Uv / HEVL filterable contact lenses

Abstract

Described herein are UV / HEVL absorbent contact lenses of the present invention, comprising a bulk hydrogel material comprising recurring units of at least one UV absorbent ethylene-based monomer, recurring units of at least one UV / HEVL absorbent ethylene-based monomer, and a derivative of reactive Cu (II)-porphyrin present in selected amounts and selected ratios. The UV / HEVL filterable contact lenses of the present invention not only can provide class I UV protection against UVA and UVB rays (i.e., filter more than 90% of UVA and 99% of UVB rays), but also can imitate natural crystalline lenses of human eyes while providing HEVL protection.

Description

[0001] The present invention relates to a contact lens, preferably a silicone hydrogel contact lens, which is capable of filtering UV light and high energy visible light (HEVL) having a wavelength of 380 nm to 450 nm. Background Art

[0002] LED lights and electronic devices, including smartphones, computer screens, LCD and LED televisions, are already widely used. They typically emit short-wavelength visible light, including violet (380-450nm) and blue (450-495nm). This type of short-wavelength visible light has been shown to be harmful to cells in both in vitro and in vivo studies reported in the following: Experimental Eye Research 2006, 83, 1493; J. Cataract Refrac Surg 2009, 35, 354; Graefe's Arch Clin Exp Ophthalmol 2008, 246, 671; Acta Ophthalmologica Scandinavica 2006, 84, 4; Br J Ophthalmol 2006, 90, 784; Optometry and Vision Science 2011, 88(6), 1. Considerable effort has been made to develop HELV filtering ophthalmic lenses (such as glasses, contact lenses, intraocular lenses, etc.) to protect the eyes from increased HEVL exposure due to the widespread use of LED lights and LED displays (e.g., smart phones, televisions, and computer monitors) (see, e.g., U.S. Patent Nos. 4,612,358, 4,528,311, 4,716,234, 4,878,748, 5,400,175, 5,662,707, 6,158,862, 6,955,430, 7,556,376, 7,803,359, 8,153,703, 8,23 2326, 8360574, 8585938, 8882267, 9377569, 9683102, 9814658, 10551637, and 10610472; U.S. Patent Application Publication Nos. 20170242274, 20180371139, 20190002415, 20190002459, 20190271798, 20190339544, 20200002267, 20200095187, 20200407324, and 20200407337).

[0003] Contact lenses (from Alcon) not only include Class I UV absorption to protect against UVA and UVB rays (ie, filter greater than 90% of UVA and 99% of UVB rays), but also filter out approximately 34% of HEVL rays (between 380nm-450nm) that enter the eye. It is the first contact lens to provide HEVL filtering capabilities that remain effective while the lens is worn, regardless of lighting conditions.

[0004] Still hope for more Contact lenses are contact lens products with much higher HELV filtering capabilities to better protect the wearer's eyes from HEVL damage, especially ultraviolet light damage. Summary of the invention

[0005] The present invention provides a UV / HEVL filtering contact lens, which comprises a bulk hydrogel material, wherein the bulk hydrogel material comprises: (1) repeating units of at least one hydrophilic vinyl monomer; (2) repeating units of at least one vinyl crosslinking agent; (3) repeating units of at least one UV absorbing vinyl monomer that absorbs UV light between 280 nm and 380 nm; (4) at least one UV / HEVL absorbing vinyl monomer that absorbs UV light between 280 nm and 380 nm and HEVL between 380 nm and 450 nm; and (5) at least one derivative of Cu(II)-porphyrin, wherein The derivative is covalently attached to the bulk hydrogel material and has an absorption peak (i.e., a Soret peak or band) in the region from 395 nm to 435 nm in the visible light absorption spectrum; wherein the components (3), (4) and (5) are present in the bulk hydrogel material in a certain amount and at a certain ratio so that the UV / HEVL filtering contact lens has a UVA %T of less than 10%, a UVB %T of less than 1%, a HEVL %T of about 60% or less, a %T at 420 nm of about 40% or less, and a %T at wavelengths between 450 nm and 500 nm of about 80% or more. BRIEF DESCRIPTION OF THE DRAWINGS

[0006] Figure 1 Shown are the UV / visible light transmission spectra of contact lenses prepared from a polymerizable composition comprising 0.9 wt % Norbloc (UV absorbing vinyl monomer), different amounts of UV28 (UV / HEVL absorbing vinyl monomer): Curve 1 (squares) - 0.2 wt % UV28; Curve 2 (triangles) - 0.3 wt % UV28; Curve 3 (circles) - 0.4 wt % UV28.

[0007] Figure 2Shown are the UV / visible transmission spectra of contact lenses prepared from polymerizable compositions comprising 0.9 wt % Norbloc, varying amounts of Cu(II)-TBP-Mam, and varying amounts of RB247 (polymerizable blue dye): Curve 1 (squares) - 0.03 wt % Cu(II)-TBP-Mam; Curve 2 (triangles) - 0.05 wt % Cu(II)-TBP-Mam; Curve 3 (circles) - 0.07 wt % Cu(II)-TBP-Mam.

[0008] Figure 3 Shown are the UV / visible light transmission spectra of contact lenses prepared from a polymerizable composition comprising: (i) 0.9 wt% Norbloc and (ii) 0.2 wt% UV28, 0.03 wt% Cu(II)TBP-Mam, or a combination thereof: Curve 1 (squares) - 0.2 wt% UV28; Curve 2 (circles) - 0.03 wt% Cu(II)-TBP-Mam; Curve 3 (triangles) - 0.03 wt% Cu(II)-TBP-Mam + 0.2 wt% UV28.

[0009] Figure 4 Shown are the UV / visible light transmission spectra of contact lenses prepared from a polymerizable composition comprising: (i) 0.9 wt% Norbloc and (ii) 0.3 wt% UV28, 0.05 wt% Cu(II)TBP-Mam, or a combination thereof: Curve 1 (squares) - 0.3 wt% UV28; Curve 2 (circles) - 0.05 wt% Cu(II)-TBP-Mam; Curve 3 (triangles) - 0.05 wt% Cu(II)-TBP-Mam + 0.3 wt% UV28. DETAILED DESCRIPTION

[0010] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those of ordinary skill in the art to which the invention belongs. In general, 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. When a term is provided in the singular, the inventors also contemplate the plural form of the term. The nomenclature used herein and the laboratory procedures described below are well-known and commonly used in the art.

[0011] As used herein, "about" means that the number referred to as "about" includes the recited number plus or minus 1%-10% of that recited number.

[0012] “Optional” or “optionally” means that the subsequently described event or circumstance may or may not occur, and that the description includes instances where said event or circumstance occurs and instances where it does not.

[0013] As used herein, "ophthalmic device" refers to contact lenses (hard or soft), intraocular lenses, corneal onlays, other ophthalmic devices used on or around the eye (eg, stents, glaucoma shunts, etc.).

[0014] "Contact lens" refers to a structure that can be placed on or in the wearer's eye. Contact lenses can correct, improve or change the user's vision, but need not do so. Contact lenses can be of any suitable material known in the art or later developed, and can be soft lenses, hard lenses or hybrid lenses.

[0015] "Hydrogel contact lens" refers to a contact lens comprising a hydrogel bulk (core) material. The hydrogel bulk material can be a non-silicone hydrogel material or, preferably, a silicone hydrogel material.

[0016] "Hydrogel" or "hydrogel material" refers to a crosslinked polymer material having a three-dimensional polymer network (ie, polymer matrix) that is insoluble in water but can hold at least 10% by weight of water in its polymer matrix when fully hydrated (or equilibrium).

[0017] Siloxanes, which are often also described as silicones, refer to molecules having at least one —Si—O—Si— moiety, wherein each Si atom carries two organic groups as substituents.

[0018] "Silicone hydrogel" or "SiHy" refers to a silicone-containing hydrogel obtained by copolymerization of a polymerizable composition comprising at least one silicone-containing monomer or at least one silicone-containing macromer or at least one crosslinkable silicone-containing prepolymer.

[0019] As used in this application, the term "non-silicone hydrogel" refers to a hydrogel that theoretically does not contain silicone.

[0020] As used herein, "hydrophilic" describes a material or portion thereof that will associate with water more readily than with lipids.

[0021] The term "room temperature" refers to a temperature of about 22°C to about 26°C.

[0022] The term "soluble" with respect to a compound or material in a solvent means that the compound or material is soluble in the solvent at room temperature (ie, about 22°C to about 26°C) to give a solution having a concentration of at least about 0.5% by weight.

[0023] The term "insoluble" with respect to a compound or material in a solvent means that the compound or material is soluble in the solvent at room temperature (as defined above) to give a solution having a concentration of less than 0.01% by weight.

[0024] "Vinyl monomer" refers to a compound having a single ethylenically unsaturated group, which is soluble in a solvent and can be polymerized actinically or thermally.

[0025] The term "ethylenically unsaturated group" is used herein in a broad sense and is intended to encompass olefinic hydrocarbons containing at least one >C=CH 2 Any group of a group. Exemplary ethylenically unsaturated groups include, but are not limited to: (meth)acryloyl ( and / or ), vinyloxycarbonylamino ( Where R o Is H or C 1 -C 4 alkyl), vinyloxycarbonyloxy Allyl, vinyl, styryl or other C=C containing groups.

[0026] As used herein, "actinically" with respect to the curing, crosslinking or polymerization of a polymerizable composition, prepolymer or material means curing (e.g., crosslinking and / or polymerization) by actinic radiation, such as UV / visible radiation, etc. Thermal curing or photochemical curing methods are well known to those skilled in the art.

[0027] "Acrylic monomer" refers to a vinyl monomer having a single (meth)acryloyl group. Examples of acrylic monomers include (meth)acryloxy (or (meth)acryloyloxy) monomers and (meth)acrylamide monomers.

[0028] "(meth)acryloxy or (meth)acryloyloxy) monomer" means a monomer having a single Group of vinyl monomers.

[0029] "(Meth)acrylamide-based monomers" refers to A vinyl monomer having a unique group, wherein R o Is H or C 1 -C 4 alkyl.

[0030] The term "(meth)acrylamide" refers to methacrylamide and / or acrylamide.

[0031] The term "(meth)acrylate" refers to methacrylate and / or acrylate.

[0032] An "N-vinylamide monomer" refers to a vinyl group (-CH=CH 2 ) amide compound.

[0033] The term "ene group" refers to a monovalent group CH that is not covalently attached to an oxygen or nitrogen atom or a carbonyl group. 2 =CH- or CH 2 =CCH 3 -.

[0034] "Ene monomer" refers to a vinyl monomer having one and only one olefinic group.

[0035] The "vinyloxycarbonylamino monomer" refers to a vinyl monomer having only one vinyloxycarbonylamino group.

[0036] "Vinylaminocarbonyloxy monomer" refers to a vinylic monomer having a unique vinylaminocarbonyloxy group.

[0037] "Vinylaminocarbonylamino monomer" refers to a vinyl monomer having one and only one vinylaminocarbonylamino group.

[0038] "Hydrophilic vinylic monomer" refers to a vinylic monomer that typically yields a homopolymer that is water soluble or that can absorb at least 10% by weight of water.

[0039] "Hydrophobic vinylic monomer" refers to a vinylic monomer that typically produces a homopolymer that is insoluble in water and can absorb less than 10% by weight of water.

[0040] As used in this application, the term "ethylene-based crosslinking agent" refers to an organic compound having at least two ethylenically unsaturated groups. "Ethylene-based crosslinking agent" refers to an ethylene-based crosslinking agent having a molecular weight of 700 Daltons or less.

[0041] The "acrylic crosslinking agent" refers to a vinyl crosslinking agent having at least two (meth)acryloyl groups.

[0042] The term "acrylic repeating units" refers to repeating units of a polymeric material, each of which is derived from an acrylic monomer or a cross-linking agent that is free radically polymerized to form the polymeric material.

[0043] The term "terminal (meth)acryloyl group" refers to one (meth)acryloyl group at one of the two terminals of the main chain (or backbone) of an organic compound.

[0044] As used in this application, the term "polymer" means a material formed by polymerizing or cross-linking one or more monomers or macromers or prepolymers, or a combination thereof.

[0045] "Macromer" or "prepolymer" refers to a compound or polymer containing ethylenically unsaturated groups and having a number average molecular weight greater than 700 Daltons.

[0046] As used in this application, the term "molecular weight" of a polymeric material (including a monomeric material or a macromolecular monomeric material) refers to the number average molecular weight, unless specifically indicated otherwise or unless the test conditions indicate otherwise. The skilled person knows how to determine the molecular weight of a polymer according to known methods, such as, for example, GPC (gel permeation chromatography) with one or more of the following: a refractive index detector, a small angle laser light scattering detector, a multi-angle laser light scattering detector, a differential viscometry detector, a UV detector, and an infrared (IR) detector; MALDI-TOF MS (matrix-assisted laser desorption / ionization time-of-flight mass spectrometry); 1 H NMR (proton nuclear magnetic resonance) spectroscopy, etc.

[0047] "Polysiloxane segments" or "polydiorganosiloxane segments" refer interchangeably to polymer chain segments (i.e., divalent groups) Where SN is an integer of 3 or greater, and R S1 and R S2 Each of which is independently selected from the group consisting of: C 1 -C 10 Alkyl; Phenyl; C 1 -C 4 -alkyl-substituted phenyl; C 1 -C 4 -alkoxy-substituted phenyl; phenyl-C 1 -C 6 -alkyl; C 1 -C 10 Fluoroalkyl; C 1 -C 10 Fluoroether; Aryl; Aryl C 1 -C 18 Alkyl; -alk-(OC 2 H 4 ) γ1 -OR o (where alk is C 1 -C 6 Alkylene diradical, R o Is H or C 1 -C 4alkyl and γ1 is an integer from 1 to 10); C 2 -C 40 An organic group having at least one selected from the group consisting of hydroxyl (-OH), carboxyl (-COOH), amino (-NR N1 R N1 '), amino linker -NR N1 -, amide linker -CONR N1 -, amide-CONR N1 R N1 ', urethane linker -OCONH- and C 1 -C 4 Alkoxy functional groups, or linear hydrophilic polymer chains, wherein R N1 and R N1 ' are independently hydrogen or C 1 -C 15 an alkyl group; and a photochromic organic group having a photochromic group.

[0048] "Polydiorganosiloxane vinylic monomer" or "polysiloxane vinylic monomer" interchangeably refers to a compound containing at least one polysiloxane segment and one unique ethylenically unsaturated group.

[0049] "Polydiorganosiloxane vinyl crosslinker" or "polysiloxane vinyl crosslinker" interchangeably refers to a compound comprising at least one polysiloxane segment and at least two ethylenically unsaturated groups.

[0050] "Linear polydiorganosiloxane vinyl crosslinker" or "linear polysiloxane vinyl crosslinker" interchangeably refers to a compound comprising a backbone comprising at least one polysiloxane segment and terminated at each of the two ends of the backbone with an ethylenically unsaturated group.

[0051] "Extended chain polydiorganosiloxane vinyl crosslinker" or "extended chain polysiloxane vinyl crosslinker" interchangeably refers to a compound comprising at least two ethylenically unsaturated groups and at least two polysiloxane segments, each pair of which is linked by a divalent group.

[0052] The term "photochromic compound" refers to a compound that has a colorless (or light-colored) form and a colored form and that can undergo a reversible change from the colorless (or light-colored) form (or the so-called "deactivated form") to the colored form (or the so-called "activated form") when exposed to UV or HEVL radiation.

[0053] The term "colorless or lightly colored state" or "unactivated state" with respect to a photochromic contact lens means the original state of the photochromic contact lens before the photochromic contact lens is irradiated with UV and / or HEVL. In this state, the photochromic contact lens is typically colorless or shows a faint color as observed by the naked eye.

[0054] The term "colored state" or "activated state" in relation to a photochromic contact lens means the state of the photochromic contact lens when the photochromic contact lens is irradiated with UV and / or HEVL. In this state, the photochromic contact lens typically shows a dark color as observed by the naked eye.

[0055] The term "fluid" as used herein indicates a material that is capable of flowing like a liquid.

[0056] As used in this application, the term "transparent" with respect to a polymerizable composition means that the polymerizable composition is a transparent solution or liquid mixture having a light transmittance of 85% or more in the range between 400 nm and 700 nm.

[0057] The free radical initiator can be a photoinitiator or a thermal initiator. "Thermal initiator" or "thermal free radical initiator" interchangeably refers to a chemical that initiates a free radical crosslinking / polymerization reaction by utilizing thermal energy. "Photoinitiator" refers to a chemical that initiates a free radical crosslinking / polymerization reaction by utilizing light.

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

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

[0060] In the present application, the term "substituted" with respect to an alkyl group or an alkylene group means that the alkyl group or the alkylene group includes at least one substituent group, which replaces one hydrogen atom of the alkyl group or the alkylene group and is selected from the group consisting of: hydroxyl (-OH), carboxyl (-COOH), -NH 2 , thiol (-SH), C 1 -C 4 Alkyl, C 1 -C 4 Alkoxy, C 1 -C 4 Alkylthio (alkyl sulfide), C 1 -C 4 Acylamino, C 1 -C 4 Alkylamino, di-C 1 -C 4 Alkylamino, and combinations thereof.

[0061] "Post-cure surface treatment" with respect to SiHy lens bulk material or SiHy contact lens means a surface treatment process performed after the SiHy lens bulk material or SiHy contact lens is formed by curing (ie, polymerizing thermally or actinically) a SiHy lens formulation.

[0062] The terms "silicone hydrogel lens formulation" or "SiHy lens formulation" interchangeably refer to a polymerizable composition comprising all necessary polymerizable components for producing a SiHy contact lens or SiHy lens bulk material.

[0063] "UV absorbing vinylic monomer" refers to a compound containing one unique ethylenically unsaturated group and which can absorb UV light primarily between 280 nm and 380 nm. It is understood that the UV absorbing vinylic monomer does not absorb or negligibly absorbs light having a wavelength greater than 400 nm (i.e., has a %T greater than 90% at 400 nm when tested with a solution of the UV absorbing vinylic monomer having a concentration of 0.1 mM and a path length of 1 cm).

[0064] "UV / HEVL absorbing vinylic monomer" refers to a compound that contains one unique ethylenically unsaturated group and that can absorb UV light between 280 nm and 380 nm and HEVL between 380 nm and 450 nm.

[0065] “UVA” refers to radiation occurring at wavelengths between 315 and 380 nanometers; “UVB” refers to radiation occurring between 280 and 315 nanometers; and “HEVL” refers to radiation occurring at wavelengths between 380 and 450 nanometers.

[0066] "UVA transmittance" (or "UVA %T"), "UVB transmittance" or "UVB %T", and "HEVL transmittance" or "HEVL %T" are calculated by the following formulas.

[0067] UVA %T = average % transmittance between 315nm and 380nm x 100

[0068] UVB %T = average % transmittance between 280nm and 315nm x 100

[0069] HEVL %T = average % transmission between 380nm and 450nm x 100

[0070] HEVL% Filtration = 100% - HEVL% T

[0071] "% T at a wavelength" refers to the percent transmittance at that wavelength.

