Contact lenses having a hydrogel coating thereon

Abstract

The present invention relates to a cost-effective method for producing coated contact lenses having a hydrogel coating thereon. The method comprises heating a contact lens precursor having carboxylic acid groups on and / or near its surface in an aqueous solution in the presence of a hydrophilic copolymer comprising monomer units of (a) at least one epoxy-containing vinyl monomer, (b) at least one amino-containing vinyl monomer having a primary or secondary amino group, (c) at least one polyethylene glycol-containing vinyl monomer, and (d) at least one phosphorylcholine-containing vinyl monomer at a temperature of about 100°C to about 140°C for at least 30 minutes, thereby forming a hydrogel coating on the contact lens precursor. Such a method can advantageously be carried out directly in the sealed lens package during autoclaving.

Description

[Technical Field]

[0001] The present invention generally relates to a cost-effective and time-efficient method for applying a hydrogel coating onto contact lenses, particularly silicone hydrogel contact lenses, to improve their hydrophilicity and lubricity. Additionally, the present invention provides an ophthalmic lens product. [Background technology]

[0002] In recent years, much effort has been made to develop contact lenses with improved wearing comfort.

[0003] One example is the incorporation of leachable wetting agents into contact lenses (see, e.g., U.S. Pat. Nos. 4,045,547, 4,042,552, 5,198,477, 5,219,965, 6,367,929, 6,822,016, 7,279,507, 8,030,369, and 9,804,295).

[0004] Another example is the incorporation of bioactive agents and hydrophobic comfort agents into contact lenses (see, eg, US Pat. No. 10,155,349).

[0005] A further example is the production of contact lenses with nano-textured surfaces that mimic the surface properties of the cornea of the human eye (see, for example, U.S. Pat. No. 9,244,195).

[0006] Yet another example is the development of a new class of soft contact lenses, water gradient contact lenses. This new class of soft contact lenses was first developed and successfully introduced to the market as a daily disposable contact lens, DAILIES® TOTAL 1® (Alcon). Weekly or monthly disposable water gradient soft contact lenses with durable hydrogel coatings and reduced uptake of positively charged antimicrobial agents present in multipurpose lens care solutions have also been developed (U.S. Pat. No. 1,256,003) and introduced to the market as a monthly replacement water gradient contact lens, TOTAL 30® (Alcon). This new class of soft contact lenses is characterized by having a water gradient structural configuration, an increase in water content observed as the lens passes from the core to the surface, and a maximum water content in the region near and including the surface of the contact lens (see U.S. Pat. No. 8,480,227). This unique design delivers an extremely smooth and exceptionally soft, moisture-rich lens surface, which in turn provides superior wear comfort to the patient.

[0007] As described in U.S. Patent Nos. 8,480,227 and 1,125,6003, manufacturing processes for water gradient contact lenses often involve the use of partially crosslinked and thermally crosslinkable hydrophilic polymeric materials in forming non-silicone hydrogel coatings on contact lenses. These processes may require extra steps to prepare the partially crosslinked and thermally crosslinkable hydrophilic polymeric materials. Therefore, it would be desirable to eliminate such extra steps to simplify the manufacturing process for producing water gradient contact lenses. Summary of the Invention [Means for solving the problem]

[0008] In one aspect, the present invention provides a method for making a coated contact lens, comprising the steps of: (1) obtaining a contact lens precursor having a concave surface and an opposite convex surface, the contact lens precursor comprising a lens bulk material and carboxylic acid groups on and / or near the anterior and posterior surfaces; (2) immersing the contact lens precursor in a container with an aqueous solution containing about 0.01% by weight of a solvent containing (a) monomer units of at least one epoxy-containing vinyl monomer, (b) monomer units of at least one amino-containing vinyl monomer having a primary or secondary amino group, (c) monomer units of at least one polyethylene glycol-containing vinyl monomer, and (d) monomer units of at least one phosphorylcholine-containing vinyl monomer. (2) heating the aqueous solution having the contact lens precursor therein at a temperature of from about 100° C. to about 140° C. for at least 30 minutes to form a coated contact lens having a hydrogel coating thereon, wherein the hydrogel coating is covalently bonded to the anterior and posterior surfaces by bonds formed between one carboxylic acid group and one epoxy group, respectively, and the hydrogel coating comprises a crosslinked polymeric material comprising polymer chains derived from the hydrophilic copolymer.

[0009] In another aspect, the present invention provides a contact lens, preferably a silicone hydrogel contact lens, comprising a front surface, an opposite rear surface, and a layered structural arrangement from the front surface to the rear surface, the layered structural arrangement comprising an outer front hydrogel layer, an inner layer, and an outer rear hydrogel layer, the inner layer being a lens bulk material, and the outer front hydrogel layer and the outer rear hydrogel layer being composed of monomer units of (a) at least one epoxy-containing vinyl monomer, (b) at least one amino-containing vinyl monomer having a primary or secondary amino group, (c) at least one polyethylene glycol and (d) a hydrophilic copolymer comprising monomer units of at least one phosphorylcholine-containing vinyl monomer, and (e) a hydrophilic copolymer comprising monomer units of at least one phosphorylcholine-containing vinyl monomer, wherein the sum of the amounts of components (a) and (b) in said at least one hydrophilic copolymer is about 40 mol % or less, wherein the outer front surface and surface hydrogel layers are covalently bonded onto the inner layer by bonds formed between one carboxylic acid group and one epoxy group, respectively, and wherein the contact lens has a water-break time (WBUT) of at least 10 seconds.

[0010] These and other aspects of the present invention, including various preferred embodiments in any combination, will become apparent from the following description of the presently preferred embodiments. This detailed description is merely exemplary of the present invention and does not limit the scope of the invention, which is defined by the appended claims and their equivalents. As will be apparent to those skilled in the art, many variations and modifications of the present invention can be effected without departing from the spirit and scope of the novel concepts of the present disclosure. [Brief explanation of the drawings]

[0011] [Figure 1] 1 is a schematic cross-sectional view of a structural configuration of a contact lens according to a preferred embodiment of the present invention; DETAILED DESCRIPTION OF THE INVENTION

[0012] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Generally, the nomenclature and laboratory procedures used herein are well known and commonly used in the art. Conventional methods are used for these procedures, such as those provided in the art and various general references. Where a term is given in the singular, the inventors also contemplate the plural of that term. The nomenclature used herein and the laboratory procedures described below are well known and commonly used in the art.

[0013] "About" as used herein in this application means that the number referred to as "about" includes the recited number, plus or minus 1 to 10% of the recited number.

[0014] "Optional" or "optionally" means that the subsequently described event or circumstance can either occur or not occur, and that the description includes instances where the event or circumstance occurs and instances where it does not occur.

[0015] "Contact lens" refers to a structure that can be placed on or in a wearer's eye. A contact lens can, but need not, correct, improve, or alter the user's vision. A contact lens can be of any suitable material known in the art or later developed, and can be a hard lens, a rigid gas permeable lens, a soft lens, or a hybrid lens.

[0016] As used in this application, the terms "front surface," "front surface," "front curve," or "FC surface" in reference to a contact lens refer interchangeably to the surface of the contact lens that faces away from the eye during wear. The front surface (FC surface) is typically substantially convex.

[0017] The terms "posterior surface," "back surface," "base curve surface," or "BC surface," as used herein, in reference to a contact lens, mean interchangeably the surface of the contact lens that faces the eye during wear. The posterior surface (BC surface) is typically substantially concave.

[0018] "Hard contact lens" refers to a contact lens that includes a hard plastic (eg, polymethyl methacrylate) as the lens bulk (or so-called "core") material.

[0019] "Rigid gas permeable contact lens" refers to a contact lens that includes a gas permeable material (e.g., a material made of fluorosilicone acrylate) as the lens bulk (or so-called "core") material.

[0020] Soft contact lenses can be non-silicone hydrogel contact lenses or silicone hydrogel contact lenses. "Non-silicone hydrogel contact lenses" refers to contact lenses that contain a non-silicone hydrogel bulk (or so-called "core") material. "Silicone hydrogel contact lenses" or "SiHy" refers to contact lenses that contain a silicone hydrogel bulk (or so-called "core") material.

[0021] A hybrid contact lens includes a lens bulk material consisting essentially of a central optic made of a gas-permeable lens material and a peripheral portion made of a silicone hydrogel or conventional hydrogel lens material, extending outward from and surrounding the central optic.

[0022] An implantable contact lens comprises a three-dimensional implantable article and a lens bulk material consisting essentially of a non-silicone hydrogel material or a silicone hydrogel material, wherein the three-dimensional implantable article is made of a non-hydrogel material and has a three-dimensional size smaller than that of a contact lens such that it is partially or more preferably completely embedded within the non-silicone hydrogel material or the silicone hydrogel material. The non-hydrogel material can be any material that absorbs less than 10% water by weight when fully hydrated (preferably about 7.5% or less, more preferably about 5.0% or less, and even more preferably about 2.5% or less).

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

[0024] As used in this application, the term "non-silicone hydrogel" refers to a hydrogel that does not, in theory, contain silicon.

[0025] Siloxane, often also referred to as silicone, refers to a molecule having at least one moiety of -Si-O-Si-, where each Si atom has two organic groups as substituents.

[0026] As used in this application, the terms "silicone hydrogel" or "SiHy" refer interchangeably to a hydrogel containing silicone. Silicone hydrogel (SiHy) is typically obtained by copolymerization of a polymerizable composition comprising at least one silicone-containing vinyl monomer, or at least one silicone-containing vinyl macromer, or at least one silicone-containing prepolymer having ethylenically unsaturated groups.

[0027] "Hydrophilic," as used herein, describes a material or portion thereof that will more readily associate with water than with lipids.

[0028] The term "room temperature" refers to a temperature of about 22°C to about 26°C.

[0029] The term "soluble" in reference to a compound or material in a solvent means that the compound or material can be dissolved in the solvent at room temperature to provide a solution at a concentration of at least about 0.5% by weight.

[0030] The term "insoluble," in reference to a compound or material in a solvent, means that the compound or material can be dissolved in the solvent at room temperature (as defined above) to provide a solution with a concentration of less than about 0.01% by weight.

[0031] "Vinyl monomer" refers to a compound that has one and only one ethylenically unsaturated group, is soluble in a solvent, and can be polymerized actinically or thermally.

[0032] As used in this application, the term "vinyl crosslinker" refers to a compound having at least two ethylenically unsaturated groups. "Vinyl crosslinker" refers to a subclass of vinyl crosslinkers each having a number average molecular weight of 700 Daltons or less.

[0033] The term "ethylenically unsaturated group" is used broadly herein and is intended to encompass any group containing at least one >C=CH group. Exemplary ethylenically unsaturated groups include, without limitation, (meth)acryloyl [ka] , vinyloxycarbonylamino ( [ka] (In the formula, R o is H or C1-C4 alkyl), vinyloxycarbonyloxy [ka] , allyl, vinyl, styrenyl, or other C=C containing groups.

[0034] "Acrylic monomer" refers to a vinyl monomer having one and only one (meth)acryloyl group. Examples of acrylic monomers include (meth)acryloxy [or (meth)acryloyloxy] monomers and (meth)acrylamide monomers.

[0035] "(Meth)acryloxy monomer" or "(meth)acryloyloxy monomer" means [ka] refers to a vinyl monomer having one and only one group.

[0036] "(Meth)acrylamide monomer" is [ka] (In the formula, R o is H or C1-C4 alkyl) refers to a vinyl monomer having one and only one group.

[0037] The term "(meth)acrylamide" refers to methacrylamide and / or acrylamide.

[0038] The term "(meth)acrylate" refers to methacrylate and / or acrylate.

[0039] "N-vinyl amide monomer" refers to an amide compound having a vinyl group (-CH=CH2) attached directly to the nitrogen atom of the amide group.

[0040] The term "ene group" refers to a monovalent radical of CH2=CH- or CH2=CCH3- that is not covalently bonded to an oxygen or nitrogen atom or a carbonyl group.

[0041] "Ene monomer" refers to a vinyl monomer having one and only one ene group.

[0042] "Vinyloxycarbonylamino monomer" refers to a vinyl monomer having one and only one vinyloxycarbonylamino group.

[0043] "Vinylaminocarbonyloxy monomer" refers to a vinyl monomer having one and only one vinylaminocarbonyloxy group.

[0044] "Vinylaminocarbonylamino monomer" refers to a vinyl monomer having one and only one vinylaminocarbonylamino group.

[0045] "Hydrophilic vinyl monomer" refers to any vinyl monomer that typically yields a homopolymer that is water soluble or capable of absorbing at least 10 weight percent water.

[0046] "Hydrophobic vinyl monomer" refers to any vinyl monomer that typically yields a homopolymer that is insoluble in water and can absorb less than 10% by weight of water.

[0047] "Acrylic crosslinker" refers to a vinyl crosslinker having at least two (meth)acryloyl groups.

[0048] The term "acrylic repeat unit" refers to a repeat unit of a polymeric material, each of which is derived from an acrylic monomer or crosslinker in a free radical polymerization to form the polymeric material.

[0049] As used herein, "actinically," in reference to curing, crosslinking, or polymerization of a polymerizable composition, prepolymer, or material, means that the curing (e.g., crosslinking and / or polymerization) is effected by actinic radiation, such as, for example, UV / visible radiation, ionizing radiation (e.g., gamma or X-ray radiation), microwave radiation, etc. Thermal curing or actinic curing methods are well known to those skilled in the art.

[0050] "Blending vinyl monomer" refers to a vinyl monomer that is capable of dissolving both the hydrophilic and hydrophobic polymerizable components of the polymerizable composition to form a solution.

[0051] The terms "silicone-containing vinyl monomer or crosslinker" or "siloxane-containing vinyl monomer or crosslinker" interchangeably refer to a vinyl monomer or crosslinker having at least one moiety of -Si-O-Si-, where each Si atom has at least two substituents (organic groups).

[0052] The term "terminal ethylenically unsaturated group" refers to an ethylenically unsaturated group at one of the two ends of the main chain (or backbone) of an organic compound, as known to those skilled in the art. The term "terminal (meth)acryloyl group" refers to a (meth)acryloyl group at one of the two ends of the main chain (or backbone) of an organic compound, as known to those skilled in the art.

[0053] "Polysiloxane segment" or "polydiorganosiloxane segment" mean the same thing: [ka] [Wherein, SN is an integer of 3 or more, and R S1 and R S2 Each of these is C1~C 10 Alkyl;Phenyl;C1-C4 alkyl-substituted phenyl;C1-C4 alkoxy-substituted phenyl;Phenyl-C1-C6 alkyl;C1-C 10 Fluoroalkyl; C1-C 10 Fluoroether;Aryl;Aryl C1-C 18 Alkyl;-alk-(OC2H4) γ1 -OR o (wherein alk is a C1-C6 alkylene diradical, and R ois H or C1-C4 alkyl, and γ1 is an integer of 1 to 10; a hydroxyl group (—OH), a carboxyl group (—COOH), an amino group (—NR N1 R N1 '), -NR N1 -amino bond, -CONR N1 -amide bond, -CONR N1 R N1 C2-C alkyl group having at least one functional group selected from the group consisting of an amide bond of -OCONH-, a urethane bond of -OCONH-, and a C1-C4 alkoxy group 40 and a linear hydrophilic polymer chain, wherein each R N1 and R N1 ' is hydrogen or C1-C 15 alkyl] refers to a polymer chain segment (i.e., a divalent radical) of

[0054] "Polydiorganosiloxane vinyl monomer" or "polysiloxane vinyl monomer" refer interchangeably to a compound containing at least one polysiloxane segment and one and only one ethylenically unsaturated group.

[0055] "Polydiorganosiloxane vinyl crosslinker" or "polysiloxane vinyl crosslinker" refer interchangeably to a compound containing at least one polysiloxane segment and at least two ethylenically unsaturated groups.

[0056] "Linear polydiorganosiloxane vinyl crosslinker" or "linear polysiloxane vinyl crosslinker" interchangeably refer to a compound comprising a backbone that includes at least one polysiloxane segment and is terminated at each of the two ends of the backbone with one ethylenically unsaturated group.

[0057] The terms "chain-extended polydiorganosiloxane vinyl crosslinker" or "chain-extended polysiloxane vinyl crosslinker" refer interchangeably to a compound containing at least two ethylenically unsaturated groups and at least two polysiloxane segments, each pair of which is linked by a divalent radical.

[0058] The term "fluid" as used herein indicates that the material is capable of flowing like a liquid.

[0059] As used in this application, the term "transparent" in relation to a polymerizable composition means that the polymerizable composition is a clear solution or liquid mixture having a light transmittance of 85% or more (preferably 90% or more) at 400 to 700 nm.

[0060] "Macromer" or "prepolymer" refers to a compound or polymer that contains ethylenically unsaturated groups and has a number average molecular weight greater than 700 Daltons.

[0061] As used in this application, the term "polymer" means a material formed by polymerizing or crosslinking one or more monomers, macromers, prepolymers, or combinations thereof.

[0062] As used in this application, the term "molecular weight" of a polymeric material (including a monomeric or macromeric material) refers to number average molecular weight unless otherwise specified or unless the test conditions dictate otherwise. Those skilled in the art will recognize that molecular weight can be measured by known methods, such as GPC (gel permeation chromatography) with one or more of a refractive index detector, a low-angle laser light scattering detector, a multi-angle laser light scattering detector, a differential viscometry detector, a UV detector, and an infrared (IR) detector; MALDI-TOF MS (matrix-assisted laser desorption / ionization time-of-flight mass spectrometry); 1 Know how to determine the molecular weight of polymers according to H NMR (proton nuclear magnetic resonance) spectroscopy etc.

[0063] The term "monovalent radical" refers to an organic radical obtained by removing a hydrogen atom from an organic compound and forming a bond with one other group in the organic compound. Examples include, without limitation, alkyl (by removing a hydrogen atom from an alkane), alkoxy (or alkoxyl) (by removing one hydrogen atom from the hydroxyl group of an alkyl alcohol), thiyl (by removing one hydrogen atom from the thiol group of an alkylthiol), cycloalkyl (by removing a hydrogen atom from a cycloalkane), cycloheteroalkyl (by removing a hydrogen atom from a cycloheteroalkane), aryl (by removing a hydrogen atom from the aromatic ring of an aromatic hydrocarbon), heteroaryl (by removing a hydrogen atom from any ring atom), amino (by removing one hydrogen atom from an amine), and the like.

[0064] The term "divalent radical" refers to an organic radical obtained by removing two hydrogen atoms from an organic compound and that forms two bonds with two other groups in the organic compound. For example, an alkylene divalent radical (i.e., alkylenyl) is obtained by removing two hydrogen atoms from an alkane, and a cycloalkylene divalent radical (i.e., cycloalkylenyl) is obtained by removing two hydrogen atoms from a cyclic ring.

[0065] In this application, the term "substituted" with reference to an alkyl or alkylenyl means that the alkyl or alkylenyl replaces one hydrogen atom of the alkyl or alkylenyl and includes at least one substituent selected from the group consisting of hydroxyl (-OH), carboxyl (-COOH), -NH, sulfhydryl (-SH), C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkylthio (alkylsulfido), C1-C4 acylamino, C1-C4 alkylamino, di-C1-C4 alkylamino, and combinations thereof.

[0066] The term "alkyl" refers to a monovalent radical obtained by removing a hydrogen atom from a straight-chain or branched alkane compound. An alkyl group (radical) forms one bond with one other group in an organic compound.

[0067] The terms "alkylene divalent group," "alkylene diradical," or "alkyl diradical," interchangeably, refer to a divalent radical obtained by removing one hydrogen atom from an alkyl. An alkylene divalent group forms two bonds with other groups in an organic compound.

[0068] The terms "alkoxy" or "alkoxyl" refer to a monovalent radical obtained by removing a hydrogen atom from the hydroxyl group of a straight-chain or branched alkyl alcohol. An alkoxy group (radical) forms one bond with one other group in an organic compound.

[0069] As used in this application, the term "amino group" refers to a group of the formula -NHR', where R', unless otherwise specified, is hydrogen or an unsubstituted or substituted C1-C 20 refers to a primary or secondary amino group of the alkyl group (which is a straight-chain or branched alkyl group).

[0070] As used in this application, the term "phosphorylcholine" means [ka] (wherein t1 is an integer of 1 to 5, and 1 R, 2 R and 3 R is C1-C8 alkyl or C1-C8 hydroxyalkyl. refers to a zwitterionic group of the formula:

[0071] As used in this application, the term "carboxyl-containing vinyl monomer" refers to any vinyl monomer having a carboxyl group (-COOH); the term "amino-containing vinyl monomer" refers to any vinyl monomer having an amino group (-NHR', where R' is H or C1-C4 alkyl); and the term "epoxy-containing vinyl monomer" refers to any vinyl monomer having an epoxide (where each R', independently of one another, is H or C1-C4 alkyl). [ka] the term "phosphorylcholine-containing vinyl monomer" refers to any vinyl monomer having a phosphorylcholine group; the term "polyethylene glycol-containing vinyl monomer" refers to any vinyl monomer having a monovalent radical of ; [ka] It refers to any vinyl monomer having a polyethylene glycol group.

