High-energy violet light-absorbing vinyl monomer

Abstract

This specification describes high-energy violet (HEVL) absorbing benzotriazole vinyl monomers that exhibit sufficient solubility in organic solvents (e.g., 1-propanol), better compatibility with polymerizable components present in hydrogel lens formulations, and absorption peaks at wavelengths of 410 nm to 425 nm. They are suitable for the manufacture of hydrogel contact lenses that can significantly block HEVL in the 380 nm to 450 nm range but cannot significantly block blue light (450 nm to 495 nm).

Description

[Technical Field]

[0001] The present invention relates to a benzotriazole vinyl monomer capable of absorbing high-energy violet light (HEVL) radiation (having wavelengths of 380 nm to 450 nm), and to its use in manufacturing hydrogel contact lenses capable of blocking ultraviolet ("UV") radiation and HEVL radiation. [Background technology]

[0002] LED lighting and electronic devices, such as smartphones, computer screens, LCDs, and LED televisions, are widely used. These typically emit short-wavelength visible light, including violet light (380–450 nm) and blue light (450–495 nm). Such short-wavelength visible light has been shown to damage cells in both in vitro and in vivo studies reported in 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; and Optometry and Vision Science 2011,88(6),1.With the widespread use of LED lighting and LED displays, such as smartphones, televisions, and computer monitors, significant efforts are being made to develop HEVL-filtering ophthalmic lenses, such as eyeglasses, contact lenses, and intraocular lenses, to protect the eyes from increasing HEVL exposure (for example, U.S. Patent Nos. 4612358, 4528311, 4716234, 4878748, 5400175, 5662707, 6158862, 6955430, 7556376, 7803359, 8153703, 8232326, etc.). Specifications No. 8360574, No. 8585938, No. 8882267, No. 9377569, No. 9683102, No. 9814658, No. 10551637, and No. 10610472, U.S. Patent Application Publication No. 20170242274, and No. 20180371139 See the following specifications: (See the document, and specifications No. 20190002415, No. 20190002459, No. 20190271798, No. 20190339544, No. 20200002267, No. 20200095187, No. 20200407324, and No. 20200407337).

[0003] TOTAL30® (manufactured by Alcon) is the first contact lens that maintains effective HEVL filtering performance while the lens is being worn, regardless of lighting conditions. TOTAL30® not only includes Class I UV absorption for protection against UVA and UVB rays (i.e., filtering over 90% of UVA and 99% of UVB rays), but can also filter approximately 33% of HEVL rays (380-450nm) that enter the eye. Alcon subsequently launched a second product, TOTAL1®, which, like TOTAL30®, can block 90% of UVA, 99% of UVB, and 33% of HEVL. Johnson & Johnson Vision Care recently launched ACUVUE® OASYS MAX 1-DAY, which, according to its published 510(k) Premarket Notification (K210930), can block up to 45% of HEVL.

[0004] However, to better protect the wearer's eyes from HEVL damage, particularly violet light damage, contact lens products with significantly higher HEVL filtering performance than currently available commercially are desirable. However, finding a suitable polymerizable HEVL-absorbing dye that can absorb a considerable amount of HEVL light, has good solubility in the lens-forming composition, good compatibility with other polymerizable components in the lens-forming composition, and good lightfastness is extremely difficult. [Overview of the project] [Problems that the invention aims to solve]

[0005] Therefore, there is still a need for novel HEVL-absorbing vinyl monomers suitable for the manufacture of hydrogel contact lenses that can significantly filter HEVL, particularly silicone hydrogel contact lenses, and for such high HEVL-filtering hydrogel contact lenses. [Means for solving the problem]

[0006] In one embodiment, the present invention provides a HEVL-absorbing vinyl monomer comprising a benzotriazole moiety and a (meth)acryloyl group, having HEVL absorption peaks at wavelengths from 410 nm and 425 nm, and having a solubility of at least 2.5 mg / mL in 1-propanol.

[0007] In another embodiment, the present invention provides a method for producing HEVL-absorbing hydrogel contact lenses from a lens formulation containing the UV-absorbing vinyl monomer of the present invention.

[0008] In a further embodiment, the present invention provides a hydrogel contact lens comprising monomer units of the HEVL-absorbing vinyl monomer of the present invention. [Brief explanation of the drawing]

[0009] [Figure 1] A preferred embodiment of the procedure for synthesizing the HEVL-absorbing benzotriazole vinyl monomer of the present invention is shown. [Figure 2] A preferred embodiment of the procedure for synthesizing the HEVL-absorbing benzotriazole vinyl monomer of the present invention is shown. [Figure 3] The UV / Visible absorption spectra of diluted solutions of two HEVL-absorbing benzotriazole-containing vinyl monomers (UV28 and UV35), measured in a 1 cm cuvette, are shown: dotted line - 40 ppm UV28, dashed line - 40 ppm UV35. [Figure 4] The UV / visible transmission spectra of contact lenses obtained from lens formulations 3-2 (dashed line) and 4-1 (dotted line) are shown. [Figure 5] The UV / Visible absorption spectra of diluted solutions of four HEVL-absorbing benzotriazole-containing vinyl monomers (UV29, UV28, UV23, and UV40) in 1-propanol, measured in a 1 cm cuvette, are shown: dotted line - 40 ppm UV29, dashed line - 40 ppm UV28, solid line - 40 ppm UV23, dashed line - 40 ppm UV40. [Modes for carrying out the invention]

[0010] Unless otherwise specified, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art to which this invention pertains. Generally, the nomenclature and experimental procedures used herein are well known and commonly used in the art. Conventional methods, such as those provided in the art and various general references, are used for these procedures. Where a term is given in the singular form, the inventors also assume that the plural form of that term exists. The nomenclature and laboratory procedures described below herein are well known and commonly adopted in the art.

[0011] As used herein, "approximately" means that the number referred to as "approximately" includes an enumerated number that is plus or minus 1 to 10% of the enumerated number.

[0012] The terms "optional" or "optional" mean that the event or situation described thereafter may or may not occur, and that the description includes both cases in which the event or situation occurs and cases in which it does not occur.

[0013] As used herein, “ophthalmic device” means contact lenses (hard or soft), intraocular lenses, corneal onlays, and other ophthalmic devices used in or near the eyeball or its periphery.

[0014] "Contact lenses" refer to structures that can be placed on or inside the eye of a wearer. Contact lenses may, but are not required to, correct, improve, or alter the wearer's vision. Contact lenses may be manufactured from any suitable material known or subsequently developed in the art, and may be soft lenses, hard lenses, or hybrid lenses.

[0015] "Hydrogel contact lenses" refer to contact lenses that contain a hydrogel bulk (core) material. The hydrogel bulk material may be a non-silicone hydrogel material or, preferably, a silicone hydrogel material.

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

[0017] Siloxanes, often also referred to as silicones, are molecules that have at least one -Si-O-Si- moiety, where each Si atom has 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, 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 silicon.

[0020] As used herein, "hydrophilic" refers to a material or part thereof that associates more readily with water than with lipids.

[0021] The term "room temperature" refers to a temperature between approximately 22°C and 26°C.

[0022] With respect to a compound or substance in a solvent, the term "soluble" means that the compound or substance can dissolve in the solvent to yield a solution with a concentration of at least about 0.5% by weight at room temperature (i.e., at a temperature of about 22°C to about 26°C).

[0023] In relation to compounds or materials in a solvent, the term "insoluble" means that the compound or material can dissolve in the solvent at room temperature (as defined above) to give a solution with a concentration of less than about 0.01% by weight.

[0024] A "vinyl monomer" refers to a compound that has a single ethylenically unsaturated group, is soluble in solvents, and can be polymerized linearly or thermally.

[0025] The term "ethylenically unsaturated group" is used herein in a broad sense and is intended to encompass any group containing at least one >C=CH2 group. Exemplary ethylenically unsaturated groups include, without limitation, (meth)acryloyl [ka] , vinyloxycarbonylamino( [ka] (In the formula, R o (It is H or C1-C4 alkyl)), vinyloxycarbonyloxy [ka] It contains allyl, vinyl, styrenyl, or other C=C-containing groups.

[0026] As used herein, “chemically ray curing” with respect to curing, crosslinking, or polymerization of polymerizable compositions, prepolymers, or materials means that curing (e.g., crosslinking and / or polymerization) is carried out by chemical ray irradiation, such as UV / visible light irradiation. Thermal curing and chemical ray 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)acryloyloxy [or (meth)acryloyloxy] monomers and (meth)acrylamide monomers.

[0028] "(meth)acryloyloxymonomer" or "(meth)acryloyloxymonomer" is [ka] This refers to a vinyl monomer that has only one group.

[0029] "(meth)acrylamide monomer" is [ka] (In the formula, R o (It is H or C1-C4 alkyl) This refers to a vinyl monomer that has only one group.

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

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

[0032] "N-vinylamide monomer" refers to an amide compound that has a vinyl group (-CH=CH2) directly bonded to the nitrogen atom of the amide group.

[0033] The term "ene group" refers to a monovalent group of CH2=CH- or CH2=CCH3- that is not covalently bonded to an oxygen or nitrogen atom or a carbonyl group.

[0034] "En monomer" refers to a vinyl monomer that has only one ene group.

[0035] "Vinyloxycarbonylamino monomer" refers to a vinyl monomer that has a single vinyloxycarbonylamino group.

[0036] "Vinylaminocarbonyloxy monomer" refers to a vinyl monomer that has a single vinylaminocarbonyloxy group.

[0037] "Vinylaminocarbonylamino monomer" refers to a vinyl monomer that has a single vinylaminocarbonylamino group.

[0038] "Hydrophilic vinyl monomers" refer to vinyl monomers that typically produce homopolymers that are water-soluble or capable of absorbing at least 10 weight percent of water.

[0039] "Hydrophobic vinyl monomers" refer to vinyl monomers that are insoluble in water and typically produce homopolymers capable of absorbing less than 10% by weight of water.

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

[0041] As used in this application, the term "polymer" means a material formed by polymerizing / crosslinking one or more monomers, macromers, or prepolymers, or combinations thereof.

[0042] A "macromer" or "prepolymer" refers to a compound or polymer containing multiple ethylenically unsaturated groups and having a number-average molecular weight exceeding 700 daltons.

[0043] When used in this application, the term "molecular weight" of a polymer material (including monomeric materials or macromeric materials) refers to the number average molecular weight, unless otherwise specified or the test conditions are otherwise indicated. Those skilled in the art know methods for determining the molecular weight of polymers according to known methods, such as gel permeation chromatography (GPC) having one or more of a refractive index detector, a low angle laser light scattering detector, a multi-angle laser light scattering detector, a differential viscosity measurement detector, a UV detector, and an infrared (IR) detector, matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF MS), 1 1H NMR (proton nuclear magnetic resonance) spectroscopy, etc.

[0044] "Polysiloxane segment" or "polydiorganosiloxane segment"

Chemical formula

[0045] "Polydiorganosiloxane vinyl monomer" or "polysiloxane vinyl monomer" interchangeably refers to a compound comprising at least one polysiloxane segment and one sole ethylenically unsaturated group.

[0046] "Polydiorganosiloxane vinyl crosslinking agent" or "polysiloxane vinyl crosslinking agent" interchangeably refers to a compound comprising at least one polysiloxane segment and at least two ethylenically unsaturated groups.

[0047] As used herein, the term "fluid" indicates that a material can flow like a liquid.

[0048] As used in this application, the term "transparent" in relation to a polymerizable composition means that the polymerizable composition is a transparent solution or liquid mixture having a light transmittance of 85% or more (preferably 90% or more) in the range of 400 to 700 nm.

[0049] Free radical initiators can be either photoinitiators or thermal initiators. A "photoinitiator" refers to a chemical substance that initiates a free radical crosslinking / polymerization reaction using light. A "thermal initiator" or "thermal free radical initiator" is interchangeable for a chemical substance that initiates a free radical crosslinking / polymerization reaction using thermal energy.

[0050] The terms "monovalent radical" and "monovalent group" refer to an organic group obtained by removing a hydrogen atom from an organic compound, which is interchangeable in forming one bond with one other group in the organic compound. Examples include, but are not limited to, alkyl (by removing a hydrogen atom from an alkane), alkoxy (or alkoxyl) (by removing one hydrogen atom from the hydroxyl group of an alkyl alcohol), thiyl (by removing one hydrogen atom from the thiol group of an alkylthiol), cycloalkyl (by removing a hydrogen atom from a cycloalkane), cycloheteroalkyl (by removing a hydrogen atom from a cycloheteroalkane), aryl (by removing a hydrogen atom from the aromatic ring of an aromatic hydrocarbon), heteroaryl (by removing a hydrogen atom from any ring atom), and amino (by removing one hydrogen atom from an amine).

[0051] The terms "divalent radical" and "divalent group" refer interchangeably to organic groups obtained by removing two hydrogen atoms from an organic compound and which form two bonds with two other groups in the organic compound. For example, an alkylene divalent group (i.e., alkylenyl) is obtained by removing two hydrogen atoms from an alkane, and a cycloalkylene divalent group (i.e., cycloalkylenyl) is obtained by removing two hydrogen atoms from a cyclic ring.

[0052] In this application, the term “substituted” in relation to alkyl or alkylenyl means that the alkyl or alkylenyl replaces one hydrogen atom of the alkyl or alkylenyl and includes at least one substituent selected from the group consisting of hydroxyl (-OH), carboxyl (-COOH), -NH2, sulfhydryl (-SH), C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkylthio (alkyl sulfide), C1-C4 acylamino, C1-C4 alkylamino, di-C1-C4 alkylamino and combinations thereof.

[0053] The terms “silicone hydrogel lens formulation” or “SiHy lens formulation” are interchangeable terms for polymerizable compositions containing all the necessary polymerizable components for manufacturing SiHy contact lenses or SiHy lens bulk materials, as is well known to those skilled in the art.

[0054] A "UV-absorbing vinyl monomer" refers to a compound that contains a single ethylenically unsaturated group and can primarily absorb UV light in the 280 nm to 380 nm range. It is understood that UV-absorbing vinyl monomers do not absorb or hardly absorb light with wavelengths above 400 nm (i.e., when tested with a 0.1 mM solution of UV-absorbing vinyl monomer and a 1 cm optical path length, the %T at 400 nm is greater than 90%).