[0072] "Derivative" with respect to Cu(II)-porphyrin means a moiety that is the product of Cu(II)-porphyrin after participating in free radical polymerization of a polymerizable composition containing Cu(II)-porphyrin to form a polymeric material, is covalently attached to the resulting polymeric material, and still has an aromatic π-electron system that is substantially similar to the aromatic π-electron system of the starting Cu(II)-porphyrin, as indicated by having a strong peak (i.e., a Soret peak or band) in the blue wavelength region of the visible spectrum.

[0073] Material's "oxygen permeability" Dk i is the rate at which oxygen passes through a material and can be measured at about 34°C-35°C according to the procedure described in Example 1. Oxygen permeability is conventionally expressed in barrers, where "barrer" is defined as [(cm 3 Oxygen)(mm) / (cm 2 )(sec)(mm Hg)]x10 -10 .

[0074] The "oxygen transmission rate" Dk / t of a lens or material is the rate at which oxygen will pass through a particular lens or material having an average thickness t [in mm] over an area measured. Oxygen transmission rate is conventionally expressed in units of barrer / mm, where "barrer / mm" is defined as [(cm 3 Oxygen) / (cm 2 )(s)(mm Hg)]x10 -9 .

[0075] The term "modulus" or "elastic modulus" with respect to a contact lens or material means the tensile modulus or Young's modulus which is a measure of the stiffness of the contact lens or material. The modulus can be measured according to the procedure described in Example 1.

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

[0077] As used herein, "surface modification" or "surface treatment" means that the article has been treated in a surface treatment process wherein (1) a coating is applied to the surface of the article, (2) a chemical substance is adsorbed onto the surface of the article, (3) the chemical nature of chemical groups on the surface of the article is changed (e.g., electrostatic charge), or (4) the surface characteristics of the article are otherwise modified. Exemplary surface treatment processes include, but are not limited to: surface treatment by energy (e.g., plasma, electrostatic charge, irradiation or other energy sources); chemical treatment; grafting of hydrophilic vinyl monomers or macromers onto the surface of the article; the mold transfer coating process disclosed in U.S. Pat. No. 6,719,929; incorporation of wetting agents into lens formulations for making contact lenses as proposed in U.S. Pat. Nos. 6,367,929 and 6,822,016; enhanced mold transfer coating disclosed in U.S. Pat. No. 7,858,000; and hydrophilic coatings consisting of covalent attachment or physical deposition of one or more layers of one or more hydrophilic polymers on the surface of the 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.

[0078] "Hydrophilic surface" with respect to a SiHy material or a contact lens means that the SiHy material or the contact lens has a surface hydrophilicity characterized by having an average water contact angle of about 90 degrees or less, preferably about 80 degrees or less, more preferably about 70 degrees or less, more preferably about 60 degrees or less.

[0079] "Average contact angle" refers to the water contact angle (static water contact angle measured by the sessile drop method) obtained by averaging the measurements of at least 3 individual contact lenses.

[0080] In the present application, "Cu(II)-meso-aryl-substituted porphyrin" refers to a copper porphyrin which comprises four aryl groups (as substituents) at positions 5, 10, 15 and 20 (i.e. the so-called meso positions) of the porphyrin as known to the person skilled in the art.

[0081] In general, the present invention relates to a UV / HEVL filtering contact lens, and more particularly to a UV / HEVL filtering SiHy contact lens having an ideal UV / HEVL absorption profile, including: UVA %T of less than 10%, UVB %T of less than 1%, HEVL %T of about 60% or less, %T at 420 nm of about 40% or less, and %T at 450 nm of about 80% or greater. The present invention is based in part on the discovery that by selecting and adding a UV-absorbing vinylic monomer, a UV / HEVL-absorbing vinylic monomer, and a reactive Cu(II)-porphyrin (preferably a Cu(II)-meso-aryl-substituted porphyrin) in certain amounts and in selected ratios to a polymerizable composition for making a contact lens, one can obtain a UV / HEVL filtering contact lens having the above-described ideal UV / HEVL absorption profile.

[0082] The contact lenses of the present invention can not only provide Class I UV protection against UVA and UVB rays (i.e., filter greater than 90% of UVA and 99% of UVB rays), but can also mimic the natural lens of the human eye while providing HEVL protection. The natural lens of the human eye typically blocks most of the HEVL light up to 410 nm, but above this wavelength, its %T filtering performance gradually decreases. It is believed that, like the natural lens of the human eye, the UV / HEVL filtering contact lenses of the present invention can provide improved protection against eye damage caused by UV and violet light while providing minimally altered color perception, minimally reduced color vision, minimized reduction in scotopic function, minimally reduced contrast sensitivity under mesopic and scotopic conditions, and minimized interference with diurnal photo-entrainment.

[0083] The present invention provides a UV / HEVL filtering contact lens comprising a bulk hydrogel material comprising: (1) repeating units of at least one hydrophilic vinyl monomer; (2) repeating units of at least one vinyl crosslinker; (3) repeating units of at least one UV absorbing vinyl monomer that absorbs UV light between 280 nm and 380 nm; (4) at least one UV / HEVL absorbing vinyl monomer that absorbs UV light between 280 nm and 380 nm and HEVL between 380 nm and 450 nm; and (5) at least one derivative of Cu(II)-porphyrin, wherein the derivative is covalently attached to the bulk hydrogel material and has an absorption range in the region from 395 nm to 435 nm in the visible light absorption spectrum. The invention relates to a UV / HEVL filtering contact lens having a UVA %T of less than 10%, a UVB %T of less than 1%, a HEVL %T of about 60% or less (preferably about 55% or less, more preferably about 50% or less, even more preferably about 45% or less), a %T at 420 nm of about 40% or less (preferably about 30% or less, preferably about 25% or less, even more preferably about 20% or less), and a %T at any wavelength between 450 nm and 500 nm of about 80% or more (preferably about 85% or more, more preferably about 90% or more).

[0084] According to the present invention, any UV absorbing vinyl monomers can be used in the present invention as long as they can provide Class I UV protection in combination with the UV / HEVL absorbing vinyl monomers. The UV absorbing vinyl monomers can be benzotriazole-containing vinyl monomers (i.e., vinyl monomers each having a benzotriazole moiety) and / or benzophenone-containing vinyl monomers (i.e., vinyl monomers each having a benzophenone moiety) known to those skilled in the art.

[0085] Examples of benzophenone-containing vinyl monomers include, but are not limited to, 2-hydroxy-4-acryloxybenzophenone; 2-hydroxy-4-methacryloxybenzophenone; 2-hydroxy-4-acryloxyethoxybenzophenone; 2-hydroxy-4-methacryloxyethoxybenzophenone; 4-allyloxy-2-hydroxybenzophenone; 4-allyloxyethoxy-2-hydroxybenzophenone; those amino-benzophenone vinyl monomers disclosed in U.S. Pat. No. 10268053 (e.g., N-(2-benzoyl-4-chlorophenyl)methacrylamide, etc.), 2-hydroxy-4-methoxy-4'-(acrylamido-N,N-dimethylpropylaminomethyl)-benzophenone and other hydroxy-benzophenone vinyl monomers disclosed in U.S. Pat. No. 10254567, and those benzophenone-containing UV absorbing vinyl monomers disclosed in U.S. Pat. No. 3162676. Benzophenone-containing vinyl monomers may be obtained from commercial suppliers or may be prepared according to the procedures described in US Pat. Nos. 3,162,676, 1,0254,567, and 1,0268,053.

[0086] In a preferred embodiment, the at least one UV absorbing vinyl monomer comprises a benzotriazole-containing vinyl monomer, preferably a vinyl monomer having formula (1):

[0087]

[0088] Where: R 1 and R 2 One of them is H, and R 1 and R 2 The other is a monovalent group -L 1 -E 1 ; E 1 is vinyl, vinyloxy, allyl, allyloxy, (meth)acryloyloxy or (meth)acrylamide; L 1 It is a direct key, C 1 -C 6 Alkylene divalent group or linking group -L 2 -X 1 -L 3 -;L 2 It is a direct key, C 1 -C 3 Alkylene divalent group, X 1 is O, NH or Where R 3 and R 4 is methyl or ethyl; L 3 It is C 1 -C 6 Alkylene divalent group.

[0089] Preferred examples of UV-absorbing vinyl monomers having formula (1) include, but are not limited to, 2-(2'-hydroxy-5'-vinylphenyl)-2H-benzotriazole, 2-(2'-hydroxy-5'-methacryloxyphenyl)-2H-benzotriazole, 2-(2'-hydroxy-5'-acryloxyphenyl)-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, and 2-(2'-hydroxy-5'-acryloxypropylphenyl)-2H-benzotriazole.

[0090] Benzotriazole-containing UV-absorbing vinyl monomers may be prepared according to the procedures described in US Pat. Nos. 3,299,173, 4,612,358, 4,716,234, 4,528,311, 10,254,567 or may be obtained from commercial suppliers.

[0091] According to the present invention, any UV / HEVL absorbing vinyl monomers can be used in the present invention as long as they can provide the desired HEVL filtration characteristic curve in combination with Cu(II)-porphyrin. The UV / HEVL absorbing vinyl monomers can be benzotriazole-containing vinyl monomers and / or benzophenone-containing vinyl monomers (i.e., vinyl monomers having a benzophenone moiety) known to those skilled in the art.

[0092] In a preferred embodiment, the at least one UV / HEVL absorbing vinyl monomer comprises a benzotriazole-containing vinyl monomer, preferably a benzotriazole-containing vinyl monomer having formula (2):

[0093]

[0094] Where: R 5 It is H, F, Cl, CF 3 , CCl 3 , CH 3 or OCH 3 ; R 6 and R 7 One of them is H, OCH 3 , F, Cl, CF 3 , CCl 3 or C 1 -C 10 Alkyl, and R 6 and R 7 The other is a monovalent group -L 1 -E1 ; E 1 is vinyl, vinyloxy, allyl, allyloxy, (meth)acryloyloxy or (meth)acrylamide; L 1 It is a direct key, C 1 -C 6 Alkylene divalent group or linking group -L 2 -X 1 -L 3 -;L 2 It is a direct key, C 1 -C 3 Alkylene divalent group, X 1 is O, NH or Where R 3 and R 4 is methyl or ethyl; L 3 It is C 1 -C 6 Alkylene divalent group, provided that R 5 , R 6 and R 7 At least two of them are not H.

[0095] Examples of preferred UV / HEVL absorbing vinyl monomers of formula (2) include, but are not limited to: 2-(2'-hydroxy-3'-methacrylamidemethyl-5'-tert-octylphenyl)-2H-benzotriazole, 2-(2'-hydroxy-5'-methacrylamidephenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-5'-methacrylamidephenyl)-5-methoxybenzotriazole, 2-(2'-hydroxy-5'-methacrylamidephenyl)-5-methoxybenzotriazole, 2-(2'-hydroxy-5'-methacryloxypropyl-3'-tert-butyl-phenyl)-5-chlorobenzotriazole, triazole, 2-hydroxy-5-methoxy-3-(5-(trifluoromethyl)-2H-benzo[d][1,2,3]triazol-2-yl)benzyl methacrylate (WL-1), 2-hydroxy-5-methoxy-3-(5-methoxy-2H-benzo[d][1,2,3]triazol-2-yl)benzyl methacrylate (WL-5), 3-(5-fluoro-2H-benzo[d][1,2,3]triazol-2-yl)-2-hydroxy-5-methoxybenzyl methacrylate (WL-2), 3-(2H-benzo[d][1,2,3]triazol-2-yl)-2-hydroxy-5-methoxybenzyl methacrylate (WL-3), 3-(5-chloro-2H-benzo[d][1,2,3]triazol-2-yl)-2-hydroxy-5-methoxybenzyl methacrylate (WL-4), 2-hydroxy-5-methoxy-3-(5-methyl-2H-benzo[d][1,2,3]triazol-2-yl)benzyl methacrylate (WL-6), 2-hydroxy-5-methyl-3-(5 -(trifluoromethyl)-2H-benzo[d][1,2,3]triazol-2-yl)benzyl methacrylate (WL-7), 4-allyl-2-(5-chloro-2H-benzo[d][1,2,3]triazol-2-yl)-6-methoxyphenol (WL-8), 2-{2'-hydroxy-3'-tert-butyl-5'[3"-(4"-vinylbenzyloxy)propoxy]phenyl}-5-methoxy-2H-benzotriazole, 2-(5-chloro-2H-benzotriazol-2-yl)-6-(1,1-dimethylethyl)-4-vinyl-phenol (UVAM), 2-{2'-hydroxy-3'-tert-butyl-5'-[3'-methacryloxypropoxy]phenyl}-2H-benzotriazole, 2-{2'-hydroxy-3'-tert-butyl-5'-[3'-methacryloxypropoxy]phenyl}-5-methoxy-2H-benzotriazole (UV13), 2-{2'-hydroxy-3'-tert-butyl-5'-[3'-methacryloxypropoxy]phenyl}-5-chloro-2H-benzotriazole (UV28), 2-[2'-hydroxy-3'-tert-butyl-5'-[3'-methacryloxypropoxy]phenyl}-5-methoxy-2H-benzotriazole (UV14), 2-{2'-hydroxy-3'-tert-butyl-5'-[3'-methacryloxypropoxy]phenyl}-5-chloro-2H-benzotriazole (UV28), butyl-5'-(3'-acryloxypropoxy)phenyl]-5-trifluoromethyl-2H-benzotriazole (UV23), 2-(2'-hydroxy-5-methylacrylamidephenyl)-5-methoxybenzotriazole (UV6), 2-(3-allyl-2-hydroxy-5-methylphenyl)-2H-benzotriazole (UV9), 2-(2-hydroxy-3-methylallyl-5-methylphenyl)-2H-benzotriazole (UV12), 2-[3'-tert-butyl-2'-hydroxy-5'-(3"-dimethylvinylsilylpropoxy)-2'-hydroxy- 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-methacrylate 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; vinyl monomers containing benzotriazole as disclosed in U.S. Patent No. 10254567.

[0096] According to the present invention, the derivative of the at least one Cu(II)-porphyrin derivative has a Soret peak (ie, an absorption peak in the region from 395 nm to 435 nm) in the visible light absorption spectrum.

[0097] Any Cu(II)-porphyrin can be used in the present invention as long as it is capable of participating in the free radical polymerization of a polymerizable composition containing Cu(II)-porphyrin to produce a Cu(II)-porphyrin derivative, which is covalently attached to the resulting polymer material formed from the polymerizable composition and still has a Soret peak in the visible light absorption spectrum (i.e., an absorption peak in the region from 395 nm to 435 nm).

[0098] Preferably, the Cu(II)-porphyrin is a Cu(II)-meso-aryl substituted porphyrin. It is believed that the aromatic π-electron system of the Cu(II)-meso-aryl substituted porphyrin can survive free radical polymerization, and the Cu(II)-meso-aryl substituted porphyrin derivative from free radical polymerization can still have a Soret peak (i.e., an absorption peak in the region from 395nm to 435nm) in the visible light absorption spectrum.

[0099] In a preferred embodiment, the Cu(II)-meso-aryl substituted porphyrin is represented by formula (3)

[0100]

[0101] in:

[0102] Each R 8 are independently H, Cl, F, substituted or unsubstituted C 1 -C 20 Alkyl, substituted or unsubstituted C 1 -C 20 Alkenyl, substituted or unsubstituted C 1 -C 20 Alkynyl, or two adjacent R 8 The groups, together with the atoms to which they are attached, form a substituted or unsubstituted C 6 -C 14 Aryl, substituted or unsubstituted C 3 -C 14 Carbocyclic, substituted or unsubstituted C 5 -C 14 Heteroaryl or substituted or unsubstituted C 3 -C 14 Heterocyclic group;

[0103] A 2 , A 3 , A 4 , A 5 and A 6 Independently of each other are H, Cl, F, CCl 3 CF 3 , CH 3 、CH(CH 3 )2 , C(CH 3 ) 3 、OCH 3 , OH, NO 2 Or a monovalent group -L 1 -E 1 ;

[0104] E 1 is vinyl, vinyloxy, allyl, allyloxy, (meth)acryloyloxy or (meth)acrylamide;

[0105] L 1 It is a direct key, C 1 -C 6 Alkylene divalent group or linking group -L 2 -X 1 -L 3 -;L 2 It is a direct key, C 1 -C 3 Alkylene divalent group, X 1 is O, NH or Where R 3 and R 4 is methyl or ethyl;

[0106] L 3 It is C 1 -C 6 Alkylene divalent group,

[0107] The premise is A 2 , A 3 , A 4 , A 5 and A 6 One of them is a monovalent group -L 1 -E 1 .

[0108] Due to the presence of ethylenically unsaturated groups, the Cu(II)-meso-aryl substituted porphyrin having formula (3) can be added to the polymerizable composition for making the UV / HEVL filtering contact lenses of the present invention.

[0109] Examples of preferred Cu(II)-meso-aryl substituted porphyrins of formula (3) include, but are not limited to, those disclosed in U.S. Patent Application No. 63 / 275,159. They can be obtained from commercial sources (e.g., High Performance Optics, Inc.) or prepared according to the procedures described in U.S. Patent Application No. 63 / 275,159.

[0110] In another preferred embodiment, the Cu(II)-meso-aryl substituted porphyrin is represented by formula (4)

[0111]

[0112] in:

[0113] Each R 9 are independently H, Cl, F, substituted or unsubstituted C 1 -C 20 Alkyl, substituted or unsubstituted C 1 -C 20 Alkenyl, substituted or unsubstituted C 1 -C 20 Alkynyl, or two adjacent R 8 The groups, together with the atoms to which they are attached, form a substituted or unsubstituted C 6 -C 14 Aryl, substituted or unsubstituted C 3 -C 14 Carbocyclic, substituted or unsubstituted C 5 -C 14 Heteroaryl or substituted or unsubstituted C 3 -C 14 Heterocyclic group;

[0114] A 7 and A 11 Independently of each other are Cl, F, CCl 3 CF 3 , CH 3 、CH(CH 3 ) 2 , C(CH 3 ) 3 、OCH 3 , OH or NO 2 (preferably Cl, F or NO 2 );

[0115] A 8 , A 9 and A 10 Independently of each other are H, Cl, F, CCl 3 CF 3 , CH 3 、CH(CH 3 ) 2 , C(CH 3 ) 3 、OCH 3 , OH, NH 2 or NO 2 .

[0116] In a preferred embodiment, A7 , A 8 , A 9 , A 10 and A 11 are identical to each other and are Cl or F; in another preferred embodiment, A 7 and A 11 are independently Cl or F; A 9 and A 10 is H; and A 8 It is Cl, F, CCl 3 CF 3 , CH 3 、CH(CH 3 ) 2 , C(CH 3 ) 3 、OCH 3 , OH, NH 2 or NO 2 In another preferred embodiment, A 7 and A 11 are independently Cl or F; A 8 and A 10 is H; and A 9 It is Cl, F, CCl 3 CF 3 , CH 3 、CH(CH 3 ) 2 , C(CH 3 ) 3 、OCH 3 , OH, NH 2 or NO 2 .