[0072] As used in this application, the term "non-reactive vinyl monomer" refers to any vinyl monomer that does not contain a carboxyl group, a primary amino group, a secondary amino group, an epoxide group, an isocyanate group, an azlactone group, an aldehyde group, an azetidinium group, or an aziridine group.

[0073] Free radical initiators can be either photoinitiators or thermal initiators. A "photoinitiator" refers to a chemical that initiates a free radical crosslinking / polymerization reaction with the use of light. A "thermal initiator" or "thermal free radical initiator" refers, interchangeably, to a chemical that initiates a free radical crosslinking / polymerization reaction with the use of heat.

[0074] The intrinsic "oxygen permeability" of the material, Dk iis the rate at which oxygen passes through the material. As used in this application, the term "oxygen permeability (Dk)" in relation to a hydrogel (silicone or non-silicone) or contact lens refers to the corrected oxygen permeability (Dk) measured at about 34-35°C and corrected for the surface resistance to oxygen flux caused by boundary layer effects according to the procedure described in ISO 18369-4. c Oxygen permeability is usually expressed in units of barrers, where "barrer" means [(cm 3 oxygen)(cm) / (cm 2 )(sec)(mmHg)]×10 -9 It is defined as follows.

[0075] The "oxygen permeability" of a lens or material, Dk / t, is the rate at which oxygen will pass through a particular lens or material of average thickness t [in mm] over the area being measured. Oxygen permeability is usually expressed in units of barrer / mm, where "barrer / mm" is [(cm 3 oxygen) / (cm 2 )(sec)(mmHg)]×10 -9 It is defined as follows.

[0076] The term "modulus" or "elastic modulus" in relation to contact lenses or materials refers to the tensile modulus or Young's modulus, which is a measure of the stiffness of a contact lens or material under tension. Those skilled in the art know how to measure the elastic modulus of a SiHy material or contact lens. For example, all commercially available contact lenses have a reported elastic modulus value.

[0077] "Coating" in relation to a contact lens means that the contact lens has on its surface a thin layer of a material that is different from the bulk material of the contact lens and that is obtained by subjecting the contact lens to a surface treatment.

[0078] "Surface modification" or "surface treatment," as used herein, means that an article has been treated in a surface treatment process in which (1) a coating is applied to the surface of the article, (2) a chemical species is adsorbed onto the surface of the article, (3) the chemical nature (e.g., electrostatic charge) of chemical groups on the surface of the article is altered, or (4) the surface properties of the article are otherwise modified. Exemplary surface treatment processes include, but are not limited to, surface treatment with energy (e.g., plasma, electrostatic charge, irradiation, or other energy source), chemical treatment, grafting of hydrophilic vinyl monomers or macromers onto the surface of the article, mold transfer coating process disclosed in U.S. Pat. No. 6,719,929, incorporation of wetting agents into lens formulations for producing contact lenses as proposed in U.S. Pat. Nos. 6,367,929 and 6,822,016, reinforced mold transfer coating disclosed in U.S. Pat. No. 7,858,000, and hydrophilic coatings comprised of covalently bonding or physically depositing one or more layers of one or more hydrophilic polymers onto the surface of a contact lens as disclosed in U.S. Pat. Nos. 8,147,897, 8,409,599, 8,557,334, 8,529,057, and 9,505,184.

[0079] In the context of a lens bulk material or a contact lens, "post-cure surface treatment" refers to a surface treatment process that occurs after the lens bulk material or contact lens has been formed by curing (i.e., thermally or actinically polymerizing) a polymerizable composition.

[0080] "Hydrophilic surface" in the context of a silicone hydrogel material or contact lens means that the silicone hydrogel material or contact lens has a surface hydrophilicity characterized by an average water contact angle of about 90 degrees or less, preferably about 80 degrees or less, more preferably about 70 degrees or less, and more preferably about 60 degrees or less.

[0081] "Average contact angle" refers to the water contact angle (static water contact angle measured by the Sessile Drop method), which is obtained by averaging measurements of at least three individual contact lenses.

[0082] "Ophthalmically compatible," as used herein, refers to a material or surface of a material that may be in intimate contact with the ocular environment for extended periods of time without significant damage to the ocular environment and without significant user discomfort.

[0083] The term "ophthalmically safe" in the context of a packaging solution for sterilizing and storing contact lenses means that contact lenses stored in the solution are safe for direct placement on the eye without rinsing after autoclaving, and that the solution is safe and sufficiently comfortable for daily contact with the eye through a contact lens. An autoclaved ophthalmically safe packaging solution has a tonicity and pH that is compatible with the eye, and is substantially free of eye irritants or cytotoxic substances in accordance with international ISO standards and U.S. FDA regulations.

[0084] The term "water gradient" in the context of a contact lens means that there is an increase in water content observed as the lens passes from the core to the surface, reaching a highest water content in regions near and including the surface of the contact lens. It is understood that the increase in water content from the core to the surface of the contact lens can be continuous and / or gradual, so long as the water content is highest in regions near and including the surface of the contact lens.

[0085] As used in this application, the term "cross section" of a contact lens refers to a lens cross section obtained by cutting the lens with a knife or cutting tool at an angle substantially perpendicular to either the anterior or posterior surface of the lens. Those skilled in the art are familiar with manually cutting (i.e., cutting by hand) or cutting with a Cryosta Microtome or on a lathe to obtain a contact lens cross section. The resulting contact lens cross section can be polished by using ion etching or similar techniques.

[0086] As used in this application, the term "equilibrium water content" in relation to a contact lens or polymeric material means the amount of water (expressed as a weight percent) present in the contact lens or polymeric material when fully hydrated (equilibrated) in phosphate buffered saline (about 0.79 wt % NaCl) and measured at room temperature.

[0087] As used herein, the terms "crosslinked coating" or "hydrogel coating" or "hydrogel layer" on a contact lens are used interchangeably to describe a crosslinked polymeric material having a three-dimensional network that can contain water when fully hydrated. The three-dimensional network of the crosslinked polymeric material can be formed by the crosslinking of two or more linear or branched polymers by crosslinking bonds.

[0088] As used in this application, the term "lens bulk material" in relation to a contact lens means, interchangeably, a layer that has the three-dimensional shape of the contact lens and includes a central curve (which divides the contact lens into two portions, one portion containing the anterior surface and the other portion containing the posterior surface), and that has a variable thickness.

[0089] As used herein, the term "exterior hydrogel layer" in relation to a contact lens means the outermost hydrogel layer immediately beneath the surface of the contact lens, which consists of an outer anterior hydrogel layer and an outer posterior hydrogel layer, which completely covers the lens bulk material. "Anterior outer hydrogel layer" in relation to a contact lens means the outermost hydrogel layer immediately beneath the anterior surface of the contact lens. "Posterior outer hydrogel layer" in relation to a contact lens means the outermost hydrogel layer immediately beneath the posterior surface of the contact lens. It is understood that the anterior surface is composed of the same material as the outer anterior hydrogel layer, while the posterior surface is composed of the same material as the outer posterior hydrogel layer.

[0090] As used in this application, the term "transition layer" in the context of a contact lens means a layer of polymeric material located between the inner layer (i.e., the lens bulk material) and one of the anterior and posterior outer hydrogel layers.

[0091] FIG. 1 schematically illustrates a contact lens of the present invention according to a preferred embodiment. In accordance with this preferred embodiment of the present invention, contact lens 100 has an anterior surface (i.e., front curve or convex surface) 101 and an opposing posterior surface (i.e., base curve or concave surface) 102 that rests on the cornea of the eye when worn by a user. Contact lens 100 includes a lens bulk material 110, an outer anterior hydrogel layer 120, and an outer posterior hydrogel layer 120. Lens bulk material 110 has a three-dimensional shape in close proximity to contact lens 100. The outer anterior and posterior hydrogel layers 120 are made of a substantially silicone-free (preferably completely silicone-free) hydrogel material that has a higher water content than that of inner layer 110. The anterior and posterior outer hydrogel layers 120 fuse together at the periphery 103 of contact lens 100, completely covering inner layer 110.

[0092] The present invention relates generally to a method for producing coated contact lenses, particularly coated SiHy contact lenses, in a cost-effective and time-efficient manner. The coated contact lenses produced by the methods of the present invention include a front surface, an opposite rear surface, and a layered configuration from the front surface to the rear surface, wherein the layered configuration includes an outer front hydrogel layer, an inner layer, and an outer rear hydrogel layer, the inner layer comprising a lens bulk material, and the outer front hydrogel layer and the outer rear hydrogel layer comprising monomer units of (a) at least one epoxy-containing vinyl monomer, (b) at least one amino-containing vinyl monomer having a primary or secondary amino group, (c) at least one polyethylene glycol-containing and (d) a hydrophilic copolymer comprising monomer units of at least one phosphorylcholine-containing vinyl monomer, wherein the sum of the amounts of components (a) and (b) in said at least one hydrophilic copolymer is about 40 mol % or less, and wherein the outer anterior hydrogel layer and the outer posterior hydrogel layer are covalently bonded onto the inner layer by bonds formed between one carboxylic acid group and one epoxy group, respectively, and the contact lens has a water-break time (WBUT) of at least 10 seconds.

[0093] The present invention is based, in part, on the discovery that coated contact lenses having a hydrogel coating thereon can be produced by autoclaving contact lens precursors having carboxylic acid groups thereon directly within a lens package containing the contact lens precursors immersed in a lens packaging solution comprising a hydrophilic copolymer comprising (a) epoxy-containing monomer units, (b) amino-containing monomer units, (c) phosphorylcholine-containing monomer units, and (d) polyethylene glycol-containing monomer units, wherein the total amount of components (a) and (b) in said at least one hydrophilic copolymer is about 40 mole % or less. Typically, contact lenses that are hydrated and packaged in a packaging solution must be sterilized. Sterilization of hydrated lenses during manufacture and packaging is typically accomplished by autoclaving. The autoclaving process involves heating the contact lens packaging to a temperature of about 118°C to about 125°C under pressure for at least 30 minutes. It is discovered that during autoclaving, a hydrogel coating can be formed on the contact lens precursor having carboxylic acid groups thereon so as to impart excellent lens surface hydrophilicity to the resulting coated contact lens.

[0094] It is believed that the amino and quaternary ammonium groups of the hydrophilic copolymer can enhance bonding of the hydrophilic copolymer to the surface of the contact lens precursor through hydrogen bonding and ionic interactions, while the epoxy groups of the hydrophilic copolymer can react with carboxylic acid groups on the surface of the contact lens precursor during autoclaving to form covalent bonds to covalently bond a layer of the hydrophilic copolymer to the contact lens precursor. It is also believed that inter- and intramolecular reactions occur between the epoxy and amino groups within and between the same molecule of the hydrophilic copolymer to form a hydrogel coating on the contact lens precursor during autoclaving. Due to the pendant hydrophilic polyethylene glycol chains and the pendant hydrophilic zwitterionic phosphorylcholine groups, the resulting hydrogel coating can provide excellent surface hydrophilicity to the resulting coated contact lens.

[0095] In one aspect, the present invention provides a method for producing a coated contact lens, comprising the steps of: (1) obtaining a contact lens precursor having a concave surface and an opposite convex surface, the contact lens precursor comprising a lens bulk material and carboxylic acid groups on and / or near the anterior and posterior surfaces; (2) immersing the contact lens precursor in a container with an aqueous solution containing from about 0.01% to about 5.0% by weight (preferably from about 0.05% to about 4%, more preferably from about 0.1% to about 3%, and even more preferably about 0.2%) of monomer units of (a) at least one epoxy-containing vinyl monomer, (b) at least one amino-containing vinyl monomer having a primary or secondary amino group, (c) at least one polyethylene glycol-containing vinyl monomer, and (d) at least one phosphorylcholine-containing vinyl monomer. and (3) heating the aqueous solution having the contact lens precursor therein at a temperature of from about 100° C. to about 140° C. for at least 30 minutes to form a coated contact lens having a hydrogel coating thereon, wherein the hydrogel coating is covalently bonded to the anterior and posterior surfaces by bonds formed between one carboxylic acid group and one epoxy group, respectively, and the hydrogel coating comprises a crosslinked polymeric material comprising polymer chains derived from the hydrophilic copolymer.

[0096] In another aspect, the present invention provides a contact lens, preferably a silicone hydrogel contact lens, comprising a front surface, an opposite rear surface, and a layered arrangement from the front surface to the rear surface, the layered arrangement comprising an outer front hydrogel layer, an inner layer, and an outer rear hydrogel layer, the inner layer comprising a lens bulk material and having carboxylic acid groups on and / or near its surface, the outer front hydrogel layer and the outer rear hydrogel layer comprising a hydrogel copolymer comprising: (a) at least one epoxy-containing vinyl monomer, (b) at least one amino-containing vinyl monomer having a primary or secondary amino group, (c) at least one polyethylene glycol-containing vinyl monomer, and (d) at least one phosphorylcholine-containing vinyl monomer. and a hydrophilic copolymer comprising a crosslinked polymeric material containing polymer chains derived from a hydrophilic polymer comprising monomer units of a carboxylic acid group (a) and a carboxylic acid group (b), wherein the total amount of components (a) and (b) in said at least one hydrophilic copolymer is about 40% or less by molar (preferably about 35% or less, more preferably about 30% or less, and even more preferably about 25% or less), wherein outer anterior and outer posterior hydrogel layers are covalently bonded onto an inner layer by bonds formed between one carboxylic acid group and one epoxy group, respectively, and wherein the contact lens has a water-break time (WBUT) of at least 10 seconds (preferably at least 12.5 seconds, more preferably 15 seconds, and even more preferably at least 17.5 seconds).

[0097] In accordance with all of the various aspects of the present invention, the contact lens precursor or inner layer of the present invention can be derived directly from a preformed contact lens. The preformed contact lens can be any contact lens that has not undergone any surface treatment after being manufactured according to any lens manufacturing process, any contact lens that has been plasma-treated or treated with chemical or physical surface modification, or any commercially available contact lens, so long as there is no hydrogel coating on the surface of the preformed contact lens. Those skilled in the art are very familiar with methods for manufacturing preformed contact lenses. For example, preformed contact lenses can be manufactured in a conventional "spin-casting mold," as described, for example, in U.S. Pat. No. 3,408,429, or by a fully cast molding process in a static form, as described in U.S. Pat. Nos. 4,347,198, 5,508,317, 5,583,463, 5,789,464, and 5,849,810, or by lathe cutting of a button of polymeric material, such as those used to manufacture customized contact lenses. In cast molding, a polymerizable composition (i.e., lens formulation) is typically dispensed into a mold and allowed to cure (i.e., polymerize and / or crosslink) within the mold to produce a contact lens.

[0098] Lens molds for producing contact lenses are well known to those skilled in the art and are used, for example, for cast molding or spin casting. For example, a mold (for cast molding) generally includes at least two mold sections (or portions) or mold halves, i.e., a first and a second mold half. The first mold half defines a first molding (or optical) surface, and the second mold half defines a second molding (or optical) surface. The first and second mold halves are configured to receive each other such that a lens-forming cavity is formed between the first and second molding surfaces. The molding surfaces of the mold halves are the cavity-forming surfaces of the mold and are in direct contact with the polymerizable composition.

[0099] Methods for manufacturing mold sections for cast molding contact lenses are generally well known to those skilled in the art. The method of the present invention is not limited to any particular method for forming a mold. In fact, any method for forming a mold can be used in the present invention. The first and second mold halves can be formed by a variety of techniques, such as injection molding or lathing. Examples of suitable processes for forming mold halves are disclosed in U.S. Patent Nos. 4,444,711, 4,460,534, 5,843,346, and 5,894,002.

[0100] Virtually any material known in the art for producing molds can be used to produce molds for producing contact lenses. For example, polymeric materials such as polyethylene, polypropylene, polystyrene, PMMA, Topas® COC Grade 8007-S10 (a transparent amorphous copolymer of ethylene and norbornene, manufactured by Ticona GmbH, Frankfurt, Germany and Summit, New Jersey) can be used. Other materials that allow UV light transmission, such as quartz glass and sapphire, could also be used.

[0101] In a preferred embodiment, a reusable mold is used and the lens-forming composition is actinically cured under the spatial confinement of actinic radiation to form a contact lens. Examples of preferred reusable molds are those disclosed in U.S. Patent Nos. 6,627,124, 6,800,225, 7,384,590, and 7,387,759. Reusable molds can be made from quartz, glass, sapphire, CaF2, cyclic olefin copolymers (e.g., Topas® COC grade 8007-S10 (a transparent amorphous copolymer of ethylene and norbornene) from Ticona GmbH of Frankfurt, Germany and Summit, New Jersey, and Zeonex® and Zeonor® from Zeon Chemicals LP, Louisville, KY), polymethyl methacrylate (PMMA), polyoxymethylene (Delrin) from DuPont, Ultem® (polyetherimide) from GEPlastics, PrimoSpire®, and the like.

[0102] In accordance with the present invention, the polymerizable composition can be introduced (dispensed) into the cavity formed by the mold by any known method.

[0103] After the polymerizable composition is dispensed into the mold, it is polymerized to produce the contact lens. Crosslinking can be initiated thermally or, preferably, actinically by exposing the polymerizable composition in the mold to spatially confined actinic radiation to crosslink the polymerizable components in the polymerizable composition.

[0104] Opening the mould so that the moulded article can be removed from the mould can be done in a manner known per se.

[0105] The molded contact lenses can be subjected to lens extraction to remove unpolymerized polymerizable components. The extraction solvent can be any solvent known to those skilled in the art. Examples of suitable extraction solvents are described below.

[0106] In a preferred embodiment, the preformed contact lens is a hard contact lens comprising a hard plastic material as the bulk material of the lens. Preferably, the hard plastic material is crosslinked polymethyl acrylate. Those skilled in the art are familiar with methods for producing hard plastic materials, such as crosslinked polymethyl methacrylate.

[0107] In another preferred embodiment, the preformed contact lens is a rigid gas permeable contact lens that includes a rigid gas permeable material as the lens bulk material. Those skilled in the art know how to make rigid gas permeable contact lenses.

[0108] In another preferred embodiment, the preformed contact lens is a hybrid contact lens and includes a lens bulk material consisting essentially of a central optic made of a gas permeable lens material and a peripheral portion made of a silicone hydrogel or conventional hydrogel lens material, extending outward from and surrounding the central optic.

[0109] In another preferred embodiment, the preformed contact lenses are non-silicone hydrogel contact lenses (ie, so-called conventional hydrogel contact lenses) that include a non-silicone hydrogel material as the lens bulk material.

[0110] Preformed non-silicone hydrogel contact lenses can be any commercially available non-silicone hydrogel contact lens or can be manufactured according to any known method. For example, with respect to the manufacture of preformed non-silicone hydrogel contact lenses, non-silicone hydrogel lens formulations for making rods for cast molding or spin casting or for use in lathe cutting of contact lenses typically contain (1) (a) at least one hydrophilic vinyl monomer (e.g., hydroxyethyl methacrylate, glycerol methacrylate, N-vinylpyrrolidone, or a combination thereof), and (b) a crosslinker, a hydrophobic vinyl monomer, a lubricant (or a so-called internal wetting agent incorporated into the lens formulation), a free radical initiator (photoinitiator or thermal initiator), a UV-absorbing vinyl monomer, a high-energy violet light ("HEVL")-absorbing vinyl monomer, a visible colorant (e.g., a reactive dye, (2) a monomer mixture comprising one or more water-soluble prepolymers and at least one component selected from the group consisting of a hydrophilic vinyl monomer, a crosslinker, a hydrophobic vinyl monomer, a lubricant (or a so-called internal wetting agent incorporated into the lens formulation), a free-radical initiator (photoinitiator or thermal initiator), a UV-absorbing vinyl monomer, an HEVL-absorbing vinyl monomer, a visible colorant (e.g., a reactive dye, a polymerizable dye, a pigment, or a mixture thereof), an antimicrobial agent (e.g., preferably silver nanoparticles), a bioactive agent, and combinations thereof. The resulting preformed hydrogel contact lens can then be subjected to extraction with an extraction solvent and hydration processes to remove unpolymerized components from the resulting lens, as known to those skilled in the art. It is understood that the presence of a lubricant in a hydrogel lens formulation can improve the lubricity of a preformed hydrogel contact lens compared to the lubricity of a control preformed hydrogel contact lens obtained from a control hydrogel lens formulation without the lubricant.

[0111] Preferred examples of water-soluble prepolymers include, without limitation: water-soluble cross-linkable poly(vinyl alcohol) prepolymers described in US Pat. Nos. 5,583,163 and 6,303,687.

