.S. Patent No. 9,720,138, the chemically modified polyamidoamine-epichlorohydrin disclosed in U.S. Patent No. 8,529,057, the copolymer of an azetidinium-containing vinyl monomer and one or more hydrophilic vinyl monomers disclosed in U.S. Patent No. 9,422,447, the chemically modified copolymer of an azetidinium-containing vinyl monomer and one or more hydrophilic vinyl monomers disclosed in U.S. Patent No. 9,422,447, or combinations thereof.

[0193] According to the present invention, the term "chemically modified" with respect to a water-soluble and thermally crosslinkable hydrophilic polymer material having an azetidinium group means that the poly(2-oxazoline-co-vinylimine)-epichlorohydrin copolymer, polyamidoamine-epichlorohydrin, or copolymer of an azetidinium-containing vinyl monomer is partially reacted with a hydrophilic enhancer having at least one reactive functional group selected from the group consisting of amino groups, carboxyl groups, thiol groups, and combinations thereof (i.e., not all of these azetidinium groups are consumed). The chemically modified poly(2-oxazoline-co-vinylimine)-epichlorohydrin copolymer or polyamidoamine-epichlorohydrin or copolymer of an azetidinium-containing vinyl monomer can be particularly useful for forming a relatively thick and soft non-silicone hydrogel coating on a silicone hydrogel contact lens.

[0194] Any suitable hydrophilic enhancer can be used in the present invention as long as they contain at least one amino group, at least one carboxyl group, and / or at least one thiol group.

[0195] A preferred class of hydrophilicity enhancers includes, but is not limited to: monosaccharides containing a primary amino group, secondary amino group, carboxyl group or mercapto group (e.g., 3-amino-1,2-propanediol, 1-mercapto glycerol, 5-keto-D-gluconic acid, galactosamine, glucosamine, galacturonic acid, gluconic acid, glucosaminic acid, mannosamine, glucaric acid 1,4-lactone, sugar acid, ketodeoxynonulosonic acid, N-methyl-D-glucosamine, 1-amino-1-deoxy-β-D-galactose, 1-amino-1-deoxysorbitol, 1-methylamino-1-deoxysorbitol, N-aminoethyl glucanamide); disaccharides containing a primary amino group, secondary amino group, carboxyl group or mercapto group (e.g., chondroitin disaccharide sodium salt, bis(β-D-xylopyranosyl)amine, digalacturonic acid, heparin disaccharide, hyaluronic acid disaccharide, lactobionic acid); and oligosaccharides containing a primary amino group, secondary amino group, carboxyl group or mercapto group (e.g., carboxymethyl-β-cyclodextrin sodium salt, trigalacturonic acid); and combinations thereof.

[0196] Another preferred class of hydrophilicity enhancers is hydrophilic polymers having one or more (primary or secondary) amino groups, carboxyl groups and / or mercapto groups. More preferably, the content of amino group (-NHR’, where R’ is as defined above), carboxyl group (-COOH) and / or mercapto group (-SH) in the hydrophilic polymer as a hydrophilicity enhancer is less than about 40% by weight, preferably less than about 30% by weight, more preferably less than about 20% by weight, and even more preferably less than about 10% by weight based on the total weight of the hydrophilic polymer.

[0197] A preferred class of hydrophilic polymers as hydrophilicity enhancers is polysaccharides containing (primary or secondary) amino groups or carboxyl groups, such as carboxymethyl cellulose (having a carboxyl group content of about 40% or less, and the carboxyl group content is estimated based on the composition of the repeating unit -[C6H 10-m O5(CH2CO2H) m -, where m is from 1 to 3), carboxyethyl cellulose (having a carboxyl group content of about 36% or less, and the carboxyl group content is estimated based on the composition of the repeating unit -[C6H 10-m O5(C2H4CO2H) m -, where m is from 1 to 3), carboxypropyl cellulose (having a carboxyl group content of about 32% or less, and the carboxyl group content is estimated based on the composition of the repeating unit -[C6H 10-m O5(C3H6CO2H) m -, where m is from 1 to 3), hyaluronic acid (having a carboxyl group content of about 11%, and the carboxyl group content is based on the repeating unit -(C 13 H 20chondroitin sulfate (having a carboxyl content of about 9.8%, the carboxyl content being estimated based on the repeating unit -(C 12 H 18 O 13 NSCO2H)-, or a combination thereof).

[0198] Another class of preferred hydrophilic polymers as hydrophilicity enhancers includes, but is not limited to: poly(ethylene glycol) (PEG) having a single - amino group (primary or secondary amino group), carboxyl group or thiol group (e.g., PEG - NH2, PEG - SH, PEG - COOH); H2N - PEG - NH2; HOOC - PEG - COOH; HS - PEG - SH; HCN - PEG - COOH; HOOC - PEG - SH; H2N - PEG - SH; multi - arm PEG having one or more amino groups (primary or secondary), carboxyl groups or thiol groups; PEG dendrimers having one or more amino groups (primary or secondary), carboxyl groups or thiol groups; diamino - (primary or secondary) or dicarboxyl - terminated homopolymers or copolymers of non - reactive hydrophilic vinyl monomers; monoamino - (primary or secondary) or monocarboxyl - terminated homopolymers or copolymers of non - reactive hydrophilic vinyl monomers; copolymers which are polymerization products of a composition comprising: (1) about 60% or less by weight, preferably about 0.1 - 30%, more preferably about 0.5 - 20%, even more preferably about 1 - 15% by weight of one or more reactive vinyl monomers, and (2) at least one non - reactive hydrophilic vinyl monomer; and combinations thereof. One or more reactive vinyl monomers and one or more non - reactive hydrophilic vinyl monomers are those described previously.

[0199] According to the present invention, the reactive vinyl monomer for manufacturing 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 acid, ethylacrylic acid, N - 2 - (methyl)acrylamido glycolic 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.

[0200] According to the present invention, the non-reactive vinyl monomer for manufacturing the hydrophilic enhancer is a vinyl monomer that does not contain any carboxyl group, primary amino group, secondary amino group, epoxy group, isocyanate group, azlactone group, or aziridinyl group. The non-reactive vinyl monomer is preferably an uncharged hydrophilic vinyl monomer that does not contain a carboxyl group or an amino group (any of those described above can be used here), a phosphorylcholine-containing vinyl monomer (any of those described above can be used here), or a combination thereof.

[0201] More preferably, the hydrophilic polymer as the hydrophilic enhancer is:

[0202] Poly(ethylene glycol) having a single -NH2, -SH or -COOH functional group;

[0203] Poly(ethylene glycol) having two terminal functional groups selected from the group consisting of -NH2, -COOH, -SH and combinations thereof;

[0204] Multi-arm poly(ethylene glycol) having one or more functional groups selected from the group consisting of -NH2, -COOH, -SH and combinations thereof;

[0205] Homopolymers or copolymers capped with a single amino group, a single carboxyl group, a di-amino group or a di-carboxyl group of a non-reactive hydrophilic vinyl monomer;

[0206] A copolymer which is a polymerization product of a composition comprising: (1) about 0.1 - 30% by weight, preferably about 0.5 - 20% by weight, more preferably about 1 - 15% by weight of a reactive vinyl monomer, and (2) at least one non-reactive vinyl monomer,

[0207] Examples of preferred reactive vinyl monomers include, but are not limited to, acrylic acid, methacrylic acid, ethylacrylic acid, 2-(meth)acrylamido glycolic 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.

[0208] Examples of preferred non-reactive hydrophilic ethylenically unsaturated monomers include, but are not limited to, alkyl (meth)acrylamides (any of those described above), N-2-dimethylaminoethyl (meth)acrylamide, dimethylaminoethyl (meth)acrylate, hydroxy-containing acrylic monomers (any of those described above), N-vinylamide monomers (any of those described above), methylene-containing pyrrolidone monomers (i.e., pyrrolidone derivatives each having a methylene group attached to the pyrrolidone ring at the 3- or 5-position) (any of those described above), acrylic monomers having a C1-C4 alkoxyethoxy group (any of those described above), vinyl ether monomers (any of those described above), allyl ether monomers (any of those described above), phosphorylcholine-containing ethylenically unsaturated monomers (any of those described above), and combinations thereof.

[0209] Preferably, the non-reactive hydrophilic 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, (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 at most 1500, poly(ethylene glycol) (meth)acrylate having a number average molecular weight of at most 1500, N-vinylpyrrolidone, N-vinyl-N-methylacetamide, N-vinylformamide, N-vinylacetamide, 1-methyl-3-methylene-2-pyrrolidone, 1-methyl-5-methylene-2-pyrrolidone, 5-methyl-3-methylene-2-pyrrolidone, tetra(ethylene glycol) methyl ether (meth)acrylate, methoxy poly(ethylene glycol) ethyl (meth)acrylamide having a number average molecular weight of at most 1500, C1-C4-alkoxy polyethylene glycol (meth)acrylate having a weight average molecular weight of at most 1500, tetra(ethylene glycol) mono vinyl ether, poly(ethylene glycol) mono vinyl 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 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, (meth)acrylamide, dimethyl(meth)acrylamide, N-2-hydroxyethyl(meth)acrylamide, N,N-bis(hydroxyethyl)(meth)acrylamide, N-2,3-dihydroxypropyl (meth) acrylamide, N-tris (hydroxymethyl) methyl (meth) acrylamide, 2-hydroxyethyl (meth) acrylate, glycerol methacrylate (GMA), poly (ethylene glycol) ethyl (meth) acrylamide having a number average molecular weight of up to 1500, poly (ethylene glycol) (meth) acrylate having a number average molecular weight of up to 1500, N-vinylpyrrolidone, N-vinyl-N-methylacetamide, methoxypoly (ethylene glycol) ethyl (meth) acrylamide having a number average molecular weight of up to 1500, methoxypolyethylene glycol (meth) acrylate having a weight average molecular weight of up to 1500, poly (ethylene glycol) mono vinyl ether, poly (ethylene glycol) methyl vinyl ether, poly (ethylene glycol) mono allyl ether, poly (ethylene glycol) methyl allyl ether, vinyl alcohol, allyl alcohol and combinations thereof, and even more preferably selected from the group consisting of: (meth) acryloyloxyethyl phosphorylcholine, (meth) acryloyloxypropyl phosphorylcholine, 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.,

[0210] PEGs with functional groups and multi-arm PEGs with functional groups can be obtained from different commercial suppliers (e.g., Polyscience, Shearwater Polymers, inc., etc.).