[0117] Examples of preferred Cu(II)-meso-aryl substituted porphyrins of formula (4) include, but are not limited to: 5,10,15,20-tetrakis(2,6-dichlorophenyl)-porphyrin-Cu(II), 5,10,15,20-tetrakis(2,6-difluorophenyl)-porphyrin-Cu(II), 5,10,15,20-tetrakis(2-chloro-6-fluorophenyl)-porphyrin-Cu(II), 5,10,15,20-tetrakis(2,6-dinitrophenyl)-porphyrin-Cu(II), 5,10,15,20- Tetrakis(2,3,6-trichlorophenyl)-porphyrin-Cu(II), 5,10,15,20-tetrakis(2,3,6-trifluorophenyl)-porphyrin-Cu(II), 5,10,15,20-tetrakis(2,4,6-trinitrophenyl)-porphyrin-Cu(II), 5,10,15,20-tetrakis(2,4,6-trimethylphenyl)-porphyrin-Cu(II), 5,10,15,20-tetrakis(2,6-dichloro-3-aminophenyl)-porphyrin-Cu(II), 5,10,15,20-tetrakis(4 -bromo-2,6-dichlorophenyl)-porphyrin-Cu(II), 5,10,15,20-tetrakis(2,6-dichloro-4-nitrophenyl)-porphyrin-Cu(II), 5,10,15,20-tetrakis(2,6-dichloro-3-nitrophenyl)-porphyrin-Cu(II), 5,10,15,20-tetrakis(2,6-dihydroxyphenyl)-porphyrin-Cu(II), 5,10,15,20-tetrakis(2,6-dimethoxyphenyl)-porphyrin-Cu(II), 5,10,15,20-tetrakis(pentachlorophenyl)-porphyrin-Cu(II), The present invention discloses 10,15,20-tris(2,6-dichlorophenyl)-5-(2,3,4,5,6-pentafluorophenyl)-porphyrin-Cu(II), 5,10,15-tris(pentafluorophenyl)-20-(2.6-dichlorophenyl)-porphyrin-Cu(II) and 10,20-bis(2,6-dichlorophenyl)-5,15-bis(2,3,4,5,6-pentafluorophenyl)-porphyrin-Cu(II).

[0118] It is found that Cu(II)-meso-aryl substituted porphyrins (e.g., 5,10,15,20-tetrakis-(2,6-dichlorophenyl)-porphyrin-Cu(II)) can participate in free radical polymerization of a polymerizable composition comprising a sufficient amount of at least one N-vinylamide monomer (e.g., N-vinylpyrrolidone), even if such Cu(II)-meso-aryl substituted porphyrins do not contain any ethylenically unsaturated groups. It is also found that the participation of Cu(II)-meso-aryl substituted porphyrins in free radical polymerization has no significant adverse effect on the properties of the resulting polymer material. The resulting polymer material having Cu(II)-meso-aryl substituted porphyrin grafted thereto still exhibits substantially similar HEVL filtration (i.e., HEVL absorption) properties to the starting Cu(II)-meso-aryl substituted porphyrin, indicating that there is no significant decomposition or destruction of the aromatic π-electron system of the Cu(II)-meso-aryl substituted porphyrin during free radical polymerization. According to the present invention, there is no need to chemically modify the HEVL absorbing compound to introduce one or more ethylenically unsaturated groups.

[0119] According to a preferred embodiment of the present invention, the bulk hydrogel material (in a dry state) of the UV / HEVL filtering contact lens contains from about 0.6% to about 3.5%, preferably from about 0.7% to about 3.0%, more preferably from about 0.8% to about 2.5% by weight of all components (3), (4) and (5). It should be understood that the weight percentages of components (3), (4) and (5) in the bulk hydrogel material in a dry state can be determined based on their weight percentages in the polymerizable composition used to form the bulk hydrogel material relative to the total weight of all polymerizable components in the polymerizable composition.

[0120] In a preferred embodiment, in the bulk hydrogel material in a dry state, the weight ratio of component (3) to component (4) is at least 1.2 (preferably at least 1.6, more preferably at least 2.0, even more preferably at least 2.4); and the weight ratio of component (4) to component (5) is at least 1.5 (preferably at least 2.0, more preferably at least 2.5, even more preferably at least 3.0). It should be understood that the weight ratio of components (3) to (4) to (5) in the bulk hydrogel material in a dry state can be determined based on their weight percentages in the polymerizable composition used to form the bulk hydrogel material relative to the total weight of all polymerizable components in the polymerizable composition.

[0121] By utilizing such weight ratios of components (3) to (4) to (5) in the bulk hydrogel material in the dry state, the UV / HEVL absorbing contact lenses can provide Class I UV protection and enhanced HEVL protection while minimizing their effects on color balance, color vision, and tinting.

[0122] Any hydrophilic vinyl monomer can be used in the present invention. Examples of preferred hydrophilic vinyl monomers are alkyl (meth) acrylamide (as described later in this application), hydroxyl group-containing acrylic monomers (described below), amino group-containing acrylic monomers (as described later in this application), carboxyl group-containing acrylic monomers (as described later in this application), N-vinyl amide monomers (as described later in this application), methylene group-containing pyrrolidone monomers (i.e., pyrrolidone derivatives each having a methylene group attached to the pyrrolidone ring at the 3-position or 5-position) (as described later in this application), C ... 1 -C 4 Alkoxyethoxy acrylic monomers (as described later in this application), vinyl ether monomers (as described later in this application), allyl ether monomers (as described later in this application), vinyl monomers containing phosphorylcholine (as described later in this application), N-2-hydroxyethyl vinyl carbamate, N-carboxyvinyl-β-alanine (VINAL), N-carboxyvinyl-α-alanine, and combinations thereof.

[0123] In one embodiment, the bulk hydrogel material is a non-silicone hydrogel material; the at least one hydrophilic vinyl monomer comprises: at least one hydroxyl-containing acrylic monomer (any of those described later in this application), at least one hydrophilic (meth)acrylamide-based monomer (any of those described later in this application), at least one N-vinylamide monomer (any of those described later in this application), at least one methylene-containing pyrrolidone monomer (any of those described later in this application), or a combination thereof; and the at least one vinyl cross-linking agent comprises at least one non-silicone vinyl cross-linking agent.

[0124] Examples of preferred hydrophilic N-vinylamide monomers include, but are not limited to, 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. Preferably, the N-vinylamide monomer is N-vinylpyrrolidone, N-vinyl-N-methylacetamide, or a combination thereof.

[0125] According to the present invention, any non-silicone vinylic crosslinking agent may be used in the present invention. Examples of preferred non-silicone vinylic crosslinking agents are described later in this application.

[0126] In another embodiment, the bulk hydrogel material is a silicone hydrogel material and further comprises: (6) repeating units of at least one siloxane-containing vinyl monomer and / or at least one polysiloxane vinyl cross-linking agent; and the at least one vinyl cross-linking agent comprises the polysiloxane vinyl cross-linking agent and / or at least one non-silicone vinyl cross-linking agent.

[0127] Any silicone-containing vinyl monomer can be used in the present invention. Examples of preferred silicone-containing vinyl monomers may be: silicone-containing (meth)acrylamide-based monomers, silicone-containing (meth)acryloyloxy monomers, silicone-containing vinyloxycarbonyloxy monomers, silicone-containing vinyloxycarbonylamino monomers, silicone-containing vinylaminocarbonylamino monomers or silicone-containing vinylaminocarbonyloxy monomers, each of which contains a bis(trialkylsilyloxy)alkylsilyl group, a tris(trialkylsilyloxy)-silyl group, or a polysiloxane chain (having 2 to 30 siloxane units and end-capped with an alkyl, hydroxyalkyl or methoxyalkyl group). Such preferred silicone-containing vinyl monomers may be obtained from commercial suppliers, or alternatively prepared according to known procedures, such as those similar to those described in U.S. Pat. Nos. 5,070,215, 6,166,236, 6,867,245, 7,214,809, 8,415,405, 8,475,529, 8,614,261, 8,658,748, 9,097,840, 9,103,965, 9,217,813, 9,315,669, and 9,475,827, or by using The present invention relates to a vinyl monomer (having a reactive functional group, such as an acid chloride, anhydride, carboxyl, hydroxyl, amino, epoxy, isocyanate, aziridine, azlactone or aldehyde group) and a siloxane-containing compound (having a reactive group selected from the group consisting of a hydroxyalkyl group, an aminoalkyl group, an alkylaminoalkyl group, a carboxylalkyl group, an isocyanatoalkyl group, an epoxyalkyl group and an aziridinylalkyl group) in the presence or absence of a coupling agent under coupling reaction conditions well known to those skilled in the art.

[0128] According to the present invention, any polysiloxane vinyl crosslinking agent may be used in the present invention. Examples of preferred polysiloxane vinyl crosslinking agents include, but are not limited to, α,ω-(meth)acryloxy-terminated polydimethylsiloxanes of different molecular weights; α,ω-(meth)acrylamide-terminated polydimethylsiloxanes of different molecular weights; α,ω-vinyl carbonate-terminated polydimethylsiloxanes of different molecular weights; α,ω-vinyl carbamate-terminated polydimethylsiloxanes of different molecular weights; bis-3-methacryloxy-2-hydroxypropyloxypropyl polydimethylsiloxanes of different molecular weights; N,N,N',N'-tetrakis(3-methacryloxy-2-hydroxypropyl)-α,ω-bis-3-aminopropyl-polydimethylsiloxanes of different molecular weights; the reaction product of glycidyl methacrylate and amino-functional polydimethylsiloxanes; the reaction product of azlactone-containing vinyl monomer (any of those described above) and hydroxy-functional polydimethylsiloxanes; selected from US 5,760,100; U.S. Pat. Nos. 4,136,250, 4,153,641, 4,182,822, 4,189,546, 4,259,467, 4,260,725, 4,261,875, 4,343,927, 4,254,248, 4,355,147, 4,276,402, 4,327,203, 4,341,889, 4,486,577, 4,543,398, 4,605,712, 4,661,575, 4,684,538, 4,703,097, 4,833,218, 4,837,289, 4,9545 86, 4954587, 5010141, 5034461, 5070170, 5079319, 5039761, 5346946, 5358995, 5387632, 5416132, 5449729, 5451617, 5486579, 5962548, 5981675, 6039913, 6762264, 7423074, 8163206, 8480227, 8529057, 8835525, 8993651, 9187601, 10081697, 10301451 and 10465047.

[0129] A preferred class of polysiloxane vinyl crosslinkers are di(meth)acryloyloxy-terminated polysiloxane vinyl crosslinkers, each of which has a dimethylsiloxane unit and a hydrophilized siloxane unit (each of which has a methyl substituent and a monovalent C having 2 to 6 hydroxyl groups). 4 -C 40Organic group substituents), more preferably polysiloxane vinyl crosslinkers having formula (H) are described later in this application and can be prepared according to the procedures disclosed in US Pat. No. 10,081,697.

[0130] Another preferred class of polysiloxane vinyl crosslinking agents is the following vinyl crosslinking agents, each of which contains a sole polysiloxane segment and two terminal (meth)acryloyl groups, which can be obtained from commercial suppliers; prepared by reacting glycidyl (meth)acrylate (meth)acryloyl chloride with di-amino-terminated polydimethylsiloxane or di-hydroxy-terminated polydimethylsiloxane; prepared by reacting isocyanatoethyl (meth)acrylate with di-hydroxy-terminated polydimethylsiloxane (prepared by reacting amino-containing acrylic monomer with di-carboxyl-terminated polydimethylsiloxane) in the presence of a coupling agent (carbodiimide); prepared by reacting carboxyl-containing acrylic monomer with di-amino-terminated polydimethylsiloxane in the presence of a coupling agent (carbodiimide); or prepared by reacting hydroxyl-containing acrylic monomer with dihydroxy-terminated polydisiloxane in the presence of a diisocyanate or diepoxy coupling agent.

[0131] Another preferred class of polysiloxane vinyl crosslinkers are extended chain polysiloxane vinyl crosslinkers, each of which has: at least two polysiloxane segments connected by a linking group 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, 1,030,1451, and 1,0465,047.

[0132] The bulk non-silicone hydrogel material or the bulk silicone hydrogel material may further include repeating units of at least one hydrophobic non-silicone vinylic monomer.

[0133] In the present invention, any hydrophobic non-silicone vinyl monomer may be used. Examples of preferred hydrophobic non-silicone vinyl monomers include: (meth) acrylic acid C 1 -C 10Alkyl esters (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, hexafluoro-isopropyl (meth)acrylate, hexafluorobutyl (meth)acrylate, and combinations thereof.

[0134] In a preferred embodiment, the bulk hydrogel material comprises repeating units of at least one polymerizable dye for coloring the bulk hydrogel material. Examples of preferred polymerizable dyes include, but are not limited to, 1,4-bis(4-(2-methacryloyloxyethyl)phenylamino)anthraquinone (Reactive Blue 246), 1,4-bis((2-hydroxyethyl)amino)-9,10-anthracenedione-bis(2-acrylate)ester (Reactive Blue 247).

[0135] According to the present invention, the lens body material of the contact lens of the present invention can be directly derived from a prefabricated contact lens. The prefabricated contact lens can be: any contact lens that has not been subjected to any surface treatment after being made according to any lens production process; any contact lens that has been plasma treated; or any commercial contact lens, as long as it does not have a water gradient structural configuration. The skilled person knows very well how to prepare prefabricated contact lenses. The skilled person knows very well how to prepare prefabricated contact lenses. For example, the prefabricated contact lens can be produced by conventional "rotational casting molding" as described, for example, in U.S. Patent No. 3,408,429, or by a full cast molding process as described in U.S. Patent Nos. 4347198; 5508317; 5583463; 5789464; and 5849810 in a static form, or by lathe cutting of polymer material buttons as used in the manufacture of customized contact lenses. In cast molding, a polymerizable composition (ie, lens formulation) is typically dispensed into a mold and cured (ie, polymerized and / or cross-linked) in the mold for making a contact lens.

[0136] Lens molds for making contact lenses (including SiHy contact lenses) are well known to those skilled in the art and are used, for example, in cast molding or spin casting. For example, a mold (for injection molding) typically includes at least two mold regions (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 so that a lens forming cavity is formed between the first molding surface and the second molding surface. The molding surface of the mold half is the cavity forming surface of the mold and is in direct contact with the polymerizable composition.

[0137] The mold halves can be formed by various techniques such as injection molding. Methods of making mold halves for cast molded contact lenses are generally well known to those of ordinary skill in the art. The methods of the present invention are not limited to any particular method of forming the molds. In fact, any method of forming the molds can be used in the present invention. The mold halves can be formed by various techniques such as injection molding or lathing. Examples of suitable methods for forming mold halves are disclosed in U.S. Patent Nos. 4,444,711; 4,460,534; 5,843,446; and 5,894,002.

[0138] Almost all materials known in the art for making molds can be used to make molds for making contact lenses. For example, polymer materials such as polyethylene, polypropylene, polystyrene, PMMA, COC grade 8007-S10 (a clear, amorphous copolymer of ethylene and norbornene from Ticona GmbH, Frankfurt, Germany and Summit, New Jersey, USA), etc. Other materials that allow UV light transmission may be used, such as quartz glass and sapphire.

[0139] According to the present invention, the polymerizable composition may be introduced (dispensed) into the cavity formed by the mold according to any known method.

[0140] After the polymerizable composition is dispensed into the mold, it is polymerized to produce a contact lens.Crosslinking may be initiated thermally or actinically to crosslink the polymerizable components in the polymerizable composition.

[0141] Thermal polymerization is conveniently carried out at a temperature of, for example, 25° C. to 120° C. and preferably 40° C. to 100° C. The reaction time may vary within a wide range, but is conveniently, for example, 30 minutes to 4 hours, or preferably 1 to 2 hours. It is advantageous to pre-degassed the components and solvents used in the polymerization and to carry out the copolymerization under an inert atmosphere, for example, under a nitrogen or argon atmosphere.

[0142] The photopolymerization can then be initiated by actinic radiation, for example light of a suitable wavelength, in particular UV light or visible light. The spectral requirements can therefore be controlled, if appropriate, by adding suitable photosensitizers.

[0143] After the curing step, the steps of opening the mold (i.e., separating the male mold half from the female mold half, with the contact lens attached to one of the male and female mold halves) and de-molding (i.e., removing the contact lens from the mold half to which it is adhered) are carried out according to any technique known to those skilled in the art.

[0144] After the molded contact lenses are delensed, they are typically extracted with an extraction medium as is well known to those skilled in the art. The extraction liquid medium is any solvent capable of dissolving the diluent, unpolymerized polymerizable material, and oligomers in the lens precursor. Water, any organic solvent described above or known to those skilled in the art, or mixtures thereof may be used in the present invention.

[0145] The extracted contact lenses may then be hydrated according to any method known to those skilled in the art.

[0146] The extracted and / or hydrated contact lenses may be further subjected to further processes such as, for example, surface treatment, packaging in lens packaging with packaging solutions well known to those skilled in the art; sterilization, such as autoclaving at from 118° C. to 124° C. for at least about 30 minutes; and the like.

[0147] Lens packages (or containers) are well known to those skilled in the art for autoclaving and storing soft contact lenses. Any lens package can be used in the present invention. Preferably, the lens package is a blister package comprising a base and a cover, wherein the cover is removably sealed to the base, wherein the base comprises a cavity for receiving a sterile packaging solution and a contact lens.

[0148] The lenses are packaged in individual packages, sealed and sterilized (eg, by autoclaving under pressure at about 120° C. or higher for at least 30 minutes) prior to distribution to users. One skilled in the art will well understand how to seal and sterilize lens packages.

[0149] According to the present invention, the bulk non-silicone hydrogel material can be formed from a polymerizable composition for forming a non-silicone hydrogel contact lens (i.e., a lens formulation). Typically, the polymerizable composition for forming the bulk non-silicone hydrogel material of the present invention is any of the following: (I) a monomer mixture comprising: (1) at least one hydrophilic vinyl monomer (e.g., a hydroxyl-containing vinyl monomer, an N-vinylamide monomer, a (meth)acrylamide-based monomer, or a combination thereof), (2) at least one non-silicone vinyl crosslinker, (3) at least one UV-absorbing vinyl monomer, (4) at least one UV / HEVL-absorbing vinyl monomer, (5) at least one Cu(II)-porphyrin, and (6) at least one component selected from the group consisting of: a hydrophobic non-silicone vinyl monomer; , a free radical initiator (a photoinitiator or a thermal initiator), a polymerizable visible colorant (i.e., a polymerizable dye), and combinations thereof; or (II) an aqueous solution comprising: one or more water-soluble prepolymers, at least one UV-absorbing vinyl monomer, at least one UV / HEVL-absorbing vinyl monomer, at least one Cu(II)-porphyrin, and a small amount of at least one component selected from the group consisting of: a hydrophilic vinyl monomer, a non-silicone vinyl crosslinker, a hydrophobic non-silicone vinyl monomer, a free radical initiator (a photoinitiator or a thermal initiator), a polymerizable visible colorant (i.e., a polymerizable dye), and combinations thereof.