[0112] Numerous non-silicone hydrogel lens formulations have been described in numerous patents and patent applications published as of the filing date of this application and have been used to produce commercially available non-silicone hydrogel contact lenses. Examples of commercially available non-silicone hydrogel contact lenses include, without limitation, alphafilcon A, acofilcon A, deltafilcon A, etafilcon A, focofilcon A, herfilcon A, herfilcon B, hylafilcon B, hyoxifilcon A, hyoxifilcon B, hyoxifilcon D, metafilcon A, metafilcon B, nelfilcon A, nesofilcon A, ocfilcon A, ocfilcon B, ocfilcon C, ocfilcon D, omafilcon A, femfilcon A, polymacon, sanfilcon A, terfilcon A, tetrafilcon A, and bifilcon A.

[0113] In a preferred embodiment, the lens bulk material is comprised of a non-silicone hydrogel material containing at least 50 mole percent repeat units of at least one hydroxyl-containing vinyl monomer, preferably selected from the group consisting of hydroxyethyl (meth)acrylate, glycerol (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-amino-2-hydroxypropyl (meth)acrylate, N-2-hydroxyethyl (meth)acrylamide, N-3-hydroxypropyl (meth)acrylamide, N-2-hydroxypropyl (meth)acrylamide, N-2,3-dihydroxypropyl (meth)acrylamide, N-tris(hydroxymethyl)methyl (meth)acrylamide, vinyl alcohol, allyl alcohol, and combinations thereof, more preferably selected from the group consisting of hydroxyethyl (meth)acrylate, glycerol (meth)acrylate, and vinyl alcohol. The mole percentage of repeat units can be calculated based on the non-silicone hydrogel lens formulation for producing the non-silicone hydrogel contact lens.

[0114] In another preferred embodiment, the preformed contact lens is a silicone hydrogel contact lens that includes a silicone hydrogel material as the lens bulk material.

[0115] The preformed silicone hydrogel contact lenses can be any commercially available silicone hydrogel contact lens or can be made according to any known method. For example, for the production of preformed silicone hydrogel (SiHy) contact lenses, SiHy lens formulations for making SiHy rods for casting or spin-casting or for use in lathe-cutting contact lenses generally include (1) at least one hydrophilic vinyl monomer (any one or more of those described later in this application), (2) at least one vinyl crosslinker (any one or more of those described later in this application) including at least one polysiloxane vinyl crosslinker and / or at least one non-silicone vinyl crosslinker (any one or more of those described later in this application), (3) at least one siloxane-containing vinyl monomer (any one or more of those described later in this application), (4) a free-radical initiator (photoinitiator or thermal initiator), and (5) at least one component selected from the group consisting of a hydrophobic non-silicone vinyl monomer (any one or more of those described later in this application), a UV-absorbing vinyl monomer, a UV / HEVL-absorbing vinyl monomer, a polymerizable visibility colorant (i.e., a polymerizable dye), and combinations thereof. The resulting preformed SiHy contact lens can then be subjected to extraction with an extraction solvent to remove unpolymerized components from the resulting lens, and to a hydration process, as known to those skilled in the art. Additionally, the preformed SiHy contact lens can be a colored contact lens (i.e., a SiHy contact lens having at least one colored pattern printed thereon, as is well known to those skilled in the art).

[0116] Any hydrophilic vinyl monomer can be used in the present invention. Examples of preferred hydrophilic vinyl monomers are alkyl(meth)acrylamides (as described later in this application), hydroxyl-containing acrylic monomers (as described below), amino-containing acrylic monomers (as described later in this application), carboxyl-containing acrylic monomers (as described later in this application), N-vinylamide monomers (as described later in this application), methylene-containing pyrrolidone monomers (i.e., pyrrolidone derivatives each having a methylene group attached to the pyrrolidone ring at the 3- or 5-position) (as described later in this application), acrylic monomers having C1-C4 alkoxyethoxy groups (as described later in this application), vinyl ether monomers (as described later in this application), allyl ether monomers (as described later in this application), phosphorylcholine-containing vinyl monomers (as described later in this application), N-2-hydroxyethyl vinyl carbamate, N-carboxyvinyl-β-alanine (VINAL), N-carboxyvinyl-α-alanine, and combinations thereof.

[0117] In accordance with the present invention, any non-silicone vinyl crosslinker may be within the scope of the present invention. Examples of preferred non-silicone vinyl crosslinkers are described later in this application.

[0118] In accordance with the present invention, any polysiloxane vinyl crosslinker can be used in the present invention. Examples of suitable polysiloxane vinyl crosslinkers include, without limitation, α,ω-(meth)acryloxy-terminated polydimethylsiloxanes of various molecular weights; α,ω-(meth)acrylamide-terminated polydimethylsiloxanes of various molecular weights; α,ω-vinyl carbonate-terminated polydimethylsiloxanes of various molecular weights; α,ω-vinyl carbamate-terminated polydimethylsiloxanes of various molecular weights; bis-3-methacryloxy-2-hydroxypropyloxypropyl polydimethylsiloxanes of various molecular weights; N,N,N',N' -tetrakis(3-methacryloxy-2-hydroxypropyl)-alpha,omega-bis-3-aminopropyl-polydimethylsiloxane; the reaction product of glycidyl methacrylate with an amino-functional polydimethylsiloxane; the reaction product of an azlactone-containing vinyl monomer (any one of the above) with a hydroxyl-functional polydimethylsiloxane; a polysiloxane-containing macromer selected from the group consisting of Macromer A, Macromer B, Macromer C, and Macromer D described in U.S. Pat. No. 5,760,100;U.S. Patent Nos. 4,136,250, 4,153,641, 4,182,822, 4,189,546, 4,259,467, 4,260,725, 4,261,875, 4,343,927, 4,254,248, 4,355,147, 4,276,402, 4,327,203, and 434,188 Specification No. 9, Specification No. 4486577, Specification No. 4543398, Specification No. 4605712, Specification No. 4661575, Specification No. 4684538, Specification No. 4703097, Specification No. 4833218, Specification No. 4837289, Specification No. 4954586, Specification No. 4954587, Specification No. 5010141, Specification No. 5034461, Specification No. 5070 Specification No. 170, Specification No. 5079319, Specification No. 5039761, Specification No. 5346946, Specification No. 5358995, Specification No. 5387632, Specification No. 5416132 5449729, 5451617, 5486579, 5962548, 5981675, 6039913, 67 Polysiloxane vinyl crosslinkers disclosed in US Pat. Nos. 62264, 7423074, 8163206, 8480227, 8529057, 8835525, 8993651, 9187601, 10081697, 10301451, and 10465047 are included;

[0119] One class of preferred polysiloxane vinyl crosslinkers comprises dimethylsiloxane units and one monovalent C4-C hydroxyl group with one methyl substituent and two to six hydroxyl groups. 40 and hydrophilized siloxane units each having an organic radical substituent, more preferably a polysiloxane vinyl crosslinker of formula (H), which can be prepared according to the procedures described later in this application and disclosed in U.S. Pat. No. 1,008,1697.

[0120] Another class of preferred polysiloxane vinyl crosslinkers are those vinyl crosslinkers each containing one unique polysiloxane segment and two terminal (meth)acryloyl groups, which can be obtained from commercial sources; can be prepared by reacting glycidyl (meth)acrylate (meth)acryloyl chloride with a diamino-terminated polydimethylsiloxane or a dihydroxyl-terminated polydimethylsiloxane; can be prepared by reacting isocyanatoethyl (meth)acrylate with a dihydroxyl-terminated polydimethylsiloxane; can be prepared by reacting an amino-containing acrylic monomer with a dicarboxyl-terminated polydimethylsiloxane in the presence of a coupling agent (carbodiimide); can be prepared by reacting a carboxyl-containing acrylic monomer with a diamino-terminated polydimethylsiloxane in the presence of a coupling agent (carbodiimide); or can be prepared by reacting a hydroxyl-containing acrylic monomer with a dihydroxyl-terminated polydisiloxane in the presence of a diisocyanate or diepoxy coupling agent.

[0121] Another class of preferred polysiloxane vinyl crosslinkers are chain-extended polysiloxane vinyl crosslinkers, each of which has at least two polysiloxane segments joined by a linker between each pair of polysiloxane segments and two terminal ethylenically unsaturated groups; which can be prepared according to the procedures described in U.S. Pat. Nos. 5,034,461, 5,416,132, 5,449,729, 5,760,100, 7,423,074, 8,529,057, 8,835,525, 8,993,651, 9,187,601, 10,301,451, and 10,465,047.

[0122] Any siloxane-containing vinyl monomer can be used in the present invention. Examples of preferred siloxane-containing vinyl monomers include siloxane-containing (meth)acrylamide monomers, siloxane-containing (meth)acryloxy monomers, siloxane-containing vinyloxycarbonyloxy monomers, siloxane-containing vinyloxycarbonylamino monomers, siloxane-containing vinylaminocarbonylamino monomers, or siloxane-containing vinylaminocarbonyloxy monomers, each of which comprises a bis(trialkylsilyloxy)alkylsilyl group, a tris(trialkylsilyloxy)silyl group, or a polysiloxane chain having 2 to 30 siloxane units and terminated with an alkyl, hydroxyalkyl, or methoxyalkyl group. Such preferred siloxane-containing vinyl monomers are available from commercial sources or, alternatively, can be prepared according to known procedures similar to those described in, for example, U.S. Pat. Nos. 5,070,215, 6,166,236, 6,867,245, 7,214,809, 8,415,405, 8,475,529, 8,614,261, 8,658,748, 9,097,840, 9,103,965, 9,217,813, 9,315,669, and 9,475,827. or can be prepared by reacting a vinyl monomer having a reactive functional group (e.g., an acid chloride, anhydride, carboxyl, hydroxyl, amino, epoxy, isocyanate, aziridine, azlactone, or aldehyde group) with a siloxane-containing compound having a reactive group selected from the group consisting of hydroxyalkyl, aminoalkyl, alkylaminoalkyl, carboxyalkyl, isocyanatoalkyl, epoxyalkyl, and aziridinylalkyl, under coupling reaction conditions well known to those skilled in the art, in the presence or absence of a coupling agent.

[0123] Any thermal polymerization initiator can be used in the present invention. Suitable thermal polymerization initiators are known to those skilled in the art and include, for example, peroxides, hydroperoxides, azo-bis(alkyl- or cycloalkylnitriles), persulfates, percarbonates, or mixtures thereof.Examples of suitable thermal polymerization initiators include, without limitation, benzoyl peroxide, t-butyl peroxide, t-amyl peroxybenzoate, 2,2-bis(tert-butylperoxy)butane, 1,1-bis(tert-butylperoxy)cyclohexane, 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane, 2,5-bis(tert-butylperoxy)-2,5-dimethyl-3-hexyne, bis(1-(tert-butylperoxy)-1-methylethyl)benzyl, 2,2-bis(tert-butylperoxy)butane, 1,1-bis(tert-butylperoxy)cyclo ...2,2-bis(tert-butylperoxy)butane, 2,2-bis(tert-butylperoxy)butane, 2,2-bis(tert-butylperoxy)butane, 2,2-bis(tert-butylperoxy)butane, 2,2-bis(tert-butylperoxy)butane, 2,2-bis(tert-butylperoxy)butane Benzene, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, di-t-butyl-diperoxyphthalate, t-butyl hydroperoxide, t-butyl peracetate, t-butyl peroxybenzoate, t-butyl peroxyisopropyl carbonate, acetyl peroxide, lauroyl peroxide, decanoyl peroxide, dicetyl peroxydicarbonate, di(4-t-butylcyclohexyl) peroxydicarbonate (Perkadox 16S), di(2-ethylhexyl) peroxydicarbonate, t-butyl peroxypivalate (Lupersol 11); t-butyl peroxy-2-ethylhexanoate (Trigonox 21-C50), 2,4-pentanedione peroxide, dicumyl peroxide, peracetic acid, potassium persulfate, sodium persulfate, ammonium persulfate, 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile) (VAZO 33), 2,2'-azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride (VAZO 44), 2,2'-azobis(2-amidinopropane) dihydrochloride (VAZO 50), 2,2'-azobis(2,4-dimethylvaleronitrile) (VAZO 52), 2,2'-azobis(isobutyronitrile) (VAZO 64 or AIBN), 2,2'-azobis-2-methylbutyronitrile (VAZO 67), 1,1-azobis(1-cyclohexanecarbonitrile) (VAZO 88); 2,2'-azobis(2-cyclopropylpropionitrile), 2,2'-azobis(methyl isobutyrate), 4,4'-azobis(4-cyanovaleric acid), and combinations thereof.Preferably, the thermal initiator is 2,2'-azobis(isobutyronitrile) (AIBN or VAZO 64).

[0124] Suitable photoinitiators are benzoin methyl ether, diethoxyacetophenone, benzoylphosphine oxide, 1-hydroxycyclohexylphenyl ketone, and Darocur and Irgacur types, preferably Darocur 1173® and Darocur 2959®, germanium-based Norrish Type I photoinitiators (e.g., those described in U.S. Pat. No. 7,605,190). Examples of benzoylphosphine initiators include 2,4,6-trimethylbenzoyldiphenylphosphine oxide; bis-(2,6-dichlorobenzoyl)-4-N-propylphenyl-phosphine oxide; and bis-(2,6-dichlorobenzoyl)-4-N-butylphenylphosphine oxide.

[0125] Any hydrophobic non-silicone vinyl monomer can be used in the present invention. Examples of preferred hydrophobic non-silicone vinyl monomers include C1-C 10 Examples of the alkyl (meth)acrylate include alkyl (meth)acrylates (e.g., methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, etc.), cyclohexyl (meth)acrylate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl valerate, styrene, chloroprene, vinyl chloride, vinylidene chloride, (meth)acrylonitrile, 1-butene, butadiene, vinyl toluene, vinyl ethyl ether, perfluorohexylethyl-thio-carbonyl-aminoethyl-methacrylate, isobornyl (meth)acrylate, trifluoroethyl (meth)acrylate, hexafluoroisopropyl (meth)acrylate, hexafluorobutyl (meth)acrylate, and combinations thereof.

[0126] Examples of preferred polymerizable dyes include, without limitation, 1,4-bis(4-(2-methacryloxyethyl)phenylamino)anthraquinone (Reactive Blue 246), 1,4-bis((2-hydroxyethyl)amino)-9,10-anthracenedione-bis(2-propenoic acid) ester (Reactive Blue 247).

[0127] Preferred examples of UV-absorbing vinyl monomers of formula (1) include, without limitation, 2-(2'-hydroxy-5'-vinylphenyl)-2H-benzotriazole, 2-(2'-hydroxy-5'-methacryloxyphenyl)-2H-benzotriazole, 2-(2'-hydroxy-5'-acryloyloxyphenyl)-2H-benzotriazole, 2-[2'-hydroxy-5'-(2-methacryloxyethyl)phenyl)]-2H-benzotriazole (Norbloc), 2-[2'-hydroxy-5'-(2-acryloxyethyl)-phenyl)]-2H-benzotriazole, 2-(2'-hydroxy-5'-methacryloxypropylphenyl)-2H-benzotriazole, 2-(2'-hydroxy-5'-acryloxypropylphenyl)-2H-benzotriazole.

[0128] Benzotriazole-containing UV-absorbing vinyl monomers can be prepared according to the procedures described in U.S. Pat. Nos. 3,299,173, 4,612,358, 4,716,234, 4,528,311, and 10,254,567, or can be obtained from commercial sources. Examples of preferred UV / HEVL absorbing vinyl monomers of formula (2) include, without limitation: 2-(2'-hydroxy-3'-methacrylamidomethyl-5'-tert-octylphenyl)-2H-benzotriazole, 2-(2'-hydroxy-5'-methacrylamidophenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-5'-methacrylamidophenyl)-5-methoxybenzotriazole, 2-(2'-hydroxy-5'-methacryloxypropyl-3'-t-butyl-phenyl)-5-chlorobenzotriazole, 2-hydroxy-5-methoxy-3-(5-(trifluoromethyl)-2H-benzo[d][1,2,3]triazol-2-yl)benzyl methacrylate (WL-1), 2-hydroxy-5-methoxy-3-(5-methoxy-2H-benzo[d][1,2,3]triazol-2-yl)benzyl methacrylate (WL-2), WL-5), 3-(5-fluoro-2H-benzo[d][1,2,3]triazol-2-yl)-2-hydroxy-5-methoxybenzyl methacrylate (WL-2), 3-(2H-benzo[d][1,2,3]triazol-2-yl)-2-hydroxy-5-methoxybenzyl methacrylate (WL-3), 3-(5-chloro-2H-benzo[d][1,2,3]triazol-2-yl)-2-hydroxy-5-methoxy Benzyl methacrylate (WL-4), 2-hydroxy-5-methoxy-3-(5-methyl-2H-benzo[d][1,2,3]triazol-2-yl)benzyl methacrylate (WL-6), 2-hydroxy-5-methyl-3-(5-(trifluoromethyl)-2H-benzo[d][1,2,3]triazol-2-yl)benzyl methacrylate (WL-7), 4-allyl-2-(5-chloro-2H-benzo[d][1,2,3]triazol-2-yl)-6-methoxyphenol (WL-8), 2-{2'-hydroxy-3'-tert-butyl-5'-[3"-(4"-vinylbenzyloxy)propoxy]phenyl}-5-methoxy-2H-benzotriazole, 2-(5-chloro-2H-benzotriazol-2-yl)-6-(1,1-dimethylethyl)-4-ethenyl-phenol (UVAM), 2-{2'-hydroxy-3'-tert-butyl-5'-[3'-methacryloyloxypropoxy]phenyl}-2H-benzotriazole, 2-{2'-hydroxy-3'-tert-butyl-5'-[3'-methacryloyloxypropoxy]phenyl}-2H-benzotriazole 2-{2'-hydroxy-3'-tert-butyl-5'-[3'-methacryloyloxypropoxy]phenyl}-5-methoxy-2H-benzotriazole (UV13), 2-{2'-hydroxy-3'-tert-butyl-5'-[3'-methacryloyloxypropoxy]phenyl}-5-chloro-2H-benzotriazole (UV28), 2-[2'-hydroxy-3'-tert-butyl-5'-(3'-acryloyloxypropoxy)phenyl]-5-trifluoromethyl-2H-benzotriazole (UV23), 2-(2'-hydroxy-5- Methacrylamidophenyl)-5-methoxybenzotriazole (UV6), 2-(3-allyl-2-hydroxy-5-methylphenyl)-2H-benzotriazole (UV9), 2-(2-hydroxy-3-methallyl-5-methylphenyl)-2H-benzotriazole (UV12), 2-[3'-t-butyl-2'-hydroxy-5'-(3"-dimethylvinylsilylpropoxy)-2'-hydroxy-phenyl)]-5-methoxybenzotriazole (UV15), 2-(2'-hydroxy-5'-methacryloylpropyl-3'-tert- butyl-phenyl)-5-methoxy-2H-benzotriazole (UV16), 2-(2'-hydroxy-5'-acryloylpropyl-3'-tert-butyl-phenyl)-5-methoxy-2H-benzotriazole (UV16A), 2-methylacrylic acid 3-[3-tert-butyl-5-(5-chlorobenzotriazol-2-yl)-4-hydroxyphenyl]-propyl ester (16-100, CAS#96478-15-8), 2-(3-(tert-butyl)-4-hydroxy-5-(5-methoxy-2H-benzo[d][1,2,3]triazol-2-yl)phenoxy)ethyl methacrylate (16-102); 2-(5-chloro-2H-benzotriazol-2-yl)-6-methoxy-4-(2-propen-1-yl)-phenol (CAS#1260141-20-5); 2-[2-hydroxy-5-[3-(methacryloyloxy)propyl]-3-tert-butylphenyl]-5-chloro-2H-benzotriazole; and those benzotriazole-containing vinyl monomers disclosed in U.S. Pat. No. 10,254,567.

[0129] The SiHy contact lens formulation may also include other necessary ingredients known to those skilled in the art, such as, for example, antimicrobial agents (e.g., preferably silver nanoparticles), bioactive agents, elutable lubricants (e.g., non-polymeric hydrophilic polymers, etc.), elutable tear stabilizers (e.g., phospholipids, monoglycerides, diglycerides, triglycerides, glycolipids, glyceroglycolipids, sphingolipids, sphingo-glycolipids, etc.), and mixtures thereof, as known to those skilled in the art.

[0130] The polymerizable composition (SiHy lens formulation), as known to those skilled in the art, can be a solvent-free clear liquid prepared by mixing all of the polymerizable components and other required ingredients, or a solution prepared by dissolving all of the desired components in any suitable solvent, such as a mixture of water and one or more organic solvents miscible with water, an organic solvent, or a mixture of one or more organic solvents. The term "solvent" refers to a chemical that cannot participate in a free-radical polymerization reaction.

[0131] Solvent-free SiHy lens formulations typically include at least one blending vinyl monomer as a reactive solvent to dissolve all other polymerizable components of the solvent-free SiHy lens formulation. Examples of preferred blending vinyl monomers are described later in this application. Preferably, methyl methacrylate is used as the blending vinyl monomer in preparing the solvent-free SiHy lens formulation.

