BR112019025262B1 - SILICONE HYDROGEL CONTACT LENSES, AND THEIR PRODUCTION METHOD - Google Patents

Abstract

The present invention generally relates to inherently wettable silicone hydrogel contact lenses formed from a silicone hydrogel lens formulation comprising a polysiloxane vinyl crosslinker having H-donating chemical moieties, a siloxane-containing vinyl monomer with or without H-donating chemical moieties, and an N-vinyl amide monomer. Inherently wettable silicone hydrogel contact lenses may have a combination of desirable contact lens properties, including relatively high oxygen permeability, relatively high water content, relatively low modulus, and relatively low surface atomic Si percentage. The present invention also relates to a method for producing such inherently wettable silicone hydrogel contact lenses.

Description

[0001] The present invention generally relates to silicone hydrogel contact lenses that have an inherently wettable surface and to a method for producing the same.

BACKGROUND

[0002] Silicone hydrogel (SiHy) contact lenses, which are produced from a hydrated cross-linked polymer material that contains silicone and a certain amount of water in the equilibrium lens polymer matrix, are becoming increasingly popular, due to the fact that they have minimal adverse effects on corneal health due to their high oxygen permeability. But the incorporation of silicone into a contact lens material may have undesirable effects on the hydrophilicity and wettability of SiHy contact lenses, due to the fact that silicon is hydrophobic and has a greater tendency to migrate to the air-exposed lens surface. Contact lens manufacturers have put a lot of effort into developing SiHy contact lenses that have a hydrophilic, wettable surface.

[0003] One approach to modifying the hydrophilicity and wettability of a SiHy contact lens is through the use of a plasma treatment, for example, commercial lenses such as AIR OPTIX® (Alcon), PremiOTM (Menicon), and PUREVISION™ (Bausch & Lomb), use this approach in their production processes. Although a plasma coating is durable and can provide adequate hydrophilicity/wetting, plasma treatment of SiHy contact lenses may not be cost-effective due to the fact that pre-treated SiHy contact lenses formed must typically be dried prior to plasma treatment and due to the relatively high capital investment associated with plasma treatment equipment.

[0004] Another approach is to attach hydrophilic polymers to the SiHy contact lens according to various mechanisms (see, e.g., US Patents 6099122, 6436481, 6440571, 6447920, 6465056, 6521352, 6586038, 6623747, 67303 66, 6734321, 6835410, 6878399, 6923978, 6440571, and 6500481, Patent Application Publications Nos. 2009-0145086 A1, 2009-0145091 A1, 2008-0142038 A1, and 2007-0122540 A1). Although these techniques may be of use when processing a wettable SiHy contact lens, they may not be cost-effective and/or time-effective for deployment in a mass production environment due to the fact that typically require relatively long time and/or involve multiple laborious steps to obtain a hydrophilic coating.

[0005] Another approach is a layer-by-layer (LbL) polyionic material deposition technique (see, e.g., US Patents 6451871, 6719929, 6793973, 6884457, 6896926, 6926965, 6940580, 7297725, 8044112, 7858000, and 8158192). Although the LbL deposition technique can provide a cost-effective process for producing a wettable SiHy contact lens, LbL coatings may not be as durable as plasma coatings and may have relatively high surface charge densities; which can interfere with contact lens cleaning and disinfecting solutions. To improve durability, cross-linking of LbL coatings on contact lenses has been proposed in US Patents 8,147,897 and 8,142,835. However, cross-linked LbL coatings may have lower hydrophilicity and/or wettability than the original LbL coatings (prior to crosslinking) and still have high surface charge densities.

[0006] Recently, a new approach was described in US Patent 8529057 to apply a non-silicone hydrogel coating on a SiHy contact lens directly to a lens package during autoclaving (sterilization). Although this new approach can provide silicone hydrogel contact lenses with durable hydrophilic coatings on them, it may not be an environmentally friendly manufacturing process due to the fact that it involves the use of organic solvents in the lens processing steps. after the lens molding step.

[0007] Another approach is the incorporation of preformed hydrophilic polymers as polymeric wetting agents into a lens formulation to produce SiHy contact lens as proposed in US Patent 6367929, 6822016, 7052131, and 7249848. This method may not require additional processes to modify the hydrophilicity and wettability of SiHy contact lenses after casting molding. However, polymeric wetting agents may not be compatible with the silicone components in the lens formulation and the incompatibility may impart cloudiness to the resulting lenses. Additionally, such surface treatment may not provide a durable surface for extended wear purposes.

[0008] An additional approach is the incorporation of monomeric wetting agents (e.g., N-vinylpyrrolidone, N-vinyl-N-methyl acetamide, or the like) into a lens formulation to produce the SiHy contact lens as proposed. in US Patents 6867245, 7268198, 7540609, 7572841, 7750079, 7934830, 8231218, 8367746, 8445614, 8481662, 8487058, 8513325, 8703891, 8820928, 8865789, 8937110, 8937111, 9057821, 9057822, 9121998, 9125808, 9140825, 9140908, 9156934 , 9164298, 9170349, 9188702, 9217813, 9296159, 9322959, 9322960, 9360594, 9529119. Commercial SiHy contact lenses, such as Biofinity® (CooperVision, Dk=128 bars, H2O 48%), Avaira® (CooperVision, Dk= 100 bars, H2O 46%), Clariti® (CooperVision, Dk=60 bars, H2O 56%), MyDay® (CooperVision, Dk=80 bars, H2O 54%), ULTRATM (Bausch & Lamb, Dk=114 bars, H2O 46%), can use this approach in their production processes. Although this approach can be used in commercial SiHy lens production to provide newly formed (unused) SiHy lenses with suitably hydrophilic surfaces, there are some limitations. For example, the higher oxygen permeability of a SiHy contact lens can be achieved according to this approach, but at the cost of its water balance content and percentage of atomic Si on the lens surface. Typically, relatively lower equilibrium water content and relatively higher atomic Si percentage are concomitant with higher oxygen permeability. Additionally, it may also have one or more of the following disadvantages: slightly higher turbidity due to incompatibility of polymerizable silicone components with monomeric wetting agents and other hydrophilic components; higher surface silicone contents; susceptibility to form dry patches and/or hydrophobic surface areas created due to air exposure, dehydration-rehydration cycles, eyelid shear forces, migration of silicone to the surface, and/or partial failure to prevent silicone from exposure; and inadequate lubricity.

SUMMARY OF THE INVENTION

[0009] The invention, in one aspect, provides a silicone hydrogel contact lens, which comprises a silicone hydrogel bulk material comprising (1) first repeat units of at least one siloxane-containing vinyl monomer which has 0 to 10 first H-donor chemical moieties, (2) second repeat units of at least one first polysiloxane vinyl crosslinker which has a number average molecular weight of about 3,000 Daltons to about 80,000 Daltons and comprises ( a) two terminal (meth)acryloyl groups, (b) at least one polysiloxane segment comprising dimethylsiloxane units and hydrophilized siloxane units each having a methyl substituent and a monovalent C4-C40 organic radical substituent that has one or more second H-donating chemical moieties, and (c) from 0 to 20 third H-donating chemical moieties that are integral parts of molecular structures outside the polysiloxane segment, (3) third hair repeat units at least one hydrophilic N-vinyl amide monomer, and (4) optionally fourth repeating units of at least one second vinyl polysiloxane crosslinker that has 0 to 35 fourth H-donating chemical moieties, wherein the first and second vinylic crosslinkers of polysiloxane are different from each other, in that the first, second, third and fourth H-donating chemical moieties independent of each other are hydroxyl groups, carboxyl groups, amino groups of -NHR°, amino bonds of -NH-, amide bonds of - CONH-, -OCONH- urethane bonds, or combinations thereof, wherein R° is H or a C1-C4 alkyl, wherein the silicone hydrogel bulk material comprises at least 8.8 mmols of the third repeating units per gram of all first, second and fourth repeating units in total and at least 0.11 meqs of all first, second, third and fourth H-donating chemical moieties in total per gram of third repeating units, wherein the Silicone hydrogel contact lens has an oxygen permeability of at least 50 bar, an elastic modulus of about 0.2 MPa to about 1.5 MPa, and an equilibrium water content of about 40% to about of 70% and is inherently wettable characterized by the fact that it has a water breakthrough time of at least 10 seconds and a water contact angle per captive bubble of about 80 degrees or less without being subjected to any powder surface treatment -cure.

[00010] In another aspect, the present invention provides a method for producing inherently wettable silicone hydrogel contact lenses. The method comprises the steps of: preparing a polymerizable composition that is clear at room temperature and optionally, but preferably, at a temperature of about 0 to about 4°C, wherein the polymerizable composition comprises (a) at least one monomer siloxane-containing vinyl that has 0 to 10 first H-donating chemical moieties, (b) at least one first polysiloxane vinyl crosslinker that has a number average molecular weight of about 3,000 Daltons to about 80,000 Daltons and comprises (i) two terminal (meth)acryloyl groups, (ii) at least one polysiloxane segment comprising dimethylsiloxane units and hydrophilized siloxane units each having a methyl substituent and a monovalent C4-C40 organic radical substituent having one or more second H-donating chemical moieties, and (iii) from 0 to 20 third H-donating chemical moieties that are integral parts of molecular structures outside the polysiloxane segment, (c) at least one hydrophilic N-vinyl amide monomer - lic, (d) optionally at least one second polysiloxane vinyl crosslinker having 0 to 35 fourth H-donating chemical moieties, and (e) at least one free radical initiator, wherein the first and second polysiloxane vinyl crosslinkers are different from each other, in that the first, second, third and fourth H-donating chemical moieties independent of each other are hydroxyl groups, carboxyl groups, amino groups of -NHR°, amino bonds of -NH-, amide bonds of - CONH-, -OCONH- urethane bonds, or combinations thereof, wherein R° is H or a C1-C4 alkyl, wherein the polymerizable composition comprises at least 8.8 mmols of component (c) per gram of all components (a), (b) and (d) in total and at least 0.11 meqs of the first, second, third and fourth H-donating chemical moieties in total per gram of component (c); introducing the polymerizable composition into a lens mold; thermally or actinically curing the polymerizable composition in the lens mold to form a silicone hydrogel contact lens, wherein the silicone hydrogel contact lens has an oxygen permeability of at least 50 bar, an elastic modulus of about of 0.2 MPa to about 1.5 MPa, and an equilibrium water content of about 40% to about 70% and is inherently wettable as characterized by having a water breakthrough time of at least 10 seconds and a captive bubble water contact angle of about 80 degrees or less without undergoing any post-cure surface treatment.