[0055] A "HEVL-absorbing vinyl monomer" refers to a compound that contains a single ethylenically unsaturated group and can primarily absorb UV light in the 380nm to 450nm range. It is understood that HEVL-absorbing vinyl monomers can also absorb UV light in the 280nm to 380nm range.

[0056] "UVA" refers to radiation that occurs at wavelengths of 315 to 380 nanometers, "UVB" refers to radiation that occurs in the range of 280 to 315 nanometers, and "HEVL" refers to radiation that occurs at wavelengths of 380 to 450 nanometers.

[0057] "UVA transmittance" (or "UVA%T"), "UVB transmittance" or "UVB%T", and "HEVL transmittance" or "HEVL%T" are calculated using the following formulas. UVA%T=315nm~380nm average % transmittance x 100 UVB%T=280nm~315nm average % transmittance x 100 HEVL%T=380nm~450nm average % transmittance x 100 HEVL% filtering = 100% - HEVL%T

[0058] "%T at wavelength" refers to the transmittance at a specific wavelength.

[0059] Generally, the present invention relates to a class of HEVL-absorbing benzotriazole vinyl monomers that have sufficient solubility in organic solvents (e.g., 1-propanol) (i.e., ≥2.5 mg), better compatibility with polymerizable components present in hydrogel lens formulations (particularly in silicone hydrogel lens formulations), and an absorption peak at wavelengths of 410 nm to 425 nm. The HEVL-absorbing benzotriazole vinyl monomers of the present invention are suitable for producing hydrogel contact lenses that can significantly filter HEVL. Furthermore, by having an absorption peak at wavelengths of 410nm to 425nm (more preferably 410nm to 422nm, and even more preferably 412nm to 420nm), the hydrogel contact lenses containing one or two of the HEVL-absorbing vinyl monomers of the present invention are thought to significantly not block blue light (450nm to 495nm), and thereafter provide minimal changes in color perception, minimal reduction in color vision, minimal reduction in scotopic visual function, minimal reduction in contrast sensitivity in crepuscular and scotopic states, and minimal interruption of circadian sunlight.

[0060] In one embodiment, the present invention relates to formula (I) [ka] (In the formula, tBu is a tert-butyl group, R' is H or CH3, R1 is Cl or CF3, and L1 is a divalent C5-C6 alkylene group or -C2H4-(OC2H4) n -(wherein n is 1, 2, or 3) is a divalent group. This provides HEVL-absorbing benzotriazole vinyl monomer.

[0061] According to this aspect of the present invention, bond L1 has an extended spacer and (compared to those having a shorter L1, e.g., L1=CH2CH2CH2) may have higher solubility in 1-propanol. Furthermore, R1 has a Hammett substituent constant (σ) of about 0.23R (R1=Cl) or about 0.54R (R1=CF3).p It is an organic group having ) the electron-withdrawing ability of the substituent on the aromatic ring of benzotriazole (Hammett substituent constant, σ). p ) is thought to correlate with the wavelength of the absorption peak. The larger the electron-withdrawing characteristic (i.e., the larger the σ p ), the red shift of the absorption peak is large. When R1 is Cl or CF3, the monomer may have an absorption peak at approximately 364 nm or approximately 368 nm.

[0062] The benzotriazole vinyl monomer of formula (I) can be prepared using the methods described in U.S. Patent Nos. 4,716,234, 8,153,703 and 8,585,938. For example, R'=CH3, R1=CF3 and L1=C5H 10 The benzotriazole vinyl monomer of formula (II) can be synthesized by following the procedure shown in Figure 1. This synthetic route begins with the preparation of 2-tert-butyl-4-(5'-hydroxypentyloxy)phenol ("Compound 1") by reacting 5-chloro-1-pentanol with tert-butylhydroquinone, as described in U.S. Patent No. 4,716,234. Then, 4-trifluoromethyl-2-nitroaniline is converted to a diazonium salt ("Compound 2") according to the procedure described in U.S. Patent No. 8,585,938, and this is azo-coupled with Compound 1. The nitroazo intermediate ("Compound 3") is then reduced with glucose and zinc powder to close the benzotriazole ring and obtain the benzotriazole compound ("Compound 4"). In the final step, compound 4 is reacted with methacryloyl chloride according to the procedure described in U.S. Patent No. 4,716,234 to obtain 2-[2'hydroxy-3'-tert-butyl5'(5''-methacryloyloxy)pentyloxyphenyl]-5-trifluoromethyl-2H-benzotriazole ("compound 5").

[0063] In the first step of Scheme I, it is understood that 5-chloro-1-pentanol can be substituted with 6-chloro-1-hexanol, hydroxyethoxyethyl chloride (ClC2H4OC2H4OH), hydroxyethoxy-ethoxyethyl chloride (ClC2H4OC2H4OC2H4OH), or hydroxyethoxyethoxyethoxyethyl chloride (ClC2H4OC2H4OC2H4OC2H4OH) to obtain the benzotriazole vinyl monomer of formula (I) (wherein L1 is one of the other cited divalent groups).

[0064] In another embodiment, the present invention relates to formula (II) [ka] (wherein tBu is a tert-butyl group, R' is H or CH3, R2 is a Hammett substituent constant (σ) that does not contain any halogen atom and is about 0.15 to about 0.70 (preferably about 0.20 to 0.65) p It is an organic group having ), and L2 is a divalent C2~C 10 Alkylene group or -C2H4-(OC2H4) n - is a divalent group, and n is 1, 2, or 3. This provides HEVL-absorbing benzotriazole vinyl monomer.

[0065] In equation (II), R2 is preferably -CH2CN(σ p approximately 0.18), -OCOCH3(σ p Approximately 0.31), -CO(CH3)3(σ p approx. 0.32), -SO3 - (σ p approximately 0.35), -CONH2(σ p Approximately 0.36), -OSO2CH3(σ p approx. 0.36), -CONHCH3(σ p Approximately 0.36), -CON(CH3)2(σ p approx. 0.36), -CH2N + (CH3)3(σ p approximately 0.44), -COOH(σ p approximately 0.45), -COOCH3(σp Approximately 0.45), -COOC2H5(σ p Approximately 0.45), -COC2H5(σ p Approximately 0.48), -COCH3(σ p Approximately 0.50) or -CN(σ p It is approximately 0.66.

[0066] The benzotriazole vinyl monomer of formula (II) can be prepared by a procedure similar to that of scheme II. For example, the benzotriazole vinyl monomer of formula (II) with R'=CH3, R2=COOCH3 and L2=C3H6 can be synthesized by the procedure shown in Figure 2. This synthetic route begins with the preparation of 2-tert-butyl4-(3'-hydroxypropoxy)phenol ("compound 6") by reacting 3-chloro-1-propanol with tert-butylhydroquinone. Methyl4-amino-3-nitrobenzoate is then converted to a diazonium salt ("compound 7"), which is azo-coupled with compound 6. The nitroazo intermediate ("compound 8") is then reduced with glucose and zinc powder to close the benzotriazole ring and obtain the benzotriazole compound ("compound 9"). In the final step, compound 9 is reacted with methacryloyl chloride to obtain methyl 2-(3-(tert-butyl)-2-hydroxy-5-(3-(methacryloyloxy)propoxy)phenyl)-2H-benzotriazole-5-carboxylate ("compound 10").

[0067] Other benzotriazole vinyl monomers of formula (II) can be obtained according to the procedure of scheme II, including tert-butylhydroquinone, chlorosubstituted alkyl alcohols (e.g., ClC4H8OH, ClC5H) 10 OH, ClC6H 12 OH, ClC7H 14 OH, ClC8H 16 OH, ClC2H4OC2H4OH, ClC2H4OC2H4OC2H4OH, ClC2H4OC2H4OC2H4OC2H4OH, etc., with substituents at the 4th position (e.g., -CH2CN, -OCOCH3, -CO(CH3)3, -SO3) -, -CONH2, -OSO2CH3, -CONHCH3, -CON(CH3)2, -CH2N + It is understood that it can be prepared from 2-nitroaniline having (CH3)3, -COOH, -COOC2H5, -COC2H5, -COCH3 or -CN).

[0068] The benzotriazole vinyl monomer of the present invention described above may find specific applications in the manufacture of UV-absorbing ophthalmic devices, preferably intraocular lenses and hydrogel contact lenses, more preferably hydrogel contact lenses.

[0069] In another aspect, the present invention relates to (1) a polymerizable composition comprising (a) at least one UV-absorbing vinyl monomer (in about 0.1% to about 2.5% by weight, preferably about 0.2% to about 2.0% by weight, more preferably about 0.3% to about 1.8% by weight, and even more preferably about 0.4% to about 1.6% by weight) and (b) (about 0.2% to about 3.0% by weight, preferably about 0.25% to about 2.5% by weight, more preferably) (c) (about 0.3% to about 2.5% by weight, more preferably about 0.35% to about 2.25% by weight) of at least one HEVL-absorbing benzotriazole vinyl monomer of formula (I) or (II) (as defined above), and (c) (about 0.1% to about 2.0% by weight, preferably about 0.25% to about 1.75% by weight, more preferably about 0.5% to about 1.5% by weight, even more preferably about 0.75% to about 1.(1) A step of obtaining a polymerizable composition comprising (d) at least a free radical initiator (25% by weight), (e) at least one blue colorant which is Cu(II)-phthalocyanine blue pigment particles or at least one polymerizable blue dye, and (f) at least one polymerizable component selected from the group consisting of hydrophilic vinyl monomers, siloxane-containing vinyl monomers, polysiloxane vinyl crosslinkers, non-silicone vinyl crosslinkers, non-silicone hydrophobic vinyl monomers and combinations thereof, and (2) introducing the polymerizable composition into a mold for manufacturing a hydrogel contact lens, wherein the mold comprises a first mold half having a first molding surface defining the front surface of the contact lens and a second half defining the rear surface of the contact lens A method for producing a HEVL filtering hydrogel contact lens is provided, comprising the steps of: (1) having a first mold half having a second mold half having a molding surface, wherein the first and second mold halves are configured to accept each other such that a cavity is formed between the first and second molding surfaces; and (2) thermally or chemically curing the lens compound in the mold to form a HEVL filtering hydrogel contact lens, wherein the formed HEVL filtering hydrogel contact lens has a UVA%T of less than 5%, a UVB%T of about 1% or less, and a HEVL%T of about 35% or less (preferably about 32% or less, more preferably about 30% or less, and even more preferably about 28% or less).

[0070] In accordance with the present invention, any UV-absorbing vinyl monomer can be used in combination with one or more HEVL-absorbing vinyl monomers of the present invention to provide Class I UV protection. Preferably, at least one UV-absorbing vinyl monomer may be one or more benzotriazole-containing vinyl monomers (i.e., each having a benzotriazole moiety) selected from the group consisting of 2-(2'-hydroxy-5'-vinylphenyl)-2H-benzotriazole, 2-(2'-hydroxy-5'-methacryloxyphenyl)-2H-benzotriazole, 2-(2'-hydroxy-5'-acryloyloxyphenyl)-2H-benzotriazole, 2-[2'-hydroxy-5'-(2-methacryloxyethyl)phenyl)]-2H-benzotriazole (Norbloc), 2-[2'-hydroxy-5'-(2-acryloxyethyl)-phenyl)]-2H-benzotriazole, 2-(2'-hydroxy-5'-methacryloxypropylphenyl)-2H-benzotriazole, 2-(2'-hydroxy-5'-acryloxypropylphenyl)-2H-benzotriazole, and combinations thereof. More preferably, at least one UV-absorbing vinyl monomer is 2-[2'-hydroxy-5'-(2-methacrylateoxyethyl)phenyl)]-2H-benzotriazole.

[0071] According to the present invention, the free radical initiator may be a free radical thermal initiator or a free radical photoinitiator.

[0072] According to the present invention, any thermal free radical initiator can be used. Suitable thermal free radical initiators are known to those skilled in the art and include, for example, peroxides, hydroperoxides, azo-bis(alkyl or cycloalkylnitriles), persulfates, percarbonates, or mixtures thereof.Examples of preferred thermal free radical initiators include, but are not limited to, benzoyl peroxide, t-butyl peroxide, t-amyl peroxybenzoate, 2,2-bis(tert-butylperoxy)butane, 1,1-bis(tert-butylperoxy)cyclohexane, 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane, 2,5-bis(tert-butylperoxy)-2,5-dimethyl-3-hexine, and bis(1-(tert-butylperoxy)-1-methylhexane (Perkadox)benzene, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, di-t-butyl-diperoxyphthalate, t-butylhydroperoxide, t-butylperacetate, t-butylperoxybenzoate, t-butylperoxyisopropylcarbonate, acetylperoxide, lauroylperoxide, decanoylperoxide, dicetylperoxydicarbonate, di(4-t-butylcyclohexyl)peroxydicarbonate (Perkadox 16S), di(2-ethylhexyl)peroxydicarbonate, t-butylperoxypivalate (Lupersol 11), t-butylperoxy-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 Examples include 52), 2,2'-azobis(isobutyronitrile) (VAZO 64 or AIBN), 2,2'-azobis-2-methylbutyronitrile (VAZO 67), 1,1-azobis(1-cyclohexanecarbonitride) (VAZO 88), 2,2'-azobis(2-cyclopropylpropionitrile), 2,2'-azobis(methylisobutyrate), 4,4'-azobis(4-cyanovaleric acid), and combinations thereof.

[0073] In accordance with the present invention, any photoinitiator can be used as long as it can generate free radicals to initiate a polymerization reaction when irradiated with visible light having a wavelength greater than 440 nm. Examples of preferred photoinitiators include, but are not limited to, benzoylphosphine photoinitiators, acylgermanium photoinitiators (i.e., germanium-based type I photoinitiators as described in U.S. Patent No. 7,605,190), and acyltin photoinitiators (e.g., tetrakis(2,4,6-trimethylbenzoyl) stannane or others as described in U.S. Patent Application No. 18 / 308210).