[0132] Any solvent can be used in the present invention. Examples of preferred organic solvents include, but are not limited to, tetrahydrofuran, tripropylene glycol methyl ether, dipropylene glycol methyl ether, ethylene glycol n-butyl ether, ketones (e.g., acetone, methyl ethyl ketone, etc.), diethylene glycol n-butyl ether, diethylene glycol methyl ether, ethylene glycol phenyl ether, propylene glycol methyl ether, propylene glycol methyl ether acetate, dipropylene glycol methyl ether acetate, propylene glycol n-propyl ether, dipropylene glycol n-propyl ether, tripropylene glycol n-butyl ether, propylene glycol n-butyl ether, dipropylene glycol n-butyl ether, tripropylene glycol n-butyl ether, ... phenyl ether, dipropylene glycol dimethyl ether, polyethylene glycol, polypropylene glycol, ethyl acetate, butyl acetate, amyl acetate, methyl lactate, ethyl lactate, i-propyl lactate, methylene chloride, 2-butanol, 1-propanol, 2-propanol, menthol, cyclohexanol, cyclopentanol and exonorborneol, 2-pentanol, 3-pentanol, 2-hexanol, 3-hexanol, 3-methyl-2-butanol, 2-heptanol, 2-octanol, 2-nonanol, 2-decanol, 3-octanol, norborneol, tert-butanol, tert-amyl alcohol, 2-methyl-2-pentanol, 2,3-dimethyl-2-butanol, 3-methyl-3-pentanol, 1-methylcyclohexanol, 2-methyl-2-hexanol, 3,7-Dimethyl-3-octanol, 1-chloro-2-methyl-2-propanol, 2-methyl-2-heptanol, 2-methyl-2-octanol, 2-2-methyl-2-nonanol, 2-methyl-2-decanol, 3-methyl-3-hexanol, 3-methyl-3-heptanol, 4-methyl-4-heptanol, 3-methyl-3-octanol, 4-methyl-4-octanol, 3-methyl-3-nonanol, 4-methyl-4-nonanol, 3-methyl-3-octanol, 3-ethyl-3-hexanol, 3-methyl-3-heptanol, 4-ethyl-4-heptanol, 4-propyl-4-heptanol, 4-isopropyl-4-heptanol, 2,4-dimethyl-2-pentanol, 1-methylcyclopentanol Examples of suitable solvents include ethanol, 1-ethylcyclopentanol, 1-ethylcyclopentanol, 3-hydroxy-3-methyl-1-butene, 4-hydroxy-4-methyl-1-cyclopentanol, 2-phenyl-2-propanol, 2-methoxy-2-methyl-2-propanol, 2,3,4-trimethyl-3-pentanol, 3,7-dimethyl-3-octanol, 2-phenyl-2-butanol, 2-methyl-1-phenyl-2-propanol, and 3-ethyl-3-pentanol, 1-ethoxy-2-propanol, 1-methyl-2-pyrrolidone, N,N-dimethylpropionamide, dimethylformamide, dimethylacetamide, dimethylpropionamide, N-methylpyrrolidinone, and mixtures thereof.

[0133] Numerous SiHy lens formulations have been described in numerous patents and patent applications published as of the filing date of this application and have been used in producing commercially available SiHy contact lenses. Examples of commercially available SiHy contact lenses include, without limitation, asmofilcon A, balafilcon A, confilcon A, derefilcon A, eflofilcon A, enfilcon A, funfilcon A, galyfilcon A, lotrafilcon A, lotrafilcon B, narafilcon A, narafilcon B, senofilcon A, senofilcon B, senofilcon C, sumafilcon A, somofilcon A, and stenfilcon A.

[0134] The SiHy lens formulation (i.e., polymerizable composition) can be cured (polymerized) thermally or actinically as known to those skilled in the art, preferably in a mold for casting contact lenses.

[0135] Thermal polymerization is conveniently carried out at temperatures of, for example, 25 to 120°C, preferably 40 to 100°C. The reaction time may vary within wide limits but is conveniently, for example, 1 to 24 hours, or preferably 2 to 12 hours. It is advantageous to previously degas the components and solvents used in the polymerization reaction and to carry out the copolymerization reaction under an inert atmosphere, for example under a nitrogen or argon atmosphere.

[0136] The actinic polymerization can then be induced by actinic radiation, such as light, in particular UV or visible light of a suitable wavelength, the spectral requirements of which can be suitably controlled, if appropriate, by the addition of suitable photosensitizers.

[0137] In accordance with the present invention, the silicone hydrogel material used as the bulk lens material has an oxygen permeability of about 50 barrers (preferably about 60, more preferably about 70, even more preferably about 90 barrers, and most preferably at least about 100 barrers) to about 180 barrers. The silicone hydrogel material may also have an equilibrium water content of about 10% (preferably about 20%, more preferably about 30%; even more preferably about 40%) to about 80% by weight. The silicone hydrogel material may further have a bulk modulus (i.e., bulk Young's modulus) of about 0.3 MPa to about 1.8 MPa, preferably 0.4 MPa to about 1.5 MPa, and more preferably about 0.4 MPa to about 1.2 MPa. The oxygen permeability, modulus, and water content of the silicone hydrogel material of the present contact lenses can be determined by measuring the oxygen permeability, modulus, and water content of a preformed contact lens. Those skilled in the art are familiar with methods for determining the modulus and equilibrium water content of silicone hydrogel materials or SiHy contact lenses. For example, all commercially available SiHy contact lenses have reported values for oxygen permeability, modulus, and water content.

[0138] The preformed contact lenses of the present invention can be obtained according to any method known to or to be developed by those skilled in the art.

[0139] In accordance with the present invention, a contact lens precursor is a preformed contact lens that either inherently contains carboxylic acid groups on and / or near its surface or has been subjected to at least one post-cure surface treatment to have carboxylic acid groups.

[0140] When a preformed contact lens inherently contains carboxylic acid groups on and / or near its surface, the contact lens precursor is comprised of a lens bulk material obtained by polymerizing a polymerizable composition (i.e., a non-silicone hydrogel lens formulation or a silicone hydrogel lens formulation) containing a vinyl monomer that further contains at least one carboxylic acid group. Examples of carboxyl-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 from about 0.1% to about 10%, preferably from about 0.25% to about 7%, more preferably from about 0.5% to about 5%, and even more preferably from about 0.75% to about 3%, by weight of such carboxyl-containing vinyl monomers.

[0141] The preformed contact lens can also be subjected to any surface treatment to have carboxylic acid groups on and / or near its surface. Any suitable surface treatment can be used in the present invention. Examples of surface treatments include, without limitation, plasma treatment; chemical treatment; chemical vapor deposition; grafting (covalent bonding) of a compound having at least one reactive functional group onto the surface (modified or unmodified) of the article; graft polymerization of a carboxyl-containing vinyl monomer onto the surface (modified or unmodified) of the article; layer-by-layer ("LbL") deposition of one or more polyanionic polymers (having carboxylic acid groups) onto the surface (modified or unmodified) of the preformed contact lens (i.e., the process of forming an LbL coating); covalent bonding of one or more polyanionic polymers (having carboxylic acid groups) onto the surface (modified or unmodified) of the preformed contact lens; or combinations thereof.

[0142] Plasma treatment refers to a process in which contact lenses are exposed to plasma to chemically modify their surfaces. The term "plasma" refers to an ionized gas (e.g., produced by an electrical glow discharge, which may consist of electrons, ions of either polarity, gas atoms and molecules in their ground state or any higher state of any form of excitation, and photons). The excited species interact with the solid surface of an article placed in the plasma, resulting in chemical and physical modification of the material surface. When the plasma is generated by subjecting a gas to an electric charge, typically at radio frequency (rf) (or microwave or other frequencies), in a vacuum chamber, it is often referred to as a "low-temperature plasma." When the plasma is generated by an atmospheric discharge (e.g., an arc discharge) and sustained at ambient atmospheric pressure, it is a "high-temperature plasma" or "atmospheric plasma."

[0143] For reviews of plasma treatment and its uses, see R. Hartmann, "Plasma polymerisation: Grundlagen, Technik und Anwendung," Jahrb. Oberflaechentechnik (1993) 49, pp. 283-296, Battelle-Inst. eV Frankfurt / Main Germany; H. Yasuda, "Glow Discharge Polymerisation," Journal of Polymer Science: Macromolecular Reviews, vol. 16 (1981), pp. 199-293; H. Yasuda, "Plasma Polymerisation," Academic Press, Inc. (1985); Frank Jansen, "Plasma Deposition Processes," in "Plasma Deposited Thin Films," ed. by T. Mort and F. Jansen, CRC Press Boca Raton (1994); O. Auciello et al. (ed.), "Plasma-Surface Interactions and Processing of Materials," publ. by Kluwer Academic Publishers in NATO ASI Series; Series E: Applied Sciences, vol. 176 (1990), pp. 377-399; and N. Dilsiz and G. Akovali, "Plasma Polymerization of Selected Organic Compounds," Polymer, vol. 37 (1996), pp. 333-341.

[0144] Known plasma treatments under low pressure include plasma deposition, plasma-induced polymerization, plasma grafting, plasma oxidation, etc. Plasma treatment under low pressure has been used in commercial products such as Focus NIGHT & DAY® and AIR OPTIX® (Alcon), and PUREVISION® (Bausch & Lomb). Advantages of plasma coatings, such as those found on Focus NIGHT & DAY®, are their durability, relatively high hydrophilicity / wettability, and low susceptibility to lipid and protein deposition and adsorption. Examples of plasma treatments are those disclosed in U.S. Pat. Nos. 4,143,949; 4,312,575; 5,464,667; 6,881,269; and 7,078,074. It is understood that preformed contact lenses typically must be dried before plasma treatment under low pressure.

[0145] Those skilled in the art are well aware that a plasma (i.e., an electric glow discharge plasma) is a partially ionized gas consisting of a high concentration of excited atomic, molecular, ionic, and free radical species and is produced by subjecting the gas in a vacuum chamber to an electric field, typically at radio frequency (rf) (or at microwave or other frequencies).

[0146] In an illustrative example of low-pressure plasma treatment of silicone hydrogel contact lenses, one or more preformed silicone hydrogel contact lenses are placed in a reactor chamber between opposing electrodes. The chamber is then sealed and depressurized by a vacuum system. A significant amount of time is required to pump the system up to operating pressure. When a suitable pressure is achieved within the chamber, a process gas is introduced into the chamber interior and the electrodes are activated. The resulting plasma cloud may apply a thin layer of polymer (or polymer coating) to the lens and / or alter the chemical composition of the top layer of the lens surface, depending on the process gas used. After a suitable time, the electrodes are turned off and the reactor chamber is returned to atmospheric pressure so that the lens can be removed.

[0147] Low-pressure plasma processing systems are known to those skilled in the art and are disclosed in patents and papers. For example, Peng Ho and Yasuda, in their paper (Journal of Biomedical Materials Research, Vol. 22, 919-937 (1988)), describe a batch-type low-pressure plasma processing system (or rotary plasma system) including a bell-shaped vacuum chamber in which opposing aluminum electrodes are arranged and a rotatable aluminum plate is positioned between the electrodes and driven by an induction motor within the system. Matsuzawa and Winterton disclose a linear low-pressure plasma system in U.S. Patent No. 6,881,269.

[0148] In accordance with the present invention, a dry, preformed contact lens is treated with a low pressure plasma generated in a plasma gas (i.e., atmosphere) comprising air, N, O, CO, or a C1-C6 hydrocarbon and air, N, O, CO, or a combination thereof (preferably a mixture of CO or a C1-C4 hydrocarbon and a secondary gas selected from the group consisting of air, CO, N, and combinations thereof, more preferably a mixture of CO or methane and a secondary gas selected from the group consisting of air, CO, N, and combinations thereof, even more preferably a mixture of CO or methane and CO).

[0149] The atmospheric plasma surface treatment disclosed in US Patent No. 9,156,213 is preferably used in the present invention. For atmospheric plasma surface treatment, the contact lens can be in a fully hydrated state.

[0150] Those skilled in the art are familiar with how to graft (covalently bond) compounds having at least one carboxylic acid group onto the surface of a contact lens according to known coupling reactions.

[0151] As used herein, "LbL coating" refers to a coating that is not covalently bonded to the polymer matrix of a contact lens and is obtained by layer-by-layer ("LbL") deposition of one or more polymeric materials onto the lens. LbL coatings can be composed of one or more layers. LbL coatings on contact lenses can be obtained according to the methods described in U.S. Patent Nos. 6,451,871, 6,719,929, 6,793,973, 6,811,805, 6,896,926, 8,044,112, 8,158,192, and 8,147,897. Preferably, the LbL coating comprises at least one layer of one or more polyanionic polymers, each containing carboxylic acid groups. The polyanionic polymer is preferably a polyanionic polymer selected from the group consisting of polyacrylic acid, polymethacrylic acid, polyethylacrylic acid, poly(acrylic acid-co-methacrylic acid), poly(acrylic acid-co-ethacrylic acid), poly(methacrylic acid-co-ethacrylic acid), and mixtures thereof, and more preferably a polyanionic polymer that is polyacrylic acid, polymethacrylic acid, poly(acrylic acid-co-methacrylic acid), or a mixture thereof.

[0152] An LbL coating of a polyanionic polymer having carboxylic acid groups can be formed on a contact lens by contacting the contact lens with a solution of the polymer. Contact between the contact lens and the polymer coating solution can occur by immersing the contact lens in the coating solution or by spraying the coating solution onto the contact lens. One contacting process involves simply immersing the contact lens in a bath of the coating solution for a period of time, or alternatively, sequentially immersing the contact lens in a series of baths of the coating solution for a shorter, fixed period of time for each bath. Another contacting process involves only spraying the coating solution. However, numerous alternatives, including various combinations of spraying and immersion steps, can be designed by one skilled in the art. The contact time between the contact lens and the reactive polymer coating solution can last up to about 10 minutes, preferably about 5 to about 360 seconds, more preferably about 5 to about 250 seconds, and even more preferably about 5 to about 200 seconds.

[0153] A solution of polyanionic polymer for forming a coating on a contact lens can be prepared by dissolving one or more polymers in water, a mixture of water and a water-miscible organic solvent, an organic solvent, or a mixture of one or more organic solvents. Preferably, the polymer is dissolved in a mixture of water and one or more organic solvents, an organic solvent, or a mixture of one or more organic solvents. A solvent system containing at least one organic solvent is believed to swell the contact lens so that a portion of the polyanionic polymer penetrates into the contact lens and enhances the durability of the coating. Examples of organic solvents are described above. The pH of the polyanionic polymer solution is preferably about 1.5 to about 4.0 to form a relatively thick, stable layer-by-layer coating. The temperature of the coating solution is preferably about 20°C to about 70°C.

[0154] Those skilled in the art know how to covalently bond one or more polymers having carboxylic acid groups to the surface of a contact lens. Exemplary methods for covalently bonding one or more hydrophilic polymers to a medical device are described in U.S. Patent Nos. 5,599,576, 5,766,158, 6,087,415, 6,096,726, 6,340,465, 6,440,571, 6,500,481, 6,534,559, 6,623,747, 6,66 Nos. 83062, 6838491, 6866936, 6923978, and 8529057, and in U.S. Patent Application Publication Nos. 2009-0145086A1, 2009-0145091A1, 2008-0142038A1, and 2007-0122540A1.

[0155] The graft polymerization of one or more vinyl monomers having at least one carboxylic acid group, in the presence or absence of a vinyl crosslinker, to form a hydrophilic polymer coating is described in numerous patents, such as U.S. Pat. Nos. 6,099,122, 6,436,481, 6,440,571, 6,447,920, 6,465,056, 6,521,352, 6,586,038, 6,730,366, 6,734,321, 6,835,410, and 6,878,399, and in Japanese Patent Application Laid-Open Publication No. 2001,075,060. For example, a dry, preformed contact lens is first subjected to plasma treatment in a plasma atmosphere with a compound having at least one reactive carboxylic acid group to form a plasma coating having carboxylic acid 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, with or without a coupling agent. The resulting contact lens having the free radical initiator moiety thereon is immersed in a solution of one or more vinyl monomers having at least one carboxylic acid group and subjected to conditions to initiate free radical polymerization of those vinyl monomers to form a polymeric layer from the grafts containing the carboxylic acid group.

[0156] In a preferred embodiment, the contact lens precursor comprises a lens bulk material and at least one polymeric material having carboxylic acid groups thereon. It is understood that the layer of at least one polymeric material having carboxylic acid groups can be directly covalently bonded to the polymer matrix of the lens bulk material or non-covalently associated with the lens bulk material. Preferably, the at least one polymeric material having carboxylic acid groups comprises polyacrylic acid, polymethacrylic acid, polyethylacrylic acid, poly(acrylic acid-co-methacrylic acid), poly(acrylic acid-co-ethacrylic acid), poly(methacrylic acid-co-ethacrylic acid), or mixtures thereof.

[0157] According to the present invention, the at least one hydrophilic copolymer is (a) preferably of the formula [ka] (b) monomer units of at least one epoxy-containing vinyl monomer, preferably of the formula [ka] (c) monomer units of at least one amino-containing acrylic monomer, preferably of the formula [ka] and (d) monomer units of at least one polyethylene glycol-containing acrylic monomer, preferably of the formula [ka] wherein: each R0, independently of one another, is H or CH3; each R0', independently of one another, is H or C1-C4 alkyl; B1, B2, and B3, independently of one another, are O or NR'; R' is H or C1-C4 alkyl; and D1, D2, and D3, independently of one another, are C1-C4 alkyl. 12is an alkylene divalent radical; D0 is a C1-C 12 an alkylene divalent radical or a divalent radical of the formula -D4-O-D5-B4-CH2-; B4 is -O- or [ka] and D4 is C1~C 12 an alkylene divalent radical; D5 is a C2-C6 alkylene divalent radical or [ka] D6 and D7, independently of each other, are C2-C6 alkylene divalent radicals; d1 is zero, 1 or 2; PEG is [ka] (wherein R″ is H or C1-C4 alkyl); t2 is an integer from 3 to 100; PC is [ka] (where t1 is an integer between 1 and 5, and 1 R, 2 R and 3 R is a zwitterionic group of C1-C8 alkyl or C1-C8 hydroxyalkyl.

[0158] In a preferred embodiment, the at least one hydrophilic copolymer has the formula (I): [ka] wherein T' and T'' independently of one another are H or a terminal group; each R0 independently of one another is H or CH3; each R0' independently of one another is H or C1-C4 alkyl; B1, B2 and B3 independently of one another are O or NR'; R' is H or C1-C4 alkyl; and D1, D2 and D3 independently of one another are C1-C4 alkyl. 12 is an alkylene divalent radical; D0 is a C1-C 12 an alkylene divalent radical or a divalent radical of the formula -D4-O-D5-B4-CH2-; B4 is -O- or [ka] and D4 is C1~C 12 an alkylene divalent radical; D5 is a C2-C6 alkylene divalent radical or [ka] D6 and D7, independently of each other, are C2-C6 alkylene divalent radicals; d1 is zero, 1 or 2; PEG is [ka] (wherein R″ is H or C1-C4 alkyl; t2 is an integer from 3 to 100); PC is a polyethylene glycol group of the formula: [ka] (wherein t1 is an integer of 1 to 5, and 1 R, 2 R and 3 R is a C1-C8 alkyl or a C1-C8 hydroxyalkyl; and a, b, c, and d, independently of one another, are integers from 5 to 100, where (a+c) / (a+b+c+d)≦0.40 (preferably ≦0.35, more preferably ≦0.30, and even more preferably ≦0.25), which is a zwitterionic group. Preferably, a / c is 10 to 0.1 (preferably 5 to 0.2, more preferably 2.5 to 0.4, and even more preferably 2 to 0.5).

[0159] Any epoxy-containing vinyl monomer can be used in the present invention. Examples of epoxy-containing vinyl monomers include, but are not limited to, 3,4-epoxy-1-butene, 1,2-epoxy-5-hexene, 2-methyl-2-vinyloxirane, glycidyl vinyl ether, glycidyl vinyloxyethyl ether, 2-(ethenoxymethyl)-3-methyloxirane, 2-(1-ethenoxypropan-2-yloxymethyl)oxirane, 2-[2-[2-(vinyloxy)ethoxy]ethoxymethyl]oxirane, 2-[2-[2-[2-(vinyloxy)ethoxy]ethoxy]ethoxymethyl]oxirane, 2-[2-[2-[2-[2-(vinyloxy)ethoxy]ethoxy]ethoxy]ethoxymethyl]oxirane, 2-(3-ethenoxypropoxy-methyl)oxirane, allyl glycidyl ether, 2-[ 2-(allyloxy)ethoxymethyl]oxirane, [2-[2-(allyloxy)ethoxy]-ethyl]glycidyl ether, 2-[2-[2-(2-prop-2-enoxyethoxy)ethoxy]ethoxymethyl]oxirane, 2-[3-(2-prop-2-enoxyethoxy)propoxymethyl]oxirane, 2-(3-prop-2-enoxypropoxymethyl)oxirane, 2-(but-3-en-2-yloxymethyl)oxirane, 2-methyl-3-(prop-2-enoxymethyl)oxirane, 2-(1-prop-2-enoxyethyl)oxirane, 2-[2-[2-[2-(2-prop-2-enoxyethoxy)ethoxy]ethoxy]ethoxymethyl]oxirane, and preferably epoxy-containing acrylic monomers.