[00011] These and other aspects of the invention will become apparent from the following description of the presently preferred embodiments. The detailed description is merely illustrative of the invention and does not limit the scope of the invention, which is defined by the attached claims and equivalents thereof.

BRIEF DESCRIPTION OF THE DRAWINGS

[00012] Figure 1 schematically shows how to measure the water break-up time of a contact lens.

DETAILED DESCRIPTION OF EMBODIMENTS OF THE INVENTION

[00013] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by an individual of ordinary skill in the art to which this invention belongs. In general, the nomenclature used herein and the laboratory procedures are well known and commonly employed in the art. Conventional methods are used for these procedures, such as those provided in the art and various general references. When a term is provided in the singular, the inventors also contemplate the plural of that term. The nomenclature used in this document and the laboratory procedures described below are those well known and commonly employed in the art. Additionally, as used in the specification including the attached claims, reference to singular forms such as "a", "an", "the" and "a" includes the plural, and reference to a particular numerical value includes at least that particular value unless the context clearly dictates otherwise. "About" as used herein means that a number designated "about" comprises the stated number plus or minus 1 to 10% of that stated number.

[00014] "Contact Lens" refers to a structure that can be placed on or in a user's eye. A contact lens can correct, improve or alter a wearer's vision, but this does not have to be the case. A contact lens may be of any suitable material known in the art or later developed, and may be a soft lens, a hard lens or a hybrid lens. A "silicone hydrogel contact lens" refers to a contact lens comprising a silicone hydrogel bulk material (core).

[00015] "Soft contact lens" refers to a contact lens that has an elastic modulus (i.e., Young's modulus) of less than 2.5 MPa.

[00016] A "hydrogel" or "hydrogel material" refers to a cross-linked polymeric material that has three-dimensional polymer networks (i.e., polymer matrix), is insoluble in water, but can retain at least 10 percent by weight of water in its polymer matrix when it is completely hydrated.

[00017] A "silicone hydrogel" refers to a silicone-containing hydrogel obtained by copolymerization of a polymerizable composition comprising at least one silicone-containing monomer or at least one silicone-containing macromer or at least one pre -polymer containing crosslinkable silicone.

[00018] As used in this application, the term "non-silicone hydrogel" refers to a hydrogel that is theoretically silicone-free.

[00019] "Hydrophilic", as used herein, describes a material or portion thereof that will associate more readily with water than with lipids.

[00020] A "vinyl monomer" refers to a compound that has a single ethylenically established group, is soluble in a solvent, and can be actinically or thermally polymerized.

[00021] The term "ambient temperature" refers to a temperature of about 21 °C to about 27 °C.

[00022] The term "soluble", in reference to a compound or material in a solvent, means that the compound or material can be dissolved in the solvent to generate a solution with a concentration of at least about 0.02% by weight at room temperature.

[00023] The term "insoluble", in reference to a compound or material in a solvent, means that the compound or material can be dissolved in the solvent to generate a solution with a concentration of less than 0.005% by weight at room temperature.

[00024] As used in this application, the term "ethylenically unsaturated group" is used herein in a broad sense and is intended to encompass any groups that contain at least one >C=C< group. Exemplary ethylenically unsaturated groups include without limitation (meth)acryloyl ( and/or ), allyl, vinyl, styrenyl or other groups containing C=C.

[00025] The term "terminal (meth) acryloyl group" refers to a (meth) acryloyl group at one of the two ends of the main chain (or backbone) of an organic compound, as known to a person skilled in the art.

[00026] The term "(meth) acrylamide" refers to methacrylamide and/or acrylamide.

[00027] The term "(meth) acrylate" refers to methacrylate and/or acrylate.

[00028] As used herein, "actinically", in reference to curing, cross-linking or polymerizing a polymerizable composition, a prepolymer or a material means that curing (e.g., cross-linked and/or polymerized ) is carried out by actinic irradiation, such as, for example, UV/visible irradiation, ionization radiation (e.g., gamma rays or X-ray irradiation), microwave irradiation, and the like. Thermal curing or actinic curing methods are well known to one skilled in the art.

[00029] A "hydrophilic vinyl monomer", as used herein, refers to a vinyl monomer that, as a homopolymer, typically yields a polymer that is soluble in water or can absorb at least 10 percent by weight of water.

[00030] A "hydrophobic vinyl monomer", as used herein, refers to a vinyl monomer that, as a homopolymer, typically yields a polymer that is insoluble in water and can absorb less than 10 percent by weight of water.

[00031] A "blending vinyl monomer" refers to a vinyl monomer with the ability to dissolve both hydrophilic and hydrophobic components of a polymerizable composition to form a solution.

[00032] An "acrylic monomer" refers to a vinyl monomer that has a unique (meth) acryloyl group.

[00033] An "N-vinyl amide monomer" refers to an amide compound that has a vinyl group which is directly attached to the nitrogen atom of the amide group.

[00034] A "macromer" or "prepolymer" refers to a compound or polymer that contains ethylenically unsaturated groups and has a number average molecular weight greater than 700 Daltons.

[00035] As used in this application, the term "vinyl crosslinker" refers to an organic compound that has at least two ethylenically unsaturated groups. A "vinyl crosslinking agent" refers to a vinyl crosslinker that has a molecular weight of 700 Daltons or less.

[00036] As used in this application, the term "polymer" means a material formed by polymerizing/crosslinking one or more monomers or macromers or prepolymers or combinations thereof.

[00037] As used in this application, the term "molecular weight" of a polymeric material (including monomeric or macromeric materials) refers to the numerical average molecular weight unless specifically noted otherwise or unless test conditions indicate otherwise.

[00038] A "polysiloxane segment" refers to a polymer chain consisting of at least three consecutively and directly linked siloxane units (divalent radical) each independent of each other that have a formula of wherein Ri' and R2' are two substituents independently selected from the group consisting of C1-C10 alkyl, C1-C4 alkyl- or phenyl substituted by C1-C4-alkoxy, C1-C10 fluoroalkyl, C1-C10 fluoroether, C6 radical -Ci8 aryl, -alc-(OC2H4)7i-OR° (where alc is a C1-C6 alkyl diradical, R° is H or C1-C4 alkyl, and y1 is an integer from 1 to 10), a C2 organic radical -C40 having at least one functional group selected from the group consisting of hydroxyl group (-OH), carboxyl group (-COOH), -NR3'R4', amino bonds of -NR3'-, amide bonds of -CONR3' -, amide of -CONR3'R4', urethane bonds of -OCONH-, and C1-C4 alkoxy group, or a linear hydrophilic polymer chain, in which R3' and R4' independent of each other are hydrogen or a C1C15 alkyl .

[00039] A "polysiloxane vinyl crosslinker" refers to a compound that comprises at least one polysiloxane segment and at least two ethylenically unsaturated groups.

[00040] A "linear polysiloxane vinyl crosslinker" refers to a compound that comprises a backbone that includes at least one polysiloxane segment and is terminated with an ethylenically unsaturated group at each of the two ends of the backbone.

[00041] A "chain-extended polysiloxane vinyl crosslinker" refers to a compound that comprises at least two ethylenically unsaturated groups and at least two polysiloxane segments that each pair is linked by a divalent radical.

[00042] The term "fluid", as used herein, indicates that a material has the ability to flow like a liquid.

[00043] As used in this application, the term "clear" in reference to a polymerizable composition means that the polymerizable composition is a transparent solution or liquid mixture (i.e., which has a light transmissibility of 85% or greater, preferably 90% or greater in the range between 400 and 700 nm).

[00044] The term "alkyl" refers to a monovalent radical obtained by removing a hydrogen atom from a linear or branched alkaline compound. An alkyl group (radical) forms a bond with another group in an organic compound.

[00045] The term "divalent alkylene group" or "alkylene diradical" or "alkyl diradical" interchangeably refers to a divalent radical obtained by removing a hydrogen atom from an alkyl. A divalent alkylene group forms two bonds with other groups in an organic compound.

[00046] The term "alkoxy" or "alkoxyl" refers to a monovalent radical obtained by removing the hydrogen atom from the hydroxyl group of a linear or branched alkyl alcohol. An alkoxy group (radical) forms a bond with another group in an organic compound.

[00047] In this application, the term "substituted" in reference to an alkyl diradical or an alkyl radical means that the alkyl diradical or the alkyl radical comprises at least one substituent that replaces a hydrogen atom of the alkyl diradical or the alkyl radical and is 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.

[00048] A free radical initiator can be a photoinitiator or a thermal initiator. A "photoinitiator" refers to a chemical that initiates the radical cross-linking/polymerization reaction by the use of light. A "thermal initiator" refers to a chemical that initiates the radical cross-linking/polymerization reaction by the use of heat energy.

[00049] The intrinsic "oxygen permeability", Dki, of a material is the rate at which oxygen will pass through a material. As used in this application, the term "oxygen permeability (Dk)" in reference to a hydrogel (silicone or non-silicone) or a contact lens means a corrected oxygen permeability (Dkc) that is measured at about 34 to 35° C and corrected for surface resistance to oxygen flow caused by the boundary layer effect, in accordance with the procedures described in Example 1 of Patent Application Publication No. 2012-0026457 A1. Oxygen permeability is conventionally expressed in units of bars, where "barr" is defined as [(cm3 oxygen)(mm)/ (cm2)(s)(mmHg)] x 10-10.

[00050] The "oxygen transmissibility", Dk/t, of a lens or material is the rate at which oxygen will pass through a specific lens or material with an average thickness of t [in units of mm] over the measured area . Oxygen transmissibility is conventionally expressed in units of bars/mm, where "barrs/mm" is defined as [(cm3 oxygen)/(cm2)(s)(mm Hg)] x 10-9.

[00051] "Ophthalmically compatible", as used herein, refers to a material or surface of a material that can be in intimate contact with the ocular environment for an extended period of time without significantly damaging the ocular environment and without significant user discomfort.

[00052] The term "modulus" or "elastic modulus" in reference to a contact lens or a material means the tensile modulus or Young's modulus which is a measure of the stiffness of a contact lens or a material. One skilled in the art is well aware of how to determine the elastic modulus of a silicone hydrogel material or a contact lens. For example, all commercial contact lenses have reported elastic modulus values. They can be measured as described in Example 1.

[00053] "UVA" refers to radiation that occurs at wavelengths between 315 and 380 nanometers; "UVB" refers to radiation that occurs between 280 and 315 nanometers; "Violet" refers to radiation occurring at wavelengths between 380 and 440 nanometers.

[00054] "UVA transmittance" (or "%T of UVA"), "UVB transmittance" or "%T of UVB", and "violet transmittance" or "%T of Violet" are calculated by the following Formula. where %T Luminescence is determined by the following Formula %T Luminescence = % Average Transmission between 780 to 380 nm.