[0074] Examples of preferred benzoylphosphine initiators include, but are not limited to, 2,4,6-trimethylbenzoyldiphenylphosphine oxide (TPO), 2,4,6-trimethylbenzoylethoxyphenylphosphine oxide (TPO-L), bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (BAPO), bis-(2,6-dichlorobenzoyl)-4-N-propylphenylphosphine oxide, bis-(2,6-dichlorobenzoyl)-4-N-butylphenylphosphine oxide, and lithium phenyl(2,4,6-trimethylbenzoyl)phosphine (LiTPO).

[0075] Preferred acylgermanium photoinitiators include, but are not limited to, bis(4-methoxybenzoyl)diethylgermanium (BMBDE-Ge), dibenzoyldiethylgermanium (DBDE-Ge), and tetrakis(2-ethylbenzoyl)-germanium (TEB-Ge).

[0076] Examples of preferred polymerizable blue dyes include, but are not limited to, 1,4-bis(4-(2-methacrylateoxyethyl)phenylamino)anthraquinone (Reactive Blue 246) and 1,4-bis((2-methacrylateoxyethyl)amino)anthraquinone (Reactive Blue 247).

[0077] Almost all hydrophilic vinyl monomers can be used in the present invention. Suitable hydrophilic vinyl monomers are used in the manufacture of non-silicone hydrogel contact lenses and silicone hydrogel contact lenses. Examples of such hydrophilic vinyl monomers include, but are not limited to, N,N-dimethyl(meth)acrylamide, 2-acrylamidoglycolic acid, N-hydroxypropyl(meth)acrylamide, N-hydroxyethyl(meth)acrylamide, N-[tris(hydroxymethyl)-methyl](meth)acrylamide, N-vinylpyrrolidone (NVP), N-vinylformamide, N-vinylacetamide, N-vinylisopropylamide, N-vinyl-N-methylacetamide (VMA), N-methyl-3-methylene-2-pyrrolidone, 1-methyl-5-methylene-2-pyrrolidone, 5-methyl-3-methylene-2-pyrrolidone, 2-hydroxyethyl(meth)acrylate, hydroxypropyl(meth)acrylate, methoxyethyl(meth)acrylate. Examples include acrylates, trimethylammonium 2-hydroxypropyl methacrylate hydrochloride, aminopropyl methacrylate hydrochloride, dimethylaminoethyl methacrylate (DMAEMA), glycerol methacrylate (GMA), C1-C4 alkoxy polyethylene glycol (meth)acrylate with a maximum weight-average molecular weight of 1500, polyethylene glycol (meth)acrylate with a maximum weight-average molecular weight of 1500, methacrylic acid, acrylic acid, methacrylateoxyethyl phosphocholine, methacrylateoxypropyl phosphocholine, N-2-hydroxyethyl vinylcarbamate, N-carboxyvinyl-β-alanine (VINAL), N-carboxyvinyl-α-alanine, and mixtures thereof.

[0078] Any siloxane-containing vinyl monomer can be used in the present invention. Preferred examples of siloxane-containing vinyl monomers may be siloxane-containing (meth)acrylamide monomers, siloxane-containing (meth)acryloxy monomers, siloxane-containing vinyloxycarbonyloxy monomers, siloxane-containing vinyloxycarbonylamino monomers, siloxane-containing vinylaminocarbonylamino monomers, or siloxane-containing vinylaminocarbonyloxy monomers, each of which contains a polysiloxane chain having a bis(trialkylsilyloxy)alkylsilyl group, a tris(trialkylsilyloxy)silyl group, or 2 to 30 siloxane units, and terminated with an alkyl, hydroxyalkyl, or methoxyalkyl group. Such preferred siloxane-containing vinyl monomers may be obtained from commercial suppliers or, instead, prepared according to known procedures similar to those described in, for example, U.S. Patent Nos. 5070215, 6166236, 6867245, 7214809, 8415405, 8475529, 8614261, 8658748, 9097840, 9103965, 9217813, 9315669, and 9475827. Alternatively, vinyl monomers having a reactive functional group (e.g., acid chloride, acid anhydride, carboxyl, hydroxyl, amino, epoxy, isocyanate, aziridine, azulactone, or aldehyde group) can be prepared by reacting a siloxane-containing compound having a reactive group selected from the group consisting of hydroxyalkyl, aminoalkyl, alkylaminoalkyl, carboxyalkyl, isocyanatoalkyl, epoxyalkyl, and aziridinylalkyl under coupling reaction conditions well known to those skilled in the art, in or out of the presence of a coupling agent.

[0079] In accordance with the present invention, any polysiloxane vinyl crosslinking agent can be used in the present invention. Examples of preferred polysiloxane vinyl crosslinking agents include, but are not limited to, α,ω-(meth)acrylooxy-terminated polydimethylsiloxanes of various molecular weights, α,ω-(meth)acrylamide-terminated polydimethylsiloxanes of various molecular weights, α,ω-vinylcarbonate-terminated polydimethylsiloxanes of various molecular weights, α,ω-vinylcarbamate-terminated polydimethylsiloxanes of various molecular weights, bis-3-methacrylooxy-2-hydroxypropyloxypropyl polydimethylsiloxanes of various molecular weights, N,N,N',N'-tetrakis(3-methacrylooxy-2-hydroxypropyl)-alpha,omega-bis-3-aminopropyl-polydimethylsiloxanes of various molecular weights, reaction products of glycidyl methacrylate and amino-functional polydimethylsiloxanes, reaction products of azulactone-containing vinyl monomers (any of the above) and hydroxyl-functional polydimethylsiloxanes, U.S. 5,760,Polysiloxane-containing macromers selected from the group consisting of macromer A, macromer B, macromer C, and macromer D as described in Specification No. 100, U.S. Patent No. 4,136,250, No. 4,153,641, No. 4182,822, No. 4189,546, No. 4259,467, No. 4260,725, No. 4261,875, No. 4343,927, No. 4254,248, and the same Specification No. 4355147, Specification No. 4276402, Specification No. 4327203, Specification No. 4341889, Specification No. 4486577, Specification No. 4543398, Specification No. 4605712, Specification No. Specification No. 4661575, Specification No. 4684538, Specification No. 4703097, Specification No. 4833218, Specification No. 4837289, Specification No. 4954586, Specification No. 4954587, Specification No. Specification No. 5010141, Specification No. 5034461, Specification No. 5070170, Specification No. 5079319, Specification No. 5039761, Specification No. 5346946, Specification No. 5358995, Specification No. Specification No. 5387632, Specification No. 5416132, Specification No. 5449729, Specification No. 5451617, Specification No. 5486579, Specification No. 5962548, Specification No. 5981675, Specification No. Examples include the polysiloxane vinyl crosslinking agents disclosed in Specification No. 6039913, No. 6762264, No. 7423074, No. 8163206, No. 8480227, No. 8529057, No. 8835525, No. 8993651, No. 9187601, No. 10081697, No. 10301451, and No. 10465047.

[0080] One preferred class of polysiloxane vinyl crosslinking agents is a monovalent C4-C2 crosslinking agent having a dimethylsiloxane unit and one methyl substituent and 2-6 hydroxyl groups. 40A di-(meth)acryloyloxy-terminated polysiloxane vinyl crosslinking agent having hydrophilic siloxane units each having an organic substituent, more preferably a polysiloxane vinyl crosslinking agent of formula (H), which can be prepared according to the procedure described later in this application and disclosed in U.S. Patent No. 1,0081,697.

[0081] Another class of preferred polysiloxane vinyl crosslinkers are vinyl crosslinkers, each containing one sole polysiloxane segment and two terminal (meth)acryloyl groups, which may be available from commercial suppliers or prepared by reacting glycidyl (meth)acrylate (meth)acryloyl chloride with diamino-terminated polydimethylsiloxane or dihydroxyl-terminated polydimethylsiloxane; by reacting isocyanatoethyl (meth)acrylate with dihydroxyl-terminated polydimethylsiloxane; by reacting amino-containing acrylic monomer with dicarboxyl-terminated polydimethylsiloxane in the presence of a coupling agent (carbodiimide); by reacting carboxyl-containing acrylic monomer with diamino-terminated polydimethylsiloxane in the presence of a coupling agent (carbodiimide); or by reacting hydroxyl-containing acrylic monomer with dihydroxyl-terminated polydisiloxane in the presence of a diisocyanate or diexope coupling agent.

[0082] Other preferred polysiloxane vinyl crosslinkers are chain-extended polysiloxane vinyl crosslinkers, each having at least two polysiloxane segments linked by a linker between each pair of polysiloxane segments and two terminal ethylenically unsaturated groups, which can be prepared according to the procedures described in U.S. Patent Nos. 5,034461, 5,416132, 5,449729, 5760100, 7423074, 8529057, 8835525, 8993651, 9187601, 10301451 and 10465047.

[0083] Examples of preferred hydrophobic non-silicone vinyl monomers include, but are not limited to, C1-C11. 10 Examples include alkyl (meth)acrylates (e.g., methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, etc.), cyclohexyl (meth)acrylate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl valerate, styrene, chloroprene, vinyl chloride, vinylidene chloride, (meth)acrylonitrile, 1-butene, butadiene, vinyltoluene, vinyl ethyl ether, perfluorohexylethyl-thio-carbonyl-aminoethyl-methacrylate, isobornyl (meth)acrylate, trifluoroethyl (meth)acrylate, hexafluoroisopropyl (meth)acrylate, hexafluorobutyl (meth)acrylate, and combinations thereof.

[0084] Examples of preferred non-silicone vinyl crosslinking agents include, but are not limited to, ethylene glycol di-(meth)acrylate, diethylene glycol di-(meth)acrylate, triethylene glycol di-(meth)acrylate, tetraethylene glycol di-(meth)acrylate, glycerol di-(meth)acrylate, 1,3-propanediol di-(meth)acrylate, 1,3-butanediol di-(meth)acrylate, 1,4-butanediol di-(meth)acrylate, glycerol Rolol 1,3-diglycerolate di-(meth)acrylate, ethylene bis[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, dimethacrylamide, N,N-di(meth)acryloyl-N-methylamine, N,N-di(meth)acryloyl-N-ethylamine Examples include 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)acrylamidepropane-2-yl dihydrogen phosphate, piperazine diacrylamide, tetraethylene glycol divinyl ether, triethylene glycol divinyl ether, diethylene glycol divinyl ether, ethylene glycol divinyl ether, triallyl isocyanurate, triallyl cyanurate, trimethylopropane trimethacrylate, pentaerythritol tetramethacrylate, bisphenol A dimethacrylate, allyl methacrylate, allyl acrylate, N-allyl-methacrylamide, N-allyl-acrylamide, or combinations thereof.

[0085] According to the present invention, the polymerizable composition of the present invention is a fluid composition, which may be a solution (i.e., one containing a non-reactive diluent-solvent) or a solvent-free blend (i.e., a fluid composition that does not contain any non-reactive diluent-solvent).

[0086] If the polymerizable composition of the present invention is a solution, it can be prepared by dissolving all the desired components in any suitable solvent known to those skilled in the art. Examples of suitable solvents, but are not limited to, water, tetrahydrofuran, tripropylene glycol methyl ether, dipropylene glycol methyl ether, ethylene glycol n-butyl ether, ketones (e.g., acetone, methyl ethyl ketone, etc.), diethylene glycol n-butyl ether, diethylene glycol methyl ether, ethylene glycol phenyl ether, propylene glycol methyl ether, propylene glycol methyl ether acetate, dipropylene glycol methyl ether acetate, propylene glycol n-propyl ether, dipropylene glycol n-propyl ether, tripropylene glycol n-butyl ether, propylene glycol n-butyl ether, dipropylene glycol n-butyl ether, tripropylene glycol n-butyl ether, propylene glycol Polyphenyl ether, dipropylene glycol dimethyl ether, polyethylene glycol, polypropylene glycol, ethyl acetate, butyl acetate, amyl acetate, methyl lactate, ethyl lactate, i-propyl lactate, methylene chloride, 2-butanol, 1-propanol, 2-propanol, menthol, cyclohexanol, cyclopentanol and exonorborneol, 2-pentanol, 3-pentanol, 2-hexanol, 3-hexanol, 3-methyl-2-butanol, 2-heptanol, 2-octanol, 2-nonanol, 2-decanol, 3-octanol, norborneol, tert-butanol, tert-amyl alcohol, 2-methyl-2-pentanol, 2,3-dimethyl-2-butanol, 3-methyl-3-pentanol, 1-methylcyclohexanol, 2-methyl-2-hexanol, 3,7-dimethyl-3-octanol, 1-chloro-2-methyl-2-propanol, 2-methyl-2-heptanol, 2-methyl-2-octanol, 2-2-methyl-2-nonanol, 2-methyl-2-decanol, 3-methyl-3-hexanol, 3-methyl-3-heptanol, 4-methyl-4-heptanol, 3-methyl-3-octanol, 4-methyl-4-octanol, 3-methyl-3-nonanol, 4-methyl-4-nonanol, 3-methyl-3-octanol, 3-ethyl-3-hexanol, 3-methyl-3-heptanol, 4-ethyl-4-heptanol, 4-propyl-4-heptanol, 4-isopropyl-4-heptanol, 2,4-dimethyl-2-pentanol, 1-methylcyclopentanol, 1-ethylcyclopentanol Examples include 1-ethylcyclopentanol, 3-hydroxy-3-methyl-1-butene, 4-hydroxy-4-methyl-1-cyclopentanol, 2-phenyl-2-propanol, 2-methoxy-2-methyl-2-propanol, 2,3,4-trimethyl-3-pentanol, 3,7-dimethyl-3-octanol, 2-phenyl-2-butanol, 2-methyl-1-phenyl-2-propanol and 3-ethyl-3-pentanol, 1-ethoxy-2-propanol, 1-methyl-2-propanol, t-amyl alcohol, isopropanol, 1-methyl-2-pyrrolidone, N,N-dimethylpropionamide, dimethylformamide, dimethylacetamide, dimethylpropionamide, N-methylpyrrolidone, and mixtures thereof. Preferably, the polymerizable composition is a solution of all desirable components in water, 1,2-propylene glycol, polyethylene glycol having a molecular weight of about 400 daltons or less, or a mixture thereof.