[0150] Examples of water-soluble prepolymers include, but are not limited to, water-soluble cross-linked poly(vinyl alcohol) prepolymers described in U.S. Pat. Nos. 5,583,163 and 6,303,687; water-soluble vinyl-terminated polyurethane prepolymers described in U.S. Pat. No. 6,995,192; derivatives of polyvinyl alcohol, polyethyleneimine, or polyvinylamine disclosed in U.S. Pat. No. 5,849,841; water-soluble cross-linkable polyurea prepolymers described in U.S. Pat. Nos. 6,479,587 and 7,977,430; cross-linkable polyacrylamide; vinyl lactams disclosed in U.S. Pat. No. 5,712,356 , MMA and comonomer crosslinkable statistical copolymers; crosslinkable copolymers of vinyl lactam, vinyl acetate and vinyl alcohol disclosed in U.S. Pat. No. 5,665,840; polyether-polyester copolymers with crosslinkable side chains disclosed in U.S. Pat. No. 6,492,478; branched polyalkylene glycol-urethane prepolymers disclosed in U.S. Pat. No. 6,165,408; polyalkylene glycol-tetra(meth)acrylate prepolymers disclosed in U.S. Pat. No. 6,221,303; crosslinkable polyallylamine gluconolactone prepolymers disclosed in U.S. Pat. No. 6,472,489.

[0151] Many lens formulations (polymerizable compositions) for forming non-silicone hydrogel materials have been described in numerous patents and patent applications published as of the filing date of this application and have been used to produce commercial non-silicone hydrogel contact lenses. Examples of commercial non-silicone hydrogel contact lenses include, but are not limited to, alfafilcon A, acofilcon A, deltafilcon A, etafilcon A, focofilcon A, helfilcon A, helfilcon B, hilafilcon B, hioxifilcon A, hioxifilcon B, hioxifilcon D, methafilcon A, methafilcon B, nelfilcon A, nesofilcon A, ocufilcon A, ocufilcon B, ocufilcon C, ocufilcon D, omafilcon A, phemfilcon A, polymacon, samfilcon A, telfilcon A, tetrafilcon A, and vifilcon A. They can be used as a base formulation for preparing the polymerizable composition for forming a bulk non-silicone hydrogel material of the present invention by adding at least one UV absorbing vinyl monomer, at least one UV / HEVL absorbing vinyl monomer, at least one Cu(II)-porphyrin to the base formulation.

[0152] Preferably, the bulk non-silicone hydrogel material comprises at least 50% by mole of repeating units of at least one hydroxyl-containing vinyl monomer, preferably selected from the group consisting of hydroxyethyl (meth)acrylate, glyceryl (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, glyceryl (meth)acrylate, hydroxyethyl (meth)acrylamide and vinyl alcohol.

[0153] According to the present invention, bulk silicone hydrogel materials can be formed from lens formulations (i.e., polymerizable compositions) for forming silicone hydrogel contact lenses. Typically, the polymerizable compositions of the present invention for forming bulk silicone hydrogel materials include: (1) at least one hydrophilic vinyl monomer (e.g., at least one hydroxyl-containing acrylic monomer, at least one N-vinylamide monomer, at least one (meth)acrylamide-based monomer, at least one methylene-containing pyrrolidone monomer, or a combination thereof), (2) at least one vinyl crosslinker, including at least one polysiloxane vinyl crosslinker and / or at least one non-silicone vinyl crosslinker, (3) at least one UV-absorbing vinyl monomer, (4) at least one UV / HEVL-absorbing vinyl monomer, (5) at least one Cu(II)-porphyrin, (6) at least one siloxane-containing vinyl monomer, and (7) at least one component selected from the group consisting of a hydrophobic non-silicone vinyl monomer, a free radical initiator (photoinitiator or thermal initiator), a polymerizable visible tint (i.e., a polymerizable dye), and combinations thereof.

[0154] A variety of lens formulations for forming silicone hydrogel contact lenses have been described in many patents and patent applications published as of the filing date of this application and have been used to produce commercial SiHy contact lenses. Examples of commercial SiHy contact lenses include, but are not limited to, asmofilcon A, balafilcon A, comfilcon A, delefilcon A, efrofilcon A, enfilcon A, fanfilcon A, galyfilcon A, lotrafilcon A, lotrafilcon B, narafilcon A, narafilcon B, senofilcon A, senofilcon B, senofilcon C, smafilcon A, somofilcon A, and stenfilcon A. They can be used as a base formulation for forming the polymerizable composition of the present invention for forming bulk silicone hydrogel materials by adding at least one UV absorbing vinyl monomer, at least one UV / HEVL absorbing vinyl monomer, and at least one Cu(II)-porphyrin to the base formulation.

[0155] According to the present invention, any thermal free radical initiator can be used in the present invention. Suitable thermal free radical initiators are known to the skilled person and include, for example, peroxides, hydroperoxides, azo-bis(alkyl- or cycloalkylnitriles), persulfates, percarbonates, or mixtures thereof. Examples of preferred thermal free radical initiators include, but are not limited to, benzoyl peroxide, tert-butyl peroxide, tert-amyl peroxybenzoate, 2,2-bis(tert-butylperoxy)butane, 1,1-bis(tert-butylperoxy)cyclohexane, 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane, 2,5-bis(tert-butylperoxy)-2,5-dimethyl-3-hexyne, bis(1-(tert-butylperoxy)-1-methylethyl)benzene, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, di-tert-butyl-diperoxyphthalate, tert-butyl hydroperoxide, tert-butyl peracetate, tert-butyl peroxybenzoate, tert-butyl peroxyisopropyl carbonate, acetyl peroxide, lauroyl peroxide, decanoyl peroxide, dicetyl peroxydicarbonate, di(4-tert-butylcyclohexyl) peroxydicarbonate (Perkadox 16S), di(2-ethylhexyl) peroxydicarbonate, tert-butyl peroxy neopentanoate (Lupersol 11); tert-butyl peroxy-2-ethylhexanoate (Trigonox 21-C50), 2,4-pentanedione peroxide, dicumyl peroxide, peracetic acid, potassium persulfate, sodium persulfate, ammonium persulfate, 2,2′-azobis(4-methoxy-2,4-dimethylvaleronitrile) (VAZO 33), 2,2′-azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride (VAZO 44), 2,2′-azobis(2-amidinopropane) dihydrochloride (VAZO 50), 2,2′-azobis(2,4-dimethylvaleronitrile) (VAZO 52), 2,2′-azobis(isobutyronitrile) (VAZO 64 or AIBN), 2,2'-azobis-2-methylbutyronitrile (VAZO 67), 1,1-azobis(1-cyclohexanecarbonitrile) (VAZO 88); 2,2'-azobis(2-cyclopropylpropionitrile), 2,2'-azobis(methyl isobutyrate), 4,4'-azobis(4-cyanovaleric acid), and combinations thereof. Preferably, the thermal initiator is 2,2'-azobis(isobutyronitrile) (AIBN or VAZO 64).

[0156] According to the invention, any photoinitiator can be used in the present invention. Suitable photoinitiators are benzoin methyl ether, diethoxyacetophenone, benzoyl-phosphine oxide, 1-hydroxycyclohexyl phenyl ketone and Darocur and Irgacur types, preferably Darocur and Darocur Germanium-based Norrish I-type photoinitiators (e.g., those described in US 7605190). 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. Reactive photoinitiators, such as those that can be incorporated into macromonomers or used as special monomers, are also suitable. Examples of reactive photoinitiators are those disclosed in EP 632329.

[0157] The polymerizable composition of the present invention may further comprise an antimicrobial agent (e.g., silver nanoparticles), a bioactive agent (e.g., a drug, an amino acid, a polypeptide, a protein, a nucleic acid, 2-pyrrolidone-5-carboxylic acid (PCA), alpha hydroxy acid, linoleic acid and gamma linoleic acid, a vitamin, or any combination thereof), a leachable lubricant (e.g., a non-crosslinkable hydrophilic polymer having an average molecular weight of from 5,000 to 500,000, preferably from 10,000 to 300,000, more preferably from 20,000 to 100,000 Daltons), a leachable tear stabilizer (e.g., a phospholipid, a monoglyceride, a diglyceride, a triglyceride, a glycolipid, a glyceroglycolipid, a sphingolipid, a sphingolipid, a fatty acid having 8 to 36 carbon atoms, a fatty alcohol having 8 to 36 carbon atoms, or a mixture thereof), or a combination thereof, as known to those skilled in the art.

[0158] According to the present invention, the polymerizable composition of the present invention is a fluid composition, which can be a solution, a solvent-free blend (ie, a fluid composition that does not contain any non-reactive diluent-organic solvent).

[0159] When the polymerizable composition of the present invention is a solution. It can be prepared by dissolving all desired components in any suitable solvent known to those skilled in the art. The example of a suitable solvent includes but is not limited to water, tetrahydrofuran, tripropylene glycol methyl ether, dipropylene glycol methyl ether, ethylene glycol n-butyl ether, ketones (such as acetone, methyl ethyl ketone, etc.), diethylene glycol n-butyl ether, diethylene glycol methyl ether, ethylene glycol phenyl ether, propylene glycol methyl ether, propylene glycol methyl ether acetate, dipropylene glycol methyl ether acetate, propylene glycol n-propyl ether, dipropylene glycol n-propyl ether, tripropylene glycol n-butyl ether, propylene glycol n-butyl ether, dipropylene glycol n-butyl ether, tripropylene glycol n-butyl ether, propylene glycol phenyl ether, dipropylene glycol dimethyl ether, polyethylene glycol, polypropylene glycol, ethyl acetate, butyl acetate, amyl acetate, methyl lactate , ethyl lactate, isopropyl lactate, 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-butyl alcohol, tert-amyl alcohol, 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 4-ethyl-4-heptanol, 3-methyl-3-octanol, 4-methyl-4-octanol, 3-methyl-3-nonanol, 4-methyl-4-nonanol, 3-methyl-3-octanol, 3-methyl-3-hexanol, 3-methyl-3-heptanol, 4-ethyl-4-heptanol, 4-propyl-4-heptanol, 4-isopropyl-4-heptanol, 2,4-dimethyl-2-pentanol, 1-methylcyclopentanol, 1-ethylcyclopentanol, 1-ethylcyclopentanol Preferably, the polymerizable composition is a solution of all desired components in water, 1,2-propylene glycol, a polyethylene glycol having a molecular weight of about 400 Daltons or less, or a mixture thereof.

[0160] When the polymerizable composition of the present invention is a solvent-free blend, it can be prepared by mixing all polymerizable components and other essential components. The solvent-free polymerizable composition typically comprises at least one blended vinyl monomer as a reactive solvent to dissolve all other polymerizable components of the solvent-free polymerizable composition. Examples of preferred blended vinyl monomers are described later in this application. Preferably, methyl methacrylate is used as a blended vinyl monomer in the preparation of the solvent-free polymerizable composition.

[0161] The contact lenses of the present invention have an oxygen permeability coefficient (at about 35° C.) of preferably at least about 40 barrer, more preferably at least about 60 barrer, even more preferably at least about 80 barrer.

[0162] The contact lenses of the present invention have an elastic modulus (at a temperature of about 22° C. to 28° C.) of about 1.5 MPa or less, preferably about 1.2 MPa or less, more preferably about 0.3 MPa to about 1.0 MPa.

[0163] The contact lenses of the present invention further have an equilibrium water content (at room temperature) of from about 15% to about 75% by weight, more preferably from about 20% to about 70% by weight, and even more preferably from about 25% to about 65% by weight when fully hydrated. The equilibrium water content of the photochromic SiHy contact lenses can be measured according to the procedure disclosed in Example 1.

[0164] All of the various embodiments of the molds, polymerizable compositions, curing, and contact lenses of the present invention described above may be used with this aspect of the invention.

[0165] Although various embodiments of the present invention have been described using specific terms, devices, and methods, such descriptions are for illustrative purposes only. The words used are descriptive and not limiting. It should be understood that changes and variations may be made by those skilled in the art without departing from the spirit or scope of the present invention as set forth in the following claims. In addition, it should be understood that aspects of the various embodiments may be interchangeable in whole or in part or may be combined and / or used together in any manner, as described below:

[0166] 1. A UV / HEVL filtering contact lens comprising a bulk hydrogel material, the bulk hydrogel material comprising:

[0167] (1) repeating units of at least one hydrophilic vinyl monomer;

[0168] (2) repeating units of at least one ethylene-based crosslinking agent;

[0169] (3) repeating units of at least one UV-absorbing vinyl monomer that absorbs UV light between 280 nm and 380 nm;

[0170] (4) at least one UV / HEVL absorbing vinylic monomer that absorbs UV light between 280 nm and 380 nm and HEVL between 380 nm and 450 nm; and

[0171] (5) at least one derivative of Cu(II)-porphyrin, wherein the derivative is covalently attached to the bulk hydrogel material and has an absorption peak (i.e., a Soret peak or band) in the region from 395 nm to 435 nm in the visible light absorption spectrum,

[0172] wherein the components (3), (4) and (5) are present in the bulk hydrogel material in certain amounts and in certain ratios such that the UV / HEVL filtering contact lens has a UVA %T of less than 10%, a UVB %T of less than 1%, a HEVL %T of about 60% or less, a %T at 420 nm of about 40% or less, and a %T at any wavelength between 450 nm and 500 nm of about 80% or greater.

[0173] 2. The UV / HEVL filtering contact lens of embodiment 1, wherein the UV / HEVL filtering contact lens has a HEVL %T of about 55% or less.

[0174] 3. The UV / HEVL filtering contact lens of embodiment 1, wherein the UV / HEVL filtering contact lens has a HEVL %T of about 50% or less.

[0175] 4. The UV / HEVL filtering contact lens of embodiment 1, wherein the UV / HEVL filtering contact lens has a HEVL %T of about 45% or less.

[0176] 5. The UV / HEVL filtering contact lens of any one of embodiments 1 to 4, wherein the UV / HEVL filtering contact lens has a %T at 420 nm of about 30% or less.

[0177] 6. The UV / HEVL filtering contact lens of any one of embodiments 1 to 4, wherein the UV / HEVL filtering contact lens has a %T at 420 nm of about 25% or less.

[0178] 7. The UV / HEVL filtering contact lens of any one of embodiments 1 to 4, wherein the UV / HEVL filtering contact lens has a %T at 420 nm of about 20% or less.

[0179] 8. The UV / HEVL filtering contact lens of any one of embodiments 1 to 7, wherein the UV / HEVL filtering contact lens has a %T of about 85% or greater.

[0180] 9. The UV / HEVL filtering contact lens of any one of embodiments 1 to 7, wherein the UV / HEVL filtering contact lens has a %T at any wavelength between 450 nm and 500 nm of about 90% or greater.

[0181] 10. The UV / HEVL filtering contact lens of any one of embodiments 1 to 9, wherein the at least one UV absorbing vinylic monomer comprises: a benzotriazole-containing vinylic monomer and / or a benzophenone-containing vinylic monomer.

[0182] 11. The UV / HEVL filtering contact lens of embodiment 10, wherein the benzophenone-containing vinyl monomer is: 2-hydroxy-4-acryloxybenzophenone, 2-hydroxy-4-methacryloxybenzophenone, 2-hydroxy-4-acryloxyethoxybenzophenone, 2-hydroxy-4-methacryloxyethoxybenzophenone, 4-allyloxy-2-hydroxybenzophenone, 4-allyloxyethoxy-2-hydroxybenzophenone, N-(2-benzoyl-4-chlorophenyl)methacrylamide, 2-hydroxy-4-methoxy-4'-(acrylamido-N,N-dimethylpropylaminomethyl)-benzophenone, or a combination thereof.

[0183] 12. The UV / HEVL filtering contact lens of any one of embodiments 1 to 11, wherein the at least one UV absorbing vinylic monomer comprises: a benzotriazole-containing vinylic monomer.

[0184] 13. The UV / HEVL filter contact lens of any one of embodiments 1 to 11, wherein the at least one UV absorbing vinylic monomer comprises a benzotriazole-containing vinylic monomer having formula (1):

[0185]

[0186] in:

[0187] R 1 and R 2 One of them is H, and R 1 and R 2 The other is a monovalent group -L 1 -E 1 ; E 1 is vinyl, vinyloxy, allyl, allyloxy, (meth)acryloyloxy or (meth)acrylamide; L 1 It is a direct key, C1 -C 6 Alkylene divalent group or linking group -L 2 -X 1 -L 3 -;L 2 It is a direct key, C 1 -C 3 Alkylene divalent group, X 1 is O, NH or Where R 3 and R 4 is methyl or ethyl; L 3 It is C 1 -C 6 Alkylene divalent group.

[0188] 14. A UV / HEVL filtering contact lens as described in any of embodiments 1 to 11, wherein the at least one UV absorbing vinylic monomer comprises: 2-(2'-hydroxy-5'-vinylphenyl)-2H-benzotriazole, 2-(2'-hydroxy-5'-methacryloxyphenyl)-2H-benzotriazole, 2-(2'-hydroxy-5'-acryloxyphenyl)-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, or a combination thereof.

[0189] 15. The UV / HEVL filtering contact lens of any one of embodiments 1 to 14, wherein the at least one UV / HEVL absorbing vinylic monomer comprises: a benzotriazole-containing vinylic monomer.

[0190] 16. The UV / HEVL filtering contact lens of any one of embodiments 1 to 14, wherein the at least one UV / HEVL absorbing vinylic monomer comprises a benzotriazole-containing vinylic monomer having formula (2):

[0191]

[0192] in:

[0193] R 5 It is H, F, Cl, CF 3 , CCl 3 , CH 3 or OCH 3 ; R6 and R 7 One of them is H, OCH 3 , F, Cl, CF 3 , CCl 3 or C 1 -C 10 Alkyl, and R 6 and R 7 The other is a monovalent group -L 1 -E 1 ; E 1 is vinyl, vinyloxy, allyl, allyloxy, (meth)acryloyloxy or (meth)acrylamide; L 1 It is a direct key, C 1 -C 6 Alkylene divalent group or linking group -L 2 -X 1 -L 3 -;L 2 It is a direct key, C 1 -C 3 Alkylene divalent group, X 1 is O, NH or Where R 3 and R 4 is methyl or ethyl; L 3 It is C 1 -C 6 Alkylene divalent group, provided that R 5 , R 6 and R 7 At least two of them are not H.

[0194] 17. The UV / HEVL filtering contact lens of any one of embodiments 1 to 14, wherein the at least one UV / HEVL absorbing vinyl monomer comprises: 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'-methacrylamidophenyl)-5-methoxybenzotriazole, 2-(2'-hydroxy-5'-methacryloxypropyl-3'-tert-butyl-phenyl)-5-chlorobenzotriazole, 4-allyl-2-(5-chloro-2H-benzo[d][1,2,3]triazol-2-yl)-6-methoxybenzotriazole. Phenol, 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-vinyl-phenol, 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, 2-{2'-hydroxy-3'-tert-butyl-5'-[3'-methacryloyloxypropoxy]phenyl}-5-chloro-2H-benzotriazole triazole, 2-[2'-hydroxy-3'-tert-butyl-5'-(3'-acryloxypropoxy)phenyl]-5-trifluoromethyl-2H-benzotriazole, 2-(2'-hydroxy-5-methacrylamidophenyl)-5-methoxybenzotriazole, 2-(3-allyl-2-hydroxy-5-methylphenyl)-2H-benzotriazole, 2-(2-hydroxy-3-methylallyl-5-methylphenyl)-2H-benzotriazole, 2-[3'-tert-butyl-2'-hydroxy-5'-(3"-dimethylvinylsilylpropoxy)-2'-hydroxy-phenyl)]-5-methoxybenzotriazole, 2-(2'-hydroxy-5'-methacryloylpropyl-3'-tert-butyl-phenyl)-5-methoxy-2 H-benzotriazole, 2-(2'-hydroxy-5'-acryloylpropyl-3'-tert-butyl-phenyl)-5-methoxy-2H-benzotriazole, 2-methacrylate 3-[3-tert-butyl-5-(5-chlorobenzotriazol-2-yl)-4-hydroxyphenyl]-propyl ester, 2-(3-(tert-butyl)-4-hydroxy-5-(5-methoxy-2H-benzo[d][1,2,3]triazol-2-yl)phenoxy)ethyl methacrylate, 2-(5-chloro-2H-benzotriazol-2-yl)-6-methoxy-4-(2-propen-1-yl)-phenol, 2-[2-hydroxy-5-[3-(methacryloyloxy)propyl]-3-tert-butylphenyl]-5-chloro-2H-benzotriazole, or a combination thereof.