[00055] An "H-donating chemical moiety" refers to a functional group comprising a hydrogen atom capable of forming a hydrogen bond with another functional group. Examples of H-donating moieties include, without limitation, hydroxyl group, amide group of -CONHR°, amide bond of -CONH-, urethane bond of -OCONH-, urea bond of -HNCONH-, carboxyl group of -COOH, amino groups of -NHR°, amino bonds of -NH-, and combinations thereof, wherein R° is H or a C1-C4 alkyl.

[00056] The term "inherently wettable" in reference to a silicone hydrogel contact lens means that the silicone hydrogel has a water break-up time (WBUT) of about 10 seconds or more and a water contact angle per captive bubble (WCAcb) of about 80 degrees or less without undergoing any surface treatment after the silicone hydrogel contact lens is formed by thermally or actinically polymerizing (i.e., curing) a lens formulation of silicone hydrogel. According to the invention, WBUT and WCAcb are measured according to the procedures described in Example 1.

[00057] "Surface modification" or "surface treatment", as used herein, means that an article has been treated in a surface treatment process (or a surface modification process) before or after the formation of the article, wherein (1) a coating is applied to the surface of the article, (2) chemical species are adsorbed on the surface of the article, (3) the chemical natures (e.g., electrostatic charge) of chemical groups on the surface of the article are altered, or (4) the surface properties of the article are otherwise modified. Exemplary surface treatment processes include, but are not limited to, an energy surface treatment (e.g., a plasma, a static electrical charge, irradiation or other energy source), chemical treatments, the grafting of hydrophilic vinyl monomers or macromers. on the surface of an article, the mold transfer coating process disclosed in US Patent 6,719,929, the incorporation of wetting agents into a lens formulation for producing contact lenses proposed in US Patent 6,367,929 and 6,822,016, the mold transfer coating disclosed in US Patent 7,858,000, and a hydrophilic coating comprising covalent attachment or physical deposition of one or more layers of one or more hydrophilic polymers onto the surface of a contact lens disclosed in US Patents 8,147,897 and 8,409,599 and Patent Application Publications No. 2011 -0134387 A1,2012-0026457 A1 and 2013-0118127 A1.

[00058] "Post-cure surface treatment", in reference to a silicone hydrogel bulk material or a SiHy contact lens, means a surface treatment process that is carried out after the silicone hydrogel bulk material or the SiHy contact lens is formed by curing (i.e., thermally or actinically polymerizing) a SiHy lens formulation. A "SiHy lens formulation" refers to a polymerizable composition comprising all polymerizable components necessary to produce a SiHy contact lens or a SiHy lens bulk material as well known to a person skilled in the art.

[00059] The invention generally relates to inherently wettable SiHy contact lenses having a relatively high oxygen permeability, a desirable water content (e.g., from about 40% to about 70% by weight), and a modulus relatively low elasticity (e.g. from about 0.2 MPa to about 1.5 MPa). This invention is based in part on the discovery that inherently wettable SiHy contact lenses can be formed from a SiHy lens formulation (i.e., a polymerizable composition) comprising a vinyl polysiloxane ("Di-PDMS") crosslinker that has H-donating chemical moieties ("HD"), a siloxane-containing vinyl monomer ("mono-PDMS") with or without H-donating chemical moieties, an N-vinyl amide ("NVA") monomer (e.g. example, N-vinylpyrrolidone, N-vinyl-N-methyl acetamide, or the like), and optionally another silicone-containing polymerizable component (or silicone-containing polymerizable components) with or without H-donating chemical moieties, as the lens formulation of SiHy comprises about 8.8 mmols or more of all N-vinyl amide monomer (or N-vinyl amide monomers) ("NVA") per gram of all silicone-containing polymerizable components (i.e. It is, and about 0.11 milliequivalent ("meq") or more of the H-donating chemical moieties per gram of all N-vinyl amide monomer (or N-vinyl amide monomers) ((i.e. ), which are contributed by the vinyl polysiloxane crosslinker and the siloxane-containing vinyl monomer, per gram of the N-vinyl amide monomer. The resulting SiHy lenses not only may be inherently wettable, they may also have a combination of desirable contact lens properties, including relatively high oxygen permeability, relatively high water content, relatively low modulus, and percentage of atomic Si. relatively low surface area.

[00060] The invention, in one aspect, provides a silicone hydrogel contact lens comprising a silicone hydrogel bulk material comprising (1) first repeat units of at least one siloxane-containing vinyl monomer including 0 to 10 first H-donor chemical moieties, (2) second repeat units of at least one first vinyl polysiloxane crosslinker having a number average molecular weight of about 3,000 Daltons to about 80,000 Daltons and comprising (a) two terminal (meth)acryloyl groups, (b) at least one polysiloxane segment comprising dimethylsiloxane units and hydrophilized siloxane units each having a methyl substituent and a monovalent C4-C40 organic radical substituent that has one or more second H-donating chemical moieties, and (c) from 0 to 20 third H-donating chemical moieties that are integral parts of molecular structures outside the polysiloxane segment, (3) third repeating units of at least one monomer of hydrophilic N-vinyl amide, and (4) optionally fourth repeating units of at least one second vinyl polysiloxane crosslinker having 0 to 35 fourth H-donating chemical moieties, wherein the first and second vinyl polysiloxane crosslinkers are different each other, wherein the first, second, third and fourth H-donating chemical moieties independent of each other are hydroxyl groups, carboxyl groups, amino groups of -NHR° wherein R° is H or a C1-C4 alkyl, bonds amino bonds of -NH-, amide bonds of -CONH-, urethane bonds of -OCONH-, or combinations thereof, wherein the silicone hydrogel bulk material comprises at least 8.8 (preferably at least 9. 0, more preferably at least 9.2, even more preferably at least 9.6) mmols of the third repeating units per gram of all first, second and fourth repeating units in total and at least 0.11 (preferably at least 0.15, more preferably at least 0.20, even more preferably at least 0.25) meqs of all first, second, third and fourth H-donating chemical moieties in total per gram of the third repeating units, wherein the Silicone hydrogel contact lens has an oxygen permeability of at least 50 bar, an elastic modulus of about 0.2 MPa to about 1.5 MPa, and an equilibrium water content of about 40% to about of 70% and is inherently wettable as characterized by having a water breakthrough time of at least 10 seconds (preferably at least 15 seconds, more preferably at least 20 seconds) and a captive bubble water contact angle of about 80 degrees or less (preferably about 75 degrees or less, more preferably about 70 degrees or less, even more preferably about 65 degrees or less) without undergoing any post-cure surface treatment.

[00061] According to the invention, the quantities (weight, mmol, and meq) of the first, second, third and fourth repeating units, as well as the H-donating chemical moieties are calculated based on the quantities of said at least one siloxane-containing vinyl monomer, said at least one first polysiloxane vinyl crosslinker, said at least one N-vinyl amide monomer and said at least one second polysiloxane vinyl crosslinker present in a polymerizable composition for producing a contact lens of silicone hydrogel of the invention. It should be understood that if any preformed homopolymer or copolymer of an N-vinyl amide monomer is present in the polymerizable composition prior to casting molding, then the repeating units of such N-vinyl amide monomer in the homopolymer or Preformed copolymer should not be included in calculations of the quantities (weight, mmol, and meq) of the first, second, third, and fourth repeating units, as well as the H-donating chemical moieties.

[00062] Any suitable siloxane-containing vinyl monomers can be used in the invention. One class of preferred siloxane-containing vinyl monomers are monoalkyl-terminated polysiloxanes terminated in mono-(meth)acryloyl. In a more preferred embodiment, the siloxane-containing vinyl monomer is a monoalkyl-terminated polysiloxane terminated in mono-(meth)acryloyl of Formula (I). where: Ro is H or methyl; Xo is O or NR1; L1 is a divalent radical of C3-C8 alkylene or a divalent radical of L1' is a divalent radical of C2-C8 that has zero or one hydroxyl group; L1" is divalent C3-C8 alkylene radical that has zero or one hydroxyl group; is a C1-C4 alkyl; X1' is O or NR1; q1 is an integer from 1 to 20; q2 is an integer from 0 to 20; n1 is an integer from 3 to 25.

[00063] Examples of polysiloxanes terminated in monoalkyl terminated in mono-(meth)acryloyl of Formula (I) include, without limitation, polydimethylsiloxane terminated in w-butyl (or w-methyl) terminated in α-(meth)acryloxypropyl, polydimethylsiloxane terminated in in w-butyl (or w-methyl) terminated in a-(meth)acryloxy-2-hydroxypropyloxypropyl, α-(2-hydroxyl-methacryloxypropyloxypropyl)-w-butyl-decamethylpentasiloxane, polydimethylsiloxane terminated in w-butyl (or w-methyl ) terminated in α-[3-(meth)acryloxyethoxy-2-hydroxypropyloxypropyl], polydimethylsiloxane terminated in w-butyl (or w-methyl) terminated in α-[3-(meth)acryloxypropyloxy-2-hydroxypropyloxypropyl], polydimethylsiloxane ending in w-butyl (or w-methyl) ending in a-[3-(meth)acryloxyisopropyloxy-2-hydroxypropyloxypropyl], polydimethylsiloxane ending in w-butyl (or w-methyl) ending in a-[3-(meth) acryloxybutyloxy-2-hydroxypropyloxypropyl], polydimethylsiloxane terminated in w-butyl (or w-methyl) terminated in α-[3-(meth)acryloxyethylamino-2-hydroxypropyloxypropyl], polydimethylsiloxane terminated in w-butyl (or w- methyl) terminated in α-[3-(meth)acryloxypropylamino-2-hydroxypropyloxypropyl], polydimethylsiloxane terminated in w-butyl (or w-methyl) terminated in α-[3-(meth)acryloxy-butylamino-2-hydroxypropyloxypropyl], polydimethylsiloxane ending in w-butyl (or w-methyl) ending in a-(meth)acryloxy(polyethyleneoxy)-2-hydroxypropyloxypropyl], polydimethylsiloxane ending in w-butyl (or w-methyl) ending in a-[(meth)acryloxy -2-hydroxypropyloxy-ethoxypropyl], polydimethylsiloxane ending in w-butyl (or w-methyl) ending in a-[(meth)acryloxy-2-hydroxypropyl-N-ethylaminopropyl], polydimethylsiloxane ending in w-butyl (or w-methyl ) ending in a-[(meth)acryloxy-2-hydroxypropyl-aminopropyl], polydimethylsiloxane ending in w-butyl (or w-methyl) ending in a-[(meth)acryloxy-2-hydroxypropyloxy (polyethyleneoxy)propyl] , polydimethylsiloxane ending in w-butyl (or w-methyl) ending in α-(meth)acryloylamidopropyloxypropyl, w-butyl (or w-methyl) polydimethylsiloxane ending in α-N-methyl-(meth)acryloylamidopropyloxypropyl, w-butyl (or w-methyl) polydimethylsiloxane terminated in α-[3-(meth)acrylamidoethoxy-2-hydroxypropyloxypropyl], polydimethylsiloxane terminated in w-butyl (or w-methyl) terminated in α-[3-(meth)acrylamido-propyloxy- 2-hydroxypropyloxypropyl], polydimethylsiloxane ending in w-butyl (or w-methyl) ending in a-[3-(meth)acrylamidoisopropyloxy-2-hydroxypropyloxypropyl], polydimethylsiloxane ending in w-butyl (or w-methyl) ending in a- [3-(meth)acrylamidobutyloxy-2-hydroxypropyl-oxypropyl], w-butyl (or w-methyl) polydimethylsiloxane terminated in α-[3-(meth)acryloylamido-2-hydroxypropyloxypropyl], polydimethylsiloxane terminated in w-butyl (or w-methyl) terminated in α-[3-[N-methyl-(meth)acryloylamido]-2-hydroxypropyloxypropyl], N-methyl-N'-(propyltetra(dimethylsiloxy)dimethylbutylsilane) (meth)acrylamide, N-(2,3-dihydroxypropane)-N'-(propyltetra(dimethylsiloxy)dimethylbutylsilane) (meth)acrylamide, (meth)acryloylamidopropyltetra(dimethylsiloxy)dimethylbutylsilane, and mixtures thereof. Monoalkyl-terminated mono-(meth)acryloyl-terminated polysiloxanes of Formula (I) can be obtained from commercial suppliers (e.g., Shin-Etsu, Gelest, etc.) or prepared according to procedures described in US Patent 6,867,245. 8415405, 8475529, 8614261, and 9217813 or by reacting a hydroxyalkyl (meth)acrylate or (meth)acrylamide or a (meth)acryloxy-polyethylene glycol with a polydimethylsiloxane terminated in mono-epoxypropyloxypropyl, reacting hydroxyalkyl (meth)acrylate glycidyl with a monocarbinol-terminated polydimethylsiloxane, a mono-aminopropyl-terminated polydimethylsiloxane, or a mono-ethylaminopropyl-terminated polydimethylsiloxane, or by reacting isocyanatoethyl (meth)acrylate with a mono-carbinol-terminated polydimethylsiloxane according to coupling reactions well known to a person skilled in the art.