[0087] If the polymerizable composition of the present invention is a solvent-free blend, it can be prepared by mixing all the polymerizable components and other necessary components. A solvent-free polymerizable composition typically contains at least one blending vinyl monomer as a reactive solvent for dissolving all the other polymerizable components of the solvent-free polymerizable composition. Examples of preferred blending vinyl monomers are described later in this application. Preferably, methyl methacrylate is used as the blending vinyl monomer when preparing a solvent-free polymerizable composition.

[0088] Many lens formulations (polymerizable compositions) for manufacturing non-silicone hydrogel contact lenses are described in numerous patents and patent applications published up to the filing date of this application and are used in the manufacture of commercially available non-silicone hydrogel contact lenses. Examples of commercially available non-silicone hydrogel contact lenses include, but are not limited to, Alphafilcon A, Acofilcon A, Deltafilcon A, Etafilcon A, Focofilcon A, Helfilcon A, Helfilcon B, Helafilcon B, Hioxyfilcon A, Hioxyfilcon B, Hioxyfilcon D, Metafilcon A, Metafilcon B, Nelfilcon A, Nesofilcon A, Okfilcon A, Okfilcon B, Okfilcon C, Okfilcon D, Omafilcon A, Femfilcon A, Polymercon, Samfilcon A, Terfilcon A, Tetrafilcon A, and Bifilcon A. These can be used as base formulations for preparing polymerizable compositions for preparing HEVL filtering non-silicone hydrogel contact lenses of the present invention by adding at least one UV-absorbing vinyl monomer (any one of the above), at least one HEVL-absorbing vinyl monomer of the present invention (above), and at least one polymerizable blue dye (above) or Cu(II) phthalocyanine blue pigment particles to a base formulation.

[0089] Many lens formulations (polymerizable compositions) for forming silicone hydrogel contact lenses are described in numerous patents and patent applications published up to the filing date of this application and are used in the manufacture of commercially available SiHy contact lenses. Examples of commercially available SiHy contact lenses include, but are not limited to, Asmofilcon A, Barafilcon A, Confilcon A, Derefilcon A, Ephrofilcon A, Enfilcon A, Funfilcon A, Galifilcon A, Lotrafilcon A, Lotrafilcon B, Narafilcon A, Narafilcon B, Senofilcon A, Senofilcon B, Senofilcon C, Sumafilcon A, Somofilcon A, and Stenfilcon A. These can be used as base formulations for forming polymerizable compositions for forming HEVL filtering silicone hydrogel contact lenses of the present invention by adding at least one UV-absorbing vinyl monomer (any one of the above), at least one HEVL-absorbing vinyl monomer of the present invention (the above), at least one polymerizable blue dye (the above), or Cu(II) phthalocyanine blue pigment particles to a base formulation.

[0090] Lens molds for manufacturing hydrogel contact lenses are well known to those skilled in the art and are used, for example, in casting or spin casting. For example, a mold (for casting) generally comprises at least two mold pieces (or parts) 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 surfaces of the mold halves are the cavity-forming surfaces of the mold and are in direct contact with the polymerizable composition.

[0091] Mold halves can be formed by various methods, such as injection molding. Methods for manufacturing mold halves for casting contact lenses are generally well known to those skilled in the art. The method of the present invention is not limited to any particular method of forming a mold. In fact, any method of forming a mold can be used in the present invention. Mold halves can be formed by various techniques, such as injection molding or turning. Examples of preferred processes for forming mold halves are disclosed in U.S. Patent Nos. 4,444,711, 4,460,534, 5,843,446, and 5,894,002.

[0092] Virtually all materials known in the art for manufacturing molds can be used to manufacture molds for manufacturing contact lenses. For example, polymer materials such as polyethylene, polypropylene, polystyrene, PMMA, and Topas® COC grade 8007-S10 (a transparent amorphous copolymer of ethylene and norbornene, manufactured by Ticona GmbH in Frankfurt, Germany and Summit, New Jersey) can be used. Other materials that can transmit UV light, such as quartz glass and sapphire, may also be used.

[0093] In accordance with the present invention, polymerizable compositions can be introduced (distributed) into cavities formed by molds according to any known method.

[0094] After the polymerizable composition is distributed into the mold, it is polymerized (cured) to produce a contact lens. Crosslinking can be initiated thermally or chemically to polymerize (cure) the polymerizable components in the polymerizable composition.

[0095] Thermal polymerization is conveniently carried out at a temperature of, for example, 25 to 120°C, preferably 40 to 100°C. The reaction time can vary over a wide range, but is conveniently, for example, 30 minutes to 4 hours, or preferably 1 to 2 hours. It is advantageous to degas the components and solvent used in the polymerization reaction beforehand and carry out the copolymerization reaction under an inert atmosphere, for example, a nitrogen or argon atmosphere.

[0096] In that case, chemical beam polymerization can be induced by chemical beams, such as visible light of an appropriate wavelength (e.g., ≥450 nm).

[0097] After the curing step, the steps of mold demolition (i.e., separating the male mold half from the female mold half with the hydrogel contact lens attached to one of the male and female mold halves) and lens removal (i.e., removing the hydrogel contact lens from the mold half to which the lens is attached) are carried out according to any technique known to those skilled in the art.

[0098] After removing the molded hydrogel contact lens, it is typically extracted using an extraction medium well known to those skilled in the art. The extraction liquid medium is any solvent capable of dissolving the diluent, unpolymerized polymerizable material, and oligomer in the lens precursor. Water, any organic solvent known to those skilled in the art, or mixtures thereof can be used in this invention.

[0099] The extracted hydrogel contact lens can then be hydrated by any method known to those skilled in the art.

[0100] The extracted and / or hydrated hydrogel contact lenses may be subjected to further processes such as surface treatment, packaging in lens packages using packaging solutions well known to those skilled in the art, and sterilization such as autoclaving at 118-124°C for at least about 30 minutes.

[0101] Lens packages (or containers) are well known to those skilled in the art for autoclaving and storing soft contact lenses. Any lens package may be used in the present invention. Preferably, the lens package is a blister package comprising a base and a cover, the cover being removably sealed to the base, and the base comprising a cavity for receiving a sterile packaging solution and the contact lens.

[0102] Hydrogel contact lenses are packaged in individual packages, sealed, and sterilized (for example, by autoclaving at 120°C or higher for at least 30 minutes under pressure) before being distributed to the user. Those skilled in the art will be well aware of the methods for sealing and sterilizing lens packages.

[0103] In a further embodiment, the present invention relates to a crosslinked polymer material comprising (1) repeating units comprising (a) at least one UV-absorbing vinyl monomer, (b) at least one HEVL-absorbing benzotriazole vinyl monomer of formula (I) or (II) (as defined above), and (c) at least one polymerizable component selected from the group consisting of hydrophilic vinyl monomers, siloxane-containing vinyl monomers, polysiloxane vinyl crosslinking agents, non-silicone vinyl crosslinking agents, non-silicone hydrophobic vinyl monomers and combinations thereof, and (2) repeating units of Cu(II)-phthalocyanine blue pigment particles and / or polymerizable blue dye dispersed therein, wherein the HEVL%T is less than 5%, about 1% or less UVB%T, about 35% or less (preferably about 32% or less, more preferably about 30% or less, and even more preferably about 28% or less) and a * ≤ -5 (preferably a * =-20~-6) and b * We provide HEVL filtering hydrogel contact lenses having a color represented by ≤ +18.

[0104] Various embodiments of UV-absorbing vinyl monomers, hydrophilic vinyl monomers, siloxane-containing vinyl monomers, polysiloxane vinyl crosslinking agents, non-silicone hydrophobic vinyl monomers, non-silicone vinyl crosslinking agents, and polymerizable blue dyes are described above and can be used in this embodiment of the present invention.

[0105] The CIE (International Commission on Illumination) has a standardized color ordering system. * a * b *The color system used in this invention is for representing colors numerically. Lightness value L * It is also called "Lstar," and defines black as 0 and white as 100. * The axis is based on the opposite colors of green and magenta, with negative values ​​moving towards green and positive values ​​moving towards magenta. * The axis represents the opposite colors blue and yellow, with negative numbers pointing towards blue and positive numbers pointing towards yellow. These values ​​can be determined by color measurement using X-rite, as shown in the examples.

[0106] The HEVL filtering hydrogel contact lens of the present invention, when fully hydrated, has at least one property selected from the group consisting of an oxygen permeability of at least about 60 bars (preferably at least about 70 bars, more preferably at least about 80 bars) (at about 35°C), an elastic modulus 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) (at a temperature of about 22°C to 28°C), and an equilibrium water content of about 15% to about 75% by weight (preferably about 20% to about 70% by weight, more preferably about 25% to about 65% by weight) (at room temperature).

[0107] While various embodiments of the present invention have been described using specific terms, devices, and methods, such descriptions are for illustrative purposes only. The terms used are descriptive rather than restrictive. It should be understood that modifications and variations can be made by those skilled in the art without departing from the spirit or scope of the invention as expressed in the following claims. In addition, it should be understood that the various embodiments may be interchangeable in whole or in part, or combined and / or used together in any manner, as shown below.

[0108] 1. Equation (I) or (II) [ka] (In the formula, tBu is a tert-butyl group, R' is H or CH3, R1 is Cl or CF3, and L1 is a divalent C5-C6 alkylene group or -C2H4-(OC2H4) n - is a divalent group, and R2 does not contain any halogen atoms and has a Hammett substituent constant (σ) of about 0.15 to about 0.70 (preferably about 0.20 to about 0.65). p It is an organic group having ), and L2 is a divalent C2~C 10 Alkylene group or -C2H4-(OC2H4) n - is a divalent group, and n is 1, 2, or 3. One of the following HEVL-absorbing benzotriazole vinyl monomers.

[0109] 2. The HEVL-absorbing benzotriazole vinyl monomer according to Embodiment 1, which is of formula (I).

[0110] 3. The HEVL-absorbing benzotriazole vinyl monomer according to Embodiment 1, which is of formula (II).

[0111] 4. R2 is a Hammett substituent constant (σ) of approximately 0.20 to 0.65. p The HEVL-absorbing benzotriazole vinyl monomer according to Embodiment 3, having the following characteristics.

[0112] 5.R2 is -CH2CN, -OCOCH3, -CO(CH3)3, -SO3 - , -CONH2, -OSO2CH3, -CONHCH3, -CON(CH3)2, -CH2N + A HEVL-absorbing benzotriazole vinyl monomer according to Embodiment 3 or 4, wherein the monomer is (CH3)3, -COOH, -COOCH3, -COOC2H5, -COC2H5, -COCH3, or -CN.

[0113] 6. A method for manufacturing HEVL filtering hydrogel contact lenses, (1) A polymerizable composition, (a) at least one UV-absorbing vinyl monomer in an amount of about 0.1% to about 2.5% by weight (preferably about 0.2% to about 2.0% by weight, more preferably about 0.3% to about 1.8% by weight, and even more preferably about 0.4% to about 1.6% by weight), (b) at least one HEVL-absorbing benzotriazole vinyl monomer described in any one of Embodiments 1 to 5, in an amount of about 0.2% to about 3.0% by weight (preferably about 0.25% to about 2.5% by weight, more preferably about 0.3% to about 2.5% by weight, and even more preferably about 0.35% to about 2.25% by weight), (c) at least a free radical initiator in an amount of about 0.1% to about 2.0% by weight (preferably about 0.25% to about 1.75% by weight, more preferably about 0.5% to about 1.5% by weight, and even more preferably about 0.75% to about 1.25% by weight), (d) Cu(II)-phthalocyanine blue pigment particles or at least one blue colorant which is at least one polymerizable blue dye, (e) at least one polymerizable component selected from the group consisting of hydrophilic vinyl monomers, siloxane-containing vinyl monomers, polysiloxane vinyl crosslinking agents, non-silicone vinyl crosslinking agents, non-silicone hydrophobic vinyl monomers, and combinations thereof. A step of obtaining a polymerizable composition containing, (2) A step of introducing a polymerizable composition into a mold for manufacturing a hydrogel contact lens, wherein the mold comprises a first mold half having a first molding surface defining the front surface of the contact lens and a second mold half having a second molding surface defining the rear surface of the contact lens, and the first and second mold halves are configured to accept each other so that a cavity is formed between the first and second molding surfaces, (3) A step of forming a HEVL filtering hydrogel contact lens by thermal or chemical radiation curing the lens compound in a mold, wherein the HEVL filtering hydrogel contact lens has less than 5% UVA%T, about 1% or less UVB%T, and about 35% or less HEVL%T (preferably about 32% or less, more preferably about 30% or less, and even more preferably about 28% or less) A method that includes this.

[0114] 7. The method according to Embodiment 6, wherein the free radical initiator is a thermal initiator and the curing step is carried out thermally.

[0115] 8. The method according to Embodiment 6, wherein the free radical initiator is a photoinitiator, and the curing step is carried out by irradiation with visible light having a wavelength in the range of 450 nm to 510 nm.

[0116] 9. The method according to Embodiment 8, wherein the photoinitiator is a benzoylphosphine oxide photoinitiator, an acylgermanium photoinitiator, an acyltin photoinitiator, or a combination thereof.

[0117] 10. The method according to Embodiment 8, wherein the photoinitiator is an acylgermanium photoinitiator.

[0118] 11. Crosslinked polymer material, (1) A repeating unit, (a) at least one UV-absorbing vinyl monomer, (b) At least one HEVL-absorbing benzotriazole vinyl monomer described in any one of Embodiments 1 to 5, and (c) At least one polymerizable component selected from the group consisting of hydrophilic vinyl monomers, siloxane-containing vinyl monomers, polysiloxane vinyl crosslinking agents, non-silicone vinyl crosslinking agents, non-silicone hydrophobic vinyl monomers, and combinations thereof. The repeating unit and (2) Cu(II)-phthalocyanine blue pigment particles and / or polymerizable blue dye repeating units dispersed therein HEVL filtering hydrogel contact lenses comprising a crosslinked polymer material containing less than 5% UVA%T, about 1% or less UVB%T, about 35% or less HEVL%T, and a * ≤ -5 and b * HEVL filtering hydrogel contact lenses having a color represented by ≤ +18.