[0211] Homopolymers or copolymers capped with one or more non-reactive hydrophilic vinyl monomers or phosphorylcholine-containing vinyl monomers having a monoamino, monocarboxyl, diamino or dicarboxyl group can be prepared according to the procedures described in U.S. Patent No. 6,218,508. For example, to prepare a homopolymer or copolymer capped with a diamino or dicarboxyl group of a non-reactive hydrophilic vinyl monomer, the non-reactive vinyl monomer, a chain transfer agent having an amino or carboxyl group (e.g., 2-aminoethanethiol, 2-mercaptopropionic acid, thioglycolic acid, thiolactic acid, or other hydroxy thiols, amino thiols, or carboxyl-containing thiols), and optionally other vinyl monomers are copolymerized (thermally or photochemically) with a reactive vinyl monomer (having an amino or carboxyl group) in the presence of a free radical initiator. Generally, the molar ratio of the chain transfer agent to all vinyl monomers except 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 this preparation, the chain transfer agent having an amino or carboxyl group is used to control the molecular weight of the resulting hydrophilic polymer and form the ends of the resulting hydrophilic polymer so as to provide a resulting hydrophilic polymer having one terminal amino or carboxyl group, while the reactive vinyl monomer provides the other terminal carboxyl or amino group to the resulting hydrophilic polymer. Similarly, to prepare a homopolymer or copolymer capped with a monoamino or monocarboxyl group of a non-reactive hydrophilic vinyl monomer, the non-reactive vinyl monomer, a chain transfer agent having an amino or carboxyl group (e.g., 2-aminoethanethiol, 2-mercaptopropionic acid, thioglycolic acid, thiolactic acid, or other hydroxy thiols, amino thiols, or carboxyl-containing thiols), and optionally other vinyl monomers are copolymerized (thermally or photochemically) in the absence of any reactive vinyl monomer.

[0212] Copolymers containing non-reactive hydrophilic vinyl monomers and reactive vinyl monomers (e.g., carboxyl-containing vinyl monomers, primary amino-containing vinyl monomers or secondary amino-containing vinyl monomers) can be prepared according to any well-known free radical polymerization method or obtained from commercial suppliers. Copolymers containing methacryloyloxyethyl phosphorylcholine and a carboxyl-containing vinyl monomer (or an amino-containing vinyl monomer) can be obtained from NOP Corporation (e.g., -AC01 and AE).

[0213] The weight average molecular weight M of the hydrophilic polymer (as a hydrophilic enhancer) having at least one amino, carboxyl or mercapto 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.

[0214] The water-soluble and thermally crosslinkable hydrophilic polymer material can be prepared according to the methods disclosed in U.S. Patent Nos. 8,529,057, 9,422,447, 9,720,138, and 11,256,003.

[0215] In a preferred embodiment, the water-soluble and thermally crosslinkable polymer material can be obtained by heating an aqueous reactive solution to a temperature of about 35 - 85 °C and maintaining said temperature for a sufficient period of time (about 8 hours or less, preferably about 5 hours, more preferably about 2 to about 4 hours), said aqueous reactive solution comprising at least one polymer of a nitrogen-containing heterocyclobutonium and at least one hydrophilic enhancer (i.e., wetting agent) having at least one reactive functional group selected from the group consisting of amino, carboxyl, mercapto, and combinations thereof. The aqueous reactive solution preferably comprises about 70 - 170 mM (preferably about 90 - 150 mM, more preferably about 100 - 130 mM) of one or more ionic compounds and has a pH of at least 8.0 (preferably at least 8.5, more preferably at least 9.0, even more preferably at least 9.5). It should be understood that the reaction time should be long enough to covalently attach the hydrophilic enhancer to the polymer chains of the nitrogen-containing heterocyclobutonium polymer, but should be short enough not to consume all of the heterocyclobutonium groups of the nitrogen-containing heterocyclobutonium polymer and not to form a gel (i.e., not water-soluble) (due to too many crosslinking bonds formed between the nitrogen-containing heterocyclobutonium polymer and the hydrophilic enhancer). The resulting polymer material is a slightly crosslinked polymer material having a highly branched structure and still containing thermally crosslinkable heterocyclobutonium groups.

[0216] Those skilled in the art well understand how to adjust the pH of the reactive mixture, for example, by adding a base (e.g., NaOH, KOH, NH4OH, or a mixture thereof) or an acid (e.g., HCl, H2SO4, H3PO4, citric acid, acetic acid, boric acid, or a mixture thereof).

[0217] According to the present invention, any ionic compound can be used in the reactive mixture. Preferably, the ionic compounds are those used as ionic strength regulators and ionic buffers used in ophthalmic solutions. Examples of preferred ionic strength regulators include, but are not limited to, sodium chloride, potassium chloride, and combinations thereof. Examples of preferred ionic buffers include various salts of phosphoric acid (e.g., NaH2PO4, Na2HPO4, Na3PO4, KH2PO4, K2HPO4, K3PO4, or a mixture thereof), various salts of boric acid (e.g., sodium borate, potassium borate, or a mixture thereof), various salts of citric acid (e.g., monosodium citrate, disodium citrate, trisodium citrate, monopotassium citrate, dipotassium citrate, tripotassium citrate, or a mixture thereof), various salts of carbonic acid (e.g., Na2CO3, NaHCO3, K2CO3, KHCO3, or a mixture thereof).

[0218] An aqueous reactive solution for preparing a water-soluble thermally crosslinkable polymeric material can be prepared by dissolving a desired amount of a polymer containing azetidinium, a desired amount of a hydrophilic enhancer having at least one reactive functional group, and a desired amount of other components (e.g., ionic buffers, ionic strength regulators, etc.) in water (or a mixture of water and a small amount of water-soluble organic solvents) to form an aqueous solution, and then adjusting the pH of the aqueous solution (if necessary).

[0219] According to the present invention, the concentration ratio of the hydrophilic enhancer to the azetidinium-containing polymer in the aqueous reactive solution must be selected so as not to render the resulting water-soluble thermally crosslinkable polymeric material insoluble in water (i.e., having a solubility of less than 0.005 g / 100 ml of water at room temperature) and so as not to consume more than about 99%, preferably about 98%, more preferably about 97%, even more preferably about 96% of the azetidinium groups of the azetidinium-containing polymer.

[0220] In a preferred embodiment, the aqueous reactive solution comprises 0.01-10% by weight (preferably 0.05-5% by weight, more preferably 0.08-1% by weight, even more preferably 0.1-0.4% by weight) of the azetidinium-containing polymer and about 0.01-10% by weight (preferably 0.02-5% by weight, more preferably 0.05-2% by weight, even more preferably 0.08-1.0% by weight) of the hydrophilic enhancer having at least one reactive functional group (carboxyl group, primary amino group, secondary amino group), and the concentration ratio of the azetidinium-containing polymer to the hydrophilic enhancer is about 1000:1 to 1:1000 (preferably about 500:1 to about 1:500, more preferably about 250:1 to about 1:250, even more preferably about 100:1 to about 1:100).

[0221] In a preferred embodiment, the water-soluble thermally crosslinkable polymeric material comprises (i) from about 20 to 95% by weight of a first polymer chain derived from polyamidoamine-epichlorohydrin or poly(2-oxazoline-co-vinylimine)-epichlorohydrin, (ii) from about 5 to 80% by weight of a hydrophilic moiety or a second polymer chain derived from at least one hydrophilic enhancer, said at least one hydrophilic enhancer having at least one reactive functional group selected from the group consisting of amino, carboxyl, mercapto, and combinations thereof (preferably carboxyl or mercapto), wherein the hydrophilic moiety or the second polymer chain is covalently attached to the first polymer chain through one or more covalent bonds formed between an azetidinium group of the polyamidoamine-epichlorohydrin or poly(2-oxazoline-co-vinylimine)-epichlorohydrin and an amino, carboxyl, or mercapto group of the hydrophilic enhancer, and (iii) azetidinium groups, which are part of the first polymer chain or are side groups or end groups covalently attached to the first polymer chain. The composition of the chemically modified poly(2-oxazoline-co-vinylimine)-epichlorohydrin or chemically modified polyamidoamine-epichlorohydrin is determined by the composition of the reactant mixture (based on the total weight of these reactants) used for such polymers in the crosslinking reaction as shown in Scheme I above. For example, if, based on the total weight of these reactants, the reactant mixture comprises about 75% by weight of polyamidoamine-epichlorohydrin and about 25% by weight of at least one hydrophilic enhancer, the resulting chemically modified polyamidoamine-epichlorohydrin comprises about 75% by weight of a first polymer chain derived from polyamidoamine-epichlorohydrin and about 25% by weight of a hydrophilic moiety or a second polymer chain derived from said at least one hydrophilic enhancer.

[0222] According to the present invention, the heating step is preferably carried out by autoclaving a preformed contact lens (obtained in step (2)) immersed in a packaging solution (i.e., a buffered aqueous solution) in a sealed lens package at a temperature of about 115 - 125°C for about 20 - 90 minutes. According to this embodiment of the present invention, the packaging solution is an ophthalmically safe buffered aqueous solution after autoclaving.

[0223] 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 the base comprises a cavity for receiving a sterile packaging solution and a contact lens.

[0224] Before being dispensed to the user, the lens packages are individually packaged, sealed, and sterilized (e.g., by autoclaving at about 120°C or higher under pressure for at least 30 minutes). Those skilled in the art will well understand how to seal and sterilize the lens packages.

[0225] 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. Examples of other ingredients include, but are not limited to, tonicity agents, surfactants, antibacterial agents, preservatives, and lubricants (e.g., cellulose derivatives, polyvinyl alcohol, polyvinylpyrrolidone).

[0226] The packaging solution contains an amount of buffer sufficient to maintain the pH of the packaging solution within a desired range (e.g., preferably from about 6.8 to about 8.5, more preferably from about 7.0 to 8.2, even more preferably from about 7.2 to about 8.0). A higher pH is found to be desirable for ensuring that all or a significant portion of the carboxyl groups of the lens body material are ionized. Thus, the resulting coated contact lenses become dimensionally stable in the packaging solution during autoclaving and storage and can have improved lubricity.

[0227] Any known physiologically compatible buffer can be used. Suitable buffers as ingredients of the contact lens care composition according to the present invention are known to those skilled in the art. Preferably, a phosphate buffer (substantially composed of a mixture of monobasic dihydrogen phosphates (e.g., NaH2PO4, KH2PO4, or a mixture thereof) and dibasic monohydrogen phosphates (e.g., Na2HPO4, K2HPO4, or a mixture thereof)) is used for maintaining the pH of the packaging solution. In various preferred embodiments, the total concentration of the monobasic dihydrogen phosphate and the dibasic monohydrogen phosphate is at least 30 mM (preferably at least 35 mM, more preferably at least 40 mM, even more preferably at least 45 mM).

[0228] The solution according to the present invention is preferably formulated to be isotonic with tear fluid. A solution isotonic with tear fluid is generally understood to be a solution having a concentration equivalent to that of a 0.9% sodium chloride solution (308 mOsm / kg). Deviations from this concentration can occur throughout.

[0229] The isotonicity with tear fluid or even 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 - 450 milliosmoles (mOsm), preferably about 250 - 350 mOsm.

[0230] In a preferred embodiment, 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, even more preferably at least 130 mM) for adjusting the tonicity of the packaging solution. It has been found that the resulting coated contact lenses can have improved lubricity when the ionic strength of the packaging solution is reduced (e.g., by replacing a portion of the NaCl with an organic tonicity agent such as propylene glycol).

[0231] In a preferred embodiment, the packaging solution contains a water-soluble thermally crosslinkable hydrophilic polymer material having an azetidinium group in an amount of preferably about 0.01 - 2% by weight, more preferably about 0.05 - 1.5% by weight, even more preferably about 0.1 - 1% by weight, and most preferably about 0.2 - 0.5% by weight.