[00064] Another class of preferred siloxane-containing vinyl monomers is that of vinyl monomers that contain a tris(trimethylsilyloxy)silyl or bis(trimethylsilyloxy)alkylsilyl group (i.e., vinyl monomer that contains tris(trimethylsilyloxy)silyl or vinyl monomer that contains bis(trimethylsilyloxy)alkylsilyl. In a more preferred embodiment, the siloxane-containing vinyl monomer is a tris(trimethylsilyloxy)silyl-containing or bis(trimethylsilyloxy)alkylsilyl-containing vinyl monomer of Formula (II). where: Ro is H or methyl; Xo is O or NR1; L2 is a divalent C3C8 alkylene radical or a divalent radical of either -L2-X2-L2"-, -(C2H4O)qi- L2"-, -(C2H4θ)qi-CONH-L2"-; or -L2-NHCOO- (C2H4O)qi-L2"- L2' is a divalent C2-C8 alkylene radical having zero or one hydroxyl group; L2" is divalent C3-C8 alkylene radical that has zero or one hydroxyl group; is a C1-C4 alkyl; q1 is an integer from 1 to 20, r1 is an integer from 2 or 3.

[00065] Examples of preferred siloxane-containing vinyl monomers of Formula (II) include, without limitation, tris(trimethylsilyloxy)silylpropyl (meth)acrylate, bis(trimethylsiloxy)methylsilane, bis(trimethylsiloxy)butylsilane, propylbis(trimethylsiloxy)methylsilane , 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-methyl acrylamide, N-(2 -hydroxy-3-(3-(tris(trimethylsilyloxy)silyl)propyloxy)propyl) (meth)acrylamide, and mixtures thereof. Preferred siloxane-containing vinyl monomers of Formula (II) can be obtained from commercial suppliers or can be prepared according to procedures described in US Patent 7214809, 8475529, 8658748, 9097840, 9103965, and 9475827.

[00066] According to the present invention, the vinyl monomer containing siloxane is a monoalkyl-terminated polysiloxane terminated in mono-(meth)acryloyl, a vinyl monomer containing bis(trimethylsilyloxy)-alkylsilyl, a vinyl monomer containing tris(trime - tilsilyloxy)silyl, or mixtures thereof, preferably a polysiloxane ending in monoalkyl ending in mono-(meth)acryloyl, a vinyl monomer containing bis(trimethylsilyloxy)alkylsilyl or combinations thereof, more preferably a polysiloxane ending in monoalkyl terminated in mono-(meth)acryloyl having a weight average molecular weight of about 2,500 Daltons or less (preferably about 2,000 Daltons or less, more preferably about 1,700 Daltons or less, even more preferably about 450 to about of 1,500 Daltons) of Formula (I), even more preferably a monoalkyl-terminated polysiloxane terminated in mono-(meth)acryloyl of Formula (I) wherein n1 is an integer from 3 to 25 (preferably 3 to 20, more preferably 3 to 15, even more preferably 3 to 10).

[00067] It is understood that, by having at least one H-donating chemical moiety, the siloxane-containing vinyl monomer may be more compatible with the hydrophilic N-vinyl amide monomer compared to one without any H-donating chemical moiety.

[00068] According to the invention, any vinyl polysiloxane crosslinker can be used in the invention as the first vinyl polysiloxane crosslinker, as long as it comprises hydrophilized siloxane units that each have a methyl substituent and an organic radical substituent. C4-C40 monovalent having at least hydroxyl groups and other optional H-donating chemical moieties and has a number average molecular weight of about 3,000 Daltons to about 80,000 Daltons (preferably from about 4,000 to about 40,000 Daltons, more preferably from about 5,000 to about 20,000 Daltons).

[00069] Without wishing to be bound by any theory, the inventors believe that such vinyl polysiloxane crosslinkers that have hydrophilized siloxane units have important functions in having high oxygen permeability and low modulus while maintaining the integrity of the contact lens during manipulation. When a vinyl polysiloxane crosslinker without H-donating chemical moieties or hydrophilic chemical moieties has a very low number average molecular weight, the modulus of the resulting SiHy lenses would be very high. However, when a vinyl polysiloxane crosslinker without H-donating chemical moieties or hydrophilic chemical moieties has a high number average molecular weight, it will not be sufficiently compatible with N-vinyl amide monomer or other hydrophilic polymerizable component and may cause clouding in lenses. resulting SiHy contact surfaces. With an adequate number of H-donating chemical moieties, a high molecular weight polysiloxane vinyl crosslinker would be sufficiently compatible with N-vinyl amide monomer and other hydrophilic polymerizable components. Furthermore, it is believed that due to the presence of these H-donating chemical moieties, the N-vinyl amide monomer molecules may be preferentially located in the vicinity of such a high molecular weight polysiloxane vinyl crosslinker due to the hydrogen bonding between the N-vinyl amide monomer and the H-donating chemical moieties. During polymerization, in situ generated poly(N-vinylamide) can preferentially form the interpenetration network with hydrophobic silicone regions and would therefore facilitate the formation of a silicone hydrogel with macroscopic homogeneity but microscopic heterogeneity (i.e., microscopic phase separation) by having minimized turbidity, high oxygen permeability, and high water content.

[00070] Preferably, the first vinyl polysiloxane crosslinker comprises: (1) a polysiloxane segment comprising dimethylsiloxane units and hydrophilized siloxane units each having a methyl substituent and a C4-C40 organic radical substituent monovalent having 2 to 6 H-donating chemical moieties, wherein the molar ratio between the hydrophilized siloxane units and the dimethylsiloxane units is about 0.035 to about 0.15; (2) two terminal (meth)acryloyl groups; and (3) from 0 to 20 third H-donating chemical moieties, wherein the polysiloxane vinyl crosslinker has a number average molecular weight of about 3,000 Daltons to about 80,000 Daltons.

[00071] More preferably, the first vinyl polysiloxane crosslinker is a compound of Formula (1) on what:

[00072] υ1 is an integer from 30 to 500 and ®1 is an integer from 1 to 75, since ®1/v1 is from about 0.035 to about 0.15 (preferably from about 0.040 to about from 0.12, to more preferably from about 0.045 to about 0.10);

[00073] X01 is O or NRn where Rn is hydrogen or C1-C10-alkyl;

[00074] Ro is hydrogen or methyl;

[00075] R2 and R3, independently of each other, are a substituted or unsubstituted C1-C10 alkylene divalent radical or a divalent radical of -R5-O-R6- in which R5 and Re independently of each other are a C1 divalent radical -C10 substituted or unsubstituted alkylene;

[00076] R4 is a monovalent radical of any one of Formula (2) to (6)

[00077] pl is zero or 1; ml is an integer from 2 to 4; m2 is an integer from 1 to 5; m3 is an integer from 3 to 6; m4 is an integer from 2 to 5;

[00078] R7 is hydrogen or methyl;

[00079] R8 is a C2-C6 hydrocarbon radical that has valences (m2+1);

[00080] R9 is a C2-C6 hydrocarbon radical that has valences (m4+1);

[00081] R10 is ethyl or hydroxymethyl;

[00082] R11 is methyl or hydromethyl;

[00083] R12 is hydroxyl or methoxy;

[00084] and the the

[00085] X4 is an amide bond of or where R14 is hydrogen or C1-C10 alkyl.

[00086] In a preferred embodiment, R4 is a monovalent radical of one of Formulas (2a) to (2y). where p1 is zero or 1 (preferably 1), m1 is an integer from 2 to 4 (preferably 3), R7 is hydrogen or methyl (preferably hydrogen).

[00087] In another preferred embodiment, R4 is a monovalent radical of one of Formulas (3a) to (3y).

[00088] where X4 is an amide bond of or where R14 is hydrogen or C1-C10 alkyl.

[00089] In another preferred embodiment, R4 is a monovalent radical of Formula (4a) or (4b).

[00090] In another preferred embodiment, R4 is a monovalent radical of one of Formulas (5a) to (5c).

[00091] In another preferred embodiment, the monovalent radical R4 is a radical of Formula (6) in which m1 is 3, p1 is 1, and R7 is hydrogen. Such a preferred first polysiloxane vinyl crosslinker is represented by Formula (A) where υ1 and ω1 are as defined above.