[0195] 18. The UV / HEVL filtering contact lens of any one of embodiments 1 to 17, wherein the at least one Cu(II)-porphyrin comprises a Cu(II)-meso-aryl substituted porphyrin.

[0196] 19. The UV / HEVL filtering contact lens of any one of Examples 1 to 17, wherein the at least one Cu(II)-porphyrin comprises a Cu(II)-meso-aryl substituted porphyrin having formula (3) or (4):

[0197]

[0198]

[0199] in:

[0200] R 8 and R 9 Each of which is independently H, Cl, F, substituted or unsubstituted C 1 -C 20 Alkyl, substituted or unsubstituted C 1 -C 20 Alkenyl, substituted or unsubstituted C 1 -C 20 Alkynyl, or two adjacent R 8 The groups, together with the atoms to which they are attached, form a substituted or unsubstituted C 6 -C 14 Aryl, substituted or unsubstituted C 3 -C 14 Carbocyclic, substituted or unsubstituted C 5 -C 14 Heteroaryl or substituted or unsubstituted C 3 -C 14 Heterocyclic group;

[0201] A 2 , A 3 , A 4 , A 5 and A 6 Independently of each other are H, Cl, F, CCl 3 CF 3 , CH 3 、CH(CH 3 ) 2 , C(CH 3 ) 3 、OCH 3 , OH, NO 2 Or a monovalent group -L 1 -E 1 ;

[0202] A 7 and A 11 Independently of each other are Cl, F, CCl 3 CF 3 , CH 3 、CH(CH 3 ) 2 , C(CH 3 ) 3 、OCH 3 , OH or NO 2 (preferably Cl, F or NO 2 );

[0203] A 8 , A 9 and A 10 Independently of each other are H, Cl, F, CCl 3 CF 3 , CH 3 、CH(CH 3 ) 2 , C(CH 3 ) 3 、OCH 3 , OH, NH 2 or NO 2 ;

[0204] E 1 is vinyl, vinyloxy, allyl, allyloxy, (meth)acryloyloxy or (meth)acrylamide;

[0205] L 1 It is a direct key, C 1 -C 6 Alkylene divalent group or linking group -L 2 -X 1 -L 3 -;

[0206] L 2 It is a direct key, C 1 -C 3 Alkylene divalent group,

[0207] X 1 is O, NH or Where R 3 and R 4 is methyl or ethyl;

[0208] L 3 It is C 1 -C 6 Alkylene divalent group,

[0209] The premise is A2 , A 3 , A 4 , A 5 and A 6 One of them is a monovalent group -L 1 -E 1 .

[0210] 20. The UV / HEVL filtering contact lens of any one of embodiments 1 to 19, wherein the bulk hydrogel material in the dry state comprises from about 0.6% to about 3.5% by weight of all components (3), (4) and (5).

[0211] 21. The UV / HEVL filtering contact lens of any one of embodiments 1 to 19, wherein the bulk hydrogel material in the dry state comprises from about 0.7% to about 3.0% by weight of all components (3), (4) and (5).

[0212] 22. The UV / HEVL filtering contact lens of any one of embodiments 1 to 19, wherein the bulk hydrogel material in the dry state comprises from about 0.8% to about 2.5% by weight of all components (3), (4) and (5).

[0213] 23. A UV / HEVL filtering contact lens as described in any of Examples 1 to 22, wherein the at least one hydrophilic vinyl monomer comprises: (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) a hydroxyl-containing acrylic monomer selected from the group consisting of N-2-hydroxyethyl (meth) acrylamide, N,N-bis (hydroxyethyl) (meth) acrylamide, N-3-hydroxypropyl (meth) acrylamide, and combinations thereof. (meth)acrylamide, N-2-hydroxypropyl (meth)acrylamide, N-2,3-dihydroxypropyl (meth)acrylamide, N-tris(hydroxymethyl)methyl (meth)acrylamide, 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, glycerol methacrylate (GMA), di(ethylene glycol) (meth)acrylate, tri(ethylene glycol) (meth)acrylate, tetra(ethylene glycol) (meth)acrylate, poly(ethylene glycol) (meth)acrylate having a number average molecular weight of up to 1500, poly(ethylene glycol)ethyl (meth)acrylamide having a number average molecular weight of up to 1500, and combinations thereof; (3) a compound selected from the group consisting of Carboxyl acrylic monomers: 2-(meth)acrylamidoglycolic acid, (meth)acrylic acid, ethylacrylic acid, 3-(meth)acrylamidopropionic acid, 5-(meth)acrylamidopentanoic acid, 4-(meth)acrylamidobutyric acid, 3-(meth)acrylamido-2-methylbutyric acid, 3-(meth)acrylamido-3-methylbutyric acid, 2-(meth)acrylamido-2-methyl-3,3-dimethylbutyric acid, 3-(meth)acrylamidohexanoic acid, 4-(meth)acrylamido-3,3-dimethylhexanoic acid, and combinations thereof; (4) amino group-containing acrylic monomers selected from the group consisting of: 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, 2-hydroxypropyl (meth)acrylate trimethylammonium hydrochloride, dimethylaminoethyl (meth)acrylate, and combinations thereof;(5) N-vinyl amide monomers selected from the group consisting of N-vinyl pyrrolidone (also known as N-vinyl-2-pyrrolidone), N-vinyl-3-methyl-2-pyrrolidone, N-vinyl-4-methyl-2-pyrrolidone, N-vinyl-5-methyl-2-pyrrolidone, N-vinyl-6-methyl-2-pyrrolidone, N-vinyl-3-ethyl-2-pyrrolidone, N-vinyl-4,5-dimethyl-2-pyrrolidone, N-vinyl-5,5-dimethyl-2-pyrrolidone, N-vinyl-3,3,5-trimethyl-2-pyrrolidone, N-vinyl piperidone ( Also known as N-vinyl-2-piperidone), N-vinyl-3-methyl-2-piperidone, N-vinyl-4-methyl-2-piperidone, N-vinyl-5-methyl-2-piperidone, N-vinyl-6-methyl-2-piperidone, N-vinyl-6-ethyl-2-piperidone, N-vinyl-3,5-dimethyl-2-piperidone, N-vinyl-4,4-dimethyl-2-piperidone, N-vinyl caprolactam (also known as N-vinyl-2-caprolactam), N-vinyl-3-methyl-2-caprolactam, N-vinyl-4-methyl-2-caprolactam, N-vinyl-7-methyl -2-caprolactam, N-vinyl-7-ethyl-2-caprolactam, N-vinyl-3,5-dimethyl-2-caprolactam, N-vinyl-4,6-dimethyl-2-caprolactam, N-vinyl-3,5,7-trimethyl-2-caprolactam, N-vinyl-N-methylacetamide, N-vinylformamide, N-vinylacetamide, N-vinylisopropylamide, N-vinyl-N-ethylacetamide, N-vinyl-N-ethylformamide, and mixtures thereof; (6) methylene-containing pyrrolidone 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-2-pyrrolidone, 1-n-butyl-3-methylene-2-pyrrolidone, 1-tert-butyl-3-methylene-2-pyrrolidone, and combinations thereof; (7) having C; 1 -C 4 Alkoxyethoxy and acrylic monomers selected from the group consisting of ethylene glycol methyl ether (meth) acrylate, di(ethylene glycol) methyl ether (meth) acrylate, tri(ethylene glycol) methyl ether (meth) acrylate, tetra(ethylene glycol) methyl ether (meth) acrylate, C with a number average molecular weight of up to 15001 -C 4-alkoxy poly(ethylene glycol) (meth)acrylate, methoxy-poly(ethylene glycol) ethyl (meth)acrylamide having a number average molecular weight of up to 1500, and combinations thereof; (8) a vinyl ether monomer selected from the group consisting of ethylene glycol monovinyl ether, di(ethylene glycol) monovinyl ether, tri(ethylene glycol) monovinyl ether, tetra(ethylene glycol) monovinyl ether, poly(ethylene glycol) monovinyl ether, ethylene glycol methyl vinyl ether, di(ethylene glycol) methyl vinyl ether, tri(ethylene glycol) methyl vinyl ether, tetra(ethylene glycol) monovinyl ether, (ethylene glycol) methyl vinyl ether, poly(ethylene glycol) methyl vinyl ether, and combinations thereof; (9) an allyl ether monomer selected from the group consisting of ethylene glycol monoallyl ether, di(ethylene glycol) monoallyl ether, tri(ethylene glycol) monoallyl ether, tetra(ethylene glycol) monoallyl ether, poly(ethylene glycol) monoallyl ether, ethylene glycol methyl allyl ether, di(ethylene glycol) methyl allyl ether, tri(ethylene glycol) methyl allyl ether, tetra(ethylene glycol) methyl allyl ether, poly(ethylene glycol) methyl allyl ether, and combinations thereof;(10) A vinyl monomer containing phosphorylcholine selected from the group consisting of (meth)acryloyloxyethyl phosphorylcholine, (meth)acryloyloxypropyl phosphorylcholine, 4-((meth)acryloyloxy)butyl-2'-(trimethylammonio)ethyl phosphate, 2-[(meth)acryloylamino]ethyl-2'-(trimethylammonio)ethyl phosphate, 3-[(meth)acryloylamino]propyl-2'-(trimethylammonio)ethyl phosphate, 4-[(meth)acryloylamino]butyl-2'-(trimethylammonio)ethyl phosphate, 5-( (Meth)acryloyloxy)pentyl-2'-(trimethylammonio)ethyl phosphate, 6-((meth)acryloyloxy)hexyl-2'-(trimethylammonio)ethyl phosphate, 2-((meth)acryloyloxy)ethyl-2'-(triethylammonio)ethyl phosphate, 2-((meth)acryloyloxy)ethyl-2'-(tripropylammonio)ethyl phosphate, 2-((meth)acryloyloxy)ethyl-2'-(tributylammonio)ethyl phosphate, 2-((meth)acryloyloxy)propyl-2'-(trimethylammonio)ethyl phosphate, 2-( (Meth)acryloyloxy)butyl-2'-(trimethylammonio)ethyl phosphate, 2-((meth)acryloyloxy)pentyl-2'-(trimethylammonio)ethyl phosphate, 2-((meth)acryloyloxy)hexyl-2'-(trimethylammonio)ethyl phosphate, 2-(vinyloxy)ethyl-2'-(trimethylammonio)ethyl phosphate, 2-(allyloxy)ethyl-2'-(trimethylammonio)ethyl phosphate, 2-(vinyloxycarbonyl)ethyl-2'-(trimethylammonio)ethyl phosphate, 2-(allyloxycarbonyl)ethyl- 2'-(trimethylammonio)-ethyl phosphate, 2-(vinylcarbonylamino)ethyl-2'-(trimethylammonio)ethyl phosphate, 2-(allyloxycarbonylamino)ethyl-2'-(trimethylammonio)ethyl phosphate, 2-(butenoyloxy)ethyl-2'-(trimethylammonio)ethyl phosphate, and combinations thereof; (11) allyl alcohol; (12) N-2-hydroxyethyl vinyl carbamate; (13) N-carboxyvinyl-β-alanine (VINAL); (14) N-carboxyvinyl-α-alanine; (15) or combinations thereof. ;

[0214] 24. The UV / HEVL filtering contact lens of any one of embodiments 1 to 23, wherein the bulk hydrogel material is a non-silicone hydrogel material.

[0215] 25. The UV / HEVL filtering contact lens of embodiment 24, wherein the non-silicone hydrogel material comprises at least 50% by mole of repeating units of at least one hydroxyl-containing vinylic monomer.

[0216] 26. The UV / HEVL filtering contact lens of embodiment 25, 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.

[0217] 27. The UV / HEVL filtering contact lens of any one of embodiments 1 to 23, wherein the bulk hydrogel material is a silicone hydrogel material.

[0218] 28. The UV / HEVL filtering contact lens of embodiment 27, wherein the silicone hydrogel material comprises repeating units of at least one siloxane-containing vinylic monomer.

[0219] 29. The UV / HEVL filtering contact lens of embodiment 28, wherein the at least one siloxane-containing vinyl monomer is selected from the group consisting of: α-(meth)acryloxypropyl terminated ω-C 1 -C 4 -alkyl-terminated polydimethylsiloxane, α-(meth)acryloyloxy-2-hydroxypropoxypropyl-terminated ω-C 1 -C 4 -alkyl-terminated polydimethylsiloxane, α-(2-hydroxy-methacryloxypropoxypropyl)-ω-C 1 -C 4 -alkyl-decamethylpentasiloxane, α-[3-(meth)acryloyloxyethoxy-2-hydroxypropoxypropyl]-terminated ω-C 1 -C 4 -alkyl-terminated polydimethylsiloxane, α-[3-(meth)acryloyloxy-propoxy-2-hydroxypropoxypropyl]-terminated ω-C 1 -C 4 -alkyl-terminated polydimethylsiloxane, α-[3-(meth)acryloyloxyisopropoxy-2-hydroxypropoxypropyl]-terminated ω-C 1 -C 4 -alkyl-terminated polydimethylsiloxane, α-[3-(meth)acryloyloxybutoxy-2-hydroxypropoxypropyl]-terminated ω-C 1 -C 4-alkyl-terminated polydimethylsiloxane, α-[3-(meth)acryloyloxyethylamino-2-hydroxypropoxypropyl]-terminated ω-C 1 -C 4 -alkyl-terminated polydimethylsiloxane, α-[3-(meth)acryloxypropylamino-2-hydroxypropoxypropyl]-terminated ω-C 1 -C 4 -alkyl-terminated polydimethylsiloxane, α-[3-(meth)acryloyloxy-butylamino-2-hydroxypropoxypropyl]-terminated ω-C 1 -C 4 -alkyl-terminated polydimethylsiloxane, α-(meth)acryloyloxy(polyethyleneoxy)-2-hydroxypropoxypropyl]-terminated ω-C 1 -C 4 -alkyl-terminated polydimethylsiloxane, α-[(meth)acryloyloxy-2-hydroxypropoxy-ethoxypropyl]-terminated ω-C 1 -C 4 -alkyl-terminated polydimethylsiloxane, α-[(meth)acryloyloxy-2-hydroxypropyl-N-ethylaminopropyl]-terminated ω-C 1 -C 4 -alkyl-terminated polydimethylsiloxane, α-[(meth)acryloyloxy-2-hydroxypropyl-aminopropyl]-terminated ω-C 1 -C 4 -alkyl-terminated polydimethylsiloxane, α-[(meth)acryloyloxy-2-hydroxypropoxy-(polyethyleneoxy)propyl]-terminated ω-C 1 -C 4 -alkyl-terminated polydimethylsiloxane, α-(meth)acrylaminopropoxypropyl-terminated ω-C 1 -C 4 -alkyl-terminated polydimethylsiloxane, α-N-methyl-(meth)acryloylaminopropoxypropyl-terminated ω-C 1 -C 4 -alkyl-terminated polydimethylsiloxane, α-[3-(meth)acrylamidoethoxy-2-hydroxypropoxy-propyl]-terminated ω-C 1 -C 4 -alkyl polydimethylsiloxane, α-[3-(meth)acrylamidopropoxy-2-hydroxypropoxypropyl]-terminated ω-C 1 -C 4 -alkyl-terminated polydimethylsiloxane, α-[3-(meth)acrylamide isopropoxy-2-hydroxypropoxypropyl]-terminated ω-C 1 -C 4-alkyl-terminated polydimethylsiloxane, α-[3-(meth)acrylamide butoxy-2-hydroxypropoxypropyl]-terminated ω-C 1 -C 4 -alkyl-terminated polydimethylsiloxane, α-[3-(meth)acryloylamino-2-hydroxypropoxypropyl]-terminated ω-C 1 -C 4 -alkyl polydimethylsiloxane, α-[3-[N-methyl-(meth)acrylamide]-2-hydroxypropoxypropyl]-terminated ω-C 1 -C 4 -alkyl-terminated polydimethylsiloxane, N-methyl-N'-(propyltetra(dimethylsiloxy)dimethylbutylsilane)(meth)acrylamide, N-(2,3-dihydroxypropane)-N'-(propyltetra(dimethylsiloxy)dimethylbutylsilane)(meth)acrylamide, (meth)acrylamidopropyltetra(dimethylsiloxy)dimethylbutylsilane, α-vinyl carbonate-terminated ω-C 1 -C 4 -alkyl-terminated polydimethylsiloxane, α-vinyl carbamate-terminated ω-C 1 -C 4 - Alkyl terminated polydimethylsiloxanes, and mixtures thereof.

[0220] 30. A UV / HEVL filtering contact lens as described in Example 28, wherein the at least one siloxane-containing vinyl monomer is selected from the group consisting of: a vinyl monomer having a bis(trialkylsilyloxy)alkylsilyl group; a vinyl monomer having a tri(trialkylsilyloxy)silyl group; a polysiloxane vinyl monomer; 3-methacryloxypropyl pentamethyldisiloxane; tert-butyldimethyl-siloxyethyl vinyl carbonate; trimethylsilylethyl vinyl carbonate; and trimethylsilylmethylvinyl carbonate; and combinations thereof.

[0221] 31. The UV / HEVL filtering contact lens of Example 28, wherein the at least one siloxane-containing vinyl monomer comprises at least one vinyl monomer having formula (M1) or (M2)

[0222]

[0223] Among them: a M1 is zero or 1; R M0 is H or methyl; X M0 Is O or NR M1 ; L M1 It is C 2 -C 8 Alkylene divalent group or divalent group -LM1 ′-X M1 -L M1 ″-、 L M1 ′-X M1 ′-CH 2 -CH(OH)-CH 2 -OL M1 "-,or L M1 ' is a C with zero or one hydroxyl group 2 -C 8 Alkylene divalent group; L M1 ” is a C with zero or one hydroxyl group 3 -C 8 Alkylene divalent group; X M1 Yes O, NR M1 、NHCOO、OCONH、CONR M1 , or NR M1 CO;R M1 is H or C with 0 to 2 hydroxyl groups 1 -C 4 Alkyl; R t1 and R t2 Independently of each other, C 1 -C 6 Alkyl; X M1 ' is O or NR M1 ; v1 is an integer from 1 to 30; m2 is an integer from 0 to 30; n1 is an integer from 3 to 40; and r1 is an integer from 2 or 3.