[0232] In another aspect, the present invention provides a method for producing a coated contact lens, which comprises the following steps: (1) obtaining a female half-mold and a male half-mold, wherein the female half-mold has a first molding surface defining the front surface of the contact lens to be molded, wherein the male half-mold has a second molding surface defining the back surface of the contact lens to be molded, and wherein the male half-mold and the female half-mold are configured to receive each other such that when the female half-mold is closed with the male half-mold, 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 zones on the first molding surface, wherein the hydrogel-forming composition comprises at least one crosslinkable polymer having hydroxyl and / or ethylenically unsaturated groups and optionally at least one hydrophobic ethylenic monomer selected from the group consisting of methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, methyl (meth)acrylate, and combinations thereof, wherein, if the at least one crosslinkable polymer does not contain any ethylenically unsaturated groups, the hydrogel-forming composition further comprises at least one hydroxyl-containing ethylenic monomer and at least one compound having two or more isocyanate groups, and wherein 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 female half-mold obtained in step (2) or (3), wherein the polymerizable composition comprises about 1.0- to 10-% by weight, based on the total amount of all polymerizable components, of at least one reactive ethylenic monomer having at least one first reactive functional group selected from the group consisting of carboxylic acid groups, primary amino groups, secondary amino groups, and combinations thereof; (5) closing the female half-mold obtained in step (4) with the male half-mold to form a molded assembly containing the polymerizable composition in the lens-forming cavity; (6) thermally curing or photocuring the polymerizable composition in the molded assembly to form a contact lens precursor having a convex surface and an opposing concave surface and comprising a lens body material having a first reactive functional group, wherein the convex surface of the contact lens precursor is partially covered in the plurality of zones on the convex surface with a second hydrogel material formed from the hydrogel-forming composition so as to prevent the first reactive functional group behind the plurality of zones from reacting with thermally crosslinkable groups that are azetidinium groups and / or epoxy groups at a temperature of about 60-140°C, and wherein the second non-silicone hydrogel material does not contain any 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 to obtain a hydrated contact lens precursor; and (8) at a temperature of about 60-140°C in a medium having a pH of about 6.5-9.Directly heating the contact lens precursor obtained in step (6) or the hydrated contact lens precursor obtained in step (7) in an aqueous solution having a pH of 5 and comprising 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) to form a coated contact lens having a front surface, an opposing rear surface, a front outer hydrogel layer, and a rear 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, wherein the second reactive functional group is a thermally crosslinkable group selected from the group consisting of azetidinium groups, epoxy groups, and combinations thereof, wherein each of the second reactive functional groups is capable of reacting with a first or third reactive functional group to form a crosslink, wherein the third reactive functional group is selected from the group consisting of carboxylic acid groups, primary amines, secondary amines, thiol groups, and combinations thereof, wherein the rear outer hydrogel layer is the first non-silicone hydrogel material layer, wherein the front outer hydrogel layer is the first non-silicone hydrogel material layer in which mold marks (e.g., grooves and / or gaps) are distributed such that the rear surface of the coated contact lens has a higher surface lubricity than the front 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 front and rear surfaces of the coated contact lens.

[0233] Various embodiments include half-molds, hydrogel-forming compositions, techniques for applying a hydrogel-forming composition to the molding surface of a female half-mold, the shape, size, and distribution of multiple zones on the molding surface of the female half-mold (rather than on the convex surface of a preformed contact lens as described above), curing a hydrogel-forming composition or a polymerizable composition, polymerizable compositions, water-soluble thermally crosslinkable hydrophilic polymer materials, and preferred embodiments of the heating step for forming a coated contact lens as described above and that can be used in this aspect of the invention.

[0234] In another aspect, the present invention provides a coated contact lens, the coated contact lens comprising: a front surface and an opposing rear surface; and a layered structure configuration that includes, in a direction from the front surface to the rear surface, a front outer hydrogel layer, an inner layer, and a rear outer hydrogel layer, wherein the inner layer is made of lens body material, wherein the rear outer hydrogel layer is a first non-silicone hydrogel material layer, wherein the front outer hydrogel layer is the first non-silicone hydrogel material layer in which mold marks (e.g., grooves and / or gaps) are distributed such that the rear outer hydrogel layer has a higher surface lubricity than the front outer hydrogel layer, wherein the coated contact lens in a fully hydrated state has a water content of about 10-70% by weight or less, an oxygen permeability of at least about 50 Barrers, and a water break-up time of at least about 10 seconds as measured on the front and rear surfaces of the coated contact lens.

[0235] Various embodiments of the preferred embodiments including the lens body material have been described above and may be incorporated in this aspect of the present invention.

[0236] In various preferred embodiments, the first non-silicone hydrogel material (constituting the front outer hydrogel layer and the rear outer hydrogel layer) is:

[0237] (1) A crosslinked polymer material comprising repeating monomer units of at least one hydrophilic ethylenically unsaturated monomer 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)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-C4-alkoxy poly(ethylene glycol) (meth)acrylate having a weight-average molecular weight of up to 1500, methoxy-poly(ethylene glycol) ethyl (meth)acrylamide having a number-average molecular weight of up to 1500, 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 mono vinyl ether, di(ethylene glycol) mono vinyl ether, tri(ethylene glycol) mono vinyl ether, tetra(ethylene glycol) mono vinyl ether, poly(ethylene glycol) mono vinyl ether, ethylene glycol methyl vinyl ether, di(ethylene glycol) methyl vinyl ether, tri(ethylene glycol) methyl vinyl ether, tetra(ethylene glycol) methyl vinyl ether, poly(ethylene glycol) methyl vinyl ether and combinations thereof (preferably 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, glycidyl 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 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, glycidyl methacrylate (GMA), poly(ethylene glycol)ethyl(meth)acrylamide having a number-average molecular weight of up to 1500, poly(ethylene glycol)(meth)acrylate having a number-average molecular weight of up to 1500, N-vinylpyrrolidone, N-vinyl-N-methylacetamide, methoxypoly(ethylene glycol)ethyl(meth)acrylamide having a number-average molecular weight of up to 1500, methoxypolyethylene glycol (meth)acrylate having a weight-average molecular weight of up to 1500, poly(ethylene glycol)monovinyl ether, poly(ethylene glycol)methyl vinyl ether, poly(ethylene glycol)monoallyl ether, poly(ethylene glycol)methyl allyl ether, vinyl alcohol, allyl alcohol and combinations thereof, even more preferably 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;

[0238] (2) A crosslinked polymer material comprising repeating monomer units of at least one phosphorylcholine-containing vinyl monomer (any of those described below) in an amount of at least 25 mol% (preferably at least 35 mol%, more preferably at least 45 mol%, even more preferably at least 55 mol%) based on moles, said phosphorylcholine-containing vinyl monomer being preferably selected from the group consisting of (meth)acryloyloxyethyl phosphorylcholine, (meth)acryloyloxypropyl phosphorylcholine, 4-((meth)acryloyloxy)butyl-2'-(trimethylammonio)ethyl phosphate, 2-[(meth)acrylamido]ethyl-2'-(trimethylammonio)ethyl phosphate, 3-[(meth)acrylamido]propyl-2'-(trimethylammonio)ethyl phosphate, 4-[(meth)acrylamido]butyl-2'-(trimethylammonio)ethyl phosphate, and combinations thereof;

[0239] (3) A crosslinked polymer material comprising poly(ethylene glycol) chains, preferably directly derived from (a) poly(ethylene glycol) having a single unique -NH2, -SH, or -COOH functional group, (b) poly(ethylene glycol) having two terminal functional groups selected from the group consisting of -NH2, -COOH, -SH, and combinations thereof, (c) multi-arm poly(ethylene glycol) having one or more functional groups selected from the group consisting of -NH2, -COOH, -SH, and combinations thereof, and (d) combinations thereof.

[0240] 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)acrylamido]ethyl-2'-(trimethylammonio)-ethyl phosphate, 3-[(meth)acrylamido]propyl-2'-(trimethylammonio)ethyl phosphate, 4-[(meth)acrylamido]butyl-2'-(trimethylammonio)ethyl phosphate, 5-((meth)acryloyloxy)pentyl-2'-(trimethylammonio)ethyl phosphate, 6-((meth)acryloyloxy)hexyl-2'-(trimethylammonio)-ethyl phosphate, 2-((meth)acryloyloxy)ethyl-2'-(triethylammonio)ethyl phosphate, 2-((meth)acryloyloxy)ethyl-2'-(tripropylammonio)ethyl phosphate, 2-((meth)acryloyloxy)ethyl-2'-(tributylammonio)ethyl phosphate, 2-((meth)acryloyloxy)propyl-2'-(trimethylammonio)-ethyl phosphate, 2-((meth)acryloyloxy)butyl-2'-(trimethylammonio)ethyl phosphate, 2-((meth)acryloyloxy)pentyl-2'-(trimethylammonio)ethyl phosphate, 2-((meth)acryloyloxy)hexyl-2'-(trimethylammonio)ethyl phosphate, 2-(vinyloxy)ethyl-2'-(trimethylammonio)ethyl phosphate, 2-(allyloxy)ethyl-2'-(trimethylammonio)ethyl phosphate, 2-(vinyloxycarbonyl)ethyl-2'-(trimethylammonio)ethyl phosphate, 2-(allyloxycarbonyl)ethyl-2'-(trimethylammonio)-ethyl phosphate, 2-(vinylcarbonylamino)ethyl-2'-(trimethylammonio)ethyl phosphate, 2-(allyloxycarbonylamino)ethyl-2'-(trimethylammonio)ethyl phosphate, 2-(butenyloxy)ethyl-2'-(trimethylammonio)ethyl phosphate, and combinations thereof.

[0241] In various preferred embodiments, the mold marks in the front external hydrogel layer include: (1) grooves in an annular shape, a curved shape, and / or a linear shape; (2) gaps in a circular shape, a triangular shape, a square shape, a rectangular shape, a hexagonal shape, a polygonal shape, and / or a star shape; or (3) combinations thereof. It should be understood that the shape of the mold marks appears in a top view.

[0242] The mold marks can have any two-dimensional dimension in the top view. Preferably, one of the two dimensions of the mold marks 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 - 0.20 mm).

[0243] According to one embodiment of the present invention, the mold marks are arranged in any pattern, preferably in a rotationally symmetric pattern with respect to the central axis of the coated contact lens, on the front surface of the coated contact lens. Preferably, the mold marks are located in an annular region that has an inner diameter of about 6.0 - 9.0 mm and an outer diameter of about 11.5 - 14.5 mm and is concentric with the central axis of the coated contact lens.

[0244] In one embodiment, the mold marks include at least three grooves in an annular shape.

[0245] In another embodiment, the mold marks include at least eight grooves in a curved or straight shape that radiate outward from a circle having a diameter of about 6.0 - 9.0 mm and that is concentric with the central axis of the coated contact lens.