[00092] A vinyl polysiloxane crosslinker of Formula (1) can be prepared by reacting a polysiloxane containing hydrosiloxane of Formula (7) with an ene monomer containing 2 to 5 hydroxyl groups wherein Xo, Ro, R2, R3, u1, and ω1, as defined above, in a platinum-catalyzed hydrosilylation reaction, as known to a person skilled in the art.

[00093] The hydrosilane-containing polysiloxane of Formula (7) can be prepared according to any methods known to a person skilled in the art. As an illustrative example, a hydrosiloxane-containing polysiloxane of Formula (7) can be prepared from polymerization of a mixture of octamethylcyclotetrasiloxane (D4) and 1,3,5,7-tetramethylcyclotetrasiloxane (H4) in the presence of 1 ,3-bis[3-(meth)acryloxypropyl]tetramethyldisiloxane, as a chain end block and in the presence of a catalyst. By controlling the molar ratio between D4 and H4, a desirable value of v>1/®1 can be obtained.

[00094] When, in Formula (1), R4 is a monovalent radical of Formula (4), (5) or (6), the preferred ene monomer is 3-allyoxy-1,2-propanediol, 2-allyloxymethyl-2 -(hydroxymethyl)-1,3-propanediol, 2-allyloxy-methyl-2-ethyl-1,3-propanediol (i.e., trimethylolpropanoallylether), allyl a-D-mannopyranoside, allyl a-D-galactopyranoside, allyl 6-deoxyhexopyranoside noside, allyl 6-deoxy-2-O-methylhexopyranoside, or a completely hydrolyzed (i.e., ring-opening) product of an epoxy-containing ene monomer that is allyloxy glycidyl ether, 1,2-epoxy-5-hexene , 3,4-epoxy-1-butene, or 2-methyl-2-vinyloxirane. The ene monomers listed above are commercially available.

[00095] When, in Formula (1), R4 is a monovalent radical of Formula (2), the preferred ene monomer is a reaction product of an epoxy-containing ene monomer with a mercaptan having 2 to 5 hydroxyl groups or a secondary amine that has 2 to 5 hydroxyl groups. Examples of commercially available epoxy-containing ene monomers include, without limitation, allyloxy glycidyl ether, 1,2-epoxy-5-hexene, 3,4-epoxy-1-butene, and 2-methyl-2-vinyloxirane. Examples of commercially available mercaptans that have 2 to 4 hydroxyl groups include, without limitation, 1-mercaptoethane-1,2-diol, 2-mercaptopropane-1,3-diol, 3-mercaptopropane-1,2-diol, 3- mercaptobutane-1,2-diol, 1-mercaptobutane-2,3-diol, 4-mercapto-1,2,3-butanetriol, and 2-mercapto-6-methylol-tetrahydropyran-3,4 ,5-triol. Examples of commercially available secondary amines that have 2 to 4 hydroxyl groups include, without limitation, bis(2-hydroxyethyl)amine, bis(2-hydroxypropyl)amine, bis(3-hydroxypropyl)amine, bis-(2,3- dihydroxypropyl) amine, isopropylamino-1,2-propanediol, 2-(2-hydroxyethylamino)-2-(hydroxymethyl)-1,3-propanediol, 2-(ethylamino)-1,3-butanediol, 6- ethylamino-1,2,4-cyclohexanetriol, 3-(methylamino)-6-methylol-tetrahydropyrantriol, 3-(ethylamino)-6-methylol-tetrahydropyrantriol, 3-methylamino-1,2- propanediol, 2-methylamino-1,3-propanediol, 1-(methylamino)-1,2,3-propanetriol, 4-methylamino-1,2-butanediol, 2-methylamino-1,4-butanediol, 2- methylamino-1,3-butanediol, N-methyl-2,3,4-trihydroxybutylamine, N-methyl-2,3,4,5-tetradroxypentylamine, N-methyl-2,3,4,5, 6-pentahydroxyhexylamine. Reactions between an epoxide and a mercaptan (to form a thiol ether bond) and between an epoxide and a secondary amine (to form an amino bond) are well known to a person skilled in the art and have been described in the literature.

[00096] When, in Formula (1), R4 is a monovalent radical of Formula (3), the preferred ene monomer is a reaction product of (1) a carboxy-containing ene monomer with a primary or secondary amine having 2 to 5 hydroxyl groups or (2) a primary amino-containing or secondary amino-containing ene monomer with an alkanoic acid having 2 to 5 hydroxyl groups, in accordance with the well-known coupling reaction between a carboxylic acid group and an amino group (primary or secondary) in the presence of 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide (EDC) and N-hydroxysuccinimide (HO-NHS), to obtain an ene monomer that has 2 to 5 hydroxyl groups and an amide bond. Examples of commercially available carboxy-containing ene monomers include, without limitation, 3-butenoic acid, 4-pentenoic acid, 5-hexenoic acid and 6-heptenoic acid. Examples of commercially available ene monomers that contain primary or secondary amino include, without limitation, allylamine, 3-butenylamine, 4-pentenylamine, 1-methyl-4-pentenylamine, 5-hexenylamine, 5-heptenylamine, 6-heptenylamine, N-ethyl-2-methylallylamine, N-ethylallylamine, N-allylmethylamine, N-allyl-1-pentanamine, N-allyl-2-methyl-1-pentanamine, N-allyl-2,3-dimethyl-1-pentanamine, N-allyl-1-hexanamine, N-allyl-2-methyl-1-hexanamine, and N-allyl-1-heptanamine. Examples of commercially available alkanoic acids that have 2 to 5 hydroxyl groups include, without limitation, 2,3-dihydroxypropanoic acid, 2,3-dihydroxybutanoic acid, 3,4-dihydroxybutanoic acid, 2,3,4-trihydroxybutanoic acid, 2,4,5-trihydroxypentanoic acid, 2,4,5-trihydroxy-2-(hydroxymethyl)pentanoic acid, 3,4,5-tri acid - hydroxy-2-methoxypentanoic acid, xylonic acid (2,3,4,5-tetrahydroxy-pentanoic acid), 3,4,5-trihydroxyhexanoic acid, 3,5,6-trihydroxy- hexanoic acid, 4,5,6-trihydroxyhexanoic acid, 2,4,5,6-tetrahydroxyhexanoic acid, 2,3,4,5-tetrahydroxyhexanoic acid, 2,3 acid, 4,5,6- pentahydroxyhexanoic acid. Examples of commercially available primary amines that have 2 to 5 hydroxyl groups include, without limitation, dihydroxyethylamine, 2,3-dihydropropylamine, 2-amino-1,3-propanediol, 2-amino-1,4 -butanediol, 2-amino-1,3-butanediol, 4-amino-1,2-butanediol, 2-amino-1,3,4-butanetriol, 4-amino-1,2,3-butanetriol, 2-amino -2-methyl-1,3-propanediol, 2-amino-2-ethyl-1,3-propanediol, 2-amino-2-(hydroxymethyl)-1,3-propanediol, 2-amino-1,5 -pentanediol, and 3-amino-6-hydroxymethyl-tetrahydropyran-2,4,5-triol. The commercially available secondary amines listed above that have 2 to 5 hydroxyl groups can be used in the reaction with a carboxy-containing ene monomer to obtain an ene monomer that has multiple hydroxyl groups and an amide bond. The reaction between a carboxylic acid group and a primary or secondary amino group to form an amide bond is well known to one skilled in the art and has been described extensively in the literature.

[00097] The procedures for preparing vinyl polysiloxane crosslinkers of Formula (1) were also described in detail in US Patent Application Publication 2017-0166673 A1.

[00098] It is understood that the fourth repeating units of at least one second polysiloxane vinyl crosslinker are optional components. Any suitable polysiloxane vinyl crosslinkers other than those polysiloxane vinyl crosslinkers having hydrophilized siloxane units described above can be used in the inventions, as long as each of them comprises at least one polysiloxane segment and at least two ethylenically unsaturated groups. Examples of such vinyl polysiloxane crosslinkers are di-(meth)acryloyloxy-terminated polydimethylsiloxanes of various molecular weights; polydimethylsiloxanes terminated in divinyl carbonate; polydimethylsiloxane terminated in divinyl carbamate; divinyl-terminated polydimethylsiloxanes of various molecular weights; di-(meth)acrylamide-terminated polydimethylsiloxanes; N,N,N',N'-tetracis(3-methacryloxy-2-hydroxypropyl)-alpha, omega-bis-3-aminopropyl-polydimethylsiloxane; chain-extended vinyl polysiloxane crosslinkers comprising at least two polysiloxane segments and at least one divalent organic radical linking each pair of adjacent polysiloxane segments and having one or more H-donating chemical moieties (see, for example, those disclosed in US Patents 5034461, 5416132, 5449729, 5760100, 7423074, 8529057, and 8993651 and Patent Application Publication No. 2018-0100053 A1); siloxane-containing macromer selected from the group consisting of Macromer A, Macromer B, Macromer C, and Macromer D described in US Patent 5760100; the reaction products of glycidyl methacrylate with starch functional polydimethylsiloxanes; polysiloxane-containing macromers disclosed in US Patents 4136250, 4153641, 4182822, 4189546, 4343927, 4254248, 4355147, 4276402, 4327203, 4341889, 4486577, 454 3398, 4605712, 4661575, 4684538, 4703097, 4833218, 4837289, 4954586, 4954587, 5010141, 5034461, 5070170, 5079319, 5039761, 5346946, 5358995, 5387632, 5416132, 5451617, 5486579, 5962548, 5981675, 6039 913, and 6762264; macromers containing polysiloxane disclosed in US Patents 4259467, 4260725 and 4261875.