[0160] Examples of preferred epoxy-containing acrylic monomers include, without limitation, glycidyl (meth)acrylate, 2-methylglycidyl (meth)acrylate, 2-[2-(oxiran-2-ylmethoxy)ethoxy]ethyl (meth)acrylate, (3-methyloxiran-2-yl)methyl (meth)acrylate, 2-[2-(oxiran-2-ylmethoxy)propoxy]-propyl (meth)acrylate, 2-[2-(oxiran-2-ylmethoxy)propoxy]ethyl (meth)acrylate, 2-[2-(oxiran-2-ylmethoxy)ethoxy]propyl (meth)acrylate, 2-(oxiran-2-yl)propan-2-yl (meth)acrylate, 2-[2-(oxiran-2-ylmethoxy)ethoxy]propyl (meth)acrylate, [3-(oxiran-2-yl)-3-oxopropyl](meth)acrylate, 1-(2-methyloxiran-2-yl)ethyl (meth)acrylate, (2,3-dimethyloxiran-2-yl)methyl (meth)acrylate, (3-ethyloxiran-2-yl)methyl (meth)acrylate, 3-(oxiran-2-ylmethoxy)butyl (meth)acrylate, 2-(oxiran-2-ylmethoxy)propyl (meth)acrylate, 1-(oxiran-2-yl)propyl (meth)acrylate, (3,3-dimethyloxiran-2-yl)methyl (meth)acrylate, 3-(oxiran-2-ylmethoxy)propyl (meth)acrylate, [3-(oxiran-2-ylmethoxy)-3-oxopropyl](meth)acrylate.

[0161] Any amino-containing vinyl monomer can be used in the present invention. Examples of amino-containing vinyl monomers include, but are not limited to, vinylamine, allylamine, N-allylmethylamine, N-allyl-N-ethylamine, 3-butenylamine, 3-(vinyloxy)propylamine, 3-ethenoxy-2-methylpropan-1-amine, 1-ethenoxypropan-1-amine, 1-ethenoxy-2-methylpropan-1-amine, 3-ethenoxy-2,2-dimethylpropan-1-amine, 1-ethenoxypropane-1,3-diamine, [2-(vinyloxy)ethyl]-amine, 3-(prop-2-en-1-yloxy)propan-1-amine, 1-prop-2-enoxy ... Pan-2-amine, 2-prop-2-enoxyethanamine, 2-methyl-3-prop-2-enoxypropan-1-amine, 2-(2-prop-2-enoxyethoxy)-ethanamine, 2-[2-(2-prop-2-enoxyethoxy)ethoxy]ethanamine, 2-[2-[2-(2-prop-2-enoxyethoxy)-ethoxy]ethoxy]ethanamine, 2-[2-[2-[2-(2-prop-2-enoxyethoxy)ethoxy]ethoxy]ethanamine, 3-methoxy-2-prop-2-enoxypropan-1-amine, and preferably amino-containing acrylic monomers.

[0162] Examples of preferred amino-containing acrylic monomers include, without limitation, N-2-aminoethyl(meth)acrylamide, N-2-methylaminoethyl(meth)acrylamide, N-2-ethylaminoethyl(meth)acrylamide, N-2-dimethylaminoethyl(meth)acrylamide, N-3-aminopropyl(meth)acrylamide, N-3-methylaminopropyl(meth)acrylamide, N-3-dimethylaminopropyl(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, trimethylammonium 2-hydroxypropyl(meth)acrylate hydrochloride, and dimethylaminoethyl(meth)acrylate.

[0163] Any polyethylene glycol-containing vinyl monomer can be used in the present invention. Examples of polyethylene glycol-containing vinyl monomers include, without limitation, tri(ethylene glycol) monovinyl ether, tetra(ethylene glycol) monovinyl ether, poly(ethylene glycol) monovinyl ether, tri(ethylene glycol) methyl vinyl ether, tetra(ethylene glycol) methyl vinyl ether, poly(ethylene glycol) methyl vinyl ether, tri(ethylene glycol) monoallyl ether, tetra(ethylene glycol) monoallyl ether, poly(ethylene glycol) monoallyl ether, tri(ethylene glycol) methyl allyl ether, tetra(ethylene glycol) methyl allyl ether, poly(ethylene glycol) methyl allyl ether, and preferably polyethylene glycol-containing acrylic monomers.

[0164] Examples of preferred polyethylene glycol-containing acrylic monomers include, without limitation, tri(ethylene glycol) methyl ether (meth)acrylate, tetra(ethylene glycol) methyl ether (meth)acrylate, C1-C4 alkoxypoly(ethylene glycol) (meth)acrylate having a number average molecular weight of 1500 or less, methoxy-poly(ethylene glycol)ethyl (meth)acrylamide having a number average molecular weight of 1500 or less, tri(ethylene glycol) (meth)acrylate, tetra(ethylene glycol) (meth)acrylate, poly(ethylene glycol) (meth)acrylate having a number average molecular weight of 1500 or less, poly(ethylene glycol)ethyl (meth)acrylamide having a number average molecular weight of 1500 or less.

[0165] Any phosphorylcholine-containing vinyl monomer can be used in the present invention.Examples of phosphorylcholine-containing vinyl monomer include, but are not limited to, 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-(allyloxycarbonylamino)ethyl-2'-(trimethylammonio)ethyl phosphate, 2-(butenoyloxy)ethyl-2'-(trimethylammonio)ethyl phosphate, and preferably phosphorylcholine-containing acrylic monomer.

[0166] Examples of preferred phosphorylcholine-containing acrylic monomers include, without limitation, (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, 5-((meth)acryloyloxy)pentyl-2'-(trimethylammonio)ethyl phosphate, 6-((meth)acryloyloxy)hexyl-2'-(trimethylammonio)ethyl phosphate, ammonio)-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, and 2-((meth)acryloyloxy)hexyl-2'-(trimethylammonio)ethyl phosphate.

[0167] The hydrophilic copolymers of the present invention can be obtained by polymerizing a polymerizable composition containing all the required vinyl monomers, a free radical initiator, and optionally a chain transfer agent (i.e., a thiol-containing compound) according to any procedure known to those skilled in the art.

[0168] In accordance with the present invention, a contact lens precursor having carboxylic acid groups thereon (i.e., on the contact lens precursor) is heated in an aqueous solution containing a hydrophilic copolymer of the present invention at a temperature of from about 50° C. to about 140° C. for a period of time to crosslink the hydrophilic copolymer of the present invention while covalently bonding the crosslinked hydrophilic copolymer onto the preformed contact lens so as to form a hydrogel coating on the surface of the preformed contact lens.

[0169] Preferably, the heating step is carried out by autoclaving the contact lens precursor having carboxylic acid groups thereon (i.e., contact lens precursor) immersed in an aqueous packaging solution (i.e., a buffered aqueous solution having a pH of 6.7 to 7.6) in a sealed lens package at a temperature of about 115°C to about 125°C for approximately 20 to 90 minutes. During autoclaving, it is believed that a small amount of epoxide (epoxy) groups not involved in the crosslinking reaction can be hydrolyzed to 2,3-dihydroxypropyl (HO-CH-CH(OH)-CH-) groups, and that hydrophilic copolymers present in the lens packaging solution can be converted, if applicable, to non-reactive polymeric wetting agents that can improve lens wear comfort. As a result, the packaging solution is ophthalmically safe after autoclaving.

[0170] Lens packages (or containers) are well known to those skilled in the art for autoclaving and storing contact lenses. Any lens package can be used in the present invention. Preferably, the lens package is a blister package comprising a base and a cover, wherein the cover is removably sealed to the base, and wherein the base comprises a cavity for receiving a sterile packaging solution and a contact lens.

[0171] In another preferred embodiment, the aqueous solution is a packaging solution for storing contact lenses individually in sealed and sterilized lens packages, as is well known to those skilled in the art. In accordance with the present invention, the packaging solution may contain one or more other components known to those skilled in the art. Examples of other components include, without limitation, one or more buffers for maintaining the pH of the packaging solution within the range of about 6.8 to about 7.5, preferably about 6.8 to about 7.4, and more preferably about 6.9 to about 7.3; surfactants; antibacterial agents; preservatives; and lubricants (e.g., cellulose derivatives, polyvinyl alcohol, polyvinylpyrrolidone).

[0172] Physiologically compatible buffers are widely used in contact lens packaging solutions and contact lens care compositions. Examples of such buffers include, without limitation, boric acid, boric acid salts (e.g., sodium borate, potassium borate), citric acid, citrates (e.g., monopotassium citrate, monosodium citrate; dipotassium citrate; disodium citrate; tripotassium citrate), phosphates (e.g., NaH2PO4, KH2PO4, Na2HPO4, K2HPO4, Na3HPO4, K3HPO4), TRIS (i.e., 2-amino-2-hydroxymethyl-1,3-propanediol), Bis-Tris [i.e., bis-(2-hydroxyethyl)imino-tris-(hydroxymethyl)-methane], Bis-Tris propane [i.e., 1,3-bis(tris(hydroxymethyl)-methylamino)propane], bis-aminopolyols, triethanolamine, ACES [i.e., N-(2-hydroxyethyl)imino-tris-(hydroxymethyl)-methane], bis-aminopolyols, triethanolamine, bis-aminopolyols ... Examples of suitable buffers include N,N'-bis(2-hydroxyethyl)-2-aminoethanesulfonic acid, BES [i.e., N,N-bis(2-hydroxyethyl)-2-aminoethanesulfonic acid], HEPES [i.e., 4-(2-hydroxyethyl)-1-piperazineethanesulfonic acid], MES [i.e., 2-(N-morpholino)ethanesulfonic acid], MOPS [i.e., 3-[N-morpholino]-propanesulfonic acid], PIPES [i.e., piperazine-N,N'-bis(2-ethanesulfonic acid], TES {i.e., N-[tris(hydroxymethyl)methyl]-2-aminoethanesulfonic acid}, salts thereof, and mixtures thereof. The total concentration of all buffers present in the aqueous solution is about 10 mM to 100 mM (preferably about 10 mM to 90 mM, more preferably about 10 mM to about 80 mM, and even more preferably about 10 mM to 70 mM).

[0173] In a preferred embodiment, the aqueous solution further comprises one or more tonicity agents, which can be ionic or nonionic, independently of each other. 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. Preferably, a nonionic tonicity agent is used to adjust the osmolality of the aqueous solution to a value of about 200 to about 450 mOsm / Kg (preferably about 230 to about 400 mOsm / Kg, more preferably about 260 to about 350 mOsm / Kg).

[0174] The lenses are packaged in individual packages, sealed, and sterilized (e.g., by autoclaving at about 120°C or higher under pressure for at least 30 minutes) before distribution to users. Those skilled in the art will be familiar with methods for sealing and sterilizing lens packages.

[0175] The layered structure of the contact lenses of the present invention can be revealed by analysis of cross sections of fully hydrated contact lenses (i.e., directly in water or buffered saline) by atomic force microscopy (AFM), environmental scanning electron microscopy, confocal fluorescence microscopy, or any other known technique, either alone or in combination with differential staining of the hydrogel coating or lens bulk material, as known to those skilled in the art.

[0176] In accordance with the present invention, the contact lenses of the present invention have at least one property selected from the group consisting of an equilibrium water content of about 15% to about 70% by weight (preferably about 20% to about 65%, more preferably about 20% to about 60%, even more preferably about 25% to about 55%), an elastic modulus of about 0.2 MPa to about 2.0 MPa (preferably about 0.25 MPa to about 1.5 MPa, more preferably about 0.3 MPa to about 1.2 MPa, even more preferably about 0.35 MPa to about 1.0 MPa), an oxygen permeability of at least 40 barrer / mm (preferably at least 60 barrer / mm, more preferably at least 80 barrer / mm, even more preferably at least 100 barrer / mm), and an average water contact angle of less than 90 degrees (preferably less than 80 degrees, more preferably less than 70 degrees, even more preferably less than 60 degrees).

[0177] Although various embodiments of the present invention have been described using specific terms, devices, and methods, such description is for illustrative purposes only. The words used are words of description rather than of limitation. As will be apparent to those skilled in the art, many variations and modifications of the present invention may be made by those skilled in the art without departing from the spirit and scope of the novel concepts of the present disclosure. In addition, it should be understood that aspects of the various embodiments of the present invention may be interchanged, either in whole or in part, or may be combined and / or used together in any manner, as exemplified below:

[0178] Embodiment 1. A method for producing a coated contact lens, comprising the steps of: (1) obtaining a contact lens precursor having a concave surface and an opposite convex surface, the contact lens precursor including a lens bulk material and carboxylic acid groups on and / or near the anterior and posterior surfaces; (2) immersing the contact lens precursor in an aqueous solution in a container, wherein the aqueous solution comprises from about 0.01% to about 5.0% by weight of at least one hydrophilic copolymer comprising monomer units of (a) at least one epoxy-containing vinyl monomer, (b) at least one amino-containing vinyl monomer having a primary or secondary amino group, (c) at least one polyethylene glycol-containing vinyl monomer, and (d) at least one phosphorylcholine-containing vinyl monomer, wherein the sum of the amounts of components (a) and (b) in the at least one hydrophilic copolymer is about 40 mol % or less; (3) heating the aqueous solution having the contact lens precursor therein at a temperature of about 100°C to about 140°C for at least 30 minutes to form a coated contact lens having a hydrogel coating thereon, wherein the hydrogel coating is covalently bonded to the anterior and posterior surfaces by bonds formed between one carboxylic acid group and one epoxy group, respectively, and the hydrogel coating comprises a crosslinked polymeric material including polymer chains derived from a hydrophilic copolymer; Including, The method, wherein the contact lens has a water break-up time (WBUT) of at least 10 seconds.

[0179] Embodiment 2. The method of embodiment 1, wherein the contact lens precursor is comprised of a bulk material having carboxylic acid groups on and / or near the surface of the lens bulk material.

[0180] Embodiment 3. The method of embodiment 2, wherein the lens bulk material is obtained by polymerizing a polymerizable composition comprising about 0.1% to about 10% by weight of a vinyl monomer further comprising at least one carboxylic acid group.

[0181] Embodiment 4. The method of embodiment 2, wherein the lens bulk material has been subjected to at least one post-cure surface treatment to have carboxylic acid groups on and / or near the surface of the lens bulk material.

[0182] Embodiment 5. The method of any one of embodiments 1-4, wherein the contact lens precursor comprises a lens bulk material and at least one layer of polymeric material having carboxylic acid groups thereon.

[0183] Embodiment 6. The method of embodiment 5, wherein the at least one polymeric material having carboxylic acid groups comprises polyacrylic acid, polymethacrylic acid, polyethylacrylic acid, poly(acrylic acid-co-methacrylic acid), poly(acrylic acid-co-ethacrylic acid), poly(methacrylic acid-co-ethacrylic acid), or a mixture thereof.

[0184] Embodiment 7. The method of any one of embodiments 1-6, wherein the method comprises, prior to step (2), contacting the contact lens precursor with a coating solution comprising at least one reactive polymer having pendant carboxylic acid groups to form a reactive base coating comprising a layer of the at least one reactive polymer.

[0185] Embodiment 8. The method of embodiment 7, wherein the at least one reactive polymer comprises a homopolymer or copolymer of acrylic acid or a C1-C3 alkyl acrylic acid.

[0186] Embodiment 9. The method of embodiment 8, wherein the homopolymer or copolymer of acrylic acid or a C1-C3 alkyl acrylic acid is polyacrylic acid, polymethacrylic acid, polyethylacrylic acid, polypropylacrylic acid, poly(acrylic acid-co-methacrylic acid), poly[(meth)acrylic acid-co-ethylacrylic acid], poly[(meth)acrylic acid-co-propylacrylic acid], poly[(meth)acrylic acid-co-acrylamide], poly[(meth)acrylic acid-co-vinylpyrrolidone], poly[ethylacrylic acid-co-acrylamide], poly[ethylacrylic acid-co-vinylpyrrolidone], poly[propylacrylic acid-co-acrylamide], poly[propylacrylic acid-co-vinylpyrrolidone], poly[(meth)acrylic acid-co-vinyl acetate], poly[ethylacrylic acid-co-vinyl acetate], poly[propylacrylic acid-co-vinyl acetate], or a combination thereof.

[0187] Embodiment 10. The method of any one of embodiments 7-9, wherein the coating solution has a pH of about 1.5 to about 5.5.

[0188] Embodiment 11. The method of any one of embodiments 7-10, wherein the coating solution is prepared by dissolving the at least one reactive polymer in water, a mixture of water and one or more organic solvents, an organic solvent, or a mixture of one or more organic solvents, and optionally adjusting the pH of the coating solution by adding an inorganic or organic acid.

[0189] Embodiment 12. The method of any one of embodiments 1 to 11, wherein the aqueous solution comprises from about 0.05% to about 4.0% by weight of the at least one hydrophilic copolymer.

[0190] Embodiment 13. The method of any one of embodiments 1 to 11, wherein the aqueous solution comprises from about 0.1% to about 3% by weight of the at least one hydrophilic copolymer.

[0191] Embodiment 14. The method of any one of embodiments 1 to 11, wherein the aqueous solution comprises from about 0.2% to about 2.5% by weight of the at least one hydrophilic copolymer.

[0192] Embodiment 15. The method of any one of embodiments 1-14, wherein the heating step is carried out by autoclaving the contact lens precursor having carboxylic acid groups thereon, immersed in the aqueous packaging solution within the sealed lens package, at a temperature of about 115°C to about 125°C for approximately 30 to 90 minutes.

[0193] Embodiment 16. A contact lens comprising a front surface, an opposite posterior surface, and a layered arrangement from the front surface to the posterior surface, the layered arrangement comprising an outer front hydrogel layer, an inner layer, and an outer posterior hydrogel layer, the inner layer comprising a lens bulk material and having carboxylic acid groups on and / or near a surface of the inner layer, the outer front hydrogel layer and the outer posterior hydrogel layer comprising a hydrogel polymer comprising at least one epoxy-containing vinyl monomer, (b) at least one amino-containing vinyl monomer having a primary or secondary amino group, (c) at least one polyethylene glycol-containing vinyl monomer, a hydrophilic copolymer comprising (a) a carboxylic acid group and (b) a vinyl monomer; and (d) a hydrophilic polymer comprising monomer units of at least one phosphorylcholine-containing vinyl monomer, wherein the sum of the amounts of components (a) and (b) in said at least one hydrophilic copolymer is about 40 mol % or less, wherein the outer anterior and outer posterior hydrogel layers are covalently bonded onto the inner layer by bonds formed between one carboxylic acid group and one epoxy group, respectively, and wherein the contact lens has a water-break time (WBUT) of at least 10 seconds.

[0194] Embodiment 17. The contact lens of embodiment 16, wherein the inner layer is comprised of a lens bulk material having carboxylic acid groups on and / or near the surface of the bulk material.

[0195] Embodiment 18. The contact lens of embodiment 16, wherein the inner layer comprises a lens bulk material and a layer of at least one polymeric material having carboxylic acid groups.