[0246] In another embodiment, the mold marks include gaps in a circular shape (preferably having a diameter of about 0.25 mm or less, more preferably having a diameter of about 0.05 - 0.20 mm) that are arranged in a rotationally symmetric pattern on the front surface of the coated contact lens. Preferably, the gaps in a circular shape are arranged in a pattern of concentric annular rings with the central axis of the coated contact lens.

[0247] According to the present invention, the surface lubricity of the front outer hydrogel layer and the rear outer hydrogel layer can preferably be evaluated by using a finger-feel lubricity test that 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 finger-feel lubricity test is described in Example 1.

[0248] In various preferred embodiments, the front 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 rear surface.

[0249] Preferably, the coated contact lens of the present invention in a fully hydrated state has a water break-up 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) as measured on the front and rear surfaces of the coated contact lens.

[0250] It should be understood that the water break-up time of the coated contact lens of the present invention is measured on the front and / or rear surfaces according to the procedure described in Example 1.

[0251] In various preferred embodiments, the coated contact lenses of the present invention in a fully hydrated state further have: a water content of about 20 - 70% by weight (preferably about 25 - 65%, more preferably about 30 - 60%); a modulus of elasticity of about 0.2 - 2.0 MPa (preferably about 0.25 - 1.5 MPa, more preferably about 0.3 - 1.2 MPa, even more preferably about 0.35 - 1.0 MPa); an oxygen permeability of at least 60 barrers / mm (preferably at least 70 barrers / mm, more preferably at least 80 barrers / mm, even more preferably at least 100 barrers / mm); 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.

[0252] Although the 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 descriptive rather than restrictive. As will be apparent to those skilled in the art, many changes and modifications can be made by those skilled in the art without departing from the spirit and scope of the novel concepts disclosed herein. In addition, it should be understood that the various aspects of the embodiments of the present invention can be interchanged in whole or in part or can be combined and / or used together in any manner, as illustrated below:

[0253] 1. A coated contact lens, comprising:

[0254] a front surface and an opposite rear surface; and

[0255] a layered structure configuration that includes a front outer hydrogel layer, an inner layer, and a rear outer hydrogel layer in a direction from the front surface to the rear surface,

[0256] wherein the inner layer is made of a lens body material, wherein the rear outer hydrogel layer is a first non - silicone hydrogel material layer, wherein the front outer hydrogel layer is the first non - silicone hydrogel material layer in which mold marks (e.g., grooves, gaps, etc.) are distributed such that the rear outer hydrogel layer has a higher surface lubricity than the front outer hydrogel layer, and 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 front and rear surfaces of the coated contact lens.

[0257] 2. A method for producing a coated contact lens, comprising the following steps:

[0258] (1) Obtain a preformed contact lens having a convex surface and an opposing concave surface, wherein the preformed contact lens is composed of a lens body material and includes first reactive functional groups on and near the convex and concave surfaces of the preformed contact lens, wherein each of the first reactive functional groups is capable of reacting with a thermally crosslinkable group at a temperature of about 60 - 140 °C and is selected from the group consisting of carboxylic acid groups, primary amino groups, secondary amino groups, thiol groups, and combinations thereof;

[0259] (2) Cover a plurality of regions on the convex surface with a second non - siloxane hydrogel material to prevent the first reactive functional groups behind the plurality of regions from reacting with the thermally crosslinkable groups, wherein the second non - siloxane hydrogel material does not contain any first reactive functional groups and does not contain any thermally crosslinkable groups;

[0260] (3) Directly heat the preformed contact lens obtained in step (2) in an aqueous solution having a pH of about 6.5 - 9.5 and containing at least one water - soluble thermally crosslinkable hydrophilic polymer material at a temperature of about 60 - 140 °C to graft a first non - siloxane hydrogel material onto each of the front and back surfaces of the preformed contact lens obtained in step (2) to form a coated contact lens having a front surface, an opposing back surface, a front outer hydrogel layer, and a back outer hydrogel layer, wherein the at least one water - soluble thermally crosslinkable hydrophilic polymer material includes second reactive functional groups and third reactive functional groups, wherein the second reactive functional groups are thermally crosslinkable groups selected from the group consisting of azetidinium groups, epoxy groups, and combinations thereof, wherein each of the second reactive functional groups is capable of reacting with a first or third reactive functional group to form a crosslink, wherein the third reactive functional groups are selected from the group consisting of carboxylic acid groups, primary amino groups, secondary amino groups, thiol groups, and combinations thereof, wherein the first non - siloxane hydrogel material is a cross - linked product of the at least one thermally crosslinkable hydrophilic polymer material, wherein the back outer hydrogel layer is the first non - siloxane hydrogel material layer, wherein the front outer hydrogel layer is the first non - siloxane hydrogel material layer in which mold marks (grooves and / or gaps) are distributed, such that the back surface of the coated contact lens has a higher surface lubricity than the front surface,

[0261] 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 front and back surfaces of the coated contact lens.

[0262] 3. The method according to embodiment 2, wherein step (2) is carried out by applying a hydrogel-forming composition to a plurality of zones on the convex surface of the preformed contact lens (preferably according to pad printing and / or inkjet printing techniques), and then thermally curing or photocuring the hydrogel-forming composition to form the second non-silicone hydrogel material to cover the plurality of zones.

[0263] 4. A method for producing a coated contact lens, comprising the steps of:

[0264] (1) obtaining a female half-mold and a male half-mold, wherein the female half-mold has a first molding surface defining the front surface of the contact lens to be molded, wherein the male half-mold has a second molding surface defining the back surface of the contact lens to be molded, and wherein the male half-mold and the female half-mold are configured to receive each other such that when the female half-mold is closed with the male half-mold, a lens molding cavity is formed between the first molding surface and the second molding surface;

[0265] (2) applying a hydrogel-forming composition to a plurality of zones on the first molding surface, wherein the hydrogel-forming composition comprises at least one crosslinkable polymer having hydroxyl and / or ethylenically unsaturated groups and optionally at least one hydrophobic ethylenic monomer selected from the group consisting of methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, methyl (meth)acrylate, and combinations thereof, wherein if the at least one crosslinkable polymer does not contain any ethylenically unsaturated groups, the hydrogel-forming composition further comprises at least one hydroxyl-containing ethylenic monomer and at least one compound having two or more isocyanate groups, and wherein 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;

[0266] (3) optionally but preferably, partially curing the hydrogel-forming composition on the first molding surface;

[0267] (4) introducing a polymerizable composition into the female half-mold obtained in step (2) or (3), wherein the polymerizable composition comprises at least one reactive ethylenic monomer having at least one first reactive functional group selected from the group consisting of carboxylic acid groups, primary amino groups, secondary amino groups, and combinations thereof, in an amount of about 1.0-10% by weight based on the total amount of all polymerizable components;

[0268] (5) closing the female half-mold obtained in step (4) with the male half-mold to form a molded assembly comprising the polymerizable composition in the lens forming cavity;

[0269] (6) Thermally cure or photocure the polymerizable composition in the molded assembly to form a contact lens precursor having a convex surface and an opposing concave surface and comprising a lens body material having a first reactive functional group, wherein the convex surface of the contact lens precursor is partially covered in the plurality of zones on the convex surface with a second non-silicone hydrogel material formed from the hydrogel-forming composition to prevent the first reactive functional group behind the plurality of zones from reacting with a thermally crosslinkable group that is an azetidinium group and / or an epoxy group at a temperature of about 60 - 140 °C, wherein the second non-silicone hydrogel material does not contain any first reactive functional groups and thermally crosslinkable groups;

[0270] (7) Optionally hydrate the contact lens precursor obtained in step (6) in water or an aqueous solution; and

[0271] (8) Directly heat the contact lens precursor obtained in step (6) or step (7) in an aqueous solution having a pH of about 6.5 - 9.5 and comprising at least one water-soluble thermally crosslinkable hydrophilic polymer material at a temperature of about 60 - 140 °C 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) to form a coated contact lens having a front surface, an opposing rear surface, a front outer hydrogel layer, and a rear 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, wherein the second reactive functional group is a thermally crosslinkable group selected from the group consisting of azetidinium groups, epoxy groups, and combinations thereof, wherein each of the second reactive functional groups is capable of reacting with a first or third reactive functional group to form a crosslink, wherein the third reactive functional group is selected from the group consisting of carboxylic acid groups, primary amines, secondary amines, thiol groups, and combinations thereof, wherein the first non-silicone hydrogel material is a crosslinked product of the at least one thermally crosslinkable hydrophilic polymer material, wherein the rear outer hydrogel layer is the first non-silicone hydrogel material layer, wherein the front outer hydrogel layer is the first non-silicone hydrogel material layer in which mold marks (grooves and / or gaps) are distributed such that the rear surface of the coated contact lens has a higher surface lubricity than the front surface,

[0272] wherein the coated contact lens has a water break-up time of at least about 10 seconds measured on the front and rear surfaces of the coated contact lens.

[0273] 5. The method according to embodiment 4, wherein the polymerizable composition is a non-silicone hydrogel lens formulation, and the non-silicone hydrogel lens formulation comprises about 1.0-10% by weight (preferably about 2.0-7%, more preferably about 2.0-5%) of at least one carboxyl-containing ethylenically unsaturated monomer and / or at least one amino-containing ethylenically unsaturated monomer.

[0274] 6. The method according to embodiment 5, wherein the at least one carboxyl-containing ethylenically unsaturated 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)acryloyloxypropionic acid, (meth)acryloyloxybutyric acid, and combinations thereof, and the at least one amino-containing ethylenically unsaturated monomer is selected from the group consisting of 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.

[0275] 7. The method according to any one of embodiments 3 to 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 ethylenically unsaturated monomer selected from the group consisting of (meth)acrylic acid methoxyethyl ester, (meth)acrylic acid ethoxyethyl ester, (meth)acrylic acid methyl ester, and combinations thereof, and wherein, if the at least one crosslinkable polymer does not contain any ethylenically unsaturated groups, the hydrogel-forming composition further comprises at least one hydroxyl-containing ethylenically unsaturated monomer and at least one compound having two or more isocyanate groups, and all polymerizable components in the hydrogel-forming composition do not contain any first reactive functional groups and any thermally crosslinkable groups that are azetidinium groups and / or epoxy groups.

[0276] 8. The method according to any one of embodiments 2 to 7, wherein the heating step is carried out by autoclaving the preformed contact lens or the contact lens precursor immersed in a packaging solution (i.e., a buffered aqueous solution) in a sealed lens package at a temperature of about 115-125 °C for about 20-90 minutes.

[0277] 9. The method according to any one of embodiments 2 to 8, wherein the at least one water-soluble and thermally crosslinkable hydrophilic polymer material comprises azetidinium groups, epoxy groups, or a combination thereof.

[0278] 10. The method according to embodiment 9, wherein the at least one water-soluble and thermally crosslinkable hydrophilic polymer material is a three-dimensional network and thermally crosslinkable groups within or attached to the network.