[0119] 12. A HEVL filtering hydrogel contact lens according to Embodiment 11, having a HEVL%T of approximately 32 or less.

[0120] 13. A HEVL filtering hydrogel contact lens according to Embodiment 11, having a HEVL%T of approximately 30 or less.

[0121] 14. A HEVL filtering hydrogel contact lens according to Embodiment 11, having a HEVL%T of approximately 28 or less.

[0122] 15.a * =-20~-6 and b * A HEVL filtering contact lens according to any one of embodiments 11 to 14, having a color represented by ≤ +18.

[0123] 16. A HEVL filtering hydrogel contact lens according to any one of Embodiments 11 to 15, wherein the crosslinked polymer material comprises at least one polymerizable blue dye which is 1,4-bis((2-methoxyethyl)amino)-anthraquinone and / or 1,4-bis(4-(2-methacrylateoxyethyl)phenylamino)-anthraquinone.

[0124] 17. A HEVL filtering hydrogel contact lens according to any one of Embodiments 11 to 15, wherein the crosslinked polymer material comprises Cu(II)-phthalocyanine blue pigment particles dispersed therein.

[0125] 18. The HEVL filtering hydrogel contact lens according to any one of embodiments 11 to 17, wherein the at least one UV-absorbing vinyl monomer includes a benzotriazole-containing vinyl monomer.

[0126] 19. The UV / HEVL filtering hydrogel contact lens according to Embodiment 18, wherein the at least one UV-absorbing vinyl monomer includes 2-(2'-hydroxy-5'-vinylphenyl)-2H-benzotriazole, 2-(2'-hydroxy-5'-methacryloxyphenyl)-2H-benzotriazole, 2-(2'-hydroxy-5'-acryloyloxyphenyl)-2H-benzotriazole, 2-[2'-hydroxy-5'-(2-methacryloxyethyl)phenyl)]-2H-benzotriazole (Norbloc), 2-[2'-hydroxy-5'-(2-acrylooxyethyl)phenyl)]-2H-benzotriazole, 2-(2'-hydroxy-5'-methacryloxypropylphenyl)-2H-benzotriazole, 2-(2'-hydroxy-5'-acrylooxypropylphenyl)-2H-benzotriazole, or a combination thereof.

[0127] 20. The HEVL filtering hydrogel contact lens according to Embodiment 18, wherein the at least one UV-absorbing vinyl monomer is 2-[2'-hydroxy-5'-(2-methacrylateoxyethyl)phenyl)]-2H-benzotriazole.

[0128] 21. The HEVL filtering hydrogel contact lens according to any one of Embodiments 11 to 20, wherein the at least one HEVL-absorbing benzotriazole vinyl monomer comprises the HEVL-absorbing benzotriazole vinyl monomer of Embodiment 2.

[0129] 22. The HEVL filtering hydrogel contact lens according to any one of Embodiments 11 to 21, wherein the at least one HEVL-absorbing benzotriazole vinyl monomer comprises the HEVL-absorbing benzotriazole vinyl monomers of Embodiments 3 to 5.

[0130] 23. Crosslinked polymer materials include N,N-dimethyl(meth)acrylamide, 2-acrylamidoglycolic acid, N-hydroxypropyl(meth)acrylamide, N-hydroxyethyl(meth)acrylamide, N-[tris(hydroxymethyl)-methyl](meth)acrylamide, N-vinylpyrrolidone, N-vinylformamide, N-vinylacetamide, N-vinylisopropylamide, N-vinyl-N-methylacetamide, N-methyl-3-methylene-2-pyrrolidone, 1-methyl-5-methylene-2-pyrrolidone, 5-methyl-3-methylene-2-pyrrolidone, 2-hydroxyethyl(meth)acrylate, hydroxypropyl(meth)acrylate, methoxyethyl(meth)acrylate, trimethylammonium 2-hydroxypropyl methacrylate hydrochloride A HEVL filtering hydrogel contact lens according to any one of Embodiments 11 to 22, comprising repeating units of at least one hydrophilic vinyl monomer selected from the group consisting of aminopropyl methacrylate hydrochloride, dimethylaminoethyl methacrylate, glycerol methacrylate, C1-C4 alkoxy polyethylene glycol (meth)acrylate having a weight-average molecular weight of up to 1500, polyethylene glycol (meth)acrylate having a weight-average molecular weight of up to 1500, methacrylic acid, acrylic acid, methacrylateoxyethyl phosphocholine, methacrylateoxypropyl phosphocholine, N-2-hydroxyethyl vinyl carbamate, N-carboxyvinyl-β-alanine, N-carboxyvinyl-α-alanine, and mixtures thereof.

[0131] 24. The HEVL filtering hydrogel contact lens according to any one of Embodiments 11 to 23, wherein the crosslinked polymer material is a silicone hydrogel material comprising repeating units of at least one siloxane-containing vinyl monomer and / or at least one polysiloxane vinyl crosslinking agent.

[0132] 25. Silicone hydrogel materials include α-(meth)acrylooxypropyl-terminated ω-C1~C4-alkyl-terminated polydimethylsiloxane, α-(meth)acrylooxy-2-hydroxypropyloxypropyl-terminated ω-C1~C4-alkyl-terminated polydimethylsiloxane, α-(2-hydroxyl-methacrylooxypropyloxypropyl)-ω-C1~C4-alkyl-decamethyl-pentasiloxane, and α-[3-(meth)acrylooxyethoxy-2-hydroxypropyloxypropyl]-terminated ω-C1~C4-alkyl α-[3-(meth)acrylooxypropyloxy-2-hydroxypropyloxypropyl]-terminated ω-C1~C4-alkyl-terminated polydimethylsiloxane, α-[3-(meth)acrylooxyisopropyloxy-2-hydroxypropyloxypropyl]-terminated ω-C1~C4-alkyl-terminated polydimethylsiloxane, α-[3-(meth)acrylooxybutyloxy-2-hydroxypropyloxypropyl]-terminated ω-C1~C4-alkyl-terminated polydimethylsiloxane, α-[3-(meth)acrylooxybutyloxy-2-hydroxypropyloxypropyl]-terminated ω-C1~C4-alkyl-terminated polydimethylsiloxane, α-[3-(meth) [T)Acryloxylethylamino-2-hydroxypropyloxypropyl]Terminal ω-C1~C4-alkyl-terminated polydimethylsiloxane, α-[3-(meth)acryloxylpropylamino-2-hydroxypropyloxypropyl]Terminal ω-C1~C4-alkyl-terminated polydimethylsiloxane, α-[3-(meth)acryloxyl-butylamino-2-hydroxypropyloxypropyl]Terminal ω-C1~C4-alkyl-terminated polydimethylsiloxane, α-(meth)acryloxyl(polyethyleneoxy)-2-hydroxy [Propyloxypropyl]-terminated ω-C1~C4-alkyl-terminated polydimethylsiloxane, α-[(meth)acrylooxy-2-hydroxypropyloxy-ethoxypropyl]-terminated ω-C1~C4-alkyl-terminated polydimethylsiloxane, α-[(meth)acrylooxy-2-hydroxypropyl-N-ethylaminopropyl]-terminated ω-C1~C4-alkyl-terminated polydimethylsiloxane, α-[(meth)acrylooxy-2-hydroxypropyl-aminopropyl]-terminated ω-C1~C4-alkyl-terminated polydimethylsiloxane,α-[(meth)acryloyloxy-2-hydroxypropyloxy-(polyethyleneoxy)propyl]-terminated ω-C1~C4-alkyl-terminated polydimethylsiloxane, α-(meth)acryloylamidopropyloxypropyl-terminated ω-C1~C4-alkyl-terminated polydimethylsiloxane, α-N-methyl-(meth)acryloylamidopropyloxypropyl-terminated ω-C1~C4-alkyl-terminated polydimethylsiloxane, α-[3-(meth)acryloylamidoethoxy-2-hydroxypropyloxy-propyl]-terminated ω -C1~C4-alkylpolydimethylsiloxane, α-[3-(meth)acrylamidepropyloxy-2-hydroxypropyloxypropyl]-terminated ω-C1~C4-alkyl-terminated polydimethylsiloxane, α-[3-(meth)acrylamideisopropyloxy-2-hydroxypropyloxypropyl]-terminated ω-C1~C4-alkyl-terminated polydimethylsiloxane, α-[3-(meth)acrylamidebutyloxy-2-hydroxypropyloxypropyl]-terminated ω-C1~C4-alkyl-terminated polydimethylsiloxane Xane, α-[3-(meth)acryloylamide-2-hydroxypropyloxypropyl]terminated ω-C1~C4-alkylpolydimethylsiloxane, α-[3-[N-methyl-(meth)acryloylamide]-2-hydroxypropyloxypropyl]terminated ω-C1~C4-alkyl-terminated polydimethylsiloxane, N-methyl-N'-(propyltetra-(dimethylsiloxy)dimethylbutylsilane)(meth)acrylamide, N-(2,3-dihydroxypropane)-N'-(propyltetra(dimethylsiloxy) A HEVL filtering hydrogel contact lens according to Embodiment 24, comprising a repeating unit of at least one siloxane-containing vinyl monomer selected from the group consisting of dimethylbutylsilane)(meth)acrylamide, (meth)acryloylamidopropyl-tetra(dimethylsiloxy)dimethylbutylsilane, α-vinylcarbonate-terminated ω-C1~C4-alkyl-terminated polydimethylsiloxane, α-vinylcarbamate-terminated ω-C1~C4-alkyl-terminated polydimethylsiloxane, and mixtures thereof.

[0133] 26. The HEVL filtering hydrogel contact lens according to Embodiment 24, wherein the silicone hydrogel material comprises repeating units of at least one siloxane-containing vinyl monomer selected from the group consisting of vinyl monomers having a bis(trialkylsilyloxy)alkylsilyl group, vinyl monomers having a tris(trialkylsilyloxy)silyl group, polysiloxane vinyl monomer, 3-methacrylateoxypropylpentamethyldisiloxane, t-butyldimethyl-siloxyethyl vinyl carbonate, trimethylsilylethyl vinyl carbonate, trimethylsilylmethyl vinyl carbonate, and combinations thereof.

[0134] 27. Silicone hydrogel materials include tris(trimethylsilyloxy)silylpropyl(meth)acrylate, [3-(meth)acrylooxy-2-hydroxypropyloxy]propylbis(trimethylsiloxy)-methylsilane, [3-(meth)acrylooxy-2-hydroxypropyloxy]propylbis(trimethylsiloxy)butylsilane, 3-(meth)acrylooxy-2-(2-hydroxyethoxy)-propyloxy)propylbis(trimethylsiloxy)methylsilane, 3-(meth) Acrylicoxy-2-hydroxypropyloxy)propyltris(trimethylsiloxy)silane, N-[tris(trimethylsiloxy)silylpropyl]-(meth)acrylamide, N-(2-hydroxy-3-(3-(bis(trimethylsilyloxy)methylsilyl)-propyloxy)propyl)-2-methyl(meth)acrylamide, N-(2-hydroxy-3-(3-(bis(trimethylsilyloxy)-methylsilyl)propyloxy)-propyl)(meth)acrylamide, N-(2-hydroxy -3-(3-(tris(trimethylsilyloxy)-silyl)propyloxy)propyl)-2-methylacrylamide, N-(2-hydroxy-3-(3-(tris(trimethylsilyloxy)silyl)-propyloxy)propyl)(meth)acrylamide, N-[tris(dimethylpropylsiloxy)silylpropyl]-(meth)acrylamide, N-[tris(dimethylphenylsiloxy)-silylpropyl](meth)acrylamide, N-[tris(dimethylethylsiloxy)-silylpropyl]( meth)acrylamide, N,N-bis[2-hydroxy-3-(3-(bis(trimethylsilyloxy)methylsilyl)-propyloxy)propyl]-2-methyl(meth)acrylamide, N,N-bis[2-hydroxy-3-(3-(bis(trimethylsilyloxy)methylsilyl)propyloxy)-propyl](meth)acrylamide, N,N-bis[2-hydroxy-3-(3-(tris(trimethylsilyloxy)silyl)propyloxy)-propyl]-2-methyl(meth)acrylamide, N,N-bis[2-hydroxy-3-(3-(tris(trimethylsilyloxy)silyl)-propyloxy)propyl](meth)acrylamide, N-[2-hydroxy-3-(3-(t-butyldimethylsilyl)propyloxy)-propyl]-2-methyl(meth)acrylamide, N-[2-hydroxy-3-(3-(t-butyldimethylsilyl)propyloxy)-propyl](meth)acrylamide, N,N-bis[2-hydroxy-3-(3-(t-butyldimethylsilyl)propyloxy)propyl]-2-methyl(meth)acrylamide, N-2-(meth)acryloxyethyl-O-(methyl-bis-trimethylsilyl The HEVL filtering hydrogel contact lens according to Embodiment 24, comprising a repeating unit of at least one siloxane-containing vinyl monomer selected from the group consisting of xy-3-propyl)silylcarbamate, 3-(trimethylsilyl)-propyl vinyl carbonate, 3-(vinyloxycarbonylthio)-propyl-tris(trimethylsiloxy)silane, 3-[tris(trimethylsiloxy)silyl]propyl vinylcarbamate, 3-[tris(trimethylsiloxy)silyl]propyl allylcarbamate, 3-[tris(trimethylsiloxy)silyl]propyl vinyl carbonate, and combinations thereof.

[0135] 28. A HEVL filtering hydrogel contact lens according to any one of embodiments 11 to 27, wherein the silicone hydrogel material comprises repeating units of at least one polysiloxane vinyl crosslinking agent.

[0136] 29. The at least one polysiloxane vinyl crosslinking agent is a dimethylsiloxane unit and a hydrophilized siloxane unit, each having one methyl substituent and one monovalent C4-C2 group having 2-6 hydroxyl groups. 40 A HEVL filtering contact lens according to Embodiment 28, comprising a di-(meth)acryloyloxy-terminated polysiloxane vinyl crosslinking agent having hydrophilized siloxane units each having an organic substituent.