[00099] Examples of preferred di-(meth)acryloyl-terminated polydiorganosiloxanes include, without limitation, α,w-bis[3-(meth)acrylamidopropyl-terminated polydimethylsiloxane, α,w-bis[3-( meth)acryloxypropyl], polydimethylsiloxane ending in a,w-bis[3-(meth)acryloxy-2-hydroxypropyloxypropyl], polydimethylsiloxane ending in a,w-bis[3-(meth)acryloxyethoxy-2-hydroxypropyloxy-propyl], polydimethylsiloxane terminated in α,w-bis[3-(meth)acryloxypropyloxy-2-hydroxypropyloxypropyl], polydimethylsiloxane terminated in a,w-bis[3-(meth)acryloxy-isopropyloxy-2-hydroxypropyloxypropyl], polydimethylsiloxane terminated in a, w-bis[3-(meth)acryloxybutyloxy-2-hydroxypropyloxypropyl], polydimethylsiloxane ending in α,w-bis[3-(meth)acrylamido-ethoxy-2-hydroxypropyloxypropyl], polydimethylsiloxane ending in α,w-bis[ 3-(meth)acrylamidopropyloxy-2-hydroxypropyloxypropyl], polydimethylsiloxane ending in a,w-bis[3-(meth)acrylamidoisopropyloxy-2-hydroxypropyloxypropyl], polydimethylsiloxane ending in α,w-bis[3-(met ) acrylamidobutyloxy-2-hydroxypropyloxypropyl], polydimethylsiloxane ending in α,w-bis[3-(meth)acryloxyethylamino-2-hydroxypropyloxypropyl], polydimethylsiloxane ending in α,w-bis[3-(meth)acryloxypropylamino-2-hydroxy - propyloxypropyl], polydimethylsiloxane terminated in α,w-bis[3-(meth)acryloxybutylamino-2-hydroxypropyloxypropyl], polydimethylsiloxane terminated in a,w-bis[(meth)acrylamidoethylamino-2-hydroxypropyloxy-propyl], polydimethylsiloxane terminated in α,w-bis[3-(meth)acrylamidopropylamino-2-hydroxypropyloxypropyl], polydimethylsiloxane ending in α,w-bis[3-(meth)acrylamide-butylamino-2-hydroxypropyloxypropyl], polydimethylsiloxane ending in a,w -bis[(meth)acryloxy-2-hydroxypropyloxy-ethoxypropyl], polydimethylsiloxane ending in a,w-bis[(meth)acryloxy-2-hydroxypropyl- N-ethylaminopropyl], a,w-bis[(meth)acryloxy-2 -hydroxypropyl-aminopropyl]- polydimethylsiloxane, polydimethylsiloxane ending in α,w-bis[(meth)acryloxy-2-hydroxypropyloxy-(polyethylenoxy)propyl], polydimethylsiloxane ending in a,w-bis[(meth)acryloxyethylamino- carbonyloxy-ethoxypropyl], polydimethylsiloxane terminated in a,w-bis[(meth)acryloxyethylamino-carbonyloxy-(polyethyleneoxy)propyl].

[000100] According to the invention, any suitable N-vinyl amide monomers can be used in the invention. Examples of preferred N-vinyl amide monomers include, without limitation, N-vinylpyrrolidone, N-vinyl piperidone, N-vinyl caprolactam, N-vinyl-N-methyl acetamide, N-vinyl formamide, N-vinyl acetamide, N- vinyl isopropylamide, N-vinyl-N-methyl acetamide, N-vinyl-N-ethyl acetamide, N-vinyl-N-ethyl formamide and mixtures thereof. Preferably, the N-vinyl amide monomer is N-vinylpyrrolidone, N-vinyl-N-methyl acetamide, or combinations thereof.

[000101] According to the invention, a silicone hydrogel contact lens of the invention may additionally comprise (but preferably comprises) repeat units of one or more non-silicone vinyl crosslinking agents, preferably in an amount of about of 1.0% or less (preferably about 0.8% or less, more preferably about 0.05% to about 0.6%) by weight relative to the dry weight of the silicone hydrogel contact lens . The amount of repeating units of a non-silicone vinyl cross-linking agent can be calculated based on the amount of the non-silicone vinyl cross-linking agent in a polymerizable composition used to prepare the silicone hydrogel contact lens over the total amount of all polymerizable components in the polymerizable composition.

[000102] Examples of preferred non-silicone vinyl crosslinking agents include, without limitation, ethylene glycol di-(meth) acrylate, ethylene glycol didi-(meth) acrylate, ethylene glycol tridi-(meth) acrylate, col, ethylene glycol tetradi(meth)acrylate, glycerol di(meth)acrylate, 1,3-propanediol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, di(meth) )1,4-butanediol acrylate, glycerol 1,3-diglycerolate di-(meth) acrylate, ethylenebis[oxy(2-hydroxypropane-1,3-diyl)] di-(meth)acrylate, bis[ phosphate 2-(meth)acryloyloxyethyl], 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'-methylene bis(meth)acrylamide, N,N'-ethylene bis(meth)acrylamide, N,N'-dihydroxyethylene bis (meth)acrylamide, N,N'-propylene bis(meth)acrylamide, N,N'-2-hydroxypropylene bis(meth)acrylamide, N,N'-2,3-dihydroxybutylene bis(meth)acrylamide, di -1,3-bis(meth)acrylamidepropano-2-yl hydrogen phosphate (i.e., N,N'-2-phosphonyloxypropylene bis(meth)acrylamide), piperazine diacrylamide (or 1,4-bis(met) )acryloyl piperazine), divinyl tetraethylene glycol ether, divinyl triethylene glycol ether, divinyl diethylene glycol ether, divinyl ethylene glycol ether, triallyl isocyanurate, triallyl cyanurate, trimethylpropane trimethacrylate, pentaerythritol tetramethacrylate, bisphenol A dimethacrylate, and combinations thereof. A preferred non-silicone vinyl crosslinking agent is tetra(ethylene glycol di(meth)acrylate), tri(ethylene glycol di(meth)acrylate), ethylene glycol di(meth)acrylate, di(ethylene glycol), divinyl tetraethylene glycol ether, divinyl triethylene glycol ether, divinyl diethylene glycol ether, divinyl ethylene glycol ether, triallyl isocyanurate, or triallyl cyanide.

[000103] According to the invention, a silicone hydrogel contact lens of the invention may additionally and preferably comprise repeating units of one or more blending vinyl monomers, preferably, in an amount of about 25% or less by weight preferably about 20% or less by weight, more preferably about 15% or less by weight, relative to the dry weight of the silicone hydrogel contact lens. The amount of repeating units of a vinyl blend monomer can be calculated based on the amount of the vinyl blend monomer in a polymerizable composition used to prepare the silicone hydrogel contact lens over the total amount of all polymerizable components in the polymerizable composition.

[000104] Examples of preferred blend vinyl monomers include C1-C10 alkyl (meth) acrylate (e.g., methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, (meth) )isopropyl acrylate, 2-ethylhexyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, etc.), cyclopentylacrylate, cyclohexylmethacrylate, cyclohexylacrylate, isobornyl (meth)acrylate , styrene, 4,6-trimethylstyrene (TMS), t-butyl styrene (TBS), trifluoroethyl (meth)acrylate, hexafluoroisopropyl (meth)acrylate, hexafluorobutyl (meth)acrylate or combinations thereof . Preferably, methyl methacrylate is used as a blending vinyl monomer.

[000105] According to a preferred embodiment of the invention, a silicone hydrogel contact lens of the invention may additionally comprise (but preferably comprises) repeat units of one or more UV-absorbing vinyl monomers and optionally (but preferably) a or more UV/HEVL absorbing vinyl monomers. The term "UV-absorbing vinyl monomer/HEVL" refers to a vinyl monomer that can absorb UV light and high-energy violet light (i.e., light that has a wavelength between 380 nm and 440 nm).

[000106] Any suitable UV-absorbing vinyl monomers and UV/HEVL absorbing vinyl monomers can be used in a polymerizable composition to prepare a polymer of the invention. Examples of preferred UV-absorbing and UV/HEVL-absorbing vinyl monomers include, without limitation: 2-(2-hydroxy-5-vinylphenyl)-2H-benzotriazole, 2-(2-hydroxy-5-acrylyloxyphenyl)- 2H- benzotriazole, 2-(2-hydroxy-3-methacrylamido methyl-5-tert octylphenyl) benzo-triazole, 2-(2'-hydroxy-5'-methacrylamidophenyl)-5-chlorobenzotriazole, 2-(2'- hydroxy -5'-methacrylamidophenyl)-5-methoxybenzotriazole, 2-(2'-hydroxy-5'-methacryloxypropyl-3'-t-butyl-phenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-5' -methacryloxypropylphenyl) benzotriazole, 2-hydroxy-5-methoxy-3-(5-(trifluoromethyl)-2H-benzo[d][1,2,3]triazol-2-yl)benzyl methacrylate (WL-1 ), 2-hydroxy-5-methoxy-3-(5-methoxy-2H-benzo[d][1,2,3]triazol-2-yl)benzyl methacrylate (WL-5), 3-( 5-fluoro-2H-benzo[d][1,2,3]triazol-2-yl)-2-hydroxy-5-methoxybenzyl (WL-2), 3-(2H-benzo[d] methacrylate [1 ,2,3] triazol-2-yl)-2-hydroxy-5-methoxybenzyl (WL-3), 3-(5-chloro-2H-benzo[d][1,2,3]triazol-2 methacrylate -yl)-2-hydroxy-5-methoxybenzyl (WL-4), 2-hydroxy-5-methoxy-3-(5-methyl-2H-benzo[d][1,2,3]triazole methacrylate -2-yl) benzyl (WL-6), 2-hydroxy-5-methyl-3-(5-(trifluoromethyl)-2H-benzo[d][1,2,3]triazol-2-yl methacrylate) benzyl (WL-7), 4-allyl-2-(5-chloro-2H-benzo[d][1,2,3]triazol-2-yl)-6-methoxyphenol (WL-8), 2-{ 2'-hydroxy-3'-tert-5'[3"-(4"- vinylbenzyloxy)propoxy]phenyl}-5-methoxy-2H-benzotriazole, phenol, 2-(5-chloro- 2H-benzotriazol-2- yl)-6-(1,1-dimethylethyl)-4-ethenyl- (UVAM), 2-[2'-hydroxy-5'-(2-methacryloxyethyl)phenyl)]-2H-benzotriazole (2-propenoic acid, 2-methyl-, 2-[3-(2H-benzotriazol-2-yl)-4-hydroxyphenyl]ethyl ester, Norbloc), 2-{2'-hydroxy-3'-tert-butyl-5'-[3 '-methacryloyloxypropoxy]phenyl}-2H-benzotriazole, 2-{2'-hydroxy-3'-tert-butyl-5'-[3'-methacryloyloxypropoxy]phenyl}-5-methoxy-2H-benzotriazole (UV13), 2 -{2'-hydroxy-3'-tert-butyl-5'-[3'-methacryloyloxypropoxy] phenyl}-5-chloro-2H-benzotriazole (UV28), 2-[2'-hydroxy-3'- tert-butyl-5'-(3'-acryloyloxypropoxy)phenyl]-5-trifluoromethyl-2H-benzotriazole (UV23), 2-(2'-hydroxy-5-methacrylamidophenyl)-5-methoxybenzotriazole (UV6), 2-( 3-allyl-2-hydroxy-5-methylphenyl)-2H-benzotriazole (UV9), 2-(2-hydroxy-3-metalyl-5-methylphenyl)-2H-benzotriazole (UV12), 2-3'- t-butyl-2'-hydroxy-5'-(3"-dimethylvinyl-silylpropoxy)-2'-hydroxy-phenyl)-5-methoxybenzotriazole (UV15), 2-(2'-hydroxy-5'-methacryloylpropyl-3 '-tert-butyl-phenyl)-5-methoxy-2H-benzotriazole (UV16), 2-(2'-hydroxy-5'-acryloylpropyl-3'-tert-butyl-phenyl)-5-methoxy-2H-benzotriazole (UV16A), 2-methylacrylic acid 3-[3-tert-butyl-5-(5-chlorobenzotriazol-2-yl)-4-hydroxyphenyl]-propyl ester (16-100, CAS No. 96478-15-8 ), 2-(3-(tert-butyl)-4-hydroxy-5-(5-methoxy-2H-benzo[d][1,2,3] triazol-2-yl)phenoxy methacrylate )ethyl (16-102); Phenol, 2-(5-chloro-2H-benzotriazol-2-yl)-6-methoxy-4-(2-propen-1-yl) (CAS No. 1260141-20-5); 2-[2-hydroxy-5-[3-(methacryloyloxy)propyl]-3-tert-butylphenyl]-5-chloro-2H-benzotriazole; phenol, 2-(5-ethenyl-2H-benzotriazol-2-yl)-4-methyl-, homopolymer (9CI) (CAS No. 83063-87-0). According to the invention, the polymerizable composition comprises about 0.1% to about 3.0%, preferably about 0.2% to about 2.5%, more preferably about 0.3% to about 2.0%, by weight, of one or more UV-absorbing vinyl monomers, related to the amount of all polymerizable components in the polymerizable composition.