[0196] Embodiment 19. The at least one hydrophilic copolymer comprises: Formula (a) [ka] monomer units of at least one epoxy-containing vinyl monomer; Formula (b) [ka] monomer units of at least one amino-containing acrylic monomer; (c) formula [ka] monomer units of at least one polyethylene glycol-containing acrylic monomer; and (d) Formula [ka] Monomer units of at least one phosphorylcholine-containing vinyl monomer Includes; During the ceremony: Each R0, independently of one another, is H or CH3; each R0', independently of one another, is H or C1-C4 alkyl; B1, B2, and B3, independently of one another, are O or NR'; R' is H or C1-C4 alkyl; D1, D2, and D3, independently of one another, are C1-C4 alkyl. 12 is an alkylene divalent radical; D0 is a C1-C 12 an alkylene divalent radical or a divalent radical of the formula -D4-O-D5-B4-CH2-; B4 is -O- or [ka] and D4 is C1~C 12 an alkylene divalent radical; D5 is a C2-C6 alkylene divalent radical or [ka] D6 and D7, independently of each other, are C2-C6 alkylene divalent radicals; d1 is zero, 1 or 2; PEG is [ka] (wherein R″ is H or C1-C4 alkyl; t2 is an integer from 3 to 100); PC is a polyethylene glycol group of the formula: [ka] (wherein t1 is an integer of 1 to 5, and 1 R, 2 R and 3 R is C1-C8 alkyl or C1-C8 hydroxyalkyl. The method of any one of embodiments 1 to 15 or the contact lens of any one of embodiments 16 to 18, wherein the zwitterionic group is

[0197] Embodiment 20. The at least one hydrophilic copolymer has formula (I): [ka] [In the ceremony T' and T'' independently of each other are H or a terminal group; each R0 independently of each other is H or CH3; each R0' independently of each other is H or C1-C4 alkyl; B1, B2 and B3 independently of each other are O or NR'; R' is H or C1-C4 alkyl; D1, D2 and D3 independently of each other are C1-C4 alkyl. 12 is an alkylene divalent radical; D0 is a C1-C 12an alkylene divalent radical or a divalent radical of the formula -D4-O-D5-B4-CH2-; B4 is -O- or [ka] and D4 is C1~C 12 an alkylene divalent radical; D5 is a C2-C6 alkylene divalent radical or [ka] D6 and D7, independently of each other, are C2-C6 alkylene divalent radicals; d1 is zero, 1 or 2; PEG is [ka] (wherein R″ is H or C1-C4 alkyl; t2 is an integer from 3 to 100); PC is a polyethylene glycol group of the formula: [ka] (wherein t1 is 1 to 5, and 1 R, 2 R and 3 R is a zwitterionic group of C1-C8 alkyl or C1-C8 hydroxyalkyl; and a, b, c, and d, independently of one another, are integers from 5 to 100, where (a+c) / (a+b+c+d)≦0.40 (preferably ≦0.35, more preferably ≦0.30, and even more preferably ≦0.25). wherein the statistical copolymer is a copolymer of the formula:

[0198] Embodiment 21. The method or contact lens of embodiment 20, wherein in formula (I), a / c is 10 to 0.1.

[0199] Embodiment 22. The method or contact lens of embodiment 20, wherein in formula (I), a / c is 5 to 0.2.

[0200] Embodiment 23. The method or contact lens of embodiment 20, wherein in formula (I), a / c is an integer from 2.5 to 0.4.

[0201] Embodiment 24. The method or contact lens of embodiment 20, wherein in formula (I), a / c is 2 to 0.5.

[0202] Embodiment 25. The method of any one of embodiments 1-15 and 19-24 or the contact lens of any one of embodiments 16-24, wherein the sum of the amount of component (a) and component (b) in the at least one hydrophilic copolymer is about 35 mole % or less.

[0203] Embodiment 26. The method of any one of embodiments 1-15 and 19-24 or the contact lens of any one of embodiments 16-24, wherein the sum of the amount of component (a) and component (b) in the at least one hydrophilic copolymer is about 30 mole % or less.

[0204] Embodiment 27. The method of any one of embodiments 1-15 and 19-24 or the contact lens of any one of embodiments 16-24, wherein the sum of the amount of component (a) and component (b) in the at least one hydrophilic copolymer is about 25 mole % or less.

[0205] Embodiment 28. The method of any one of embodiments 1-15 and 19-27 or the contact lens of any one of embodiments 16-27, wherein the lens bulk material is a hard plastic material.

[0206] Embodiment 29. The method or contact lens of embodiment 28, wherein the hard plastic material is a crosslinked polymethacrylate.

[0207] Embodiment 30. The method of any one of embodiments 1-15 and 19-27 or the contact lens of any one of embodiments 16-27, wherein the lens bulk material is a rigid gas permeable lens material.

[0208] Embodiment 31. The method of any one of embodiments 1-15 and 19-27, or the contact lens of any one of embodiments 16-27, wherein the lens bulk material consists essentially of a central optic portion made essentially of a gas permeable lens material and a peripheral portion made essentially of a non-silicone hydrogel material having an equilibrium water content of about 10% to 80% by weight.

[0209] Embodiment 32. The method of any one of embodiments 1-15 and 19-27, or the contact lens of any one of embodiments 16-27, wherein the lens bulk material consists essentially of a three-dimensional article and a non-silicone hydrogel material, wherein the three-dimensional article is made of the non-hydrogel material and has a three-dimensional size smaller than that of the contact lens such that the three-dimensional article is completely embedded within the non-silicone hydrogel material, having an equilibrium water content of about 10% to 80% by weight.

[0210] Embodiment 33. The method of any one of embodiments 1-15 and 19-27 or the contact lens of any one of embodiments 16-27, wherein the lens bulk material is a non-silicone hydrogel material having an equilibrium water content of about 10% to 80% by weight.

[0211] Embodiment 34. The method or contact lens of any one of embodiments 31-33, wherein the non-silicone hydrogel material comprises at least 50 mole % of repeat units of at least one hydroxyl-containing vinyl monomer.

[0212] Embodiment 35. The method or contact lens of embodiment 34, wherein the at least one hydroxyl-containing vinyl monomer is selected from the group consisting of hydroxyethyl (meth)acrylate, glycerol (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-amino-2-hydroxypropyl (meth)acrylate, N-2-hydroxyethyl (meth)acrylamide, N-3-hydroxypropyl (meth)acrylamide, N-2-hydroxypropyl (meth)acrylamide, N-2,3-dihydroxypropyl (meth)acrylamide, N-tris(hydroxymethyl)methyl (meth)acrylamide, vinyl alcohol, allyl alcohol, and combinations thereof.

[0213] Embodiment 36. The method or contact lens of embodiment 34, wherein the at least one hydroxyl-containing vinyl monomer is selected from the group consisting of hydroxyethyl (meth)acrylate, glycerol (meth)acrylate, and vinyl alcohol.

[0214] Embodiment 37. The method of any one of embodiments 1-15 and 19-27 or the contact lens of any one of embodiments 31-36, wherein the lens bulk material is a silicone hydrogel material.

[0215] Embodiment 38. The method of any one of embodiments 1-15 and 19-27 or the contact lens of any one of embodiments 16-27, wherein the lens bulk material consists essentially of a central optic made essentially of a rigid gas permeable lens material, surrounded by a peripheral portion made essentially of a silicone hydrogel material.

[0216] Embodiment 39. The method of any one of embodiments 1 to 15 and 19 to 27, or the coated contact lens of any one of embodiments 16 to 27, wherein the lens bulk material consists essentially of a three-dimensional article and a silicone hydrogel material, the three-dimensional article being made of a non-hydrogel material and having a three-dimensional size smaller than that of a preformed implantable contact lens such that the three-dimensional article is fully embedded within the silicone hydrogel material.

[0217] Embodiment 40. The method or contact lens of any one of embodiments 37-39, wherein the silicone hydrogel material comprises repeat units of at least one hydrophilic vinyl monomer, repeat units of at least one siloxane-containing vinyl monomer, and repeat units of at least one vinyl crosslinker.

[0218] Embodiment 41. The at least one hydrophilic vinyl monomer is (1) an alkyl(meth)acrylamide 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, and combinations thereof; (2) N-2-hydroxyethyl(meth)acrylamide, N,N-bis(hydroxyethyl)(meth)acrylamide, ... (3) a hydroxyl-containing acrylic monomer selected from the group consisting of 2-(meth)acrylamidoglycolic acid, (meth)acrylic acid, ethyl acrylic acid, ethyl acrylic acid, 3-(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, 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 1500 or less, poly(ethylene glycol)ethyl(meth)acrylamide having a number average molecular weight of 1500 or less, and combinations thereof; (4) a hydroxyl-containing acrylic monomer selected from the group consisting of 2-(meth)acrylamidoglycolic acid, (meth)acrylic acid, ethyl acrylic acid, 3-(meth)acrylamidopropionic acid, 5-(meth)acrylamidopentanoic acid, 4-(meth)acrylamidobutane (3) a carboxyl-containing acrylic monomer selected from the group consisting of N-2-aminoethyl (meth)acrylamide, N-2-methylaminoethyl (meth)acrylamide, N-2-ethyl ...N-2-Dimethylaminoethyl (meth)acrylamide, N-3-aminopropyl (meth)acrylamide, N-3-methylaminopropyl (meth)acrylamide, N-3-dimethylaminopropyl (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, trimethylammonium (5) an amino-containing acrylic monomer selected from the group consisting of 2-hydroxypropyl (meth)acrylate hydrochloride, dimethylaminoethyl (meth)acrylate, and combinations thereof; (6) an amino-containing acrylic monomer selected from the group consisting of N-vinylpyrrolidone, N-vinyl-3-methyl-2-pyrrolidone, N-vinyl-4-methyl-2-pyrrolidone, N-vinyl-5-methyl-2-pyrrolidone, N-vinyl-6-methyl-2-pyrrolidone, N-vinyl-3-ethyl-2-pyrrolidone, N-vinyl-4,5-dimethyl-2-pyrrolidone, N-vinyl-5,5-dimethyl-2-pyrrolidone, N-vinyl-3,3,5-trimethyl-2-pyrrolidone, N-vinylpiperidone, N-vinyl-3-methyl-2-piperidone, N-vinyl-4-methyl-2-piperidone, N-vinyl-5-methyl-2-piperid ...6-methyl-2-pyrrolidone, N-vinyl-6-methyl-2-pyrrolidone, N-vinyl-6-methyl-2-pyrrolidone, N-vinyl-6-methyl-2-pyrrolidone, N-vinyl N-vinyl-2-piperidone, N-vinyl-6-ethyl-2-piperidone, N-vinyl-3,5-dimethyl-2-piperidone, N-vinyl-4,4-dimethyl-2-piperidone, N-vinylcaprolactam, N-vinyl-3-methyl-2-caprolactam, N-vinyl-4-methyl-2-caprolactam, N-vinyl-7-methyl-2-caprolactam, N-vinyl-7-ethyl-2-caprolactam, N-vinyl-3,5-dimethyl-2-caprolactam, N-vinyl-4,6-dimethyl-2-caprolactam, N-vinyl-3,5,7-trimethyl-2-caprolactam, N-vinyl-N-methylacetamide, N-vinylformamide, N-vinylacetamide, N-vinylisopropylamide, N-vinyl-N-ethylacetamide, N-vinyl-N-ethylformamide,and mixtures thereof; (6) N-vinylamide monomers selected from the group consisting of 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- (7) methylene-containing pyrrolidone monomers selected from the group consisting of 2-pyrrolidone, 1-n-butyl-3-methylene-2-pyrrolidone, 1-tert-butyl-3-methylene-2-pyrrolidone, and combinations thereof; (8) methylene-containing pyrrolidone monomers having a C1-C4 alkoxyethoxy group, and 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, having a number average alkyl group of 1500 or less. (8) acrylic monomers selected from the group consisting of C1-C4-alkoxypoly(ethylene glycol)(meth)acrylates having a number average molecular weight of 1,500 or less, methoxy-poly(ethylene glycol)ethyl(meth)acrylamides having a number average molecular weight of 1,500 or less, and combinations thereof; (9) vinyl ether monomers selected from the group consisting of ethylene glycol monovinyl ether, di(ethylene glycol) monovinyl ether, tri(ethylene glycol) monovinyl ether, tetra(ethylene glycol) monovinyl ether, poly(ethylene glycol) monovinyl ether, ethylene glycol methyl vinyl ether, di(ethylene glycol) methyl vinyl ether, tri(ethylene glycol) methyl vinyl ether, tetra(ethylene glycol) methyl vinyl ether, poly(ethylene glycol) methyl vinyl ether, and combinations thereof; (10) ethylene glycol monoallyl ether, di(ethylene glycol) monoallyl ether, tri(ethylene glycol) monoallyl ether, tetra(ethylene glycol) monoallyl ether, poly(ethylene glycol) monoallyl ether,(10) allyl ether monomers selected from the group consisting of ethylene glycol methyl allyl ether, di(ethylene glycol) methyl allyl ether, tri(ethylene glycol) methyl allyl ether, tetra(ethylene glycol) methyl allyl ether, poly(ethylene glycol) methyl allyl ether, and combinations thereof; (11) (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, 5-((meth)acryloxy)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)acryloxy)ethyl-2'-(tributylammonio)ethyl phosphate, 2-((meth)acryloyloxy)propyl-2'-(trimethylammonio)ethyl phosphate, 2-((meth)acryloyloxy)butyl-2'-(trimethylammonio)ethyl phosphate, 2-((meth)acryloxy)pentanone butyl-2'-(trimethylammonio)ethyl phosphate, 2-((meth)acryloyloxy)hexyl-2'-(trimethylammonio)ethyl phosphate, 2-(vinyloxy)ethyl-2'-(trimethylammonio)ethyl phosphate, 2-(allyloxy)ethyl-2'-(trimethylammonio)ethyl phosphate, 2-(vinyloxycarbonyl)ethyl-2'-(trimethylammonio)ethyl phosphate, 2-(allyloxycarbonyl)ethyl-2'-(trimethylammonio)ethyl phosphate,41. The method or contact lens of embodiment 40, comprising a phosphorylcholine-containing vinyl monomer selected from the group consisting of 2-(vinylcarbonylamino)ethyl-2'-(trimethylammonio)ethyl phosphate, 2-(allyloxycarbonylamino)ethyl-2'-(trimethylammonio)ethyl phosphate, 2-(butenoyloxy)ethyl-2'-(trimethylammonio)ethyl phosphate, and combinations thereof; (11) allyl alcohol; (12) N-2-hydroxyethyl vinyl carbamate; (13) N-carboxyvinyl-β-alanine; (14) N-carboxyvinyl-α-alanine; (15), or a combination thereof.

[0219] Embodiment 42. The at least one siloxane-containing vinyl monomer is selected from the group consisting of α-(meth)acryloxypropyl-terminated ω-C1-C4 alkyl-terminated polydimethylsiloxane, α-(meth)acryloxy-2-hydroxy-propyloxypropyl-terminated ω-C1-C4 alkyl-terminated polydimethylsiloxane, α-(2-hydroxyl-methacryloxypropyloxypropyl)-ω-C1-C4 alkyldecamethylsiloxane, α-[3-(meth)acryloxy-ethoxy-2-hydroxypropyloxypropyl]-terminated ω-C1-C4 alkyldecamethylsiloxane, and α-[3-(meth)acryloxy-ethoxy-2-hydroxypropyloxypropyl]-terminated ω-C1-C4 alkyldecamethylsiloxane. Alkyl-terminated polydimethylsiloxane, α-[3-(meth)acryloxy-propyloxy-2-hydroxypropyloxypropyl]-terminated ω-C1-C4 alkyl-terminated polydimethylsiloxane, α-[3-(meth)acryloxyisopropyloxy-2-hydroxypropyloxypropyl]-terminated ω-C1-C4 alkyl-terminated polydimethylsiloxane, α-[3-(meth)acryloxybutyloxy-2-hydroxypropyloxypropyl]-terminated ω-C1-C4 alkyl-terminated polydimethylsiloxane, α-[3- [(meth)acryloxyethyl-amino-2-hydroxypropyloxypropyl]-terminated ω-C1 to C4 alkyl terminated polydimethylsiloxane, α-[3-(meth)acryloxypropylamino-2-hydroxypropyloxypropyl]-terminated ω-C1 to C4 alkyl terminated polydimethylsiloxane, α-[3-(meth)acryloxy-butylamino-2-hydroxypropyloxypropyl]-terminated ω-C1 to C4 alkyl terminated polydimethylsiloxane, α-(meth)acryloxy(polyethyleneoxy)-2-hydroxypropyl [(meth)acryloxy-2-hydroxypropyloxypropyl]-terminated ω-C1 to C4 alkyl terminated polydimethylsiloxane, α-[(meth)acryloxy-2-hydroxypropyloxy-ethoxypropyl]-terminated ω-C1 to C4 alkyl terminated polydimethylsiloxane, α-[(meth)acryloxy-2-hydroxypropyl-N-ethylaminopropyl]-terminated ω-C1 to C4 alkyl terminated polydimethylsiloxane, α-[(meth)acryloxy-2-hydroxypropyl-aminopropyl]-terminated ω-C1 to C4 alkyl terminated polydimethylsiloxane,α-[(meth)acryloxy-2-hydroxypropyloxy-(polyethyleneoxy)propyl]-terminated ω-C1-C4 alkyl terminated polydimethylsiloxane, α-(meth)acryloylamidopropyloxy-propyl-terminated ω-C1-C4 alkyl terminated polydimethylsiloxane, α-N-methyl-(meth)acryloylamidopropyloxypropyl-terminated ω-C1-C4 alkyl terminated polydimethylsiloxane, α-[3-(meth)acrylamidoethoxy-2-hydroxypropyloxy-propyl]-terminated ω-C1-C4 alkyl terminated polydimethylsiloxane, α-[3-(meth)acrylamidopropyloxy-2-hydroxypropyloxypropyl]-terminated ω-C1-C4 alkyl terminated polydimethylsiloxane, α-[3-(meth)acrylamidoisopropyloxy-2-hydroxypropyloxypropyl]-terminated ω-C1-C4 alkyl terminated polydimethylsiloxane, α-[3-(meth)acrylamidobutyloxy-2-hydroxypropyloxypropyl]-terminated ω-C1-C4 alkyl terminated polydimethylsiloxane, α-[3-(meth)acryloylamido-2-hydroxypropyloxypropyl] terminated ω-C1-C4 alkyl polydimethylsiloxane, α-[3-[N-methyl-(meth)acryloylamido]-2-hydroxypropyloxypropyl] terminated ω-C1-C4 alkyl polydimethylsiloxane, N-methyl-N'-(propyl-tetra(dimethylsiloxy)dimethylbutylsilane)(meth)acrylamide, N-(2,3-dihydro 42. The method or contact lens of embodiment 40 or 41, wherein the hydroxypropyl methyl acrylate is selected from the group consisting of (propyloxypropane)-N'-(propyltetra(dimethylsiloxy)dimethylbutylsilane)(meth)acrylamide, (meth)acryloylamidopropyltetra(dimethylsiloxy)dimethylbutylsilane, α-vinyl carbonate-terminated ω-C1-C4 alkyl terminated polydimethylsiloxane, α-vinyl carbamate-terminated ω-C1-C4 alkyl terminated polydimethylsiloxane, and mixtures thereof.

[0220] Embodiment 43. The method or contact lens of embodiment 40 or 41, wherein the at least one siloxane-containing vinyl monomer is selected from the group consisting of vinyl monomers having bis(trialkylsilyloxy)alkylsilyl groups, vinyl monomers having tris(trialkylsilyloxy)silyl groups, polysiloxane vinyl monomers, 3-methacryloxypropylpentamethyldisiloxane, t-butyldimethyl-siloxyethyl vinyl carbonate, trimethylsilylethyl vinyl carbonate, and trimethylsilylmethyl vinyl carbonate, and combinations thereof.

[0221] Embodiment 44. The at least one siloxane-containing vinyl monomer has the formula (M1) or (M2): [ka] (In the formula: a M1 is zero or one; R M0 is H or methyl; X M0 is O or NR M1 and;L M1 is a C2-C8 alkylene divalent radical or -LM1'-XM1-LM1''-, [ka] [ka] is a divalent radical of; L M1 ' is a C2-C8 alkylene divalent radical having zero or one hydroxyl group; L M1 '' is a C3-C8 alkylene divalent radical having zero or one hydroxyl group; X M1 , O, NR M1 , NHCOO, OCONH, CONR M1 , or NR M1 CO;R M1 is H or C1-C4 alkyl having 0-2 hydroxyl groups; t1and R t2 is C1-C6 alkyl; X M1 ' is O or NR M1 v1 is an integer of 1 to 30, m2 is an integer of 0 to 30, n1 is an integer of 3 to 40, and r1 is 2 or 3. 42. The method or contact lens of embodiment 40 or 41, comprising at least one vinyl monomer of

[0222] Embodiment 45. The at least one siloxane-containing vinyl monomer is selected from the group consisting of tris(trimethylsilyloxy)silylpropyl(meth)acrylate, [3-(meth)acryloxy-2-hydroxypropyloxy]propylbis(trimethylsiloxy)methylsilane, [3-(meth)acryloxy-2-hydroxypropyloxy]propylbis(trimethylsiloxy)butylsilane, 3-(meth)acryloxy-2-(2-hydroxyethoxy)-propyloxy)propylbis(trimethylsiloxy)methyl ... -(meth)acryloxy-2-hydroxypropyloxy)propyl-tris(trimethylsiloxy)silane, N-[tris(trimethylsiloxy)silylpropyl]-(meth)acrylamide, N-(2-hydroxy-3-(3-(bis(trimethylsilyloxy)methylsilyl)propyloxy)propyl)-2-methyl(meth)acrylamide, N-(2-hydroxy-3-(3-(bis(trimethylsilyloxy)methylsilyl)propyloxy)propyl)(meth)acrylamide, N-(2-hydroxy-3-(3-(bis(trimethylsilyloxy)methylsilyl)propyloxy)propyl)-(meth)acrylamide N-hydroxy-3-(3-(tris(trimethylsilyloxy)silyl)propyloxy)propyl)-2-methylacrylamide, N-(2-hydroxy-3-(3-(tris(trimethylsilyloxy)silyl)propyloxy)propyl)(meth)acrylamide, N-[tris(dimethylpropylsiloxy)-silylpropyl]-(meth)acrylamide, N-[tris(dimethylphenylsiloxy)-silylpropyl](meth)acrylamide, N-[tris(dimethylethylsiloxy)-silylpropyl]( meth)acrylamide, N,N-bis[2-hydroxy-3-(3-(bis(trimethylsilyloxy)methylsilyl)-propyloxy)propyl]-2-methyl(meth)acrylamide, N,N-bis[2-hydroxy-3-(3-(bis(trimethylsilyloxy)methylsilyl)propyloxy)-propyl](meth)acrylamide, N,N-bis[2-hydroxy-3-(3-(tris(trimethylsilyloxy)silyl)propyloxy)-propyl]-2-methyl(meth)acrylamide, N,N-bis[2-hydroxy-3-(3-(tris(trimethylsilyloxy)silyl)-propyloxy)propyl](meth)acrylamide, N-[2-hydroxy-3-(3-(t-butyldimethylsilyl)propyloxy)-propyl]-2-methyl(meth)acrylamide, N-[2-hydroxy-3-(3-(t-butyldimethylsilyl)propyloxy)-propyl](meth)acrylamide, N,N-bis[2-hydroxy-3-(3-(t-butyldimethylsilyl)propyloxy)propyl]-2-methyl(meth)acrylamide, N-2-(meth)acrylamide 42. The method or contact lens of embodiment 40 or 41, comprising 3-(vinyloxycarbonylthio)-propyl-tris(trimethylsiloxy)silane, 3-[tris(trimethylsiloxy)silyl]propyl vinylcarbamate, 3-[tris(trimethylsiloxy)silyl]propyl allylcarbamate, 3-[tris(trimethylsiloxy)silyl]propyl vinylcarbonate, or combinations thereof.