[0137] 30. The at least one polysiloxane vinyl crosslinking agent has the formula (G)

Chemical formula

Chemical formula

Chemical formula

[0138] 31. The at least one polysiloxane vinyl crosslinking agent is (i) a vinyl crosslinking agent comprising one unique polydiorganosiloxane segment and two terminal ethylenically unsaturated groups selected from the group consisting of (meth)acryloyloxy group, (meth)acryloylamino group, vinyl carbonate group, vinyl carbamate group, and / or (ii) a chain extension polysiloxane vinyl crosslinking agent comprising at least two polydiorganosiloxane segments and a covalent linker, the covalent linker between each pair of polydiorganosiloxane segments and two terminal ethylenically unsaturated groups selected from the group consisting of (meth)acryloyloxy group, (meth)acryloylamino group, vinyl carbonate group, vinyl carbamate group. The HEVL filtering hydrogel contact lens according to Embodiment 28.

[0139] 32. The at least one polysiloxane vinyl crosslinking agent is α,ω-bis[3-(meth)acrylamidepropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acryloxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acryloxy-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acryloxyethoxy-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acryloxy [Cipropyloxy-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acrylooxyisopropyloxy-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acrylooxybutyloxy-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acrylamideethoxy-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth) [Acrylamidopropyloxy-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acrylamideisopropyloxy-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acrylamidebutyloxy-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acryloxyethylamino-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acryloxypropylamino-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acryloxybutylamino-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane, α,ω-bis[(meth)acrylamideethylamino-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acrylamidepropylamino-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acrylamide-butylamino-2-hydroxypropyloxypropyl]terminated polydimethylsiloxane, α,ω-bis[(meth)acryloxy-2-hydroxypropyloxy-ethoxypropyl]terminated polydimethylsiloxane, α,ω-bis[(meth)acryloxy-2-hydroxypropyl-N-ethylaminopropyl]terminated polydimethylsiloxane, α,ω-bis[(meth)acryloxy-2-hydroxypropyl-aminopropyl]-polydimethylsiloxane, α,ω-bis[(meth)acryloxy A HEVL filtering hydrogel contact lens according to Embodiment 28, comprising a first polysiloxane vinyl crosslinking agent selected from the group consisting of C-2-hydroxypropyloxy-(polyethyleneoxy)propyl]-terminated polydimethylsiloxane, α,ω-bis[(meth)acrylooxyethylamino-carbonyloxy-ethoxypropyl]-terminated polydimethylsiloxane, α,ω-bis[(meth)acrylooxyethylamino-carbonyloxy-(polyethyleneoxy)propyl]-terminated polydimethylsiloxane, or a combination thereof.

[0140] 33. The HEVL filtering hydrogel contact lens according to any one of embodiments 24 to 32, wherein the at least one hydrophilic vinyl monomer comprises at least one hydrophilic N-vinylamide monomer selected from the group consisting of N-vinylpyrrolidone, N-vinylpiperidone, N-vinylcaprolactam, N-vinyl-N-methylacetamide, N-vinylformamide, N-vinylacetamide, N-vinylisopropylamide, N-vinyl-N-methylacetamide, N-vinyl-N-ethylacetamide, N-vinyl-N-ethylformamide, and mixtures thereof.

[0141] 34. The HEVL filtering hydrogel contact lens according to any one of embodiments 24 to 32, wherein the at least one hydrophilic vinyl monomer comprises N-vinylpyrrolidone and / or N-vinyl-N-methylacetamide.

[0142] 35. The at least one hydrophilic vinyl monomer is (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N-ethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-propyl(meth)acrylamide, N-isopropyl(meth)acrylamide, N-3-methoxypropyl(meth)acrylamide, N-2-hydroxylethyl(meth)acrylamide, N,N-bis(hydroxyethyl)(meth)acrylamide, N-3-hydroxypropyl(meth)acrylamide, N-2-hydroxypropyl(meth)acrylamide, N-2,3-dihydroxypropyl(meth)acrylamide, N-tris(hydroxymethyl)methyl(meth)acrylamide, poly(ethylene glycol)ethyl(meth)acrylamide having a number average molecular weight up to 1500, 2-(meth)acrylamide glycolic acid, 3-(meth)acrylamide propionic acid, 5-(meth)acrylamide pentanoic acid, 4-( HEVL filtering hydrogel contact lenses according to any one of embodiments 24 to 32, comprising meth)acrylamidebutanoic acid, 3-(meth)acrylamide-2-methylbutanoic acid, 3-(meth)acrylamide-3-methylbutanoic acid, 2-(meth)acrylamide-2-methyl-3,3-dimethylbutanoic acid, 3-(meth)acrylamidehexanoic acid, 4-(meth)acrylamide-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 up to 1500, or a combination thereof.

[0143] 36. The HEVL filtering hydrogel contact lens according to any one of Embodiments 24 to 32, wherein the at least one hydrophilic vinyl monomer includes (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, or a combination thereof.

[0144] 37. The HEVL filtering hydrogel contact lens according to any one of Embodiments 24 to 36, wherein the at least one hydrophilic vinyl monomer includes 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, or a combination thereof.

[0145] 38. The HEVL filtering hydrogel contact lens according to any one of embodiments 24 to 37, wherein the at least one hydrophilic vinyl monomer includes 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, or a combination thereof.

[0146] 39. A HEVL filtering hydrogel contact lens according to any one of embodiments 24 to 38, having an oxygen permeability of at least 60 bars (at approximately 35°C) when fully hydrated.

[0147] 40. A HEVL filtering hydrogel contact lens according to any one of embodiments 24 to 38, having an oxygen permeability of at least 70 bars (at approximately 35°C) when fully hydrated.

[0148] 41. A HEVL filtering hydrogel contact lens according to any one of embodiments 24 to 38, having an oxygen permeability of at least 80 bars (at approximately 35°C) when fully hydrated.

[0149] 42. A HEVL filtering hydrogel contact lens according to any one of embodiments 24 to 41, having an elastic modulus of about 2.0 MPa or less (at a temperature of 22°C to 28°C) when fully hydrated.

[0150] 43. A HEVL filtering hydrogel contact lens according to any one of Embodiments 24 to 41, having an elastic modulus of about 1.5 MPa or less (at a temperature of 22°C to 28°C) when fully hydrated.

[0151] 44. A HEVL filtering hydrogel contact lens according to any one of embodiments 24 to 41, having an elastic modulus of about 1.2 MPa or less (at a temperature of 22°C to 28°C) when fully hydrated.

[0152] 45. A HEVL filtering hydrogel contact lens according to any one of embodiments 24 to 41, having 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.

[0153] 46. ​​A HEVL filtering hydrogel contact lens according to any one of embodiments 24 to 45, having a water content of approximately 15% to approximately 70% (at a temperature of 22°C to 28°C) when fully hydrated.

[0154] 47. A HEVL filtering hydrogel contact lens according to any one of embodiments 24 to 45, having a water content of approximately 20% to approximately 70% (at a temperature of 22°C to 28°C) when fully hydrated.

[0155] 48. A HEVL filtering hydrogel contact lens according to any one of embodiments 24 to 45, having a water content of approximately 25% to approximately 70% (at a temperature of 22°C to 28°C) when fully hydrated.

[0156] 49. A HEVL filtering hydrogel contact lens according to any one of embodiments 24 to 45, having a water content of approximately 30% to approximately 65% ​​(at a temperature of 22°C to 28°C) when fully hydrated.

[0157] 50. The HEVL filtering hydrogel contact lens according to any one of embodiments 24 to 49, wherein the silicone hydrogel material further comprises repeating units of at least one silicone vinyl crosslinking agent.

[0158] 51. The at least one non-silicone vinyl crosslinking agent is ethylene glycol di-(meth)acrylate, diethylene glycol di-(meth)acrylate, triethylene glycol di-(meth)acrylate, tetraethylene glycol di-(meth)acrylate, glycerol di-(meth)acrylate, 1,3-propanediol di-(meth)acrylate, 1,3-butanediol di-(meth)acrylate, 1,4-butanediol di-(meth)acrylate, glycerol 1,3-diglycerol Lorate 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, dimethacrylamide, N,N-di(meth)acryloyl-N-methylamine, N,N-di(meth)acryloyl-N-ethylamine, N,N'-methylenebis(meth) HEVL filtering hydrogel contact lenses according to Embodiment 50, comprising 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)acrylamidepropane-2-yl dihydrogen phosphate, piperazine diacrylamide, tetraethylene glycol divinyl ether, triethylene glycol divinyl ether, diethylene glycol divinyl ether, ethylene glycol divinyl ether, triallyl isocyanurate, triallyl cyanurate, trimethylopropane trimethacrylate, pentaerythritol tetramethacrylate, bisphenol A dimethacrylate, allyl methacrylate, allyl acrylate, N-allyl-methacrylamide, N-allyl-acrylamide, or a combination thereof.

[0159] 52. The HEVL filtering hydrogel contact lens according to any one of embodiments 24 to 51, wherein the silicone hydrogel material further comprises repeating units of at least one hydrophobic non-silicone vinyl monomer.

[0160] 53. The at least one hydrophobic non-silicone vinyl monomer is C1-C 10 HEVL filtering hydrogel contact lenses according to Embodiment 52, comprising alkyl (meth)acrylate, cyclopentyl acrylate, cyclohexyl methacrylate, cyclohexyl acrylate, isobornyl (meth)acrylate, styrene, 4,6-trimethylstyrene, t-butylstyrene, trifluoroethyl (meth)acrylate, hexafluoroisopropyl (meth)acrylate, hexafluorobutyl (meth)acrylate, or a combination thereof.

[0161] 54. The silicone hydrogel material is a repeating unit of at least one polysiloxane vinyl monomer as described in Embodiment 30, a repeating unit of at least one hydrophilic N-vinylamide monomer selected from the group consisting of N-vinylpyrrolidone, N-vinylpiperidone, N-vinylcaprolactam, N-vinyl-N-methylacetamide, N-vinylformamide, N-vinylacetamide, N-vinylisopropylamide, N-vinyl-N-methylacetamide, N-vinyl-N-ethylacetamide, N-vinyl-N-ethylformamide and mixtures thereof, a repeating unit of at least one non-silicone vinyl crosslinking agent, C1-C 10HEVL filtering hydrogel contact lens according to Embodiment 30, comprising repeating units of at least one hydrophobic non-silicone vinyl monomer selected from the group consisting of alkyl (meth)acrylate, cyclopentyl acrylate, cyclohexyl methacrylate, cyclohexyl acrylate, isobornyl (meth)acrylate, styrene, 4,6-trimethylstyrene, t-butylstyrene, trifluoroethyl (meth)acrylate, hexafluoroisopropyl (meth)acrylate, hexafluorobutyl (meth)acrylate, and combinations thereof.

[0162] 55. The HEVL filtering hydrogel contact lens according to Embodiment 54, wherein the at least one hydrophilic N-vinylamide monomer is N-vinylpyrrolidone and / or N-vinyl-N-methylacetamide, the at least one hydrophobic non-silicone vinyl monomer is methyl methacrylate, and the at least one non-silicone vinyl crosslinking agent 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, triallyl isocyanurate, allyl methacrylate, or a combination thereof.

[0163] 56. The HEVL filtering hydrogel contact lens according to Embodiment 24, wherein the dry silicone hydrogel material comprises at least 90% by weight of (a) at least one hydrophilic (meth)acrylamide monomer as the at least one hydrophilic vinyl monomer, (b) at least one siloxane-containing (meth)acrylamide monomer as the at least one siloxane-containing vinyl monomer, and (c) repeating units of the at least one polysiloxane vinyl monomer.

[0164] 57. The at least one hydrophilic (meth)acrylamide monomer is (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N-ethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-propyl(meth)acrylamide, N-isopropyl(meth)acrylamide, N-3-methoxypropyl(meth)acrylamide, N-2-hydroxylethyl(meth)acrylamide, N,N-bis(hydroxyethyl)(meth)acrylamide, N-3-hydroxypropyl(meth)acrylamide, N-2-hydroxypropyl(meth)acrylamide, N-2,3-dihydroxypropyl(meth) Acrylamide, N-4-hydroxybutyl(meth)acrylamide, N,N-bis(2-hydroxyethyl)(meth)acrylamide, N-tris(hydroxymethyl)methyl(meth)acrylamide, 2-(meth)acrylamide glycolic acid, 3-(meth)acrylamide propionic acid, 4-(meth)acrylamide butanoic acid, 3-(meth)acrylamide-2-methylbutanoic acid, 3-(meth)acrylamide-3-methylbutanoic acid, 2-(meth)acrylamide-2-methyl-3,3-dimethylbutanoic acid, 5-(meth)acrylamide pentanoic acid, 3-(meth)acrylamide hexanoic acid, 4-(meth)acrylamide-3,HEVL filtering hydrogel contact lenses according to Embodiment 56, comprising 3-dimethylhexanoic acid, (3-(meth)acrylamidephenyl)boronic acid, 3-((3-methacrylamidopropyl)dimethylammonio)-propane-1-sulfonate, 3-((3-acrylamidopropyl)dimethylammonio)propane-1-sulfonate, 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, poly(ethylene glycol)ethyl(meth)acrylamide having a number average molecular weight of up to 700, methoxy-poly(ethylene glycol)ethyl(meth)acrylamide having a number average molecular weight of up to 700, or a combination thereof.

[0165] 58. The HEVL filtering hydrogel contact lens according to Embodiment 56, wherein the at least one hydrophilic (meth)acrylamide monomer includes N,N-dimethyl(meth)acrylamide, N-ethyl(meth)acrylamide, N-2-hydroxyethyl(meth)acrylamide, N-3-hydroxypropyl(meth)acrylamide, N-2-hydroxypropyl(meth)acrylamide, N-2,3-dihydroxypropyl(meth)acrylamide, (meth)acrylamide, N-(2-aminoethyl)(meth)acrylamide, N-(3-aminopropyl)(meth)acrylamide, or a combination thereof.

[0166] 59. The HEVL filtering hydrogel contact lens according to Embodiment 56, wherein the at least one hydrophilic (meth)acrylamide monomer comprises N,N-dimethyl(meth)acrylamide.