[0224] 32. The UV / HEVL filter contact lens of Example 28, wherein the at least one siloxane-containing vinyl monomer comprises: tris(trimethylsilyloxy)silylpropyl(meth)acrylate, [3-(meth)acryloxy-2-hydroxypropoxy]propylbis(trimethylsiloxy)methylsilane, [3-(meth)acryloxy-2-hydroxypropoxy]propylbis(trimethylsiloxy)butylsilane, 3-(meth)acryloxy-2-(2-hydroxyethoxy)-propoxy)propylbis(trimethylsiloxy)methylsilane, 3-(meth)acryloxy-2-hydroxypropoxy )propyltri(trimethylsiloxy)silane, N-[tri(trimethylsiloxy)silylpropyl]-(meth)acrylamide, N-(2-hydroxy-3-(3-(bis(trimethylsiloxy)methylsilyl)propoxy)propyl)-2-methyl(meth)acrylamide, N-(2-hydroxy-3-(3-(bis(trimethylsiloxy)methylsilyl)propoxy)propyl)(meth)acrylamide, N-(2-hydroxy-3-(3-(tri(trimethylsiloxy)silyl)propoxy)propyl)-2-methylacrylamide, N-(2-hydroxy-3-(3-(tri(trimethylsiloxy)silyl)propoxy)propyl)-2-methylacrylamide, 1-(1-(1-(1-(1-(1-(1-(1-(1-trimethylsilyloxy)methylsilyl)-propyl))-methyl)acrylamide, N-[tris(dimethylpropylsilyloxy)silylpropyl]-(methyl)acrylamide, N-[tris(dimethylphenylsilyloxy)silylpropyl]-(methyl)acrylamide, N-[tris(dimethylethylsilyloxy)silylpropyl]-(methyl)acrylamide, N,N-bis[2-hydroxy-3-(3-(bis(trimethylsilyloxy)methylsilyl)-propoxy)propyl]-2-methyl(methyl)acrylamide, N,N-bis[2-hydroxy-3-(3-(bis(trimethylsilyloxy)methylmethyl) Silyl) propoxy)-propyl] (meth) acrylamide, N,N-bis[2-hydroxy-3-(3-(tris(trimethylsilyloxy)silyl) propoxy)propyl]-2-methyl(meth) acrylamide, N,N-bis[2-hydroxy-3-(3-(tris(trimethylsilyloxy)silyl) propoxy)propyl] (meth) acrylamide, N-[2-hydroxy-3-(3-(tert-butyldimethylsilyl) propoxy)-propyl]-2-methyl(meth) acrylamide, N-[2-hydroxy-3-(3-(tert-butyldimethylsilyl) propoxy)-propyl] (meth) acrylamide, N,N-bis[2-hydroxy-3-(3-(tert-butyldimethylsilyl)propoxy)propyl]-2-methyl(meth)acrylamide, N-2-(meth)acryloyloxyethyl-O-(methyl-bis-trimethylsiloxy-3-propyl)silylcarbamate, 3-(trimethylsilyl)propylvinylcarbamate, 3-(vinyloxycarbonylthio)-propyl-tris(trimethyl-siloxy)silane, 3-[tris(trimethylsiloxy)silyl]propylvinylcarbamate, 3-[tris(trimethylsiloxy)silyl]propylallylcarbamate, 3-[tris(trimethylsiloxy)silyl]propylvinylcarbonate, or a combination thereof.

[0225] 33. The UV / HEVL filtering contact lens of any one of embodiments 27 to 32, wherein the at least one ethylene-based cross-linking agent comprises at least one polysiloxane ethylene-based cross-linking agent.

[0226] 34. The UV / HEVL filtering contact lens of embodiment 33, wherein the at least one polysiloxane vinyl crosslinker comprises: a di-(meth)acryloyloxy terminated polysiloxane vinyl crosslinker having dimethylsiloxane units and hydrophilized siloxane units, wherein the dimethylsiloxane units and the hydrophilized siloxane units each have: a methyl substituent; and a monovalent C having 2 to 6 hydroxyl groups. 4 -C 40 Organic group substituent.

[0227] 35. The UV / HEVL filtering contact lens of embodiment 33, wherein the at least one polysiloxane vinyl crosslinker comprises: at least one hydrophilized polysiloxane vinyl crosslinker having formula (G):

[0228]

[0229] in:

[0230] d1 is an integer from 30 to 500, and d2 is an integer from 1 to 75, with the proviso that d2 / d1 is from about 0.035 to about 0.15;

[0231] X 01 Is O or NR IN , where R IN is hydrogen or C 1 -C 10 -alkyl;

[0232] R I0 is hydrogen or methyl;

[0233] R I1 and R I2are independently substituted or unsubstituted C 1 -C 10 Alkylene divalent group or divalent group -R I4 -OR I5 -, where R I4 and R I5 are independently substituted or unsubstituted C 1 -C 10 Alkylene divalent group;

[0234] R I3 is a monovalent group having any one of formulae (G-1) to (G-5)

[0235]

[0236]

[0237] 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;

[0238] R I6 is hydrogen or methyl;

[0239] R I7 is C with (m2+1) valence 2 -C 6 Hydrocarbon;

[0240] R I8 It is C with (m4+1) valence 2 -C 6 Hydrocarbon;

[0241] R I9 is ethyl or hydroxymethyl;

[0242] R I10 is methyl or hydroxymethyl;

[0243] R I11 is hydroxy or methoxy;

[0244] X I1 is a sulfur linker -S- or a tertiary amino linker -NR I12 -, where R I12 It is C 1 -C 1 Alkyl, hydroxyethyl, hydroxypropyl or 2,3-dihydroxypropyl; and

[0245] X I2 is an amide linker Where R I13 is hydrogen or C 1 -C 10 alkyl.

[0246] 36. A UV / HEVL filtering contact lens as described in Example 33, wherein the at least one polysiloxane vinyl crosslinker comprises: (i) a vinyl crosslinker comprising a unique polydiorganosiloxane segment and two terminal ethylenically unsaturated groups, wherein the terminal ethylenically unsaturated groups are selected from the group consisting of: (meth)acryloyloxy, (meth)acryloylamino, vinyl carbonate groups, and vinyl carbamate groups; and / or (ii) an extended chain polysiloxane vinyl crosslinker comprising at least two polydiorganosiloxane segments and a covalent linker between each pair of polydiorganosiloxane segments and two terminal ethylenically unsaturated groups, wherein the terminal ethylenically unsaturated groups are selected from the group consisting of: (meth)acryloyloxy, (meth)acryloylamino, vinyl carbonate groups, and vinyl carbamate groups.

[0247] 37. A UV / HEVL filtering contact lens as described in Example 33, wherein the at least one polysiloxane vinyl crosslinker comprises: α,ω-bis[3-(meth)acrylamidopropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acryloxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acryloxy-2-hydroxypropoxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acryloxyethoxy-2-hydroxypropoxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acryloxypropoxy-2-hydroxypropoxypropyl]-terminated polydimethylsiloxane, [3-(Meth)acryloxy-isopropoxy-2-hydroxypropoxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acryloxybutoxy-2-hydroxypropoxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acrylamideethoxy-2-hydroxypropoxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acrylamidepropoxy-2-hydroxypropoxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acrylamidepropoxy-2-hydroxypropoxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acrylamideisopropoxy-2-hydroxypropoxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acrylamidebutoxy-2-hydroxypropoxypropyl] -terminated polydimethylsiloxane, α,ω-bis[3-(meth)acryloxyethylamino-2-hydroxypropoxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acryloxypropylamino-2-hydroxypropoxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acryloxybutylamino-2-hydroxypropoxypropyl]-terminated polydimethylsiloxane, α,ω-bis[(meth)acryloxyethylamino-2-hydroxypropoxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acryloxypropylamino-2-hydroxypropoxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acryloxybutylamino-2-hydroxypropoxypropyl]-terminated polydimethylsiloxane, Acrylamide-butylamino-2-hydroxypropoxypropyl]-terminated polydimethylsiloxane, α,ω-bis[(meth)acryloxy-2-hydroxypropoxy-ethoxypropyl]-terminated polydimethylsiloxane, α,ω-bis[(meth)acryloxy-2-hydroxypropyl-N-ethylaminopropyl]-terminated polydimethylsiloxane, α,ω-bis[(meth)acryloxy-2-hydroxypropyl-aminopropyl]-polydimethylsiloxane, α,ω-bis[(meth)acryloxy-2-hydroxypropyl-(polyethyleneoxy)propyl]-terminated polydimethylsiloxane, α,ω-bis[(meth)acryloxyethylamino-carbonyloxy-ethoxypropyl]-terminated polydimethylsiloxane, α,ω-bis[(meth)acryloyloxyethylamino-carbonyloxy-(polyethyleneoxy)propyl]-terminated polydimethylsiloxane, or a combination thereof.

[0248] 38. A UV / HEVL filtering contact lens as described in any of Examples 27 to 37, wherein the at least one hydrophilic vinyl monomer comprises at least one hydrophilic N-vinyl amide monomer selected from the group consisting of: N-vinyl pyrrolidone, N-vinyl piperidone, N-vinyl caprolactam, N-vinyl-N-methylacetamide, N-vinyl formamide, N-vinyl acetamide, N-vinyl isopropyl amide, N-vinyl-N-methylacetamide, N-vinyl-N-ethylacetamide, N-vinyl-N-ethylformamide, and mixtures thereof.

[0249] 39. The UV / HEVL filtering contact lens of any one of embodiments 27 to 37, wherein the at least one hydrophilic vinyl monomer comprises N-vinyl pyrrolidone and / or N-vinyl-N-methylacetamide.

[0250] 40. A UV / HEVL filtering contact lens as described in any of Examples 27 to 39, wherein the at least one hydrophilic vinyl monomer comprises a hydrophilic (meth)acrylamide-based monomer selected from the group consisting of (meth)acrylamide, N,N-dimethyl (meth)acrylamide, N-ethyl (meth)acrylamide, N,N-diethyl (meth)acrylamide, N-propyl (meth)acrylamide, N-isopropyl (meth)acrylamide, N-3-methoxypropyl (meth)acrylamide, N-2-hydroxyethyl (meth)acrylamide, N,N-bis (hydroxyethyl) (meth)acrylamide, N-3-hydroxypropyl (meth)acrylamide, N-2-hydroxypropyl (meth)acrylamide, N-2,3-dihydroxypropyl (meth)acrylamide, N-tris (hydroxymethyl)methyl (meth)acrylamide, poly (ethylene glycol) ethyl (meth)acrylamide having a number average molecular weight of up to 1500, 2- (meth)acrylamide amidoglycolic acid, 3-(meth)acrylamidopropionic acid, 5-(meth)acrylamidopentanoic acid, 4-(meth)acrylamidobutyric acid, 3-(meth)acrylamido-2-methylbutyric acid, 3-(meth)acrylamido-3-methylbutyric acid, 2-(meth)acrylamido-2methyl-3,3-dimethylbutyric 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 up to 1500, and combinations thereof.

[0251] 41. A UV / HEVL filtering contact lens as described in any of Examples 27 to 39, wherein the at least one hydrophilic vinyl monomer comprises a hydrophilic (meth)acrylamide-based 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.

[0252] 42. A UV / HEVL filtering contact lens as described in any of Examples 27 to 41, wherein the at least one hydrophilic vinyl monomer comprises a hydroxyl-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.

[0253] 43. The UV / HEVL filtering contact lens of any one of embodiments 27 to 42, 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.

[0254] 44. The UV / HEVL filtering contact lens of any one of embodiments 27 to 43, wherein the UV / HEVL filtering contact lens has an oxygen permeability (at about 35° C.) of at least 40 barrers when fully hydrated.

[0255] 45. The UV / HEVL filtering contact lens of any one of embodiments 27 to 43, wherein the UV / HEVL filtering contact lens has an oxygen permeability (at about 35° C.) of at least 60 barrers when fully hydrated.

[0256] 46. ​​The UV / HEVL filtering contact lens of any one of embodiments 27 to 43, wherein the UV / HEVL filtering contact lens has an oxygen permeability (at about 35° C.) of at least 80 barrers when fully hydrated.

[0257] 47. The UV / HEVL filtering contact lens of any one of embodiments 1 to 46, wherein the at least one ethylenic cross-linking agent comprises at least one non-silicone ethylenic cross-linking agent.

[0258] 48. The UV / HEVL filtering contact lens of embodiment 47, wherein the at least one non-silicone vinyl crosslinker comprises: 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-propylene glycol di-(meth)acrylate, 1,3-butylene glycol di-(meth)acrylate, 1,4-butylene glycol di-(meth)acrylate, glycerol 1,3-diglycerate di-(meth)acrylate, ethylenebis[oxy(2-hydroxypropane-1,3-diyl)]di-(meth)acrylate, bis[2-(meth)acryloyloxyethyl]phosphate, trimethylolpropane di-(meth)acrylate, and 3,4-bis[(meth)acryloyl]tetrahydrofuran, diacrylamide, dimethylacrylamide, N,N-di(meth)acryloyl-N- Methylamine, N,N-di(meth)acryloyl-N-ethylamine, N,N'-methylenebis(meth)acrylamide, N,N'-ethylenebis(meth)acrylamide, N,N'-dihydroxyethylenebis(meth)acrylamide, N,N'-propylenebis(meth)acrylamide, N,N'-2-hydroxypropylenebis(meth)acrylamide, N,N'-2,3-dihydroxybutylenebis(meth)acrylamide, 1,3-bis(meth)acrylamide Alkane-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, trimethylolpropane trimethacrylate, pentaerythritol tetramethacrylate, bisphenol A dimethacrylate, allyl methacrylate, allyl acrylate, N-allyl-methacrylamide, N-allyl-acrylamide, or a combination thereof.

[0259] 49. The UV / HEVL filtering contact lens of any one of embodiments 1 to 48, wherein the bulk hydrogel material further comprises repeating units of at least one hydrophobic non-silicone vinylic monomer.

[0260] 50. The UV / HEVL filter contact lens of embodiment 46, wherein the at least one hydrophobic vinyl monomer comprises: (meth)acrylic acid C 1 -C 10 Alkyl esters, cyclopentyl acrylate, cyclohexyl methacrylate, cyclohexyl acrylate, isobornyl (meth)acrylate, styrene, 4,6-trimethylstyrene (TMS), tert-butylstyrene (TBS), trifluoroethyl (meth)acrylate, hexafluoro-isopropyl (meth)acrylate, hexafluorobutyl (meth)acrylate, or a combination thereof.

[0261] 51. The UV / HEVL filtering contact lens of any one of embodiments 1 to 50, wherein the bulk hydrogel material further comprises repeating units of a polymerizable dye.

[0262] 52. The UV / HEVL filtering contact lens of embodiment 51, wherein the polymerizable dye is: 1,4-bis(4-(2-methacryloyloxyethyl)phenylamino)anthraquinone (Reactive Blue 246), 1,4-bis((2-hydroxyethyl)amino)-9,10-anthracenedione-bis(2-acrylate)ester (Reactive Blue 247), or a combination thereof.

[0263] 53. A UV / HEVL filtering contact lens as described in any of Examples 1 to 52, wherein the weight ratio of component (3) to component (4) in the bulk hydrogel material in a dry state is at least 1.2, and the weight ratio of component (4) to component (5) is at least 1.5.

[0264] 54. The UV / HEVL filtering contact lens of embodiment 53, wherein the weight ratio of component (3) to component (4) in the bulk hydrogel material in a dry state is at least 1.6.

[0265] 55. The UV / HEVL filtering contact lens of embodiment 53, wherein the weight ratio of component (3) to component (4) in the bulk hydrogel material in a dry state is at least 2.0.

[0266] 56. The UV / HEVL filtering contact lens of embodiment 53, wherein the weight ratio of component (3) to component (4) in the bulk hydrogel material in a dry state is at least 2.4.

[0267] 57. The UV / HEVL filtering contact lens of any one of embodiments 53 to 56, wherein the weight ratio of component (4) to component (5) is at least 2.0.

[0268] 58. The UV / HEVL filtering contact lens of any one of embodiments 53 to 56, wherein the weight ratio of component (4) to component (5) is at least 2.5.

[0269] 59. The UV / HEVL filtering contact lens of any one of embodiments 53 to 56, wherein the weight ratio of component (4) to component (5) is at least 3.0.

[0270] 60. The UV / HEVL filtering contact lens of any one of embodiments 1 to 59, wherein the UV / HEVL filtering contact lens has an elastic modulus (at a temperature of 22°C to 28°C) of about 2.0 MPa or less when fully hydrated.

[0271] 61. The UV / HEVL filtering contact lens of any one of embodiments 1 to 59, wherein the UV / HEVL filtering contact lens has an elastic modulus (at a temperature of 22°C to 28°C) of about 1.5 MPa or less when fully hydrated.

[0272] 62. The UV / HEVL filtering contact lens of any one of embodiments 1 to 59, wherein the UV / HEVL filtering contact lens has an elastic modulus (at a temperature of 22°C to 28°C) of about 1.2 or less when fully hydrated.

[0273] 63. The UV / HEVL filtering contact lens of any one of embodiments 1 to 59, wherein the UV / HEVL filtering contact lens has an elastic modulus of about 0.4 MPa to about 1.0 MPa (at a temperature of 22°C to 28°C) when fully hydrated.

[0274] 64. The UV / HEVL filtering contact lens of any one of embodiments 1 to 63, wherein the UV / HEVL filtering contact lens has a water content (at a temperature of 22°C to 28°C) of about 15% to about 70% when fully hydrated.

[0275] 65. The UV / HEVL filtering contact lens of any one of embodiments 1 to 63, wherein the UV / HEVL filtering contact lens when fully hydrated has a water content (at a temperature of 22°C to 28°C) of about 20% to about 70%.

[0276] 66. The UV / HEVL filtering contact lens of any one of embodiments 1 to 63, wherein the UV / HEVL filtering contact lens when fully hydrated has a water content (at a temperature of 22°C to 28°C) of about 25% to about 70%.

[0277] 67. The UV / HEVL filtering contact lens of any one of embodiments 1 to 63, wherein the UV / HEVL filtering contact lens has a water content (at a temperature of 22°C to 28°C) of about 30% to about 65% when fully hydrated.

[0278] The above disclosure will enable those skilled in the art to practice the present invention. Various modifications, variations and combinations may be made to the various embodiments described herein. In order to enable the reader to better understand the specific embodiments and advantages thereof, it is recommended to refer to the following examples. It is intended that this specification and examples be considered exemplary.

[0279] Example 1

[0280] Oxygen permeability measurement

[0281] Unless otherwise specified, the oxygen permeability (Dk / t), intrinsic (or edge-corrected) oxygen permeability (Dk i or Dk c ).

[0282] Balanced water content

[0283] The equilibrium water content (EWC) of contact lenses is measured as follows.

[0284] The amount of water (expressed as a weight percentage) present in a fully hydrated hydrogel contact lens equilibrated in saline solution is determined at room temperature. After blotting the lenses with fabric, quickly stack the lenses and transfer the lens stack to an aluminum pan on an analytical balance. The number of lenses used for each sample pan is typically five (5). Record the hydrated weight of the pan plus the lenses. Cover the pan with aluminum foil. Place the pan in a laboratory oven at 100°C ± 2°C and dry for 16-18 hours. Remove the pan plus lenses from the oven and cool in a desiccator for at least 30 minutes. Remove a single pan from the desiccator and remove the aluminum foil. Weigh the pan plus the dried lens sample on an analytical balance. Repeat for all pans. The wet and dry weights of the lens sample can be calculated by subtracting the weight of the empty weighing pan.