[0223] Embodiment 46. The method or contact lens of any one of embodiments 40-45, wherein the at least one vinyl crosslinker comprises at least one polysiloxane vinyl crosslinker.

[0224] Embodiment 47. The at least one polysiloxane vinyl crosslinker comprises dimethylsiloxane units and one monovalent C4-C6 siloxane unit, each having one methyl substituent and two to six hydroxyl groups. 40 47. The method or contact lens of embodiment 46, comprising a di-(meth)acryloyloxy-terminated polysiloxane vinyl crosslinker having hydrophilized siloxane units with organic radical substituents.

[0225] Embodiment 48. The at least one polysiloxane vinyl crosslinker has formula (G): [ka] [In formula: d1 is an integer between 30 and 500, and d2 is an integer between 1 and 75, provided that d2 / d1 is between about 0.035 and about 0.15; X 01 is O or NR IN where R IN is hydrogen or C1-C 10 is alkyl; R I0 is hydrogen or methyl; Independent R I1 and R I2 is a substituted or unsubstituted C1 to C 10 Alkylene divalent radical or -R I4 -OR I5 -, where, independently of each other, R I4 and R I5 is a substituted or unsubstituted C1-C 10 is an alkylene divalent radical; R I3 is expressed by the formulas (G-1) to (G-5) [ka] (k1 is zero or 1; m1 is an integer from 2 to 4; m2 is an integer from 1 to 5; m3 is an integer from 3 to 6; m4 is an integer from 2 to 5; R I6 is hydrogen or methyl; R I7 is a C2-C6 hydrocarbon radical with a valence of (m2+1); R I8 is a C2-C6 hydrocarbon radical with a valence of (m4+1); R I9 is ethyl or hydroxymethyl; R I10 is methyl or hydromethyl; R I11 is hydroxyl or methoxy; X I1 is a sulfur bond of -S- or -NR I12- is a tertiary amino bond, where R I12 is C1-C1 alkyl, hydroxyethyl, hydroxypropyl, or 2,3-dihydroxypropyl; X I2 teeth, [ka] where R I13 is hydrogen or C1-C 10 alkyl) is one of the monovalent radicals 47. The method or contact lens of embodiment 46, comprising at least one hydrophilizing polysiloxane vinyl crosslinker of

[0226] Embodiment 49. The method or contact lens of embodiment 46, wherein the at least one polysiloxane vinyl crosslinker comprises (i) a vinyl crosslinker comprising one and only one polydiorganosiloxane segment and two terminal ethylenically unsaturated groups selected from the group consisting of (meth)acryloyloxy, (meth)acryloylamino, vinyl carbonate, and vinyl carbamate groups, and / or (ii) a chain-extended polysiloxane vinyl crosslinker comprising at least two polydiorganosiloxane segments and a covalent linker between each pair of polydiorganosiloxane segments and the two terminal ethylenically unsaturated groups selected from the group consisting of (meth)acryloyloxy, (meth)acryloylamino, vinyl carbonate, and vinyl carbamate groups.

[0227] Embodiment 50. The at least one polysiloxane vinyl crosslinker is selected from the group consisting of α,ω-bis[3-(meth)acrylamidopropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acryloxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acryloxy-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acryloxyethoxy-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acryloxypro α,ω-bis[3-(meth)acryloxy-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acryloxy-isopropyloxy-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acryloxybutyloxy-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acrylamidoethoxy-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acryloxybutyloxy-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane α,ω-bis[3-(meth)acrylamidopropyloxy-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acrylamidobutyloxy-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acrylamidobutyloxy-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acrylamidobutyloxy-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acrylamidobutyloxy-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane -(meth)acryloxypropylamino-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acryloxybutylamino-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane, α,ω-bis[(meth)acrylamidoethylamino-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acrylamidopropylamino-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane, α,47. The method or contact lens of embodiment 46, comprising ω-bis[3-(meth)acrylamido-butylamino-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane, α,ω-bis[(meth)acryloxy-2-hydroxypropyloxy-ethoxypropyl]-terminated polydimethylsiloxane, α,ω-bis[(meth)acryloxy-2-hydroxypropyl-N-ethylaminopropyl]-terminated polydimethylsiloxane, α,ω-bis[(meth)acryloxy-2-hydroxypropyl-aminopropyl]-polydimethylsiloxane, α,ω-bis[(meth)acryloxy-2-hydroxypropyloxy-(polyethyleneoxy)propyl]-terminated polydimethylsiloxane, α,ω-bis[(meth)acryloxyethylamino-carbonyloxy-ethoxypropyl]-terminated polydimethylsiloxane, α,ω-bis[(meth)acryloxyethylamino-carbonyloxy-(polyethyleneoxy)propyl]-terminated polydimethylsiloxane, or combinations thereof.

[0228] Embodiment 51. The method of any one of embodiments 40-50, wherein the at least one vinyl crosslinker comprises at least one non-silicone vinyl crosslinker.

[0229] Embodiment 52. The at least one non-silicone vinyl crosslinker is selected from the group consisting of ethylene glycol di-(meth)acrylate, diethylene glycol di-(meth)acrylate, triethylene glycol di-(meth)acrylate, tetraethylene glycol di-(meth)acrylate, glycerol di-(meth)acrylate, 1,3-propanediol di-(meth)acrylate, 1,3-butanediol di-(meth)acrylate, 1,4-butanediol di-(meth)acrylate, glycerol 1,3-diglycerol di-(meth)acrylate, 1,4-butanediol di-(meth)acrylate, 1,3-propanedi ... Cerolate di-(meth)acrylate, ethylene bis[oxy(2-hydroxypropane-1,3-diyl)]di-(meth)acrylate, bis[2-(meth)acryloxyethyl]phosphate, trimethylolpropane di-(meth)acrylate, and 3,4-bis[(meth)acryloyl]tetrahydrofuran, diacrylamide, dimethacrylamide, N,N-di(meth)acryloyl-N-methylamine, N,N-di(meth)acryloyl-N-ethylamine, N,N'-methylenebis 52. The method or contact lens of embodiment 51, comprising (meth)acrylamide, N,N'-ethylenebis(meth)acrylamide, N,N'-dihydroxyethylenebis(meth)acrylamide, N,N'-propylenebis(meth)acrylamide, N,N'-2-hydroxypropylenebis(meth)acrylamide, N,N'-2,3-dihydroxybutylenebis(meth)acrylamide, 1,3-bis(meth)acrylamidopropan-2-yl dihydrogen phosphate, piperazine diacrylamide, tetraethylene glycol divinyl ether, triethylene glycol divinyl ether, diethylene glycol divinyl ether, ethylene glycol divinyl ether, triallyl isocyanurate, triallyl cyanurate, trimethylopropane trimethacrylate, pentaerythritol tetramethacrylate, bisphenol A dimethacrylate, allyl methacrylate, allyl acrylate, N-allyl-methacrylamide, N-allyl-acrylamide, or combinations thereof.

[0230] Embodiment 53. The method or contact lens of any one of embodiments 40 to 52, wherein the silicone hydrogel comprises repeat units of at least one blending vinyl monomer.

[0231] Embodiment 54. The at least one blending vinyl monomer is a C1-C 10 54. The method or contact lens of embodiment 53, comprising an alkyl(meth)acrylate, cyclopentyl acrylate, cyclohexyl methacrylate, cyclohexyl acrylate, isobornyl(meth)acrylate, styrene, 2,4,6-trimethylstyrene (TMS), t-butylstyrene (TBS), trifluoroethyl(meth)acrylate, hexafluoro-isopropyl(meth)acrylate, hexafluorobutyl(meth)acrylate, or a combination thereof.

[0232] Embodiment 55. The method or contact lens of embodiment 53, wherein the at least one blending vinyl monomer comprises methyl methacrylate.

[0233] Embodiment 56. The method or contact lens of any one of embodiments 40-55, wherein the at least one hydrophilic vinyl monomer comprises at least one hydrophilic N-vinylamide monomer selected from the group consisting of N-vinylpyrrolidone, N-vinylpiperidone, N-vinylcaprolactam, N-vinyl-N-methylacetamide, N-vinylformamide, N-vinylacetamide, N-vinylisopropylamide, N-vinyl-N-methylacetamide, N-vinyl-N-ethylacetamide, N-vinyl-N-ethylformamide, and mixtures thereof.

[0234] Embodiment 57. The method or contact lens of any one of embodiments 40 to 55, wherein the at least one hydrophilic vinyl monomer comprises N-vinylpyrrolidone and / or N-vinyl-N-methylacetamide.

[0235] Embodiment 58. The at least one hydrophilic vinyl monomer is selected from the group consisting of (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N-ethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-propyl(meth)acrylamide, N-isopropyl(meth)acrylamide, N-3-methoxypropyl(meth)acrylamide, N-2-hydroxylethyl(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, poly(ethylene glycol)ethyl(meth)acrylamide having a number average molecular weight of 1500 or less, 2-(meth)acrylamidoglycolic acid, 3-(meth)acrylamidopropionic acid, 5-(meth)acrylamidopentanoic acid, 4-(meth)acrylamide 58. The method or contact lens of any one of embodiments 40 to 57, comprising a hydrophilic (meth)acrylamide monomer selected from the group consisting of butanoic acid, 3-(meth)acrylamido-2-methylbutanoic acid, 3-(meth)acrylamido-3-methylbutanoic acid, 2-(meth)acrylamido-2-methyl-3,3-dimethylbutanoic acid, 3-(meth)acrylamidohexanoic acid, 4-(meth)acrylamido-3,3-dimethylhexanoic acid, N-2-aminoethyl(meth)acrylamide, N-2-methylaminoethyl(meth)acrylamide, N-2-ethylaminoethyl(meth)acrylamide, N-2-dimethylaminoethyl(meth)acrylamide, N-3-aminopropyl(meth)acrylamide, N-3-methylaminopropyl(meth)acrylamide, N-3-dimethylaminopropyl(meth)acrylamide, methoxy-poly(ethylene glycol)ethyl(meth)acrylamide having a number average molecular weight of 1500 or less, and combinations thereof.

[0236] Embodiment 59. The method or contact lens of any one of embodiments 40-57, wherein the at least one hydrophilic vinyl monomer comprises a hydrophilic (meth)acrylamide monomer selected from the group consisting of (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N-ethyl(meth)acrylamide, N-propyl(meth)acrylamide, N-isopropyl(meth)acrylamide, N-3-methoxypropyl(meth)acrylamide, N-2-hydroxyethyl(meth)acrylamide, N-3-hydroxypropyl(meth)acrylamide, and combinations thereof.

[0237] Embodiment 60. The method or contact lens of any one of embodiments 40-59, wherein the at least one hydrophilic vinyl monomer comprises a hydroxy-containing vinyl monomer selected from the group consisting of hydroxyethyl (meth)acrylate, glycerol (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-amino-2-hydroxypropyl (meth)acrylate, N-2-hydroxyethyl (meth)acrylamide, N-3-hydroxypropyl (meth)acrylamide, N-2-hydroxypropyl (meth)acrylamide, N-2,3-dihydroxypropyl (meth)acrylamide, N-tris(hydroxymethyl)methyl (meth)acrylamide, vinyl alcohol, allyl alcohol, and combinations thereof.

[0238] Embodiment 61. 61. The method or contact lens of any one of claims 40 to 60, wherein the at least one hydrophilic vinyl monomer comprises a methylene-containing pyrrolidone monomer selected from the group consisting of 1-methyl-3-methylene-2-pyrrolidone, 1-ethyl-3-methylene-2-pyrrolidone, 1-methyl-5-methylene-2-pyrrolidone, 1-ethyl-5-methylene-2-pyrrolidone, 5-methyl-3-methylene-2-pyrrolidone, 5-ethyl-3-methylene-2-pyrrolidone, 1-n-propyl-3-methylene-2-pyrrolidone, 1-n-propyl-5-methylene-2-pyrrolidone, 1-isopropyl-3-methylene-2-pyrrolidone, 1-isopropyl-5-methylene-2-pyrrolidone, 1-n-butyl-3-methylene-2-pyrrolidone, 1-tert-butyl-3-methylene-2-pyrrolidone, and combinations thereof.

[0239] Embodiment 62. The method or contact lens of any one of embodiments 40-61, wherein the silicone hydrogel comprises repeat units of at least one UV-absorbing vinyl monomer, and optionally at least one UV / HEVL-absorbing vinyl monomer.

[0240] Embodiment 63. The method or contact lens of any one of embodiments 40 to 62, wherein the silicone hydrogel material has an equilibrium water content of about 10% to about 80% by weight.

[0241] Embodiment 64. The method or contact lens of any one of embodiments 40 to 63, wherein the silicone hydrogel material has an oxygen permeability of from about 50 barrers to about 180 barrers.

[0242] Embodiment 65. The method or contact lens of any one of embodiments 40 to 63, wherein the silicone hydrogel material has an oxygen permeability of from about 60 barrers to about 180 barrers.

[0243] Embodiment 66. The method or contact lens of any one of embodiments 40 to 63, wherein the silicone hydrogel material has an oxygen permeability of about 70 barrers to about 180 barrers.

[0244] Embodiment 67. The method or contact lens of any one of embodiments 40 to 63, wherein the silicone hydrogel material has an oxygen permeability of about 80 barrers to about 180 barrers.

[0245] Embodiment 68. The method of any one of embodiments 1-15 and 19-67 or the contact lens of any one of embodiments 16-67, wherein the contact lens has a water break-up time of at least 12.5 seconds.

[0246] Embodiment 69. The method of any one of embodiments 1 to 15 and 19 to 67 or the contact lens of any one of embodiments 16 to 67, wherein the contact lens has a water break-up time of at least 15 seconds.

[0247] Embodiment 70. The method of any one of embodiments 1-15 and 19-67 or the contact lens of any one of embodiments 16-67, wherein the contact lens has a water break-up time of at least 17.5 seconds.

[0248] Embodiment 71. The method of any one of embodiments 1-15 and 19-67 or the contact lens of any one of embodiments 16-67, wherein the contact lens has a water break-up time of at least 20 seconds.

[0249] The above disclosure will enable those skilled in the art to practice the present invention. Various modifications, variations, and combinations can be made to the various embodiments described herein. In order to better enable the reader to understand specific embodiments and their advantages, reference to the following examples is suggested. It is intended that the specification and examples be considered as illustrative. [Example]

[0250] Example 1 Oxygen permeability measurement Unless otherwise specified, the oxygen permeability (Dk / t) of the lens and lens material, the intrinsic (or edge-corrected) oxygen permeability (Dk i or Dk c ) is measured according to the procedure described in ISO 18369-4.

[0251] Finger rubbing treatment Rub the lenses with your fingers (wearing disposable, powder-free rubber gloves) for 20 seconds with RENU® Multipurpose Lens Care Solution (or another multipurpose lens care solution), then rinse with saline. Repeat the above procedure i times (i.e., i cycles of finger rubs) to begin daily cleaning in an i-day lens care regime, e.g., 7 times (i.e., 7 cycles of finger rubs) to begin daily cleaning and disinfection in a 7-day lens care regime, or 30 times (i.e., 30 cycles of finger rubs) to begin daily cleaning and disinfection in a 30-day lens care regime.

[0252] Lubricity evaluation. The lubricity of contact lenses is assessed by using a finger-felt lubricity test, which qualitatively characterizes the slipperiness of the lens surface on a friction rating scale of 0 to 4. The higher the friction rating, the less slipperiness (or lubricity).

[0253] Commercially available lenses: DAILIES® TOTAL 1®; ACUVUE® OASYS™; ACUVUE® ADVANCE PLUS™; DAILIES® Aqua Comfort Plus®; and AIR OPTIX® are assigned friction ratings (hereinafter referred to as "FR") of 0, 1, 2, 3, and 4, respectively, and are used as standard lenses for determining the friction ratings of the tested lenses.

[0254] The samples are placed in PBS for at least two rinses of 30 minutes each, then transferred to fresh PBS before evaluation. Prior to evaluation, hands are rinsed with soapy water, thoroughly rinsed with DI water, and then dried with a KimWipe® towel. The samples are handled between the fingers and assigned a numerical value compared to the standard lenses described above. For example, if the lenses are determined to be only slightly better than AIR OPTIX® lenses, they are assigned the number 3. Friction ratings are obtained by averaging the results of at least two friction ratings of contact lenses by two or more people, and / or by averaging friction ratings of two or more contact lenses (from the same batch of lens production) by one person.

[0255] The finger lubricity (i.e., friction rating) of contact lenses can be determined either directly out of the pack (OOP) but after immersion in PBS for 30 minutes or more, or after one cycle (e.g., 7, 14, 21, or 30 cycles) of finger rubbing, or after simulated wear cycling according to the procedure described above.

[0256] Surface Wettability Test The water contact angle (WCA) on contact lenses is a common measure of the surface wettability of a contact lens. In particular, a lower water contact angle corresponds to a more wettable surface. The average contact angle (droplet) on a contact lens is measured using a VCA 2500 XE contact angle measuring instrument manufactured by AST, Inc., located in Boston, Massachusetts. This instrument measures the advancing contact angle (θ a ) or receding contact angle (θ r) or sessile drop (static) contact angles can be measured. Unless otherwise specified, water contact angles are sessile drop (static) contact angles on the front surface of a contact lens. Measurements are performed on fully hydrated contact lenses immediately after wiping them dry. The wiped-dry lens is then mounted front-side up on a contact angle measurement stage, and the sessile drop contact angle is measured automatically using software provided by the manufacturer. The deionized (ultrapure) water used to measure water contact angles has a resistivity of >18 MΩcm, and the drop volume used is 2 μl. The tweezers and stage are thoroughly washed with isopropanol and rinsed with (deionized) water before contact with the contact lens. Each static water contact angle is the average of the left and right water contact angles. The static water contact angle for a contact lens is the average water contact angle obtained by averaging the static water contact angles measured on at least five contact lenses.

[0257] Water Breakdown Time (WBUT) Test The surface hydrophilicity of the lenses (after autoclaving) is assessed by measuring the time it takes for the water film to begin to break down on the lens surface. Lenses exhibiting a WBUT of ≥ 10 seconds are considered to have a hydrophilic surface and are expected to exhibit sufficient wettability (ability to support a tear film) on the eye.

[0258] The lenses are prepared for water-break measurements by removing them from their blisters with soft plastic tweezers (Menicon) and placing them in beakers containing phosphate-buffered saline. The beakers contain at least 20 mL of phosphate-buffered saline per lens, with a maximum of three lenses per beaker. The lenses are allowed to soak for a minimum of 30 minutes and a maximum of 24 hours, after which they are transferred with soft plastic tweezers into a 96-well plastic tray containing fresh phosphate-buffered saline.

[0259] Water Break-Up Time (WBUT) is measured at room temperature as follows: With soft plastic tweezers, pick up the lens as close to the edge of the lens as possible, with the base curve facing the user, taking care not to let the lens touch the sides of the well after removal from the saline solution. Shake the lens under test once to remove excess saline, and start the timer. Ideally, the water film on the base curve surface of the lens will recede from the point of contact with the tip of the tweezers in a uniform, circular pattern. When approximately 30% of the hydrated area has receded, stop the timer and record this time as the water break-up time (WBUT). Lenses that do not show the ideal retraction pattern can be rehydrated for at least 30 seconds, then returned to the tray and remeasured.