[0167] 60. The HEVL filtering hydrogel contact lens according to any one of Embodiments 56 to 59, wherein the at least one siloxane-containing (meth)acrylamide monomer comprises a (meth)acrylamide monomer containing a tris(trialkylsiloxy)silyl group.

[0168] 61. (Meth)acrylamide monomers containing a tris(trialkylsiloxy)silyl group include N-[tris(trimethylsiloxy)silylpropyl](meth)acrylamide, N-[tris(dimethylethylsiloxy)-silylpropyl](meth)acrylamide, N-[tris(dimethylpropylsiloxy)silylpropyl]acrylamide, N-[tris(dimethylphenyl-siloxy)silylpropyl](meth)acrylamide, and N-(2-hydroxy-3-(3-(tris(trimethylsilyloxy)silyl)propyloxy)-propyl) HEVL filtering hydrogel contact lenses according to Embodiment 60, which are -2-methylacrylamide, N-(2-hydroxy-3-(3-(tris(trimethylsilyloxy)silyl)propyloxy)propyl)acrylamide, N,N-bis[2-hydroxy-3-(3-(tris(trimethylsilyloxy)silyl)propyloxy)propyl]-2-methylacrylamide, N,N-bis[2-hydroxy-3-(3-(tris(trimethylsilyloxy)silyl)propyloxy)propyl]acrylamide, or a combination thereof.

[0169] 62. The HEVL filtering hydrogel contact lens according to any one of Embodiments 56 to 59, wherein the at least one siloxane-containing (meth)acrylamide monomer comprises a (meth)acrylamide monomer containing a bis(trialkylsilyloxy)alkylsilyl group.

[0170] 63. The HEVL filtering hydrogel contact lens according to any one of embodiments 56 to 59, wherein the at least one siloxane-containing (meth)acrylamide monomer comprises a (meth)acrylamide monomer containing a polysiloxane segment having 2 to 20 siloxane units.

[0171] 64. The HEVL filtering hydrogel contact lens according to any one of Embodiments 56 to 63, wherein the at least one polysiloxane vinyl crosslinking agent includes α,ω-(meth)acrylooxy-terminated polydimethylsiloxane, α,ω-(meth)acrylamide-terminated polydimethylsiloxane, α,ω-vinylcarbonate-terminated polydimethylsiloxane, α,ω-vinylcarbamate-terminated polydimethylsiloxane, bis-3-methacryloxy-2-hydroxypropyloxypropyl polydimethylsiloxane, N,N,N',N'-tetrakis(3-methacryloxy-2-hydroxypropyl)-alpha,omega-bis-3-aminopropyl-polydimethylsiloxane of various molecular weights, reaction products of glycidyl methacrylate and diamino-functionalized polydimethylsiloxane, reaction products of azulactone-containing vinyl monomer and dihydroxyl-functionalized polydimethylsiloxane, or combinations thereof.

[0172] 65. The HEVL filtering hydrogel contact lens according to any one of embodiments 56 to 63, wherein the at least one polysiloxane vinyl crosslinking agent comprises (1) a vinyl crosslinking agent comprising one sole polydiorganosiloxane segment and two terminal ethylenically unsaturated groups selected from the group consisting of (meth)acryloyloxy, (meth)acryloylamino, vinyl carbonate, and vinyl carbamate groups, and / or (2) a chain-extended polysiloxane vinyl crosslinking agent comprising at least two polydiorganosiloxane segments and a covalent linker, the covalent linker between each pair of polydiorganosiloxane segments and two terminal ethylenically unsaturated groups selected from the group consisting of (meth)acryloyloxy, (meth)acryloylamino, vinyl carbonate, and vinyl carbamate groups.

[0173] 66. The at least one polysiloxane vinyl crosslinking agent is α,ω-bis[3-(meth)acrylamidepropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acryloxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acryloxy-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acryloxyethoxy-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acryloxy [Cipropyloxy-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acrylooxyisopropyloxy-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acrylooxybutyloxy-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acrylamideethoxy-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth) [Acrylamidopropyloxy-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acrylamideisopropyloxy-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acrylamidebutyloxy-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acryloxyethylamino-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acryloxypropylamino-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acryloxybutylamino-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane, α,ω-bis[(meth)acrylamideethylamino-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acrylamidepropylamino-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acrylamide-butylamino-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane, α,ω-bis[(meth)acryloxy-2-hydroxypropyloxy-ethoxypropyl]-terminated polydimethylsiloxane, α,ω-bis[(meth)acryloxy-2-hydroxypropyl-N-ethylaminopropyl]-terminated polydimethylsiloxane, α,ω-bis[(meth)acryloxy-2-hydroxypropyl-aminopropyl]-polydimethylsiloxane, α,ω-bis[(meth)acryloxy-2-hydroxypropyl-aminopropyl]-polydimethylsiloxane A HEVL filtering hydrogel contact lens according to any one of embodiments 56 to 63, comprising a first polysiloxane vinyl crosslinking agent selected from the group consisting of droxypropyloxy-(polyethyleneoxy)propyl]-terminated polydimethylsiloxane, α,ω-bis[(meth)acrylooxyethylamino-carbonyloxy-ethoxypropyl]-terminated polydimethylsiloxane, α,ω-bis[(meth)acrylooxyethylamino-carbonyloxy-(polyethyleneoxy)propyl]-terminated polydimethylsiloxane, or a combination thereof.

[0174] 67. The crosslinked polymer material includes a non-silicone hydrogel material, as described in any one of Embodiments 11 to 23, for the HEVL filtering hydrogel contact lens.

[0175] 68. The non-silicone hydrogel material comprises repeating units of hydroxy-containing vinyl monomers, as described in Embodiment 67, for the HEVL filtering hydrogel contact lens.

[0176] 69. The HEVL filtering hydrogel contact lens according to Embodiment 68, wherein the 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.

[0177] 70. A non-silicone hydrogel material comprising repeating units of N-vinylpyrrolidone, N-vinyl-N-methylacetamide, 1-methyl-3-methylene-2-pyrrolidone, or a combination thereof, as an HEVL filtering hydrogel contact lens of Embodiment 67.

[0178] The foregoing disclosure will enable those skilled in the art to implement the invention. Various modifications, changes, and combinations of the various embodiments described herein are possible. References to the following examples are proposed to enable the reader to better understand the particular embodiments and their advantages. This specification and the examples are intended to be illustrative. [Examples]

[0179] Example 1 Measurement of oxygen permeability coefficient Unless otherwise specified, the oxygen permeability coefficient (Dk / t) of the lens and lens material, and the intrinsic (or edge-corrected) oxygen permeability (Dk i or Dk c ) is measured according to the procedure described in ISO 18369-4.

[0180] equilibrium moisture content The equilibrium water content (EWC) of contact lenses is measured as follows:

[0181] The amount of water (expressed as a weight percentage) present in a hydrated hydrogel contact lens, fully equilibrated in physiological saline, is measured at room temperature. The lenses are quickly stacked, wiped with a cloth, and then the lens stack is transferred to an aluminum pan on an analytical balance. Typically, there are 5 lenses per sample pan. The hydrated weight of the pan + lenses is recorded. The pan is covered with aluminum foil. The pan is dried in a laboratory oven at 100±2°C for 16-18 hours. The pan + lenses is removed from the oven and cooled in a desiccator for at least 30 minutes. Only one pan is removed from the desiccator, and the aluminum foil is discarded. The pan + dried lens sample is weighed 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.

[0182] modulus of elasticity The elastic modulus of a contact lens is measured using the MTS Insight instrument. The contact lens is first cut into 3.12 mm wide strips using a Precision Concept two-stage cutter. Five thickness values ​​are measured within a gauge length of 6.5 mm or less. The strips are mounted on the instrument grip and immersed in PBS (phosphate-buffered saline) at a controlled temperature of 21 ± 2°C. Typically, a 5N load cell is used for the test. A constant force and velocity are applied to the sample until it breaks. Force and displacement data are collected using TestWorks software. The elastic modulus value is calculated by TestWorks software and is the slope or tangent of the stress-to-strain curve near zero elongation in the elastic deformation region.

[0183] Transmittance The contact lens is manually placed in a specially manufactured sample holder that maintains the lens shape as if it were on the eye. This holder is then immersed in a 1 cm path length quartz cell containing phosphate-buffered saline (PBS, pH approximately 7.0-7.4) as a reference. A UV / visible spectrophotometer, such as a Varian Cary 3E UV-Visible spectrophotometer equipped with a LabSphere DRA-CA-302 beam splitter, can be used for this measurement. Percentage transmission spectra are collected in the wavelength range of 250-800 nm, and %T values ​​are collected at 0.5 nm intervals. This data is transferred to an Excel spreadsheet and used to determine whether the lens matches Class 1 UV absorbance. The transmittance is calculated using the following formula: UVA%T=315nm~380nm average % transmittance x 100 UVB%T=280nm~315nm average % transmittance x 100 HEVL%T=380nm~450nm average % transmittance x 100.

[0184] chemicals CE-PDMS has three polydimethylsiloxane (PDMS) segments linked between two PDMS segments via diurethane bonds, and two urethane bonds located between one terminal methacrylate group and one PDMS segment, respectively, and is a polysiloxane vinyl crosslinking agent prepared in a manner similar to that described in Example 2 of U.S. Patent No. 9,315,669. 1The following are descriptive terms: Mw = 10.1K (determined by HNMR spectroscopy), TRIS-Am represents N-[tris(trimethylsiloxy)-silylpropyl]acrylamide, mPDMS represents monomethacrylate-terminated butyl-terminated polydimethylsiloxane (Mw: 600-800 Daltons), MMA represents methyl methacrylate, NVP represents N-vinylpyrrolidone, EGMA represents ethylene glycol methyl ether methacrylate, TEGDMA represents triethylene glycol dimethacrylate, AMA represents allyl methacrylate, DMA represents N,N-dimethylacrylamide, L-PEG2000 represents N-(carbonylmethoxypolyethylene glycol-2000)-1,2-distearoyl-sn-glycero-3-phosphoethanolamine, sodium salt, and DMPC represents 1,2-dimyristoyl-sn-glyceropropyl H-TEMPO represents 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl, Norbloc represents 2-[2'-hydroxy-5'-(2-methacrylateoxyethyl)phenyl)]-2H-benzotriazole from Aldrich, PrOH represents n-propanol, and UV28 represents 2-{2'-hydroxy-3'-tert-butyl-5'-[3'-methacrylate UV35 represents liloyloxypropoxy]phenyl}-5-chloro-2H-benzotriazole, RB247 represents 2-propenoic acid, 2-methyl-, 2-[2-[3-(5-chloro-2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxyphenoxy]ethoxy]ethyl ester, and RB247 represents 1,4-bis((2-methacryloyloxyethyl)amino)-anthraquinone (Reactive Blue 247) represents VAZO64, 2,2'-dimethyl-2,2'-azodipropiononitrile, BMBDE-Ge represents bis(4-methoxybenzoyl)diethylgermanium, TEB-Ge represents tetrakis(2-ethylbenzoyl)germanium, MEK represents methyl ethyl ketone, PBS has a pH of 7.2±0.2 at 25°C and contains approximately 0.044 wt% NaH2PO4·H2O, approximately 0.388 wt% Na2HPO4·2H2O, and approximately 0.79 wt% NaCl and 98.This represents phosphate-buffered saline containing 78% by weight of water. "G1" represents the di-methacryloyloxypropyl-terminated polysiloxane (Mn approximately 7.5-8.1 kg / mol, OH content approximately 1.25-1.55 mol / g) shown in formula (A) below. [ka]

[0185] Example 2 This example uses HEVL-absorbing vinyl monomer. [ka] (In the formula, L1 is -(CH2)3- or -(CH2)2-O-(CH2)2-) This shows the correlation between the melting point and solubility.

[0186] A correlation has been reported between lower melting points and compound solubility (Bathori, NBActa Cryst., 2014, A70, C990).

[0187] When linker L1 is extended from -(CH2)3- in UV28 to -(CH2)2-O-(CH2)2- in UV35, the melting points are found to decrease significantly from 112-113°C to 62-65°C, respectively. As expected, the solubility in 1-propanol improves to >4.0 mg / mL (Table 1). However, the UV / visible absorption profiles of UV28 and UV35 are equivalent, as shown in Figure 3.

[0188] [Table 1]

[0189] Example 3 Preparation of lens formulations Two types of lens formulations are prepared to have the compositions shown in Table 2.

[0190] [Table 2]

[0191] All components listed in Table 2 (excluding the germanium-based photopolymerization initiator) are added to an amber vial. Then, TEB-Ge or BMBDE-Ge (whose structures are listed in Table 3) is added to the vial under yellow light, and all components are mixed for 30 minutes in a water bath preheated to 40°C. After all solids have dissolved, the mixture is filtered through a glass microfilter (5.0 μm Millex®-SV filter).

[0192] [Table 3]

[0193] PAA coating solution. The polyacrylic acid (PAA) coating solution is prepared by dissolving PAA (MW: 450 kDa, from Lubrizol) in a predetermined amount of 1-propanol (1-PrOH) to a concentration of approximately 0.44% by weight, and adjusting the pH to approximately 2.0 with formic acid.

[0194] Preparation of in-package coating solution (IPC physiological saline). Poly(AAm-co-AA)(90 / 10) partial sodium salt (approximately 90% solids, poly(AAm-co-AA)90 / 10, Mw200,000) is purchased from Polysciences, Inc. and used as received. Polyamidoamine epichlorohydrin (PAE) (Kymene, azetidinium content 0.46 as analyzed by NMR) is purchased as an aqueous solution from Ashland and used as received. IPC saline is prepared by dissolving approximately 0.07% w / w poly(AAm-co-AA) (90 / 10) and approximately 0.10% PAE (initial azetidinium millimolar equivalent of approximately 8.8 mmol) in phosphate-buffered saline (PBS) (approximately 0.044 w / w% NaH2PO4·H2O, approximately 0.388 w / w% Na2HPO4·2H2O, approximately 0.79 w / w% NaCl) and adjusting the pH to 7.2-7.6. Next, the IPC is heat-pretreated at approximately 60°C for approximately 6 hours (heat pretreatment). During this heat pretreatment, the poly(AAm-co-AA) and PAE are partially crosslinked with each other (i.e., not all azetidinium groups of the PAE are consumed), forming a water-soluble and heat-crosslinkable hydrophilic polymer material containing azetidinium groups within a branched polymer network in the IPC saline. After heat pretreatment, the IPC is cooled to room temperature and filtered through a 0.22 micron PES membrane filter.