[0279] 11. The method according to embodiment 9, wherein the at least one water-soluble and thermally crosslinkable hydrophilic polymer material is: one or more multi-arm polyethylene glycols each having terminal epoxy groups; a mixture of a multi-arm polyethylene glycol having terminal epoxy groups and one or more polyethylene glycols each having a terminal functional group selected from the group consisting of primary amine groups, secondary amine groups, carboxyl groups, thiol groups, and combinations thereof; a partial reaction product of a multi-arm polyethylene having terminal epoxy groups and a hydrophilic enhancer having at least one reactive functional group selected from the group consisting of amino groups, carboxyl groups, and thiol groups; or a combination thereof.

[0280] 12. The method according to embodiment 9, wherein the at least one water-soluble and thermally crosslinkable hydrophilic polymer material comprises azetidinium groups and is a partial reaction product of an azetidinium-containing polymer and a hydrophilic enhancer having at least one reactive functional group selected from the group consisting of primary amine groups, secondary amine groups, carboxyl groups, thiol groups, and combinations thereof.

[0281] 13. The method according to embodiment 12, wherein the azetidinium-containing polymer is a poly(2-oxazoline-co-vinylimine)-epichlorohydrin copolymer, a polyamidoamine-epichlorohydrin, a copolymer of an azetidinium-containing vinyl monomer and one or more hydrophilic vinyl monomers, or a combination thereof.

[0282] 14. The method according to embodiment 12 or 13, wherein the hydrophilic enhancer is: a monosaccharide containing a primary amino group, a secondary amino group, a carboxyl group, or a thiol group; a disaccharide containing a primary amino group, a secondary amino group, a carboxyl group, or a thiol group; an oligosaccharide containing a primary amino group, a secondary amino group, a carboxyl group, or a thiol group; or a combination thereof.

[0283] 15. The method according to embodiment 12 or 13, wherein the hydrophilic enhancer is a hydrophilic polymer having one or more primary amino groups or secondary amino groups, one or more carboxyl groups, one or more thiol groups, or a combination thereof.

[0284] 16. The method according to embodiment 15, wherein the hydrophilic enhancer is a polysaccharide having primary amine groups, secondary amine groups, carboxyl groups, or a combination thereof.

[0285] 17. The method according to embodiment 15, wherein the hydrophilic enhancer is:

[0286] Poly(ethylene glycol) having a single unique -NH2, -SH, or -COOH functional group;

[0287] Poly(ethylene glycol) having two terminal functional groups selected from the group consisting of -NH2, -COOH, -SH, and combinations thereof;

[0288] Multi-arm poly(ethylene glycol) having one or more functional groups selected from the group consisting of -NH2, -COOH, -SH, and combinations thereof;

[0289] Homo- or co-polymers capped with mono-amino, mono-carboxyl, di-amino, or di-carboxyl of non-reactive hydrophilic vinyl monomers;

[0290] A copolymer which is a polymerization product of a composition comprising: (1) about 0.1 - 30% (preferably about 0.5 - 20%, more preferably about 1 - 15%) of a reactive vinyl monomer, and (2) at least one non-reactive hydrophilic vinyl monomer,

[0291] wherein the reactive vinyl monomer is a vinyl monomer having a functional group selected from the group consisting of a carboxyl group, a primary amine group, and a secondary amine group,

[0292] wherein the non-reactive hydrophilic monomer is a hydrophilic vinyl monomer that does not contain any carboxyl group, primary amine group, secondary amine group, epoxy group, isocyanate group, azlactone group, or aziridinyl group.

[0293] 18. The method according to embodiment 17, wherein the reactive vinyl monomer is acrylic acid, methacrylic acid, ethylacrylic acid, 2-(meth)acrylamido glycolic 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.

[0294] 19. The method according to embodiment 17 or 18, wherein the non-reactive hydrophilic ethylenically unsaturated monomer is selected from the group consisting of acrylamide, N,N-dimethylacrylamide, N-vinylpyrrolidone, (meth)acryloyloxyethyl phosphorylcholine, N-vinyl-N-methylacetamide, (meth)acrylic acid glycerol ester, (meth)acrylic acid hydroxyethyl ester, N-hydroxyethyl (meth)acrylamide, C1-C4-alkoxy polyethylene glycol (meth)acrylate having a weight average molecular weight of up to 400 daltons, vinyl alcohol, and combinations thereof,

[0295] wherein the non-reactive hydrophilic ethylenically unsaturated monomer is selected from the group consisting of (meth)acryloyloxyethyl phosphorylcholine, (meth)acryloyloxypropyl phosphorylcholine, 4-((meth)acryloyloxy)butyl-2'-(trimethylammonio)ethyl phosphate, 2-[(meth)acrylamido]ethyl-2'-(trimethylammonio)ethyl phosphate, 3-[(meth)acrylamido]propyl-2'-(trimethylammonio)ethyl phosphate, 4-[(meth)acrylamido]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, methoxy poly(ethylene glycol) ethyl (meth)acrylamide having a number average molecular weight of up to 1500, C1-C4-alkoxy polyethylene glycol (meth)acrylate having a weight average molecular weight of up to 1500, tetra(ethylene glycol) mono vinyl ether, poly(ethylene glycol) mono vinyl 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.

[0296] 20. The method according to any one of embodiments 2 to 19, wherein the aqueous solution has a pH of about 7.0 to about 8.2, and wherein the aqueous solution comprises about 0.01 - 2% by weight (preferably about 0.05 - 1.5%, more preferably about 0.1 - 1%, even more preferably about 0.2 - 0.5%) of the at least one water-soluble thermally crosslinkable hydrophilic polymer material.

[0297] 21. The method according to any one of embodiments 2 to 20, wherein the aqueous solution comprises a mixture of monobasic dihydrogen phosphate and dibasic monohydrogen phosphate for maintaining the pH of the aqueous solution, and wherein the total concentration of the monobasic dihydrogen phosphate and the dibasic monohydrogen phosphate is at least 30 mM.

[0298] 22. The method according to embodiment 21, wherein the total concentration of the monobasic dihydrogen phosphate and the dibasic monohydrogen phosphate is at least 35 mM.

[0299] 23. The method according to embodiment 21, wherein the total concentration of the monobasic dihydrogen phosphate and the dibasic monohydrogen phosphate is at least 40 mM.

[0300] 24. The method according to embodiment 21, wherein the total concentration of the monobasic dihydrogen phosphate and the dibasic monohydrogen phosphate is at least 45 mM.

[0301] 25. The method according to any one of embodiments 2 to 24, wherein the tonicity of the aqueous solution is adjusted to about 200 to about 450 milliosmoles (mOsm), and wherein 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 wherein the total concentration of the one or more organic tonicity agents is at least 70 mM.

[0302] 26. The method according to embodiment 25, wherein the total concentration of the one or more organic tonicity agents is at least 90 mM.

[0303] 27. The method according to embodiment 25, wherein the total concentration of the one or more organic tonicity agents is at least 110 mM.

[0304] 28. The method according to embodiment 25, wherein the total concentration of the one or more organic tonicity agents is at least 130 mM.

[0305] 29. The coated contact lens according to embodiment 1 or the method according to any one of embodiments 2 to 28, wherein the front surface of the coated contact lens has a friction rating that is at least 0.25 greater than the friction rating of the back surface as evaluated by a finger feel lubricity test.

[0306] 30. The coated contact lens as described in Embodiment 1 or the method as described in any one of Embodiments 2 to 28, wherein the front surface of the coated contact lens has a friction rating that is at least 0.50 greater than the friction rating of the back surface as evaluated by a finger-feel lubricity test.

[0307] 31. The coated contact lens as described in Embodiment 1 or the method as described in any one of Embodiments 2 to 28, wherein the front surface of the coated contact lens has a friction rating that is at least 0.75 greater than the friction rating of the back surface as evaluated by a finger-feel lubricity test.

[0308] 32. The coated contact lens as described in any one of Embodiments 1 and 29 to 31 or the method as described in any one of Embodiments 2 to 31, wherein the coated contact lens in a fully hydrated state has a water break-up time of at least about 15 seconds as measured on the front and back surfaces of the coated contact lens.

[0309] 33. The coated contact lens as described in any one of Embodiments 1 and 29 to 31 or the method as described in any one of Embodiments 2 to 31, wherein the coated contact lens in a fully hydrated state has a water break-up time of at least about 20 seconds as measured on the front and back surfaces of the coated contact lens.

[0310] 34. The coated contact lens as described in any one of Embodiments 1 and 29 to 31 or the method as described in any one of Embodiments 2 to 31, wherein the coated contact lens in a fully hydrated state has a water break-up time of at least about 25 seconds as measured on the front and back surfaces of the coated contact lens.

[0311] 35. The coated contact lens as described in any one of Embodiments 1 and 29 to 31 or the method as described in any one of Embodiments 2 to 31, wherein the coated contact lens in a fully hydrated state has a water break-up time of at least about 30 seconds as measured on the front and back surfaces of the coated contact lens.

[0312] 36. The coated contact lens as described in any one of Embodiments 1 and 29 to 35 or the method as described in any one of Embodiments 2 to 35, wherein the mold marks include: (1) grooves having an annular shape, a curved shape, and / or a linear shape in a top view; (2) gaps having a circular shape, a triangular shape, a square shape, a rectangular shape, a hexagonal shape, a polygonal shape, and / or a star shape in a top view.

[0313] 37. The coated contact lens or method according to embodiment 36, wherein in a top view, one of the two dimensions of each of the mold marks is about 0.40 mm or less.

[0314] 38. The coated contact lens or method according to embodiment 36, wherein in a top view, one of the two dimensions of each of the mold marks is about 0.30 mm or less.

[0315] 39. The coated contact lens or method according to embodiment 36, wherein in a top view, one of the two dimensions of each of the mold marks is about 0.25 mm or less.

[0316] 40. The coated contact lens or method according to embodiment 36, wherein in a top view, one of the two dimensions of each of the mold marks is about 0.05 - 0.20 mm.

[0317] 41. The coated contact lens according to any one of embodiments 1 and 29 to 40 or the method according to any one of embodiments 2 to 40, wherein the mold marks on the front surface of the coated contact lens are arranged in a rotationally symmetric pattern with respect to the central axis of the coated contact lens.

[0318] 42. The coated contact lens according to any one of embodiments 1 and 29 to 40 or the method according to any one of embodiments 2 to 40, wherein the mold marks on the front surface of the coated contact lens are located in an annular region having an inner diameter of about 6.0 - 9.0 mm and an outer diameter of about 11.5 - 14.5 mm and are concentric with respect to the central axis of the coated contact lens.

[0319] 43. The coated contact lens according to any one of embodiments 1 and 29 to 42 or the method according to any one of embodiments 2 to 42, wherein the mold marks include at least three grooves that are annular in shape in a top view.

[0320] 44. The coated contact lens according to any one of embodiments 1 and 29 to 43 or the method according to any one of embodiments 2 to 43, wherein the mold marks include at least eight grooves that are curved or linear in shape and radiate outward from a circle having a diameter of about 6.0 - 9.0 mm and that is concentric with respect to the central axis of the coated contact lens.

[0321] 45. The coated contact lens according to any one of embodiments 1 and 29 to 44 or the method according to any one of embodiments 2 to 44, wherein the mold marks include gaps that are circular in shape in a top view.