[0285] Elastic modulus

[0286] The elastic modulus of contact lenses was determined using an MTS insight instrument. The contact lenses were first cut into 3.12 mm wide bands using a Precision Concept two-stage cutter. Five thickness values ​​were measured within a 6.5 mm gauge length. The band was mounted on the instrument holder and immersed in PBS (phosphate buffered saline), where the temperature was controlled at 21 ± 2 ° C. A 5N load cell was typically used for testing. Constant force and velocity were applied to the sample until the sample broke. Force and displacement data were collected by TestWorks software. The elastic modulus value was calculated by TestWorks software, which is the slope or tangent of the stress versus strain curve close to zero elongation in the elastic deformation region.

[0287] Transmittance

[0288] The contact lens is manually placed in a specially made sample holder or the like that maintains the shape of the lens as it would be placed on the eye. The holder is then submerged in a quartz cell of 1 cm path length containing phosphate buffered saline (PBS, pH about 7.0-7.4) as a reference. A UV / visible spectrophotometer, for example, a Varian Cary 3E UV-Visible spectrophotometer with a LabSphere DRA-CA-302 beam splitter or the like, can be used in this measurement. Percent transmittance spectra are collected at a wavelength range of 250-800 nm, with %T values ​​collected at 0.5 nm intervals. This data is converted to an Excel spreadsheet and used to determine whether the lens meets Level 1 UV absorbance. Transmittance is calculated using the following equation:

[0289] UVA %T = average % transmittance between 315nm and 380nm x 100

[0290] UVB %T = average % transmittance between 280nm and 315nm x 100

[0291] HEVL %T = average % transmission between 380 nm and 450 nm x 100.

[0292] Chemicals

[0293] CE-PDMS represents polysiloxane vinyl crosslinker (Mw = 10.1K, represented by H 1NMR spectroscopy), having three polydimethylsiloxane (PDMS) segments connected via a diurethane linker between two PDMS segments and two urethane linkers each between a terminal methacrylate group and a PDMS segment, and 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; DMA represents N,N-dimethylacrylamide; L-PEG 2000 represents N-(carbonyl-methoxypolyethylene glycol-2000)-1,2-distearoyl-sn-glycero-3-phosphoethanolamine, sodium salt; DMPC represents 1,2-dimyristoyl-sn-glycero-3-phosphocholine; H-TEMPO represents 4-hydroxy-2,2,6,6-tetramethylpiperidin-1-oxyl; Norbloc is 2-[2′-hydroxy-5′-(2-methacryloyloxyethyl)phenyl)]-2H-benzotriazole (from Aldrich); PrOH represents n-propanol; UV28 represents 2-{2′-hydroxy-3′-tert-butyl-5′-[3′-methacryloyloxypropyloxy]phenyl}-5-chloro-2H-benzotriazole; Cu-TBP-MAm represents Cu(II)-tetrakis(dimethylaminopropyl-methacrylamidophenyl)porphine; Ge PI represents bis(4-methoxybenzoyl)diethylgermanium; RB247 represents 1,4-bis((2-hydroxyethyl)amino)-9,10-anthracenedione-bis(2-acrylate) ester (Reactive Blue 247); MEK represents methyl ethyl ketone; PBS represents phosphate buffered saline having a pH of 7.2±0.2 at 25° C. and containing about 0.044 wt.% NaH 2 PO 4 ·H 2 O, about 0.388wt.%Na 2 HPO 4 ·2H 2 O and about 0.79 wt. % NaCl and 98.78 wt. % water; wt. % means weight percentage.

[0294] PAA-coating solution. A polyacrylic acid (PAA) coating solution was prepared by dissolving a certain amount of PAA (molecular weight: 450 kDa, from Lubrizol) in a given volume of 1-propanol (1-PrOH) to have a concentration of about 0.44% by weight, and adjusting the pH to about 2.0 with formic acid.

[0295] Preparation of in-package coating solution (IPC saline). Poly(AAm-co-AA) (90 / 10) partial sodium salt (about 90% solids content, poly(AAm-co-AA) 90 / 10, Mw 200,000) was purchased from Polysciences, Inc. and used as received. Polyamidoamine epichlorohydrin (PAE) (Kymene, azetidinium content of 0.46 as determined by NMR) was purchased from Ashland as an aqueous solution and used as received. IPC saline was prepared by dissolving about 0.07% w / w poly(AAm-co-AA) (90 / 10) and about 0.10% PAE (about 8.8 mmol initial azetidinium millimolar equivalent) in phosphate buffered saline (PBS) (about 0.044 w / w% NaH 2 PO 4 ·H 2 O, about 0.388w / w / %Na 2 HPO 4 ·2H 2 O, about 0.79w / w% NaCl) and adjusting the pH to 7.2-7.6. The IPC was then heat-pretreated at about 60°C for about 6 hours (heat pretreatment). During this heat pretreatment, poly(AAm-co-AA) and PAE partially cross-linked with each other (i.e., without consuming all the azetidinium groups of PAE) to form a water-soluble and heat-crosslinkable hydrophilic polymer material containing azetidinium groups within the branched polymer network in the IPC saline. After the heat pretreatment, the IPC was cooled to room temperature and then filtered using a 0.22 micron PES membrane filter.

[0296] Example 2

[0297] Preparation of lens formulations with 0.2% UV28

[0298] A lens formulation was prepared having the following components: 0.20 parts by weight of UV28; 23.12 parts by weight of DMA; 22.49 parts by weight of PrOH; 0.02 parts by weight of RB247; 31.67 parts by weight of CE-PDMS; 19.66 parts by weight of TRIS-Aam; 0.76 parts by weight of DMPC; 0.61 parts by weight of L-PEG2000; 0.04 parts by weight of H-TEMPO; 0.90 parts by weight of Norbloc; and 0.60 parts by weight of GePI.

[0299] UV28, DMA and PrOH, RB247, CE-PDMS, Tris-Aam, DMPC, L-PEG2000, H-TEMPO and Norbloc were added to an amber vial. GePI was then added to the vial under yellow light and all components were mixed in a water bath preheated to 40°C for 30 minutes. After all solids were dissolved, the sample was filtered through a glass microfilter (5.0 μm filter) to filter the preparation.

[0300] Lens manufacturing

[0301] In the same manner as in U.S. Pat. No. 7,384,590 Figure 1 To Figures 6 and 7,387,759 ( Figure 1 Lenses were prepared by injection molding from the lens forming composition prepared above in a reusable mold (quartz female mold half and glass male mold half) similar to the mold shown in FIG. 6 ). The lens formulation in the mold was illuminated with 452 nm LED light at 55.4 mW / cm 2 After demolding and stripping, the injection molded contact lenses were then extracted and coated by dipping in the following series of baths: 3 methyl ethyl ketone (MEK) baths (approximately 22 seconds, 78 seconds, and 224 seconds, respectively); DI water bath (56 seconds); PAA dipping solution prepared in Example 1 (44 seconds); 50 / 50 n-propanol / water bath (56 seconds); 3 DI water baths (56 seconds each), and then equilibrated into PBS solution.

[0302] The resulting silicone hydrogel contact lenses were packaged / sealed in polypropylene lens packaging shells (or blisters) (one lens per shell) containing 0.65 mL of IPC saline prepared in Example 1 and autoclaved at 121°C for 45 minutes.

[0303] The UV-vis spectra of lenses containing 0.2% UV28 (UV / HEVL blocker) were recorded and presented in Figure 1 UV-VIS spectra of lenses containing 0.3% and 0.4% UV28 were generated based on lenses manufactured with 0.2% UV28. For the 0.3% UV28 lens, the absorbance from the 0.2% UV28 lens was multiplied by 1.5 and then converted to %T. Similarly, for the 0.4% UV28 lens, the absorbance from the 0.2% UV28 lens was multiplied by 2 and then converted to %T. Both graphs are plotted and presented in Figure 1 All lens properties are presented in the table below.

[0304]

[0305] 1. UV-VIS spectrum generated based on lens made with 0.2% UV28 Example 3

[0306] Preparation of lens formulations with 300 ppm, 500 ppm, 700 ppm Cu-TBP-MAm

[0307] A lens formulation was prepared having the following components: 0.03 to 0.07 parts by weight of Cu-TBP-MAm; 23.12 parts by weight of DMA; 22.49 parts by weight of PrOH; 0.02 parts by weight of RB247; 31.67 parts by weight of CE-PDMS; 19.66 parts by weight of TRIS-Aam; 0.76 parts by weight of DMPC; 0.61 parts by weight of L-PEG2000; 0.04 parts by weight of H-TEMPO; 0.90 parts by weight of Norbloc; and 0.60 parts by weight of GePI.

[0308] Cu-TBP-MAm, DMA and PrOH were placed in a first amber vial and mixed at 300 rpm for 30 minutes at room temperature with a stirring rod. RB247, CE-PDMS, Tris-Aam, DMPC, L-PEG2000, H-TEMPO and Norbloc were added to a second amber vial. GePI was then added to a second vial under yellow light, and all components were mixed at 300 rpm for 30 minutes at room temperature. When all solids were dissolved, a disposable glass pipette was used to transfer the contents of the first jar to the second jar under yellow light. The mixture was allowed to stir in a water bath preheated to 40°C for at least 30 minutes. After all solids were dissolved, a glass microfilter (5.0 μm filter) to filter the preparation.

[0309] Lens manufacturing

[0310] In the same manner as in U.S. Pat. No. 7,384,590 Figure 1 To Figures 6 and 7,387,759 ( Figure 1 Lenses were prepared by injection molding from the lens forming composition prepared above in a reusable mold (quartz female mold half and glass male mold half) similar to the mold shown in FIG. 6 ). The lens formulation in the mold was illuminated with 452 nm LED light at 55.4 mW / cm 2 After demolding and stripping, the injection molded contact lenses were then extracted and coated by dipping in the following series of baths: 3 methyl ethyl ketone (MEK) baths (approximately 22 seconds, 78 seconds, and 224 seconds, respectively); DI water bath (56 seconds); PAA dipping solution prepared in Example 1 (44 seconds); 50 / 50 n-propanol / water bath (56 seconds); 3 DI water baths (56 seconds each), and then equilibrated into PBS solution.

[0311] The resulting silicone hydrogel contact lenses were packaged / sealed in polypropylene lens packaging shells (or blisters) (one lens per shell) containing 0.65 mL of IPC saline prepared in Example 1 and autoclaved at 121°C for 45 minutes.

[0312] The lenses contained 300ppm, 500ppm and 700ppm of Cu-TBP-MAm (HEVL blocker). UV-vis spectra were recorded and are presented in Figure 2 The lens properties are presented in the table below.

[0313]

[0314] Example 4

[0315] Preparation of lens formulations with 300 ppm Cu-TBP-MAm with 0.2% UV28

[0316] A lens formulation was prepared having the following components: 0.03 parts by weight of Cu-TBP-MAm; 23.12 parts by weight of DMA; 22.49 parts by weight of PrOH; 0.02 parts by weight of RB247; 31.67 parts by weight of CE-PDMS; 19.66 parts by weight of TRIS-Aam; 0.76 parts by weight of DMPC; 0.61 parts by weight of L-PEG2000; 0.04 parts by weight of H-TEMPO; 0.90 parts by weight of Norbloc; 0.20 parts by weight of UV28 and 0.60 parts by weight of GePI.

[0317] Cu-TBP-MAm, DMA and PrOH were placed in a first amber vial and mixed at 300 rpm for 30 minutes at room temperature with a stirring rod. RB247, CE-PDMS, Tris-Aam, DMPC, L-PEG2000, H-TEMPO, UV28 and Norbloc were added to a second amber vial. GePI was then added to a second vial under yellow light, and all components were mixed at 300 rpm for 30 minutes at room temperature. When all solids were dissolved, a disposable glass pipette was used to transfer the contents of the first jar to the second jar under yellow light. The mixture was allowed to stir in a water bath preheated to 40°C for at least 30 minutes. After all solids were dissolved, a glass microfilter (5.0 μm filter) to filter the preparation.

[0318] Lens manufacturing

[0319] In the same manner as in U.S. Pat. No. 7,384,590 Figure 1 To Figures 6 and 7,387,759 ( Figure 1 Lenses were prepared by injection molding from the lens forming composition prepared above in a reusable mold (quartz female mold half and glass male mold half) similar to the mold shown in FIG. 6 ). The lens formulation in the mold was illuminated with 452 nm LED light at 55.4 mW / cm 2 After demolding and stripping, the injection molded contact lenses were then extracted and coated by dipping in the following series of baths: 3 methyl ethyl ketone (MEK) baths (approximately 22 seconds, 78 seconds, and 224 seconds, respectively); DI water bath (56 seconds); PAA dipping solution prepared in Example 1 (44 seconds); 50 / 50 n-propanol / water bath (56 seconds); 3 DI water baths (56 seconds each), and then equilibrated into PBS solution.

[0320] The resulting silicone hydrogel contact lenses were packaged / sealed in polypropylene lens packaging shells (or blisters) (one lens per shell) containing 0.65 mL of IPC saline prepared in Example 1 and autoclaved at 121°C for 45 minutes.

[0321] The lenses contained 300 ppm Cu-TBP-MAm (HEVL blocker) and 0.2% UV28 (UV / HEVL blocker). UV-vis spectra were recorded and are presented at Figure 4 The lens properties are presented in the table below.

[0322] Preparation of lens formulations with 500 ppm Cu-TBP-MAm with 0.3% UV28

[0323] A lens formulation was prepared having the following components: 0.05 parts by weight of Cu-TBP-MAm; 23.12 parts by weight of DMA; 22.49 parts by weight of PrOH; 0.02 parts by weight of RB247; 31.67 parts by weight of CE-PDMS; 19.66 parts by weight of TRIS-Aam; 0.76 parts by weight of DMPC; 0.61 parts by weight of L-PEG2000; 0.04 parts by weight of H-TEMPO; 0.90 parts by weight of Norbloc; 0.30 parts by weight of UV28 and 0.60 parts by weight of GePI.

[0324] Cu-TBP-MAm, DMA and PrOH were placed in a first amber vial and mixed at 300 rpm for 30 minutes at room temperature with a stirring rod. RB247, CE-PDMS, Tris-Aam, DMPC, L-PEG2000, H-TEMPO, UV28 and Norbloc were added to a second amber vial. GePI was then added to a second vial under yellow light, and all components were mixed at 300 rpm for 30 minutes at room temperature. When all solids were dissolved, a disposable glass pipette was used to transfer the contents of the first jar to the second jar under yellow light. The mixture was allowed to stir in a water bath preheated to 40°C for at least 30 minutes. After all solids were dissolved, a glass microfilter (5.0 μm filter) to filter the preparation.

[0325] Lens manufacturing

[0326] In the same manner as in U.S. Pat. No. 7,384,590 Figure 1 To Figures 6 and 7,387,759 ( Figure 1 Lenses were prepared by injection molding from the lens forming composition prepared above in a reusable mold (quartz female mold half and glass male mold half) similar to the mold shown in FIG. 6 ). The lens formulation in the mold was illuminated with 452 nm LED light at 55.4 mW / cm 2 After demolding and stripping, the injection molded contact lenses were then extracted and coated by dipping in the following series of baths: 3 methyl ethyl ketone (MEK) baths (approximately 22 seconds, 78 seconds, and 224 seconds, respectively); DI water bath (56 seconds); PAA dipping solution prepared in Example 1 (44 seconds); 50 / 50 n-propanol / water bath (56 seconds); 3 DI water baths (56 seconds each), and then equilibrated into PBS solution.

[0327] The resulting silicone hydrogel contact lenses were packaged / sealed in polypropylene lens packaging shells (or blisters) (one lens per shell) containing 0.65 mL of IPC saline prepared in Example 1 and autoclaved at 121°C for 45 minutes.

[0328] The lenses contained 500 ppm Cu-TBP-MAm (HEVL blocker) and 0.3% UV28 (UV / HEVL blocker). UV-vis spectra were recorded and are presented at Figure 3 middle.

[0329] The lens properties are presented in the table below.

[0330]

[0331] All publications and patents cited above are hereby incorporated by reference in their entirety.

Claims

1. A UV / HEVL filtering contact lens comprising a bulk hydrogel material, the bulk hydrogel material comprising: (1) repeating units of at least one hydrophilic vinyl monomer; (2) repeating units of at least one ethylene-based crosslinking agent; (3) repeating units of at least one UV-absorbing vinyl monomer that absorbs UV light between 280 nm and 380 nm; (4) at least one UV / HEVL absorbing vinylic monomer that absorbs UV light between 280 nm and 380 nm and HEVL between 380 nm and 450 nm; and (5) at least one derivative of Cu(II)-porphyrin, wherein the derivative is covalently attached to the bulk hydrogel material and has an absorption peak (i.e., a Soret peak or band) in the region from 395 nm to 435 nm in the visible light absorption spectrum, wherein the components (3), (4) and (5) are present in the bulk hydrogel material in certain amounts and in certain ratios such that the UV / HEVL filtering contact lens has a UVA %T of less than 10%, a UVB %T of less than 1%, a HEVL %T of about 60% or less, a %T at 420 nm of about 40% or less, and a %T at any wavelength between 450 nm and 500 nm of about 80% or greater.

2. The UV / HEVL filtering contact lens according to claim 1, wherein: The at least one UV absorbing vinyl monomer comprises: a benzotriazole-containing vinyl monomer and / or a benzophenone-containing vinyl monomer.

3. The UV / HEVL filtering contact lens of claim 1, wherein: The at least one UV absorbing vinyl monomer comprises a benzotriazole-containing vinyl monomer having formula (1) in: One of R1 and R2 is H, and the other of R1 and R2 is a monovalent group -L1-E1; E1 is a vinyl group, a vinyloxy group, an allyl group, an allyloxy group, a (meth)acryloyloxy group, or a (meth)acrylamide group; L1 is a direct bond, a C1-C6 alkylene divalent group, or a linking group -L2-X1-L3-; L2 is a direct bond, a C1-C3 alkylene divalent group, X1 is O, NH or Wherein R3 and R4 are methyl or ethyl; L3 is a C1-C6 alkylene divalent group, wherein the at least one UV / HEVL absorbing vinyl monomer comprises a benzotriazole-containing vinyl monomer having formula (2) in: R5 is H, F, Cl, CF3, CCl3, CH3 or OCH3; one of R6 and R7 is H, OCH3, F, Cl, CF3, CCl3 or Cl-C 10 alkyl, and the other of R6 and R7 is a monovalent group -L1-E1; E1 is vinyl, vinyloxy, allyl, allyloxy, (meth)acryloyloxy or (meth)acrylamide; L1 is a direct bond, a C1-C6 alkylene divalent group or a linking group -L2-X1-L3-; L2 is a direct bond, a C1-C3 alkylene divalent group, X1 is O, NH or wherein R3 and R4 are methyl or ethyl; L3 is a C1-C6 alkylene divalent group, provided that at least two of R5, R6 and R7 are not H.