[0195] Lens manufacturing (Lightstream) The lenses are prepared by casting from the lens-forming composition prepared above in a reusable mold (half female mold made of quartz and half male mold made of glass) similar to the molds shown in Figures 1-6 of U.S. Patent No. 7,384,590 and No. 7,387,759 (Figures 1-6). The lens compound in the mold is subjected to a pressure of 50 mW / cm². 2The lenses were cured for 30 seconds with 452 nm (BMBDE-Ge formulation) or 464 nm (TEB-Ge formulation) LED light at a total intensity. After demolding and lens removal, the cast contact lenses were extracted and coated by immersion in the following series of baths: three methyl ethyl ketone (MEK) baths (approximately 22 seconds, 78 seconds, and 224 seconds each), a DI water bath (56 seconds), the PAA dip solution prepared above (44 seconds), a 50 / 50n-propanol / water bath (56 seconds), four DI water baths (56 seconds each), and then equilibrated in PBS solution.

[0196] The resulting silicone hydrogel contact lenses are packaged / sealed in polypropylene lens packaging shells (or blisters) containing 0.65 mL of IPC saline solution prepared above (one lens per shell), and autoclaved at 121°C for 45 minutes.

[0197] Example 4 Preparation of lens formulations The lens compound (4-1) is prepared to have the composition shown in Table 4.

[0198] [Table 4]

[0199] Lens manufacturing (thermosetting) Lenses are prepared by casting from the polymerizable compositions shown in Table 4. The polymerizable composition is placed in a polypropylene mold and heat-cured in an oven with the following curing profile: heating from room temperature to 55°C at a rate of approximately 7°C / min, holding at 55°C for approximately 30 minutes, heating from 55°C to 80°C at a rate of approximately 7°C / min, holding at 80°C for approximately 30 minutes, heating from 80°C to 100°C at a rate of approximately 7°C / min, and holding at 100°C for approximately 30 minutes.

[0200] After release, the cast SiHy contact lenses are extracted with a PAA coating solution at 40 °C for 30 minutes and at 40 °C for 90 minutes, and then rinsed in PB (phosphate buffer containing about 0.077 wt% NaH2PO4·H2O and about 0.31 wt% Na2HPO4·2H2O) for 15 minutes. The resulting silicone hydrogel contact lenses are packaged / sealed in a polypropylene lens packaging shell (or blister) (one lens per shell) together with 0.65 mL of IPC physiological saline, and then autoclaved (sterilized) at 121 °C for 45 minutes.

[0201] Example 5 The properties of the lenses prepared in Examples 3 and 4 are evaluated and the results are reported in Table 5.

[0202]

Table 5

[0203] Figure 4 shows the UV / visible transmission spectra of the contact lenses obtained from lens formulations 3-2 and 4-1.

[0204] Example 6 This example reports a study on the solubility and stability of UV35.

[0205] Preparation of lens formulations Four lens formulations are prepared to have the compositions shown in Tables 6 and 7.

[0206]

Table 6

Table 7

[0208] Mix 10g of the total formulation at room temperature for 1-2 hours. After the initial mixing, mix the Lightstream formulations (6-1 and 6-2) at 40°C for a further 1-2 hours. UV28 in the Lightstream control formulation (6-1) does not dissolve, and this formulation cannot be subjected to stability testing. Conversely, UV35 dissolves completely in Lightstream formulation 6-2 after stirring at 40°C for 30 minutes. Both benzotriazole UV28 and UV35 dissolve in the thermosetting formulations (6-3 and 6-4). The formulations are subjected to storage stability testing, and the results are shown in Table 8. Tests are performed under room temperature and refrigerated (3°C) conditions.

[0209] [Table 8]

[0210] Example 7 In this example, four HEVL-absorbing vinyl monomers listed in Table 9 are used. They can be represented by the following structural formulas. [ka]

[0211] [Table 9]

[0212] Table 9 shows that the HEVL absorption peak of HEVL-absorbing vinyl monomers can be shifted to longer wavelengths by changing the electron-withdrawing or electron-donating ability of substituents R on the aromatic ring.

[0213] The effect of changes in the electron-withdrawing or electron-donating ability of substituents on absorption peaks has been reported to be expressible using linear free energy relations, particularly the Hammett equation (Jaffe, HHChem. Rev., 1953, 53, 191).

[0214] Table 9 shows the empirical substituent parameters (σ para This shows the correlation between the shift in absorbance peaks and the value of the absorbance peak.

[0215] Figure 5 shows the UV-VIS absorption spectra of dilute solutions of four HEVL-absorbing benzotriazole-containing vinyl monomers in 1-propanol.

[0216] Generally, the higher the electron-withdrawing property, the larger the red shift. In the case of UV40 (R = -C(O)OCH3), there may be some other factors that cause a significantly higher red shift than that predicted based on the value of the empirical substituent parameter (σ para ).

[0217] All publications and patents cited herein are hereby incorporated by reference in their entirety.

Claims

1. Formula (I) or (II) 【Chemistry 1】 (where tBu is a tert-butyl group, R' is H or CH ３ and R １ is Cl or CF ３ and L １ is a divalent C ５ to C ６ alkylene group or -C ２ H ４ -(OC ２ H ４ ) ｎ -divalent group, R ２ contains no halogen atoms and has a Hammett substituent constant (σ ｐ ) of about 0.15 to about 0.70 (preferably about 0.20 to about 0.65), an organic group, L ２ is a divalent C ２ to C １０ alkylene group or -C ２ H ４ -(OC ２ H ４ ) ｎ -divalent group, and n is 1, 2 or 3) One of the following HEVL-absorbing benzotriazole vinyl monomers.

2. The HEVL-absorbing benzotriazole vinyl monomer according to claim 1, which is of formula (I).

3. The HEVL-absorbing benzotriazole vinyl monomer according to claim 1, which is of formula (II).

4. R ２ The Hammett substituent constant (σ) is approximately 0.20 to approximately 0.

65. ｐ The HEVL absorbed benzotriazole vinyl monomer according to claim 3, having the following characteristics:

5. R ２ is, -CH ２ CN, -OCOCH ３ , -CO(CH ３ ) ３ , -SO ３ － , -CONH ２ , -OSO ２ CH ３ , -CONHCH ３ , -CON(CH ３ ) ２ ien-CH ２ N ＋ (CH ３ ) ３ , -COOH, -COOCH ３ , -COOC ２ H ５ , -COC ２ H ５ , -COCH ３ The HEVL-absorbing benzotriazole vinyl monomer according to claim 3 or 4, wherein the monomer is -CN.

6. A method for manufacturing HEVL filtering hydrogel contact lenses, (1) A polymerizable composition, (a) at least one UV-absorbing vinyl monomer in an amount of about 0.1% to about 2.5% by weight (preferably about 0.2% to about 2.0% by weight, more preferably about 0.3% to about 1.8% by weight, and even more preferably about 0.4% to about 1.6% by weight), (b) at least one HEVL-absorbing benzotriazole vinyl monomer according to any one of claims 1 to 5, in an amount of about 0.2% to about 3.0% by weight (preferably about 0.25% to about 2.5% by weight, more preferably about 0.3% to about 2.5% by weight, and even more preferably about 0.35% to about 2.25% by weight), (c) at least a free radical initiator in an amount of about 0.1% to about 2.0% by weight (preferably about 0.25% to about 1.75% by weight, more preferably about 0.5% to about 1.5% by weight, and even more preferably about 0.75% to about 1.25% by weight), (d) Cu(II)-phthalocyanine blue pigment particles or at least one blue colorant which is at least one polymerizable blue dye, (e) At least one polymerizable component selected from the group consisting of hydrophilic vinyl monomers, siloxane-containing vinyl monomers, polysiloxane vinyl crosslinking agents, non-silicone vinyl crosslinking agents, non-silicone hydrophobic vinyl monomers, and combinations thereof. A step of obtaining a polymerizable composition containing, (2) A step of introducing the polymerizable composition into a mold for manufacturing a hydrogel contact lens, wherein the mold comprises a first mold half having a first molding surface defining the front surface of the contact lens and a second mold half having a second molding surface defining the rear surface of the contact lens, and the first and second mold halves are configured to accept each other such that a cavity is formed between the first and second molding surfaces, (3) A step of forming the HEVL filtering hydrogel contact lens by thermally or chemically curing the lens compound in the mold, wherein the HEVL filtering hydrogel contact lens has less than 5% UVA%T, about 1% or less UVB%T, and about 35% or less HEVL%T (preferably about 32% or less, more preferably about 30% or less, and even more preferably about 28% or less) A method that includes this.

7. The method according to claim 6, wherein the free radical initiator is a thermal initiator, and the curing step is performed thermally.

8. The method according to claim 6, wherein the free radical initiator is a photoinitiator, and the curing step is performed by irradiation with visible light having a wavelength in the range of 450 nm to 510 nm.

9. The method according to claim 8, wherein the photoinitiator is a benzoylphosphine oxide photoinitiator, an acylgermanium photoinitiator, an acyltin photoinitiator, or a combination thereof.

10. The method according to claim 8, wherein the photoinitiator is an acylgermanium photoinitiator.

11. A crosslinked polymer material, (1) A repeating unit, (a) at least one UV-absorbing vinyl monomer, (b) at least one HEVL-absorbing benzotriazole vinyl monomer according to any one of claims 1 to 5, and (c) At least one polymerizable component selected from the group consisting of hydrophilic vinyl monomers, siloxane-containing vinyl monomers, polysiloxane vinyl crosslinking agents, non-silicone vinyl crosslinking agents, non-silicone hydrophobic vinyl monomers, and combinations thereof. The repeating unit and (2) Cu(II)-phthalocyanine blue pigment particles and / or repeating units of polymerizable blue dye dispersed therein A HEVL filtering hydrogel contact lens comprising a crosslinked polymer material containing less than 5% UVA%T, about 1% or less UVB%T, about 35% or less HEVL%T, and a ＊ ≤ -5 and b ＊ HEVL filtering hydrogel contact lenses having a color represented by ≤ +18.

12. The HEVL filtering hydrogel contact lens according to claim 11, wherein the crosslinked polymer material comprises at least one polymerizable blue dye which is 1,4-bis((2-methoxyethyl)amino)-anthraquinone and / or 1,4-bis(4-(2-methacrylateoxyethyl)phenylamino)-anthraquinone.

13. The HEVL filtering hydrogel contact lens according to claim 11 or 12, wherein the crosslinked polymer material comprises Cu(II)-phthalocyanine blue pigment particles dispersed therein.

14. The HEVL filtering hydrogel contact lens according to any one of claims 11 to 13, wherein the at least one UV-absorbing vinyl monomer includes 2-(2'-hydroxy-5'-vinylphenyl)-2H-benzotriazole, 2-(2'-hydroxy-5'-methacryloxyphenyl)-2H-benzotriazole, 2-(2'-hydroxy-5'-acryloyloxyphenyl)-2H-benzotriazole, 2-[2'-hydroxy-5'-(2-methacryloxyethyl)phenyl)]-2H-benzotriazole (Norblock), 2-[2'-hydroxy-5'-(2-acryloxyethyl)phenyl)]-2H-benzotriazole, 2-(2'-hydroxy-5'-methacryloxypropyl-phenyl)-2H-benzotriazole, 2-(2'-hydroxy-5'-acryloxypropylphenyl)-2H-benzotriazole, or a combination thereof.

15. The HEVL filtering hydrogel contact lens according to claim 14, wherein the at least one UV-absorbing vinyl monomer is 2-[2'-hydroxy-5'-(2-methacrylateoxyethyl)phenyl)]-2H-benzotriazole.

16. The HEVL filtering hydrogel contact lens according to any one of claims 11 to 15, comprising the HEVL-absorbing benzotriazole vinyl monomer described in claim 2.

17. The HEVL filtering hydrogel contact lens according to any one of claims 11 to 16, wherein the at least one HEVL-absorbing benzotriazole vinyl monomer comprises the HEVL-absorbing benzotriazole vinyl monomer according to any one of claims 3 to 5.

18. The aforementioned crosslinked polymer material is N,N-dimethyl(meth)acrylamide, 2-acrylamidoglycolic acid, N-hydroxypropyl(meth)acrylamide, N-hydroxyethyl(meth)acrylamide, N-[tris(hydroxymethyl)-methyl](meth)acrylamide, N-vinylpyrrolidone, N-vinylformamide, N-vinylacetamide, N-vinylisopropylamide, N-vinyl-N-methylacetamide, N-methyl-3-methylene-2-pyrrolidone, 1-methyl-5-methylene-2-pyrrolidone, 5-methyl-3-methylene-2-pyrrolidone, 2-hydroxyethyl(meth)acrylate, hydroxypropyl(meth)acrylate, methoxyethyl(meth)acrylate, trimethylammonium 2-hydroxypropyl methacrylate hydrochloride, aminopropyl methacrylate hydrochloride, dimethylaminoethyl methacrylate (DMAEMA), glycerol methacrylate (GMA), and C with a maximum weight-average molecular weight of 1500. １ ~C ４ - A HEVL filtering hydrogel contact lens according to any one of claims 11 to 17, comprising repeating units of at least one hydrophilic vinyl monomer selected from the group consisting of alkoxy polyethylene glycol (meth)acrylate, polyethylene glycol (meth)acrylate having a weight-average molecular weight of up to 1500, methacrylic acid, acrylic acid, methacrylateoxyethyl phosphocholine, methacrylateoxypropyl phosphocholine, N-2-hydroxyethyl vinylcarbamate, N-carboxyvinyl-β-alanine, N-carboxyvinyl-α-alanine, and mixtures thereof.

19. The HEVL filtering hydrogel contact lens according to any one of claims 11 to 18, wherein the crosslinked polymer material is a silicone hydrogel material comprising repeating units of at least one siloxane-containing vinyl monomer and / or at least one polysiloxane vinyl crosslinking agent.

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