[000107] In a preferred embodiment, a silicone hydrogel contact lens of the invention comprises repeating units of a UV-absorbing vinyl monomer and repeating units of a UV/HEVL absorbing vinyl monomer. More preferably, the silicone hydrogel contact lens is characterized by having a UVB transmittance of about 10% or less (preferably about 5% or less, more preferably about 2.5% or less, even more preferably about of 1% or less) between 280 and 315 nanometers and a UVA transmittance of about 30% or less (preferably about 20% or less, more preferably about 10% or less, even more preferably about 5% or less ) between 315 and 380 nanometers and a Violet transmittance of about 70% or less, preferably about 60% or less, more preferably about 50% or less, even more preferably about 40% or less) between 380 nm and 440nm. Even more preferably, the UV-absorbing vinyl monomer is 2-[2'-hydroxy-5'-(2-methacryloxyethyl)phenyl)]-2H-benzotriazole (Norbloc), and the UV/HEVL absorbing vinyl monomer is 2-{2'-hydroxy-3'-tert-butyl-5'-[3'-methacryloyloxypropoxy]phenyl}-2H-benzotriazole, 2-{2'-hydroxy-3'-tert-butyl-5'-[ 3'-methacryloyloxypropoxy]phenyl}-5-methoxy-2H-benzotriazole (UV13), 2-{2'-hydroxy-3'-tert-butyl-5'-[3'-methacryloyloxypropoxy]phenyl}-5-chloro- 2H-benzotriazole (UV28), 2-[2'-hydroxy-3'-tert-butyl-5'-(3'-acryloyloxy-propoxy)phenyl]-5-trifluoromethyl-2H-benzotriazole (UV23), or combinations thereof same.

[000108] According to the invention, a silicone hydrogel contact lens of the invention may additionally comprise repeating units of one or more hydrophilic acrylic monomers, preferably in an amount of about 10% or less (preferably -referentially about 8% or less, more preferably about 5% or less) by weight relative to the dry weight of the silicone hydrogel contact lens. The amount of repeating units of a hydrophilic acrylic monomer can be calculated based on the amount of the hydrophilic acrylic monomer in a polymerizable composition used to prepare the silicone hydrogel contact lens over the total amount of all polymerizable components in the composition. polymerizable.

[000109] Examples of preferred hydrophilic acrylic monomers include, without limitation, N,N-dimethyl (meth) acrylamide, (meth) acrylamide, N-hydroxylethyl (meth) acrylamide, N-hydroxypropyl (meth) acrylamide, hydroxyethyl (meth)acrylate, glycerol methacrylate (GMA), polyethylene glycol (meth)acrylate having a number average molecular weight of up to 1,500, polyethylene glycol C1-C4-alkyl ether (meth)acrylate having a molecular weight average numerical value up to 1,500, N-[tris(hydroxymethyl) methyl]-acrylamide, (meth)acrylic acid, ethylacrylic acid, and combinations thereof. Preferably, the hydrophilic vinyl monomer is N,N-dimethyl (meth) acrylamide, hydroxyethyl (meth) acrylate, N-hydroxylethyl (meth) acrylamide, glycerol methacrylate (GMA), or combinations thereof.

[000110] A silicone hydrogel contact lens of the invention may also comprise other necessary components known to a person skilled in the art, such as, for example, one or more free radical initiators, a visibility tinting agent (e.g., repeating units of one or more polymerizable dyes, pigments, or mixtures thereof), antimicrobial agents (e.g., preferably silver nanoparticles), a bioactive agent, leachable lubricants, leachable tear stabilizing agents, and mixtures thereof, as known to a person skilled in the art.

[000111] Suitable thermal polymerization initiators are known to the artisan skilled in the art and comprise, for example, peroxides, hydroperoxides, azo-bis (alkyl- or cycloalkylnitriles), persulfates, percarbonates or mixtures thereof. Examples are benzoylperoxide, tert-butyl peroxide, di-tert-butyl-diperoxyphthalate, tert-butyl hydroperoxide, azo-bis(isobutyronitrile) (AIBN), 1,1-azodiisobutyramidine, 1,1'-azo- bis(1-cyclohexanecarbonitrile), 2,2'-azo-bis(2,4-dimethylvaleronitrile) and the like.

[000112] Suitable photoinitiators are benzoin methyl ether, diethoxyacetophenone, a benzoylphosphine oxide, 1-hydroxycyclohexyl phenyl ketone and types Darocur and Irgacur, preferably Darocur 1173® and Darocur 2959®, Type I Norrish photoinitiators based on Germane. Examples of benzoylphosphine initiators include 2,4,6-trimethylbenzoyldiphenylphosphine oxide; bis-(2,6-dichlorobenzoyl)-4-N-propylphenylphosphine oxide; and bis-(2,6-dichlorobenzoyl)-4-N-butylphenylphosphine oxide. Photoinitiators, which can be incorporated, for example, into a macromer or can be used as a special monomer, are also suitable. Examples of reactive photoinitiators are those disclosed in document no. EP 632 329.

[000113] When a vinyl monomer with the ability to absorb ultraviolet radiation and high energy violet light (HEVL) is used in the invention, a Type I Norrish photoinitiator based on Germane and a light source including a light in the region of about 400 to about 550 nm are preferably used to initiate a free radical polymerization. Any Germane-based Norrish Type I photoinitiators can be used in this invention, as long as they have the ability to initiate a free radical polymerization upon irradiation with a light source including a light in the region of about 400 to about 550 nm. Examples of Type I Norrish photoinitiators based on Germane are acylgermanium compounds described in US Patent 7,605,190.

[000114] The bioactive agent is any compound that can prevent an eye disease or reduce the symptoms of an eye disease. The bioactive agent may be a drug, an amino acid (e.g., taurine, glycine, etc.), a polypeptide, a protein, a nucleic acid, or any combination thereof. Examples of drugs useful herein include, but are not limited to, rebamipide, ketotifen, olaptidine, cromoglycolate, cyclosporine, nedocromil, levocabastin, lodoxamide, ketotifen or the pharmaceutically acceptable salt or ester thereof. Other examples of bioactive agents include 2-pyrrolidone-5-carboxylic acid (PCA), alpha hydroxylic acids (e.g. glycolic, lactic, malic, tartaric, mandelic and citric acids and salts thereof, etc.), linolenic and gamma acids. linolenic, and vitamins (e.g. B5, A, B6, etc.).

[000115] Examples of leachable lubricants include, without limitation, mucin-like materials (e.g., polyglycolic acid) and non-crosslinkable hydrophilic polymers (i.e., without ethylenically unsaturated groups). Any hydrophilic polymers or copolymers without any ethylenically unsaturated groups can be used as leachable lubricants. Preferred examples of non-crosslinkable hydrophilic polymers include, but are not limited to, polyvinyl alcohols (PVAs), polyamides, polyimides, polylactone, a homopolymer of a vinyl lactam, a copolymer of at least one vinyl lactam in the presence or absence of a or more hydrophilic vinyl comonomers, a homopolymer of acrylamide or methacrylamide, a copolymer of acrylamide or methacrylamide with one or more hydrophilic vinyl monomers, polyethylene oxide (i.e., polyethylene glycol (PEG)), a polyoxyethylene derivative, polyethylene N-N-dimethylacrylamide, polyacrylic acid, poly 2 ethyl oxazoline, heparin polysaccharides, polysaccharides, and mixtures thereof. The numerical average molecular weight Mw of the non-crosslinkable hydrophilic polymer is preferably 5,000 to 1,000,000.

[000116] Examples of leachable tear stabilizing agents include, without limitation, phospholipids, monoglycerides, diglycerides, triglycerides, glycolipids, glyceroglycolipids, sphingolipids, sphingoglycolipids, fatty alcohols, fatty acids, mineral oils and mixtures thereof. Preferably, a tear stabilizing agent is a phospholipid, a monoglyceride, a diglyceride, a triglyceride, a glycolipid, a glyceroglycolipid, a sphingolipid, a sphingo-glycolipid, a fatty acid having 8 to 36 carbon atoms. , a fatty alcohol that has 8 to 36 carbon atoms, or a mixture thereof.

[000117] In a preferred embodiment, a silicone hydrogel contact lens of the invention comprises about 60% or more by weight (preferably about 65% or more by weight, more preferably about 70% or more by weight , even more preferably about 75% or more by weight) of the first, second, and third repeat units relative to the dry weight of the silicone hydrogel contact lens. The total amount of the first, second, and third repeating units can be calculated based on the sum of the amounts of the siloxane-containing vinyl monomer, the first polysiloxane vinyl crosslinker, and the hydrophilic N-vinyl amide monomer in a polymerizable composition used to prepare the silicone hydrogel contact lens about the total amount of all polymerizable components in the polymerizable composition.

[000118] A silicone hydrogel contact lens of the invention can be prepared from a polymerizable composition (i.e., a lens-forming composition or a lens formulation) in accordance with a method of the invention which is another aspect of the invention.