4. The UV / HEVL filtering contact lens according to claim 3, wherein: The at least one UV absorbing vinyl monomer comprises: 2-(2'-hydroxy-5'-vinylphenyl)-2H-benzotriazole, 2-(2'-hydroxy-5'-methacryloxyphenyl)-2H-benzotriazole, 2-(2'-hydroxy-5'-acryloxyphenyl)-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, or a combination thereof, wherein the at least one UV / HEVL absorbing vinyl monomer comprises: 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'-methacrylamidophenyl)-5-methoxybenzotriazole, 2-(2'-hydroxy-5'-methacryloxypropyl-3'-tert-butyl-phenyl)-5-chlorobenzotriazole, 4-allyl-2-(5-chloro-2H-benzo[d][1,2,3]triazol-2-yl)-6-methoxyphenol, 2-{2'-hydroxy-3'-tert-butyl-5'-[3"- 2-(4"-vinylbenzyloxy)propoxy]phenyl}-5-methoxy-2H-benzotriazole, 2-(5-chloro-2H-benzotriazol-2-yl)-6-(1,1-dimethylethyl)-4-vinyl-phenol, 2-[2'-hydroxy-3'-tert-butyl-5'-(3'-methacryloxypropoxy)phenyl]-2H-benzotriazole, 2-{2'-hydroxy-3'-tert-butyl-5'-[3'-methacryloxypropoxy]phenyl}-5-methoxy-2H-benzotriazole, 2-{2'-hydroxy-3'-tert-butyl-5'-[3'-methacryloxypropoxy]phenyl}-5-chloro-2H-benzotriazole, 2-[2'-hydroxy-3'-tert-butyl 2-[3'-tert-butyl-2'-hydroxy-5'-(3'-dimethylvinylsilylpropoxy)-2'-hydroxy-phenyl]-5-methoxybenzotriazole, 2-(2'-hydroxy-5-methacrylamidophenyl)-5-methoxybenzotriazole, 2-(3-allyl-2-hydroxy-5-methylphenyl)-2H-benzotriazole, 2-(2-hydroxy-3-methylallyl-5-methylphenyl)-2H-benzotriazole, 2-[3'-tert-butyl-2'-hydroxy-5'-(3"-dimethylvinylsilylpropoxy)-2'-hydroxy-phenyl)]-5-methoxybenzotriazole, 2-(2'-hydroxy-5'-methacryloylpropyl-3'-tert-butyl-phenyl)-5-methoxy-2H-benzotriazole, 2- (2'-Hydroxy-5'-acryloylpropyl-3'-tert-butyl-phenyl)-5-methoxy-2H-benzotriazole, 2-methacrylate 3-[3-tert-butyl-5-(5-chlorobenzotriazol-2-yl)-4-hydroxyphenyl]-propyl ester, 2-(3-(tert-butyl)-4-hydroxy-5-(5-methoxy-2H-benzo[d][1,2,3]triazol-2-yl)phenoxy)ethyl methacrylate, 2-(5-chloro-2H-benzotriazol-2-yl)-6-methoxy-4-(2-propen-1-yl)-phenol, 2-[2-hydroxy-5-[3-(methacryloyloxy)propyl]-3-tert-butylphenyl]-5-chloro-2H-benzotriazole, or a combination thereof.

5. The UV / HEVL filtering contact lens according to any one of claims 1 to 4, wherein: The at least one Cu(II)-porphyrin comprises a Cu(II)-meso-aryl substituted porphyrin.

6. The UV / HEVL filtering contact lens according to any one of claims 1 to 4, wherein:The at least one Cu(II)-porphyrin comprises a Cu(II)-meso-aryl substituted porphyrin having formula (3) or (4) in: Each of R8 and R9 is independently H, Cl, F, substituted or unsubstituted C1-C 20 Alkyl, substituted or unsubstituted C1-C 20 Alkenyl, substituted or unsubstituted C1-C 20 Alkynyl, or two adjacent R8 groups together with the atoms to which they are attached form a substituted or unsubstituted C6-C 14 Aryl, substituted or unsubstituted C3-C 14 Carbocyclic, substituted or unsubstituted C5-C 14 Heteroaryl or substituted or unsubstituted C3-C 14 Heterocyclic group; A2, A3, A4, A5 and A6 are independently H, Cl, F, CCl3, CF3, CH3, CH(CH3)2, C(CH3)3, OCH3, OH, NO2 or a monovalent group -L1-E1; A7 and A 11 Each of them is independently Cl, F, CCl3, CF3, CH3, CH(CH3)2, C(CH3)3, OCH3, OH or NO2 (preferably Cl, F or NO2); A8, A9 and A 10 are independently H, Cl, F, CCl3, CF3, CH3, CH(CH3)2, C(CH3)3, OCH3, OH, NH2 or NO2; E1 is vinyl, vinyloxy, allyl, allyloxy, (meth)acryloyloxy or (meth)acrylamide; L1 is a direct bond, a C1-C6 alkylene divalent group or a linking group -L2-X1-L3-; L2 is a direct bond, a C1-C3 alkylene divalent group, X1 is O, NH or Wherein R3 and R4 are methyl or ethyl; L3 is a C1-C6 alkylene divalent group, The prerequisite is that one of A2, A3, A4, A5 and A6 is a monovalent group -L1-E1.

7. The UV / HEVL filtering contact lens according to any one of claims 1 to 6, wherein The bulk hydrogel material in the dry state comprises from about 0.6% to about 3.5% by weight of all components (3), (4) and (5).

8. The UV / HEVL filtering contact lens according to any one of claims 1 to 7, wherein The at least one hydrophilic vinyl monomer comprises: (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) a hydroxyl-containing acrylic monomer selected from the group consisting of N-2-hydroxyethyl (meth) acrylamide, N,N-bis (hydroxyethyl) (meth) acrylamide, N-3-hydroxypropyl (meth) acrylamide, N-2-hydroxypropyl (meth) acrylamide, N-2,3-dihydroxypropyl (meth)acrylamide, N-tris(hydroxymethyl)methyl (meth)acrylamide, 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, glycerol methacrylate (GMA), di(ethylene glycol) (meth)acrylate, tri(ethylene glycol) (meth)acrylate, tetra(ethylene glycol) (meth)acrylate, poly(ethylene glycol) (meth)acrylate having a number average molecular weight of up to 1500, poly(ethylene glycol)ethyl (meth)acrylamide having a number average molecular weight of up to 1500, and combinations thereof; (3) a carboxyl-containing acrylic monomer selected from the group consisting of: 2-(meth)acrylic acid; Amidoglycolic acid, (meth)acrylic acid, ethylacrylic acid, 3-(meth)acrylamidopropionic acid, 5-(meth)acrylamidopentanoic acid, 4-(meth)acrylamidobutyric acid, 3-(meth)acrylamido-2-methylbutyric acid, 3-(meth)acrylamido-3-methylbutyric acid, 2-(meth)acrylamido-2-methyl-3,3-dimethylbutyric acid, 3-(meth)acrylamidohexanoic acid, 4-(meth)acrylamido-3,3-dimethylhexanoic acid, and combinations thereof; (4) amino-containing acrylic monomers selected from the group consisting of N-2-aminoethyl (meth)acrylamide, N-2-methylaminoethyl (meth)acrylamide, N-2-ethylamino ethyl(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, 2-hydroxypropyl(meth)acrylate trimethylammonium hydrochloride, dimethylaminoethyl(meth)acrylate, and combinations thereof;(5) N-vinyl amide monomers selected from the group consisting of N-vinyl pyrrolidone (also known as N-vinyl-2-pyrrolidone), N-vinyl-3-methyl-2-pyrrolidone, N-vinyl-4-methyl-2-pyrrolidone, N-vinyl-5-methyl-2-pyrrolidone, N-vinyl-6-methyl-2-pyrrolidone, N-vinyl-3-ethyl-2-pyrrolidone, N-vinyl-4,5-dimethyl-2-pyrrolidone, N-vinyl-5,5-dimethyl-2-pyrrolidone, N-vinyl-3,3,5-trimethyl-2-pyrrolidone, N-vinyl piperidine ketone (also known as N-vinyl-2-piperidone), N-vinyl-3-methyl-2-piperidone, N-vinyl-4-methyl-2-piperidone, N-vinyl-5-methyl-2-piperidone, N-vinyl-6-methyl-2-piperidone, N-vinyl-6-ethyl-2-piperidone, N-vinyl-3,5-dimethyl-2-piperidone, N-vinyl-4,4-dimethyl-2-piperidone, N-vinyl caprolactam (also known as N-vinyl-2-caprolactam), N-vinyl-3-methyl-2-caprolactam, N-vinyl-4-methyl-2-caprolactam, N-vinyl-7 -methyl-2-caprolactam, N-vinyl-7-ethyl-2-caprolactam, N-vinyl-3,5-dimethyl-2-caprolactam, N-vinyl-4,6-dimethyl-2-caprolactam, N-vinyl-3,5,7-trimethyl-2-caprolactam, N-vinyl-N-methylacetamide, N-vinylformamide, N-vinylacetamide, N-vinylisopropylamide, N-vinyl-N-ethylacetamide, N-vinyl-N-ethylformamide, and mixtures thereof; (6) a methylene-containing pyrrolidone monomer selected from the group consisting of: 1-methyl-3-methylene-2-pyrrolidinone monomers: 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;(7) acrylic monomers having C1-C4 alkoxyethoxy groups and selected from the group consisting of ethylene glycol methyl ether (meth) acrylate, di(ethylene glycol) methyl ether (meth) acrylate, tri(ethylene glycol) methyl ether (meth) acrylate, tetra(ethylene glycol) methyl ether (meth) acrylate, C1-C4-alkoxy poly(ethylene glycol) (meth) acrylate having a number average molecular weight of up to 1500, methoxy-poly(ethylene glycol) ethyl (meth) acrylamide having a number average molecular weight of up to 1500, and combinations thereof; (8) vinyl ether monomers selected from the group consisting of ethylene glycol monovinyl ether, di(ethylene glycol) monovinyl ether, tri(ethylene glycol) monovinyl ether (9) an allyl ether monomer selected from the group consisting of ethylene glycol monoallyl ether, di(ethylene glycol) monoallyl ether, tri(ethylene glycol) monoallyl ether, tetra(ethylene glycol) monoallyl ether, poly(ethylene glycol) monoallyl ether, ethylene glycol methyl vinyl ether, di(ethylene glycol) methyl vinyl ether, tri(ethylene glycol) monoallyl ether, tetra(ethylene glycol) monoallyl ether, poly(ethylene glycol) monoallyl ether, ethylene glycol methyl allyl ether, di(ethylene glycol) methyl allyl ether, tri(ethylene glycol) methyl allyl ether, tetra(ethylene glycol) methyl allyl ether, poly(ethylene glycol) methyl allyl ether, and combinations thereof;(10) A vinyl monomer containing phosphorylcholine selected from the group consisting of (meth)acryloyloxyethyl phosphorylcholine, (meth)acryloyloxypropyl phosphorylcholine, 4-((meth)acryloyloxy)butyl-2'-(trimethylammonio)ethyl phosphate, 2-[(meth)acryloylamino]ethyl-2'-(trimethylammonio)ethyl phosphate, 3-[(meth)acryloylamino]propyl-2'-(trimethylammonio)ethyl phosphate, 4-[(meth)acryloylamino]butyl-2'-(trimethylammonio)ethyl phosphate, 5-( (Meth)acryloyloxy)pentyl-2'-(trimethylammonio)ethyl phosphate, 6-((meth)acryloyloxy)hexyl-2'-(trimethylammonio)ethyl phosphate, 2-((meth)acryloyloxy)ethyl-2'-(triethylammonio)ethyl phosphate, 2-((meth)acryloyloxy)ethyl-2'-(tripropylammonio)ethyl phosphate, 2-((meth)acryloyloxy)ethyl-2'-(tributylammonio)ethyl phosphate, 2-((meth)acryloyloxy)propyl-2'-(trimethylammonio)ethyl phosphate, 2-( (Meth)acryloyloxy)butyl-2'-(trimethylammonio)ethyl phosphate, 2-((meth)acryloyloxy)pentyl-2'-(trimethylammonio)ethyl phosphate, 2-((meth)acryloyloxy)hexyl-2'-(trimethylammonio)ethyl phosphate, 2-(vinyloxy)ethyl-2'-(trimethylammonio)ethyl phosphate, 2-(allyloxy)ethyl-2'-(trimethylammonio)ethyl phosphate, 2-(vinyloxycarbonyl)ethyl-2'-(trimethylammonio)ethyl phosphate, 2-(allyloxycarbonyl)ethyl- 2'-(trimethylammonio)-ethyl phosphate, 2-(vinylcarbonylamino)ethyl-2'-(trimethylammonio)ethyl phosphate, 2-(allyloxycarbonylamino)ethyl-2'-(trimethylammonio)ethyl phosphate, 2-(butenoyloxy)ethyl-2'-(trimethylammonio)ethyl phosphate, and combinations thereof; (11) allyl alcohol; (12) N-2-hydroxyethyl vinyl carbamate; (13) N-carboxyvinyl-β-alanine (VINAL); (14) N-carboxyvinyl-α-alanine; (15) or combinations thereof. ; 9. The UV / HEVL filtering contact lens according to any one of claims 1 to 8, wherein The non-silicone hydrogel material comprises: at least 50% by mole of repeating units of at least one hydroxyl-containing vinyl monomer.

10. The UV / HEVL filtering contact lens according to any one of claims 1 to 8, wherein The bulk hydrogel material is a silicone hydrogel material, which comprises: (1) repeating units of at least one siloxane-containing vinyl monomer selected from the group consisting of: a vinyl monomer having a bis(trialkylsilyloxy)alkylsilyl group, a vinyl monomer having a tri(trialkylsilyloxy)silyl group, a polysiloxane vinyl monomer, 3-methacryloxypropyl pentamethyldisiloxane, tert-butyldimethyl-siloxyethyl vinyl carbonate, trimethylsilylethyl vinyl carbonate, and trimethylsilylmethylvinyl carbonate, and combinations thereof; and / or (2) a repeating unit of at least one ethylene-based crosslinking agent comprising at least one polysiloxane ethylene-based crosslinking agent, wherein the polysiloxane ethylene-based crosslinking agent comprises: (i) a di-(meth)acryloyloxy-terminated polysiloxane ethylene-based crosslinking agent having a dimethylsiloxane unit and a hydrophilized siloxane unit, wherein the dimethylsiloxane unit and the hydrophilized siloxane unit each have: a methyl substituent and a monovalent C4-C ... 40 Organic group substituent, (ii) a hydrophilized polysiloxane vinyl crosslinking agent having formula (G) in: d1 is an integer from 30 to 500, and d2 is an integer from 1 to 75, with the proviso that d2 / d1 is from about 0.035 to about 0.15; X 01 Is O or NR IN , where R IN is hydrogen or C1-C 10 -alkyl; R I0 is hydrogen or methyl; R I1 and R I2 are independently substituted or unsubstituted C1-C 10 Alkylene divalent group or divalent group -R I4 -OR I5 -, where R I4 and R I5 are independently substituted or unsubstituted C1-C 10 Alkylene divalent group; R I3 is a monovalent group having any one of formulae (G-1) to (G-5) 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 group having a valence of (m2+1); R I8 is a C2-C6 hydrocarbon group having a valence of (m4+1); R I9 is ethyl or hydroxymethyl; R I10 is methyl or hydroxymethyl; R I11 is hydroxy or methoxy; X I1 is a sulfur linker -S- or a tertiary amino linker -NR I12 -, where R I12 is C1-C1 alkyl, hydroxyethyl, hydroxypropyl or 2,3-dihydroxypropyl; and X I2 is an amide linker Where R I13 is hydrogen or C1-C 10 alkyl, (iii) an ethylene-based crosslinking agent comprising a single polydiorganosiloxane segment and two terminal ethylenically unsaturated groups selected from the group consisting of (meth)acryloyloxy, (meth)acryloylamino, vinyl carbonate, vinyl urethane, (iv) a chain-extended polysiloxane vinyl crosslinker comprising at least two polydiorganosiloxane segments and a covalent linking group between each pair of polydiorganosiloxane segments and two terminal ethylenically unsaturated groups selected from the group consisting of: (meth)acryloyloxy, (meth)acryloylamino, vinyl carbonate, vinyl carbamate, (v) a polysiloxane vinyl crosslinking agent 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)acryloxypropyloxy-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acryloxyisopropyloxy- 2-Hydroxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acryloxybutyloxy-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acrylamideethoxy-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acrylamidepropyloxy-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acrylamidepropyloxy-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acrylamidebutyloxy-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane siloxane, α,ω-bis[3-(meth)acryloxyethylamino-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acryloxypropylamino-2-hydroxypropyloxy-propyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acryloxybutylamino-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane, α,ω-bis[(meth)acrylamideethylamino-2-hydroxypropyloxy-propyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acrylamidepropylamino-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane, -butylamino-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane, α,ω-bis[(meth)acryloyloxy-2-hydroxypropyloxy-ethoxypropyl]-terminated polydimethylsiloxane, α,ω-bis[(meth)acryloyloxy-2-hydroxypropyl-N-ethylaminopropyl]-terminated polydimethylsiloxane, α,ω-bis[(meth)acryloyloxy-2-hydroxypropyl-aminopropyl]-polydimethylsiloxane, α,ω-bis[(meth)acryloyloxy-2-hydroxypropyloxy-(polyethyleneoxy)propyl]-terminated polydimethylsiloxane, α,ω-bis[(meth)acryloyloxyethylamino-carbonyloxy-ethoxypropyl]-terminated polydimethylsiloxane, α,ω-bis[(meth)acryloyloxyethylamino-carbonyloxy-(polyethyleneoxy)propyl]-terminated polydimethylsiloxane or a combination thereof, or, (vi) any combination thereof.

11. The UV / HEVL filtering contact lens of claim 10, wherein: The UV / HEVL filtering contact lens has: an oxygen permeability of at least 40 barrers at about 35°C; an elastic modulus of about 2.0 MPa or less at a temperature of 22°C to 28°C; and a water content of about 15% to about 70% at a temperature of 22°C to 28°C when fully hydrated.

12. The UV / HEVL filtering contact lens according to any one of claims 1 to 11, wherein The at least one vinylic cross-linking agent includes at least one non-silicone vinylic cross-linking agent.

13. The UV / HEVL filtering contact lens according to any one of claims 1 to 12, wherein: The bulk hydrogel material further comprises: repeating units of at least one hydrophobic non-silicone vinyl monomer; and / or repeating units of a polymerizable dye.

14. The UV / HEVL filtering contact lens of claim 13, wherein: The at least one hydrophobic vinyl monomer comprises: C1-C 10 Alkyl (meth) acrylate, cyclopentyl acrylate, cyclohexyl methacrylate, cyclohexyl acrylate, isobornyl (meth) acrylate, styrene, 4,6-trimethylstyrene (TMS), tert-butylstyrene (TBS), trifluoroethyl (meth) acrylate, hexafluoro-isopropyl (meth) acrylate, hexafluorobutyl (meth) acrylate or a combination thereof, wherein the polymerizable dye is 1,4-bis (4- (2-methacryloyloxyethyl) phenylamino) anthraquinone (Reactive Blue 246), 1,4-bis ((2-hydroxyethyl) amino) -9,10- anthracene dione -bis (2-acrylate) ester (Reactive Blue 247) or a combination thereof.

15. The UV / HEVL filtering contact lens according to any one of claims 1 to 14, wherein The weight ratio of component (3) to component (4) in the bulk hydrogel material in a dry state is at least 1.2, and the weight ratio of component (4) to component (5) is at least 1.5.

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