[0322] 46. The coated contact lens or method according to embodiment 45, wherein the gaps that are circular in top view each have a diameter of about 0.25 mm or less.

[0323] 47. The coated contact lens or method according to embodiment 45, wherein the gaps that are circular in top view each have a diameter of about 0.05 - 0.20 mm.

[0324] 48. The coated contact lens or method according to any one of embodiments 45 to 47, wherein the gaps that are circular in top view are each arranged in a rotationally symmetric pattern on the front surface of the coated contact lens.

[0325] 49. The coated contact lens or method according to embodiment 48, wherein the gaps that are circular in top view are arranged in a pattern of concentric annular rings centered on the central axis of the coated contact lens.

[0326] 50. A coated contact lens as described in any one of embodiments 1 and 29 to 44 or a method as described in any one of embodiments 2 to 49, wherein the first non-silicone hydrogel material is a crosslinked polymer material comprising repeating monomer units of at least one hydrophilic vinyl monomer selected from the group consisting of, by mole, at least 35%: (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, methoxy poly(ethylene glycol) ethyl (meth)acrylamide having a number average molecular weight of up to 1500, C1-C4-alkoxy poly(ethylene glycol) (meth)acrylate having a weight average molecular weight of up to 1500, tetra(ethylene glycol) mono vinyl ether, poly(ethylene glycol) mono vinyl ether, tetra(ethylene glycol) methyl vinyl ether, poly(ethylene glycol) methyl vinyl ether, tetra(ethylene glycol) mono allyl ether, poly(ethylene glycol) mono allyl ether, tetra(ethylene glycol) methyl allyl ether, poly(ethylene glycol) methyl allyl ether, vinyl alcohol, allyl alcohol, and combinations thereof.

[0327] 51. The coated contact lens according to any one of embodiments 1 and 29 to 44, or the method according to any one of embodiments 2 to 49, wherein the first non-silicone hydrogel material is a crosslinked polymer material comprising repeating monomer units of at least one hydrophilic vinyl monomer selected from the group consisting of, on a molar basis, at least 45%: (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, 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) mono vinyl 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.

[0328] 52. The coated contact lens according to any one of embodiments 1 and 29 to 44, or the method according to any one of embodiments 2 to 49, wherein the first non-silicone hydrogel material is a crosslinked polymer material comprising repeating monomer units of at least one hydrophilic vinyl monomer selected from the group consisting of, on a molar basis, at least 55%: (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.

[0329] 53. The coated contact lens according to any one of embodiments 1 and 29 to 44, or the method according to any one of embodiments 2 to 49, wherein the first non-silicone hydrogel material is a crosslinked polymer material comprising repeating monomer units of at least one phosphorylcholine-containing vinyl monomer on a molar basis of at least 25%.

[0330] 54. The coated contact lens according to any one of embodiments 1 and 29 to 44 or the method according to any one of embodiments 2 to 49, wherein the first non-silicone hydrogel material is a crosslinked polymer material comprising repeating monomer units of at least one phosphorylcholine-containing vinyl monomer in an amount of at least 35 mol%.

[0331] 55. The coated contact lens according to any one of embodiments 1 and 29 to 44 or the method according to any one of embodiments 2 to 49, wherein the first non-silicone hydrogel material is a crosslinked polymer material comprising repeating monomer units of at least one phosphorylcholine-containing vinyl monomer in an amount of at least 45 mol%.

[0332] 56. The coated contact lens according to any one of embodiments 1 and 29 to 44 or the method according to any one of embodiments 2 to 49, wherein the first non-silicone hydrogel material is a crosslinked polymer material comprising repeating monomer units of at least one phosphorylcholine-containing vinyl monomer in an amount of at least 55 mol%.

[0333] 57. The coated contact lens or method according to any one of embodiments 53 to 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)acrylamido]-ethyl-2'-(trimethylammonio)ethyl phosphate, 3-[(meth)acrylamido]propyl-2'-(trimethylammonio)-ethyl phosphate, 4-[(meth)acrylamido]butyl-2'-(trimethylammonio)ethyl phosphate, and combinations thereof.

[0334] 58. The coated contact lens according to any one of embodiments 1 and 29 to 44 or the method according to any one of embodiments 2 to 49, wherein the first non-silicone hydrogel material is a crosslinked polymer material comprising poly(ethylene glycol) chains, preferably directly derived from (a) poly(ethylene glycol) having a single unique -NH2, -SH, or -COOH functional group, (b) poly(ethylene glycol) having two terminal functional groups selected from the group consisting of -NH2, -COOH, -SH, and combinations thereof, (c) multi-arm poly(ethylene glycol) having one or more functional groups selected from the group consisting of -NH2, -COOH, -SH, and combinations thereof, and (d) combinations thereof.

[0335] 59. The coated contact lens according to any one of embodiments 1 and 29 to 58 or the method according to any one of embodiments 2 to 58, wherein the lens body material is a hard plastic material (preferably crosslinked polymethacrylate).

[0336] 60. The coated contact lens as described in any one of Embodiments 1 and 29 to 58 or the method as described in any one of Embodiments 2 to 58, wherein the lens body material is a rigid gas-permeable material.

[0337] 61. The coated contact lens as described in any one of Embodiments 1 and 29 to 58 or the method as described in any one of Embodiments 2 to 58, wherein the lens body material substantially consists of a central optical zone and a peripheral zone, the central optical zone is made of a gas-permeable lens material, and the peripheral zone is made of a silicone hydrogel or a third non-silicone hydrogel lens material and extends outward from the central optical zone and surrounds the central optical zone.

[0338] 62. The coated contact lens as described in any one of Embodiments 1 and 29 to 58 or the method as described in any one of Embodiments 2 to 58, wherein the lens body material is a third non-silicone hydrogel material in a fully hydrated state and having a water content of about 10 - 70% by weight or less.

[0339] 63. The coated contact lens as described in any one of Embodiments 1 and 29 to 58 or the method as described in any one of Embodiments 2 to 58, wherein the lens body material is a third non-silicone hydrogel material in a fully hydrated state and having a water content of about 10 - 70% by weight or less and contains repeating units of at least one hydroxy-containing vinyl monomer in an amount of at least 50 mol%, preferably selected from the group consisting of: 2-hydroxyethyl (meth)acrylate, glycerol (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-amino-Propyl-2-hydroxy (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: 2-hydroxyethyl (meth)acrylate, glycerol (meth)acrylate, and vinyl alcohol.

[0340] 64. The coated contact lens as described in any one of Embodiments 1 and 29 to 58 or the method as described in any one of Embodiments 2 to 58, wherein the lens body material is a fully hydrated silicone hydrogel material, the silicone hydrogel material having a water content of about 10 - 70% by weight or less and an oxygen permeability of at least about 50 Barrers.

[0341] 65. The coated contact lens or method according to embodiment 64, wherein the coated contact lens has a water content of about 20 - 70% by weight (preferably about 25 - 65%, more preferably about 30 - 60%), a modulus of elasticity of about 0.2 - 2.0 MPa (preferably about 0.25 - 1.5 MPa, more preferably about 0.3 - 1.2 MPa, even more preferably about 0.35 - 1.0 MPa), an oxygen permeability of at least 60 Barrers / mm (preferably at least 70 Barrers / mm, more preferably at least 80 Barrers / mm, even more preferably at least 100 Barrers / 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).

[0342] 66. The method according to any one of embodiments 2 to 65, wherein the plurality of zones have a circular shape, a triangular shape, a square shape, a rectangular shape, a hexagonal shape, a polygonal shape, a star shape, an annular ring shape, a curved shape, a straight shape, or a combination thereof.

[0343] 67. The method according to any one of embodiments 2 to 66, wherein one of the two dimensions of the plurality of zones is about 0.40 mm or less.

[0344] 68. The method according to any one of embodiments 2 to 66, wherein one of the two dimensions of the plurality of zones is about 0.30 mm or less.

[0345] 69. The method according to any one of embodiments 2 to 66, wherein one of the two dimensions of the plurality of zones is about 0.25 mm or less.

[0346] 70. The method according to any one of embodiments 2 to 66, wherein one of the two dimensions of the plurality of zones is about 0.05 - 0.20 mm.

[0347] 71. The method according to any one of embodiments 2 to 70, wherein the plurality of zones are arranged in a rotationally symmetric pattern with respect to the central axis of the preformed contact lens or the female half - mold.

[0348] 72. The method according to any one of embodiments 2 to 71, wherein the plurality of zones are located in an annular zone having an inner diameter of about 6.0 - 9.0 mm and an outer diameter of about 11.5 - 14.5 mm and are concentric with respect to the central axis of the preformed contact lens or the female half - mold.

[0349] 73. The method according to any one of embodiments 2 to 72, wherein the plurality of zones include at least three annular rings.

[0350] 74. The method according to any one of embodiments 2 to 73, wherein the plurality of zones includes at least eight curves or straight lines radiating outward from a circle having a diameter of about 6.0 - 9.0 mm and concentric with the central axis of the preformed contact lens or the female half - mold.

[0351] 75. The method according to any one of embodiments 2 to 74, wherein the plurality of zones includes circular dots having a diameter of about 0.25 mm or less.

[0352] 76. The method according to any one of embodiments 2 to 74, wherein the plurality of zones includes circular dots having a diameter of about 0.05 - 0.20 mm.

[0353] 77. The method according to embodiment 75 or 76, wherein the circular dots are arranged in a rotationally symmetric pattern on the convex surface of the preformed contact lens or the molding surface of the female half - mold with respect to the central axis of the preformed contact lens or the female half - mold.

[0354] 78. The method according to any one of embodiments 75 to 77, wherein the circular dots are arranged in an annular ring concentric with the central axis of the preformed contact lens or the female half - mold. Examples

[0355] The foregoing disclosure will enable those of ordinary skill in the art to practice the present invention. Various modifications, variations, and combinations can be made to the various embodiments described herein. To enable the reader to better understand its specific embodiments and advantages, reference is recommended to the following examples. The specification and examples are to be considered exemplary.

[0356] Example 1

[0357] Oxygen permeability measurement

[0358] Unless otherwise specified, the oxygen permeability (Dk / t), intrinsic (or edge - corrected) oxygen permeability (Dk i or Dk c ) of the lens and lens material is determined according to the procedure described in ISO 18369 - 4.

[0359] Water break - up time (WBUT) test

[0360] The surface hydrophilicity of the lens was evaluated by using the interfacial dewetting and drainage optical platform (iDDroP) to determine the time required for the water film to start breaking on the lens surface, as described by Bhamla et al. in their article titled Influence of Lipid Coatings on Surface Wettability Characteristics of Silicone Hydrogels published in Langmuir. 2015, 31: 3820-3828. During the IDDrop test, the lens was placed on the stage and immersed in PBS. Then, a small surface of the lens was exposed to air. An electric linear stage and motion controller were used to expose the contact lens at a specified depth. A video of the water breakage was taken to evaluate the water breakage time and the mode of water film breakage.