[0260] equilibrium water content The equilibrium water content (EWC) of a contact lens is measured as follows: The amount of water (expressed as weight percent) present in hydrated hydrogel contact lenses that have been fully equilibrated in saline is measured at room temperature using an analytical balance. The lenses are removed from the saline solution, quickly wiped dry with a cloth, stacked, and then transferred to aluminum pans of pre-recorded weight. The number of lenses per sample pan is typically five. The hydrated weight of the pan plus lenses is recorded. Cover the pans with aluminum foil. Place the pans in a laboratory oven at 100±2°C and dry for 16-18 hours. Remove the pans plus lenses from the oven and cool in a desiccator for at least 30 minutes. Remove the pans from the desiccator and discard the aluminum foil. Weigh the pans plus dry lens samples on an analytical balance. The wet and dry weights of the lens samples can be calculated by subtracting the weight of the empty weight pan, and the EWC is calculated from the missing weight divided by the number of lenses.

[0261] Elastic modulus The modulus of elasticity of contact lenses is measured using an MTS Insight instrument. Contact lenses are first cut into 3.12 mm wide strips using a Precision Concept two-stage cutter. Five thickness values are measured within a 6.5 mm gauge length. The strips are attached to the instrument grips and submerged in PBS at a controlled temperature of 21 ± 2°C. A 5 N load cell is typically used for testing. The grips are released at a constant rate until the sample breaks. Force and displacement data are collected by TestWorks software. The modulus value is calculated by the TestWorks software and is the slope or tangent of the stress versus strain curve near zero elongation in the elastic deformation region.

[0262] Low pH contamination test The integrity of the hydrogel coating on the contact lens can be determined according to the Nile Red staining test.

[0263] Prepare Nile-red stock solution by dissolving 25 mg of Nile-red dye in 250 mL of 1-propanol. Prepare Nile-red solution by diluting Nile-red stock solution with n-heptane in a 1:20 ratio.

[0264] The contact lenses to be tested are first immersed in an aqueous HCl solution (0.1 N) for 30 seconds, then removed from the HCl solution, immersed in a Nile Red solution for 2 seconds, and finally removed from the Nile Red solution and immersed in USP purified water for 30-60 seconds with agitation to rinse off excess Nile Red solution. A Nile Red solution (12.5 μg / mL) in n-heptane is prepared by diluting 250 μL of a Nile Red stock solution (250 μg / mL) in 1-propanol with 4750 μL of n-heptane.

[0265] Remove the lens from the blister. Gently tap the lens on a wipe to remove excess saline retained on the lens. Place the lens in 0.1N HCl (aqueous) solution for 30 seconds. Remove the lens and gently tap the lens on a wipe to remove excess HCl solution. Place in Nile-red solution for 2 seconds. Remove the lens and gently tap the lens on a wipe to remove excess Nile-red solution. Place the lens in DI water for at least 30 seconds to rinse off excess Nile-red solution. Fill the lens sample holder with DI water and place the lens in the holder. Add additional DI water on top of the lens. Place a cover glass on top of the water meniscus. Place the lens sample holder into the sample chamber.

[0266] The contact lens is illuminated with blue light of 470 nm wavelength to stimulate fluorescence. The Nile-red dye attaches itself to hydrophobic regions on the lens surface. The less red light emitted from the lens and the less Nile-red dye, the better the hydrophilic coating. Fluorescence images are recorded with a camera equipped with a filter that blocks the excitation light and only allows the fluorescent wavelengths of light to pass. As a result, areas of incomplete hydrogel coating appear bright orange in the fluorescence images. Observation of no contamination at all, a small bright orange stain, or a few small stains or small areas of low, intense orange indicates a "pass" of the test (i.e., intact hydrogel coating on the contact lens). Observation of strong orange overall staining, large areas and stains of even bright strong orange with more black areas than orange areas, large areas and stains of strong orange with equal black and orange areas, or large areas and stains of strong orange with less black area than orange areas indicates a "fail" of the test (i.e., the hydrogel coating is not intact on the contact lens).

[0267] As controls, silicone hydrogel contact lenses without any coating and silicone hydrogel contact lenses with a base coating (polyacrylic or polymethacrylic layer) are also tested. Because these contact lenses in the control experiments do not contain a hydrogel coating on them, Nile Red is able to penetrate into the bulk silicone hydrogel material of the contact lenses. They will fail the Nile Red staining test.

[0268] chemicals The following abbreviations are used in the following examples: MPC stands for 2-methacryloyloxyethyl phosphorylcholine; PEGMA300 stands for polyethylene glycol methacrylate with a number average molecular weight of 300; APMAm stands for N-(3-aminopropyl) methacrylamide; GM stands for glycidyl methacrylate; DMA stands for N,N-dimethylacrylamide; CE-PDMS stands for polysiloxane vinyl crosslinker (H 1The polymer (Mw approximately 11-12 KDa as determined by NMR spectroscopy) comprises three polydimethylsiloxane (PDMS) segments linked by diurethane bonds between two PDMS segments, with each of the two urethane bonds being located between one terminal methacrylate group and one PDMS segment, and was prepared according to a method similar to that described in Example 2 of U.S. Pat. No. 9,315,669; TRIS-Am represents N-[tris(trimethylsiloxy)-silylpropyl]acrylamide; Vazo-56 represents 2,2'-azobis(2-amidinopropane) dihydrochloride; Vazo-64 represents 2,2'-dimethyl-2,2'-azodipropionitrile; Norbloc represents 2-[2'-hydroxy-5'-(2-methacryloxyethyl)phenyl)]-2H-benzotriazole; and UV28 represents 2-( 3'-tert-butyl-2'-hydroxy-5'-(3"-methacryloyloxypropoxy)phenyl)-5-chloro-2H-benzotriazole; PAA represents polyacrylic acid; poly(AA-co-Am)(10 / 90) represents a copolymer of acrylic acid (AA, 10 mole%) and acrylamide (Am, 90 mole%); PAE represents polypolyamidoamine-epichlorohydrin. DI represents deionized water; EtOH represents ethanol; PrOH represents 1-propanol; MEK represents methyl ethyl ketone; 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, where wt% represents weight percent.

[0269] Example 2 Preparation of hydrophilic copolymers Dissolve 20.19 g of MPC and 20.24 g of PEGMA300 in 100 mL of water. Dissolve 5.01 g of APMAm in 25 mL of DI water. Dissolve 5.023 g of GMA in 75 mL of DI water and 45 g of EtOH. Dissolve 0.1342 g of Vazo-56 in 5 mL of DI water. Add all of the above prepared solutions to a 1 L jacketed reactor. Rinse the vessel with 200 mL of DI water and add the rinse water to the reactor. Purge the solution with nitrogen at a flow rate of approximately 100 mL / min for 10-12 minutes. After purging is complete, continue the nitrogen atmosphere at a flow rate of approximately 50 mL / min throughout the polymerization. Ramp the solution temperature from room temperature to 53°C over 2 hours and hold this temperature for 10 hours. Purify by ultrafiltration (10 kDa) using 4 bed volumes to remove residual monomers.

[0270] Kellification Research: To demonstrate the self-crosslinking capability, the hydrophilic copolymer prepared above (containing both epoxy and primary amino groups) is concentrated to 6.6% solids in water by rotovap. The measured pH is 6.5. The sample is divided into a control and two experimental samples (A and B). Sample A has a pH of 6.5 (original pH), and sample B has a pH of approximately 8.5 brought about by the addition of 3N NaOH. Both samples A and B are autoclaved for 45 minutes. The results are reported in Table 1. The increase in viscosity indicates inter- and intramolecular crosslinking of the hydrophilic copolymer.

[0271] [Table 1]

[0272] A second gel study was performed. PAA (M w A 5 wt. % aqueous solution of PAA (450 KD) is mixed with a 5 wt. % aqueous solution of the prepared hydrophilic copolymer after adjusting the pH to 7. After mixing the solutions, gelation occurs immediately. A section of the formed gel is removed and placed in excess water. The gel does not dissolve. This result indicates inter- and intramolecular cross-linking of the PAA and hydrophilic copolymer.

[0273] Example 3 Preparation of phosphate-buffered saline Phosphate buffered saline is prepared by dissolving 0.044 wt% NaH2PO4·H2O, 0.388 wt% Na2HPO4·2H2O, and 0.79% NaCl in DI water.

[0274] Preparation of 0.44% PAA solution 0.88 g of poly(acrylic acid) (PAA, M w Dissolve 191.66g of 1-propanol (approximately 450KD). Add 7.46g of formic acid and mix until the solution is homogeneous.

[0275] Preparation of IPC saline In-package cross-linked packaging saline ("IPC saline") is prepared according to the procedure described in Example 19 of U.S. Patent No. 8,480,227. The prepared IPC saline contains a partially cross-linked and thermally cross-linkable hydrophilic polymer material produced by an extra step, i.e., preheating PBS saline (pH 7.2-7.4) containing 0.07 wt% poly(Aam-co-AA) (90 / 10) Mw 200 KD and 0.15 wt% PAE.

[0276] Preparation of packaging saline Three packaging saline solutions ("Salines") are prepared with concentrations of hydrophilic copolymer (prepared in Example 2) by weight: 0.1% (Saline A), 0.5% (Saline B), and 2.0% (Saline C), as follows: Weigh purified copolymer solution (6.6% solids, prepared in Example 2) into a 20 mL scintillation vial. Add the remaining amounts of reagents, as shown in Table 2, to the vial and mix until completely dissolved.

[0277] [Table 2]

[0278] Preparation of Lens Formulations A lens formulation is prepared having the following composition: 10 parts by weight of PrOH; 32 parts by weight of DMA; 1.5 parts by weight of Norbloc; 0.4 parts by weight of UV28; 28 parts by weight of TRIS-Am; 40 parts by weight of CE-PDMS; and 0.5 parts by weight of Vazo-64. All ingredients are added to a clean bottle with a stir bar for mixing at 600 rpm for 30 minutes at room temperature. After all solids are dissolved, the formulation is filtered through a glass microfilter (2.7 μm GMP filter).

[0279] Lens manufacturing Lenses are prepared by cast molding from the lens formulation prepared above. The lens formulation is purged with nitrogen at room temperature for 30-35 minutes. The N2-purged lens formulation is introduced into a polypropylene mold. The mold with the lens formulation therein is placed in an oven at room temperature, and the oven is purged with N2 for 30 minutes. The mold with the lens formulation therein is placed in an oven at room temperature. The oven is then N2-purged for 30 minutes, and the heat-curing process proceeds according to the curing profile (heating from room temperature to 110°C at a ramp rate of approximately 5°C / min and immediately cooling).

[0280] The lens molds, each with one molded silicone hydrogel lens precursor therein, are mechanically opened. The molded silicone hydrogel precursor adheres to the male mold half and is removed (i.e., delensed) from the lens-attached male mold half by using liquid nitrogen.

[0281] After delensing, the SiHy Lens Precursor prepared above is subjected to the following post-molding steps (ie, immersion of the SiHy Lens Precursor in a series of different solution baths) as shown in Table 3.

[0282] [Table 3]

[0283] The SiHy contact lenses have the following properties: Dkc about 140 barrer; EWC about 32% by weight; modulus of elasticity about 0.79 MPa.

[0284] Application of cross-linked hydrophilic coatings (hydrogel coatings) After the above post-molding steps, the resulting SiHy contact lenses are individually placed into polypropylene lens packaging shells (or blisters) (one lens per shell) each containing 0.65 mL of Saline A, Saline B, Saline C, PBS, or IPC Saline. The blisters are then sealed with foil and autoclaved at about 121° C. for about 45 minutes.

[0285] Lens Testing: After autoclaving, the coated SiHy contact lenses are evaluated by low pH CLAN to test for the presence of a homogeneous, cross-linked lens surface coating. The negative control (without any hydrogel coating thereon) fails this test, while the positive control (with hydrogel coating thereon) and the three tested lenses pass the test, indicating the presence of a cross-linked, homogeneous surface coating (hydrogel coating). The coated SiHy contact lenses are also subjected to one cycle of manual rubbing to evaluate the durability of the hydrogel. These tested lenses still pass the low pH CLAN test, indicating some durability of the hydrogel coating. A finger lubricity test also indicates good lubricity of the lens surface.

[0286] [Table 4]

[0287] All publications, patents and published patent applications cited herein above in this application are hereby incorporated by reference in their entirety.

Claims

1. 1. A method for producing a coated contact lens, comprising: (1) obtaining a contact lens precursor having a concave surface and an opposite convex surface, the contact lens precursor including a lens bulk material and carboxylic acid groups on and / or near the anterior and posterior surfaces; (2) immersing the contact lens precursor in an aqueous solution in a container, wherein the aqueous solution comprises from about 0.01% to about 5.0% by weight of at least one hydrophilic copolymer comprising (a) monomer units of at least one epoxy-containing vinyl monomer, (b) monomer units of at least one amino-containing vinyl monomer having a primary or secondary amino group, (c) monomer units of at least one polyethylene glycol-containing vinyl monomer, and (d) monomer units of at least one phosphorylcholine-containing vinyl monomer, wherein the sum of the amounts of components (a) and (b) in the at least one hydrophilic copolymer is about 40 mole % or less; (3) heating the aqueous solution having the contact lens precursor therein at a temperature of about 100° C. to about 140° C. for at least 30 minutes to form a coated contact lens having a hydrogel coating thereon, wherein the hydrogel coating is covalently bonded to the anterior and posterior surfaces by bonds formed between one carboxylic acid group and one epoxy group, respectively, and the hydrogel coating comprises a crosslinked polymeric material including polymer chains derived from the hydrophilic copolymer; Including, The method, wherein the contact lens has a water break-up time (WBUT) of at least 10 seconds.

2. 10. The method of claim 1, wherein the contact lens precursor is comprised of a lens bulk material having carboxylic acid groups on and / or near a surface of the bulk material.

3. 3. The method of claim 2, wherein the lens bulk material is obtained by polymerizing a polymerizable composition comprising about 0.1% to about 10% by weight of a vinyl monomer further comprising at least one carboxylic acid group.

4. 3. The method of claim 2, wherein the lens bulk material has been subjected to at least one post-cure surface treatment to have carboxylic acid groups on and / or near the surface of the lens bulk material.

5. 10. The method of claim 1, wherein the contact lens precursor comprises a lens bulk material and at least one layer of polymeric material having carboxylic acid groups thereon.

6. The at least one polymeric material having carboxylic acid groups is selected from acrylic acid or C １ ~C ３ 6. The method of claim 5, comprising a homopolymer or copolymer of an alkylacrylic acid.

7. 7. The method of any one of claims 1 to 6, wherein the heating step is carried out by autoclaving the contact lens precursor having carboxylic acid groups thereon, immersed in the aqueous solution that is a packaging solution in a sealed lens package, at a temperature of about 115°C to about 125°C for approximately 30 to 90 minutes.

8. 1. A contact lens comprising a front surface, an opposite posterior surface, and a layered arrangement from the front surface to the posterior surface, the layered arrangement comprising an outer front hydrogel layer, an inner layer, and an outer posterior hydrogel layer, the inner layer comprising a lens bulk material and having carboxylic acid groups on and / or near a surface of the inner layer, the outer front hydrogel layer and the outer posterior hydrogel layer comprising: (a) monomer units of at least one epoxy-containing vinyl monomer; (b) monomer units of at least one amino-containing vinyl monomer having a primary or secondary amino group; (c) monomer units of at least one polyethylene glycol-containing vinyl monomer; 1. A contact lens comprising a crosslinked polymeric material comprising polymer chains derived from a hydrophilic polymer comprising monomer units of a vinyl-containing monomer, and (d) monomer units of at least one phosphorylcholine-containing vinyl monomer, wherein the sum of the amounts of components (a) and (b) in said at least one hydrophilic copolymer is about 40 mol % or less, wherein said outer anterior hydrogel layer and said outer posterior hydrogel layer are covalently bonded onto said inner layer by bonds formed between one carboxylic acid group and one epoxy group, respectively, and wherein said contact lens has a water-break time (WBUT) of at least 10 seconds.

9. 9. The contact lens of claim 8, wherein the inner layer is comprised of a lens bulk material having carboxylic acid groups on and / or near a surface of the bulk material.

10. The inner layer comprises a lens bulk material and a layer of at least one polymeric material having carboxylic acid groups, the at least one polymeric material having carboxylic acid groups being acrylic acid or C １ ~C ３ 9. The contact lens of claim 8, comprising a homopolymer or copolymer of an alkylacrylic acid.

11. The at least one hydrophilic copolymer is (a) Formula 【Chemical 1】 monomer units of at least one epoxy-containing vinyl monomer; (b) Formula 【Chemistry 2】 monomer units of at least one amino-containing acrylic monomer; (c) Formula 【Chemistry 3】 and monomer units of at least one polyethylene glycol-containing acrylic monomer of (d) Formula 【Chemistry 4】 Monomer units of at least one phosphorylcholine-containing acrylic monomer Including, During the ceremony: Each R is independent of the others ０ is H or CH ３ and each R ０ ' is H or C １ ~C ４ alkyl; and each independently B １ , B ２ and B ３ is O or NR'; R' is H or C １ ~C ４ alkyl; and each independently D １ , D ２ and D ３ is C １ ~C １２ an alkylene divalent radical; D ０ is C １ ~C １２ Alkylene divalent radical or -D ４ -O-D ５ -B ４ -CH ２ - is a divalent radical; B ４ is -O- or 【Chemistry 5】 and D ４ is C １ ~C １２ an alkylene divalent radical; D ５ is C ２ ~C ６ an alkylene divalent radical or 【Chemistry 6】 and independently D ６ and D ７ is C ２ ~C ６ is an alkylene divalent radical; d1 is zero, 1, or 2; PEG is 【Chemistry 7】 (Wherein R″ is H or C １ ~C ４ alkyl; t2 is an integer from 3 to 100); PC is a polyethylene glycol group of the formula: 【Chemistry 8】 (wherein t1 is an integer of 1 to 5, and １ R, ２ R and ３ R is C １ ~C ８ Alkyl or C １ ~C ８ The method of any one of claims 1 to 7 or the contact lens of any one of claims 8 to 10, wherein the zwitterionic group is hydroxyalkyl.

12. The at least one hydrophilic copolymer has formula (I): 【Chemistry 9】 [In the formula, T′ and T″, independently of each other, are H or a terminal group; ０ is H or CH ３ and each R ０ ' is H or C １ ~C ４ alkyl; and each independently B １ , B ２ and B ３ is O or NR'; R' is H or C １ ~C ４ alkyl; and each independently D １ , D ２ and D ３ is C １ ~C １２ an alkylene divalent radical; D ０ is C １ ~C １２ Alkylene divalent radical or -D ４ -O-D ５ -B ４ -CH ２ - is a divalent radical; B ４ is -O- or 【Chemistry 10】 and D ４ is C １ ~C １２ an alkylene divalent radical; D ５ is C ２ ~C ６ an alkylene divalent radical or 【Chemistry 11】 and independently D ６ and D ７ is C ２ ~C ６ is an alkylene divalent radical; d1 is zero, 1, or 2; PEG is 【Chemistry 12】 (Wherein R″ is H or C １ ~C ４ alkyl; t2 is an integer from 3 to 100); PC is a polyethylene glycol group of the formula: 【Chemistry 13】 (wherein t1 is an integer of 1 to 5, and １ R, ２ R and ３ R is C １ ~C ８ Alkyl or C １ ~C ８ a, b, c, and d, independently of one another, are integers from 5 to 100, where (a+c) / (a+b+c+d)≦0.

40. The method according to any one of claims 1 to 7 or the contact lens according to any one of claims 8 to 10, wherein the copolymer is a statistical copolymer of

13. 13. The method of any one of claims 1 to 7, 11 and 12 or the contact lens of any one of claims 8 to 12, wherein the lens bulk material is (i) a hard plastic material, (ii) a rigid gas permeable lens material, (iii) a non-silicone hydrogel material, or (iv) a silicone hydrogel material.

14. 13. The method of any one of claims 1 to 7, 11 and 12 or the contact lens of any one of claims 8 to 12, wherein the lens bulk material consists essentially of: (a) a central optic made essentially of a rigid gas permeable lens material and surrounded by a peripheral portion made essentially of a silicone hydrogel material; or (b) a three-dimensional article and a silicone hydrogel material, wherein the three-dimensional article is made of a non-hydrogel material and has a three-dimensional size smaller than that of a pre-formed implantable contact lens such that the three-dimensional article is completely embedded within the non-silicone hydrogel material.

15. 13. The method of any one of claims 1 to 7, 11 and 12 or the contact lens of any one of claims 8 to 12, wherein the lens bulk material consists essentially of: (a) a central optic made essentially of a rigid gas permeable lens material and surrounded by a peripheral portion made essentially of a non-silicone hydrogel material; or (b) a three-dimensional article and a non-silicone hydrogel material, wherein the three-dimensional article is made of a non-hydrogel material and has a three-dimensional size smaller than that of a pre-formed implantable contact lens such that the three-dimensional article is completely embedded within the non-silicone hydrogel material.

Images