[0361] Equilibrium water content

[0362] The equilibrium water content (EWC) of the contact lens (i.e., the water content of the contact lens in a fully hydrated state) was determined according to the procedure described in Example 1 of U.S. Patent Application Publication No. 20210181379A1.

[0363] Elastic modulus

[0364] The elastic modulus of the contact lens was determined according to the procedure described in Example 1 of U.S. Patent Application Publication No. 20210181379A1.

[0365] Light transmittance

[0366] The contact lens was manually placed in a specially fabricated sample holder or the like that could hold the shape of the lens as it would be when placed on the eye. This holder was then immersed in a 1 cm path length quartz cell containing phosphate buffered saline (PBS, pH approximately 7.0 - 7.4) as a reference. A UV / visible spectrophotometer, e.g., a Varian Cary 3E UV-visible spectrophotometer with a LabSphere DRA-CA-302 beam splitter or the like, could be used in this measurement. The percent transmission spectrum was collected in the wavelength range of 250 - 800 nm, where the %T values were collected at 0.5 nm intervals. The light transmittance of the contact lens was the average % transmission between 400 nm and 700 nm.

[0367] Measurement of water contact angle (WCA). The water contact angle (WCA) was measured using a DSA 10 Drop Shape Analysis System from Krüss GmbH, Germany, by the sessile drop method with pure water (Fluka, surface tension 72.5 mN / m at 20 °C). For the measurement, the contact lens was taken out of the storage solution with forceps and the excess storage solution was removed by gently shaking. The contact lens was placed on the male part of the lens mold and gently blotted with a dry and clean cloth. Then a water droplet (about 1 μl) was added to the apex of the lens, and the change in the contact angle of the water droplet over time (WCA(t), circular fit model) was monitored. The WCA was calculated by extrapolating the curve WCA(t) to t = 0.

[0368] Lubricity evaluation

[0369] The lubricity of the contact lens was evaluated by using a finger-feel lubricity test, which qualitatively characterized 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 lubricity). During this test, the lens was felt between the thumb and index finger, and a rating of 0 - 4 was qualitatively given based on the friction level perceived by the tester. The rating given was compared with 5 commercial lenses used as the standard for this test, corresponding to 5 levels of lubricity.

[0370] The levels and standards are as follows: The standard rating of the lens (Alcon) on the scale is 0, OASYS TM The standard rating of the lens (Johnson & Johnson) is 1, The standard rating of the lens (Bausch & Lamb) is 2, AquaComfort The standard rating of the lens (Alcon) is 3, and AIR The standard rating of the Aqua lens is 4.

[0371] The sample was placed in PBS and rinsed at least twice for 30 minutes each time, and then transferred to fresh PBS before evaluation. Before evaluation, the hands were rinsed with soap solution, thoroughly rinsed with DI water and then dried with a towel. When evaluating the lubricity of the front surface, the lens was placed on the index finger with its back surface facing the index finger and the thumb was moved against the front surface to feel the slipperiness (or lubricity) of the front surface. When evaluating the lubricity of the back surface, the lens was first inverted and then placed on the index finger with the inverted front surface facing the index finger, and then the thumb was moved against the inverted back surface to feel the slipperiness (or lubricity) of the back surface.

[0372] Each sample was assigned a friction rating relative to the above-described reference lens. The value of the friction rating was obtained by averaging the results of at least two friction ratings of the contact lens by two or more individuals and / or by averaging the friction ratings of two or more contact lenses (produced from lenses of the same lot) by one individual.

[0373] The finger lubricity (i.e., friction rating) of the contact lens can be determined out-of-pack (OOP) directly according to the procedure described above but after soaking in PBS for ≥ 30 min.

[0374] Lens removability assessment

[0375] The overall removability of each lens set was measured using a 3-D printed eye model that included the soft cornea, orbital bone, and nasal bone. Including these details allowed for a biologically accurate perturbation during the wearing and removal of the contact lens. A blind test was conducted in which two testers determined the number of attempts to remove the test lens. A'remove attempt' was defined as a shearing removal movement on the surface of the model eye with the contact lens placed on the ocular region of the eye. This was done with a minimal downward force applied to the surface of the model eye in order to simulate an actual lens removal movement. After placing the contact lens on the eye, a single drop of artificial tears was also applied to the eye to simulate the hydrating effect of a blink.

[0376] Chemicals

[0377] The following abbreviations are used in the following examples: HEMA represents 2-hydroxyethyl methacrylate; EOEMA represents ethoxyethyl methacrylate; MAA represents methacrylic acid; AA represents acrylic acid; PEG-DA represents poly(ethylene glycol) diacrylate (Mn ~800 g / mol); PG represents propylene glycol; Vazo 64 represents 2,2'-azobis(2-methylbutyronitrile); AIBN represents azobis(isobutyronitrile); Perkadox 16 is bis(4-tert-butylcyclohexyl) peroxydicarbonate; MPC represents 2-methacryloyloxyethyl phosphorylcholine; EGMA is 2-methoxyethyl methacrylate; AMA is allyl methacrylate; TEGDVE is tris(ethylene glycol) divinyl ether; Nobloc is 2-[3-(2H-benzotriazol-2-yl)-5-hydroxyphenyl]ethyl methacrylate; RB247 is Reactive Blue 247; HDI represents hexamethylene diisocyanate; ELA represents ethyl lactate; ME represents 2-mercaptoethanol; PBS represents phosphate buffered saline which has a pH of 7.2 ± 0.2 at 25 °C and contains approximately 0.044 wt% NaH2PO4·H2O, approximately 0.388 wt% Na2HPO4·2H2O, and approximately 0.79 wt% NaCl, and wt% represents weight percentage; "G2" macromonomer represents dimethacryloyloxypropyl-capped polysiloxane of formula (A) (Mn ~8K g / mol, OH content ~3.5 meq / g).

[0378]

[0379] Example 2

[0380] Preparation of the Polymerizable Composition

[0381] A polymerizable composition (SiHy lens formulation) was prepared to have the composition shown in Table 1.

[0382] Table 1

[0383]

[0384] These formulations were prepared by adding the listed components in their target amounts to a clean bottle and mixing at 600 rpm for 30 minutes with a stir bar at room temperature. After all solids had dissolved, the formulations were filtered using a 2.7 μm glass microfiber filter (GMF).

[0385] Cast-Molded Silicone Hydrogel Contact Lenses

[0386] The lens preparation was purged with nitrogen at room temperature for 30 - 35 minutes. The N2-purged lens preparation was introduced into a polypropylene mold and thermally cured in an oven under nitrogen at the following curing conditions: ramping from room temperature to 55°C at a ramp rate of about 7°C / minute; holding at 55°C for about 30 minutes; ramping from 55°C to 80°C at a ramp rate of about 7°C / minute; holding at 80°C for about 30 minutes; ramping from 80°C to 100°C at a ramp rate of about 7°C / minute; and holding at 100°C for about 30 minutes. The mold was opened and the molded lens was adhered to the male half-mold.

[0387] Example 3

[0388] Phosphate Buffered Saline (PBS)

[0389] Phosphate Buffered Saline was prepared by dissolving NaH2PO4·H2O, Na2HPO4·2H2O, and NaCl in a given volume of purified water (distilled or deionized) to have the following composition: about 0.044 w / w% NaH2PO4·H2O, about 0.388 w / w / % Na2HPO4·2H2O, and about 0.79 w / w% NaCl.

[0390] Preparation of the in-package coated saline - IPC-1

[0391] IPC saline (IPC-1) was prepared by mixing appropriate amounts of poly(AAm-co-AA) with PAE in phosphate buffered saline and pre-treating at a certain temperature for the desired time. Poly(AAm-co-AA)(90 / 10) partial sodium salt (poly(AAm-co-AA) 90 / 10, Mw 200,000) was manufactured in-house. Kymene or PAE solutions with different solid contents were purchased as aqueous solutions from Solenis and used as received. About 0.05% by weight of PAE; 0.035% by weight of poly(AAm-co-AA)(90 / 10), 0.776% by weight of Na2HPO4·2H2O, 0.044% by weight of NaH2PO4·H2O, 0.160% by weight of NaCl; and q.s. with water to 100%. The prepared aqueous solution was pre-treated at 60°C for about 1 hour. After the thermal pre-treatment, the IPC saline was filtered using a 0.22 micron membrane filter and cooled back to room temperature. 5 ppm hydrogen peroxide can be added to the final IPC saline to prevent bioburden growth, and the IPC saline was filtered using a 0.22 micron membrane filter.

[0392] Preparation of the hydrogel-forming composition

[0393] The crosslinkable polymer having hydroxyl groups was 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 procedure described in U.S. Patent No. 4,668,240.

[0394] A hydrogel-forming composition was prepared to have the following composition: 49.7 wt of the crosslinkable polymer prepared above; 16 wt% HEMA; 1.8 wt% EOEMA; 3.2 wt% HDI; 0.1 wt% Vazo 64; 29.2 wt% ELA.

[0395] Preparation of stereotype plates

[0396] Image patterns with different dot diameters and densities were engraved in the printing plate to obtain metal stereotype plates, polymer stereotype plates or ceramic stereotype plates for use in pad printing instruments. The depth of all patterns was 15 microns.

[0397] Figure 1 A shows a 0.25 pt. printing pattern (5 rings) of dots each having a diameter of 90 μm. The inner diameter of the smallest ring is 7.5 mm.

[0398] Figure 1 B shows a 0.50 pt. printing pattern (5 rings) of dots each having a diameter of 170 μm. The inner diameter of the smallest ring is 6.4 mm.

[0399] Figure 1 C shows a 0.75 pt. printing pattern (5 rings) of dots each having a diameter of 90 μm. The inner diameter of the smallest ring is 7.5 mm.

[0400] Figure 1 D shows a 1.0 pt. printing pattern (5 rings) of dots each having a diameter of 170 μm. The inner diameter of the smallest ring is 6.4 mm.

[0401] Figure 1 E shows a circular ring pt. printing pattern having an inner diameter of 4.4 mm and an outer diameter of 11.1 mm.

[0402] Production of water gradient contact lenses

[0403] According to the pad printing procedure described in Example 4 of US2020 / 0376787 A1, the hydrogel-forming composition prepared above was applied to the front surface (convex surface) of the preformed SiHy contact lens (dry lens adhered to the male half-mold) prepared in Example 2 in the printing pattern described above. The lens can receive a single printing (1 layer) or two printings (2 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 in order to achieve different surface properties on the lens. The lens was removed from the mold (demolded), packaged in IPC saline and hydrated for 30 minutes, and then autoclaved at 121 °C for 45 minutes.

[0404] The control lens was not subjected to printing with the hydrogel formulation, but was packaged and autoclaved in the same IPC saline.

[0405] The resulting fully hydrated water gradient contact lens has a water content of approximately 47%, an oxygen permeability (Dkc) of approximately 65 Barrers, and an elastic modulus of approximately 0.7 MPa.

[0406] Lubricity evaluation

[0407] Finger feel lubricity testing was performed using the water gradient contact lens prepared above according to the procedure described in Example 1. Lenses with a friction rating between 0 and 1 were designated 0.5, and lenses with a friction rating slightly greater than 0 were designated 0.25. The results are reported in Table 2.

[0408] Table 2

[0409]

[0410]

[0411] Water break-up time determined by IDDrop

[0412] The water break-up time of the water gradient contact lens prepared above was determined using IDDrop according to the procedure described in Example 1. The results are reported in Table 3.

[0413] Table 3

[0414]

[0415] During the IDDrop test, it was observed that the break-up pattern on the non-printed lens was a fairly uniform propagation. The water break-up on the printed lenses, especially on the group with 2-layer larger dot size printing, was less uniform as the water tended to pool around the printed areas.

[0416] Lens removability evaluation

[0417] The lens removability of the water-gradient contact lenses prepared above was evaluated according to the procedure described in Example 1. The results are reported in Table 4.

[0418] Table 4

[0419]

[0420] All publications, patents, and patent application publications cited herein in this application are hereby incorporated by reference in their entireties.

Claims

1. A coated contact lens, comprising: A front surface and an opposing rear surface; And A layered structure configuration that includes a front outer hydrogel layer, an inner layer, and a rear outer hydrogel layer in a direction from the front surface to the rear surface, Wherein the inner layer is the lens body material, wherein the rear outer hydrogel layer is a first non-silicone hydrogel material layer, wherein the front outer hydrogel layer is the first non-silicone hydrogel material layer in which mold marks are distributed, such that the rear outer hydrogel layer has a higher surface lubricity than the front outer hydrogel layer, and 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 front surface and the rear surface of the coated contact lens.

2. A method for producing a coated contact lens, comprising the steps of: (1) Obtaining a preformed contact lens having a convex surface and an opposing concave surface, wherein the preformed contact lens is made of a lens body material and includes first reactive functional groups on and near the convex surface and the concave surface of the preformed contact lens, and wherein each of the first reactive functional groups is capable of reacting with a thermally crosslinkable group at a temperature of about 60 - 140°C and is selected from the group consisting of carboxylic acid groups, primary amino groups, secondary amino groups, thiol groups, and combinations thereof; (2) Covering a plurality of regions on the convex surface with a first non-silicone hydrogel material to prevent the first reactive functional groups behind the plurality of regions from reacting with the thermally crosslinkable groups, wherein the first non-silicone hydrogel material does not contain any first reactive functional groups and does not contain any thermally crosslinkable groups; (3) Directly heating the preformed contact lens obtained in step (2) in an aqueous solution having a pH of about 6.5 - 9.5 and containing at least one water-soluble thermally crosslinkable hydrophilic polymer material at a temperature of about 60 - 140°C to graft a second non-silicone hydrogel material onto each of the front surface and the rear surface of the preformed contact lens obtained in step (2) to form a coated contact lens having a front surface, an opposing rear surface, a front outer hydrogel layer, and a rear outer hydrogel layer, wherein the at least one water-soluble thermally crosslinkable hydrophilic polymer material includes a second reactive functional group and a third reactive functional group, wherein the second reactive functional group is a thermally crosslinkable group selected from the group consisting of azetidinium groups, epoxy groups, and combinations thereof, and wherein each of the second reactive functional groups is capable of reacting with a first or third reactive functional group to form a crosslinking bond, wherein the third reactive functional group is selected from the group consisting of carboxylic acid groups, primary amino groups, secondary amino groups, thiol groups, and combinations thereof, and wherein the second non-silicone hydrogel material is a crosslinked product of the at least one thermally crosslinkable hydrophilic polymer material. The front outer hydrogel layer has mold marks (grooves and / or gaps) distributed therein such that the back surface of the coated contact lens has a higher surface lubricity than the front surface, and the coated contact lens in a fully hydrated state has a water break-up time of at least about 10 seconds measured on the front and back surfaces of the coated contact lens.

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

4. A method of producing a coated contact lens, comprising the steps of: (1) Obtaining a female half-mold and a male half-mold, wherein the female half-mold has a first molding surface defining the front surface of the contact lens to be molded, and the male half-mold has a second molding surface defining the back surface of the contact lens to be molded, and the male half-mold and the female half-mold are configured to receive each other such that when the female half-mold is closed with the male half-mold, 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 zones on the first molding surface, wherein the hydrogel-forming composition comprises at least one crosslinkable polymer having hydroxyl and / or ethylenically unsaturated groups and optionally at least one hydrophobic ethylenic monomer selected from the group consisting of methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, methyl (meth)acrylate, and combinations thereof, and wherein if the at least one crosslinkable polymer does not contain any ethylenically unsaturated groups, the hydrogel-forming composition further comprises at least one hydroxyl-containing ethylenic monomer and at least one compound having two or more isocyanate 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 female half-mold obtained in step (2) or (3), wherein, based on the total amount of all polymerizable components, the polymerizable composition comprises about 1.0 - 10% by weight of at least one reactive ethylenic monomer having at least one first reactive functional group, and the first reactive functional group is selected from the group consisting of carboxylic acid groups, primary amino groups, secondary amino groups, and combinations thereof; (5) Closing the female half-mold obtained in step (4) with the male half-mold to form a molded assembly containing the polymerizable composition in the lens forming cavity; (6) Thermally cure or photocure the polymerizable composition in the molded assembly to form a contact lens precursor having a convex surface and an opposing concave surface and comprising a lens body material having a first reactive functional group, wherein the convex surface of the contact lens precursor is partially covered in the plurality of zones on the convex surface with a first hydrogel material formed from the hydrogel-forming composition to prevent the first reactive functional group behind the plurality of zones from reacting with a thermally crosslinkable group that is an azetidinium group and / or an epoxy group at a temperature of about 60 - 140 °C, wherein the first non-silicone hydrogel material does not contain any first reactive functional groups and thermally crosslinkable groups; (7) Optionally, hydrate the contact lens precursor obtained in step (6) in water or an aqueous solution; and (8) Directly heat the contact lens precursor obtained in step (6) or step (7) in an aqueous solution having a pH of about 6.5 - 9.5 and comprising at least one water-soluble thermally crosslinkable hydrophilic polymer material at a temperature of about 60 - 140 °C to graft a 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) to form a coated contact lens having a front surface, an opposing rear surface, a front outer hydrogel layer, and a rear 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, wherein the second reactive functional group is a thermally crosslinkable group selected from the group consisting of azetidinium groups, epoxy groups, and combinations thereof, wherein each of the second reactive functional groups is capable of reacting with a first or third reactive functional group to form a crosslinking bond, and wherein the third reactive functional group is selected from the group consisting of carboxylic acid groups, primary amino groups, secondary amino groups, thiol groups, and combinations thereof, wherein the front outer hydrogel layer has mold marks (grooves and / or gaps) distributed therein such that the rear surface of the coated contact lens has a higher surface lubricity than the front 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 front and rear surfaces of the coated contact lens.

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

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

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

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

9. The coated contact lens according to claim 1 or the method according to any one of claims 2-8, wherein the mold mark comprises: (1) Grooves having an annular shape, a curved shape, and / or a linear shape in a top view; (2) Gaps having a circular shape, a triangular shape, a square shape, a rectangular shape, a hexagonal shape, a polygonal shape, and / or a star shape in a top view.

10. The coated contact lens according to claim 1 or 9 or the method according to any one of claims 2-9, wherein the mold marks on the front surface of the coated contact lens are arranged in a rotationally symmetric pattern with respect to the central axis of the coated contact lens.

11. The coated contact lens according to claim 1 or 9 or the method according to any one of claims 2-9, wherein the mold marks on the front surface of the coated contact lens are located in an annular region having an inner diameter of about 6.0-9.0 mm and an outer diameter of about 11.5-14.5 mm and are concentric with respect to the central axis of the coated contact lens.

12. The coated contact lens according to any one of claims 1 and 9-11 or the method according to any one of claims 2-11, wherein the mold marks comprise at least three grooves having an annular shape in a top view.

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

14. The coated contact lens according to any one of claims 1 and 9 - 13, or the method according to any one of claims 2 - 13, wherein the mold marks include gaps that are circular in a top view.

15. The coated contact lens or method according to claim 14, wherein the gaps that are circular in a top view are each arranged in a rotationally symmetric pattern on the front surface of the coated contact lens.

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

17. The coated contact lens according to any one of claims 1 and 9 - 16, or the method according to any one of claims 2 - 16, wherein the first non - silicone hydrogel material is: (1) A crosslinked polymeric material comprising repeating monomer units of at least one hydrophilic ethylenic monomer selected from the group consisting of at least 25 mol% 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)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-C4-alkoxy poly(ethylene glycol) (meth)acrylate having a weight-average molecular weight of up to 1500, methoxy-poly(ethylene glycol) ethyl (meth)acrylamide having a number-average molecular weight of up to 1500, 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 mono vinyl ether, di(ethylene glycol) mono vinyl ether, tri(ethylene glycol) mono vinyl ether, tetra(ethylene glycol) mono vinyl ether, poly(ethylene glycol) mono vinyl ether, ethylene glycol methyl vinyl ether, di(ethylene glycol) methyl vinyl ether, tri(ethylene glycol) methyl vinyl ether, tetra(ethylene glycol) methyl vinyl ether, poly(ethylene glycol) methyl vinyl ether and combinations thereof; (2) A cross - linked polymeric material comprising repeating monomer units of at least one phosphorylcholine - containing vinyl monomer in an amount of at least 25 mol%. (3) A cross - linked polymeric material comprising poly(ethylene glycol) chains, wherein the poly(ethylene glycol) chains are preferably directly derived from (a) poly(ethylene glycol) having a single unique - NH2, - SH, or - COOH functional group, (b) poly(ethylene glycol) having two terminal functional groups selected from the group consisting of - NH2, - COOH, - SH, and combinations thereof, (c) multi - arm poly(ethylene glycol) having one or more functional groups selected from the group consisting of - NH2, - COOH, - SH, and combinations thereof, and (d) combinations thereof; or (4) Combinations thereof.

18. The method according to any one of claims 2 - 17, wherein the plurality of zones have a circular shape, a triangular shape, a square shape, a rectangular shape, a hexagonal shape, a polygonal shape, a star shape, an annular ring shape, a curved shape, a straight shape, or combinations thereof.

19. The method according to any one of claims 2 - 18, wherein the plurality of zones are arranged in a rotationally symmetric pattern with respect to the central axis of the pre - formed contact lens or the female half - mold.

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

21. The method according to any one of claims 2 - 20, wherein the plurality of zones include at least three concentric annular rings.

22. The method according to any one of claims 2 - 21, wherein the plurality of zones include at least eight curves or straight lines radiating outward from a circle having a diameter of about 6.0 - 9.0 mm and concentric with the central axis of the pre - formed contact lens or the female half - mold.

23. The method according to claim 22, wherein the plurality of zones include circular dots, and the circular dots are arranged in a rotationally symmetric pattern with respect to the central axis of the pre - formed contact lens or the female half - mold on the convex surface of the pre - formed contact lens or the molding surface of the female half - mold.

24. The method according to claim 22, wherein the plurality of zones includes circular dots, and wherein the circular dots are arranged in an annular ring concentric with the central axis of the preformed contact lens or the female half mold.

Images