[000119] A polymerizable composition can be prepared by dissolving all desirable components in any suitable solvent, such as a mixture of water and one or more water-miscible organic solvents, an organic solvent, or a mixture of one or more organic solvents, as known to a person skilled in the art. The term "solvent" refers to a chemical that cannot participate in the free radical polymerization reaction.

[000120] Examples of organic solvents include, without limitation, 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-ether propyl ether, tripropylene glycol n-butyl ether, propylene glycol n-butyl ether, dipropylene glycol n-butyl ether, tripropylene glycol n-butyl ether, propylene glycol phenyl ether, dipropylene glycol dimethyl ether, polyethylene glycols, polypropylene glycols, 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, 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, dimethyl formamide, dimethyl acetamide, dimethyl propionamide, N-methyl pyrrolidinone, and mixtures thereof.

[000121] In another aspect, the present invention provides a method for producing inherently wettable silicone hydrogel contact lenses. The method comprises the steps of: preparing a polymerizable composition that is clear at room temperature and optionally but preferably at a temperature of about 0 to about 4°C, wherein the polymerizable composition comprises (a) at least one vinyl monomer which contains siloxane including 0 to 10 first H-donating chemical moieties, (b) at least one first vinyl polysiloxane crosslinker which has (iv) a number average molecular weight of about 3,000 Daltons to about 80,000 Daltons and comprises (i) two terminal (meth)acryloyl groups, (ii) at least one polysiloxane segment comprising dimethylsiloxane units and hydrophilized siloxane units each having a methyl substituent and a C4-C40 organic radical substituent mo- novalent that has one or more second H-donating chemical moieties, and (iii) from 0 to 20 third H-donating chemical moieties that are integral parts of molecular structures outside the polysiloxane segment, (c) at least one N-monomer hydrophilic vinyl amide, (d) optionally at least one second polysiloxane vinyl crosslinker that has 0 to 35 H-donating chemical moieties, and (e) at least one free radical initiator, wherein the first and second crosslinkers Polysiloxane vinyls are different from each other in that the first, second, third and fourth H-donating chemical moieties independent of each other are hydroxyl groups, carboxyl groups, amino groups of -NHR°, amino bonds of -NH-, -CONH- amide, -OCONH- urethane linkages, or combinations thereof, wherein R° is H or a C1-C4 alkyl, wherein the polymerizable composition comprises at least 8.8 (preferably at least 9, more preferably at least 9.2, even more preferably 9.6) mmols of component (c) per gram of all components (a), (b) and (d) in total and at least 0.11 (preferably at least 0.15, more preferably at least 0.20, even more preferably at least 0.25) meqs of the first, second, third and fourth H-donating chemical moieties in total per gram of component (c); introducing the polymerizable composition into a lens mold; thermally or actinically curing the polymerizable composition in the lens mold to form a silicone hydrogel contact lens, wherein the silicone hydrogel contact lens has an oxygen permeability of at least 50 bar, an elastic modulus of about of 0.2 MPa to about 1.5 MPa, and an equilibrium water content of about 40% to about 70% and is inherently wettable as characterized by having a water breakthrough time of at least 10 seconds and a captive bubble water contact angle of about 80 degrees or less without undergoing any post-cure surface treatment.

[000122] Various embodiments described above of siloxane-containing vinyl monomers, polysiloxane vinyl crosslinkers, hydrophilic N-vinyl amide monomers, non-silicone vinyl crosslinking agents, blending vinyl monomers, water-absorbing vinyl monomers UV, hydrophilic vinyl monomers, free radical initiators, visibility coloring agents and solvents should be incorporated into this aspect of the invention.

[000123] In a preferred embodiment, a polymerizable composition of the invention comprises about 60% or more by weight (preferably, about 65% or more by weight, more preferably, about 70% or more by weight, even more preferably, about 75% or more by weight) of all components (a), (b) and (c) in total relative to the total weight of all polymerizable components in the polymerizable composition.

[000124] Thermal polymerization is conveniently carried out in a solvent mentioned above at elevated temperature, for example, at a temperature of 25 to 100 °C and, preferably, 40 to 80 °C. The reaction time may vary within wide limits, but is conveniently, for example, 1 to 24 hours or, preferably, 2 to 12 hours. It is advantageous to previously degas the components and solvents used in the polymerization reaction and carry out said copolymerization reaction under an inert atmosphere, for example, under a nitrogen or argon atmosphere.

[000125] Actinic polymerization can then be triggered by actinic radiation, for example, light, in particular, UV light or visible light of a suitable wavelength. Spectral requirements can be controlled accordingly, if appropriate, by adding suitable photosensitizers.

[000126] Lens molds for manufacturing contact lenses are well known to one skilled in the art and, for example, are used in casting molding or centrifugal casting. For example, a mold (for casting molding) generally comprises at least two mold sections (or portions) or mold halves, i.e., first and second mold halves. The first mold half defines a first molding (or optical) surface and the second mold half defines a second molding (or optical) surface. The first and second mold halves are configured to receive each other so that a lens forming cavity is formed between the first molding surface and the second molding surface. The molding surface of a mold half is the mold cavity forming surface and in direct contact with lens forming material.

[000127] Methods for manufacturing mold sections for casting molding a contact lens are generally well known to those skilled in the art. The process of the present invention is not limited to any particular method of forming a mold. In fact, any method for forming a mold can be used in the present invention. The first and second mold halves can be formed using various techniques, such as injection molding or turning. Examples of suitable processes for forming mold halves are disclosed in US patent 4,444,711; 4460534; 5843346; and 5894002.

[000128] Virtually all materials known in the art for making molds can be used to make molds for manufacturing contact lenses. For example, polymeric materials such as polyethylene, polypropylene, polystyrene, PMMA, Topas® COC grade 8007-S10 (transparent amorphous copolymer of ethylene and norbornene, available from Ticona GmbH of Frankfurt, Germany and Summit, New Jersey) can be used. , or similar. Other materials that allow UV light transmission could be used, such as quartz glass and sapphire.

[000129] According to the invention, the polymerizable composition can be introduced (dispensed) into a cavity formed by a mold according to any known methods.

[000130] After the polymerizable composition is dispensed into the mold, it is polymerized to produce a contact lens. Crosslinking can be initiated thermally or actinically to crosslink the polymerizable components in the polymerizable composition.

[000131] Opening the mold so that the molded article can be removed from the mold can occur in a manner known per se.

[000132] The molded contact lens can be subjected to lens extraction to remove unpolymerized polymerizable components. The extraction solvent may be any solvent known to one of skill in the art. Examples of suitable extraction solvent are those solvents described above. After extraction, the lenses can be hydrated in water or an aqueous solution of a wetting agent (e.g., a hydrophilic polymer).

[000133] Molded contact lenses may further be subjected to additional processes, such as, for example, hydration, placing in lens packaging with a packaging solution that is well known to one skilled in the art; sterilization by autoclaving at 118 to 124 °C for at least about 30 minutes; and similar.

[000134] Lens packages (or containers) are well known to one skilled in the art for autoclaving and storing a soft contact lens. Any lens packaging can be used in the invention. Preferably, a lens package is a blister package comprising a base and a cover, wherein the cover is separably sealed to the base, wherein the base includes a cavity for receiving a sterile packaging solution and the contact lens.

[000135] The lenses are packaged in individual packages, sealed and sterilized (for example, by autoclaving at about 120 ° C or higher for at least 30 minutes under pressure) before dispensing to users. One skilled in the art will understand well how to seal and sterilize lens packages.

[000136] According to the invention, a packaging solution contains at least one buffering agent and one or more other ingredients known to one skilled in the art. Examples of other ingredients include, without limitation, tonic agents, surfactants, bactericidal agents, preservatives and lubricants (for example, cellulose derivatives, polyvinyl alcohol, polyvinylpyrrolidone).

[000137] Although various embodiments of the invention have been described using specific terms, devices and methods, such description is for illustrative purposes only. The words used are words of description rather than limitation. As would be obvious to one skilled in the art, many variations and modifications of the invention can be made by those skilled in the art without deviating from the spirit and scope of the innovative concepts of the disclosure. Furthermore, it should be understood that aspects of the various embodiments of the invention may be interchanged in whole or in part or may be combined in any manner and/or used together, as illustrated below:

[000138] 1. A silicone hydrogel contact lens comprising a silicone hydrogel bulk material comprising: (1) first repeat units of at least one siloxane-containing vinyl monomer including 0 to 10 first chemical moieties H donors, (2) second repeat units of at least one first polysiloxane vinyl crosslinker that has a number average molecular weight of about 3,000 Daltons to about 80,000 Daltons and comprises (a) two terminal (meth)acryloyl groups, (b) at least one polysiloxane segment comprising dimethylsiloxane units and hydrophilized siloxane units each having a methyl substituent and a monovalent C4-C40 organic radical substituent having one or more second moieties H-donating chemicals, and (c) from 0 to 20 third H-donating chemical moieties that are integral parts of molecular structures outside the polysiloxane segment, (3) third repeating units of at least one hydrophilic N-vinyl amide monomer , and (4) optionally fourth repeating units of at least one second vinyl polysiloxane crosslinker having 0 to 35 fourth H-donating chemical moieties, wherein the first and second vinyl polysiloxane crosslinkers are different from each other, wherein the first, second, third and fourth H-donating chemical moieties independent of each other are hydroxyl groups, carboxyl groups, amino groups of -NHR°, amino bonds of -NH-, amide bonds of -CONH-, urethane bonds of -OCONH-, or combinations thereof, wherein R° is H or a C1-C4 alkyl, wherein the silicone hydrogel bulk material comprises at least 8.8 mmols of the third repeating units per gram of all first, second, and fourth repeat units in total (i.e., and at least 0.11 meqs of all first, second, third, and fourth H-donating chemical moieties in total per gram of the third repeating units (i.e., ), wherein the silicone hydrogel contact lens has an oxygen permeability of at least 50 bar, an elastic modulus of about 0.2 MPa to about 1.5 MPa, and an equilibrium water content from about 40% to about 70% and is inherently wettable as characterized by having a water breakthrough time of at least 10 seconds and a captive bubble water contact angle of about 80 degrees or less without subjecting to any post-cure surface treatment.

[000139] 2. The silicone hydrogel contact lens of embodiment 1, wherein the silicone hydrogel bulk material comprises at least 9.0 mmols of the third repeat units per gram of all first, second and fourth units of repetition in total.

[000140] 3. The silicone hydrogel contact lens of embodiment 1, wherein the silicone hydrogel bulk material comprises at least 9.2 mmols of the third repeat units per gram of all first, second and fourth units of repetition in total.

[000141] 4. The silicone hydrogel contact lens of embodiment 1, wherein the silicone hydrogel bulk material comprises at least 9.6 mmols of the third repeating units per gram of all first, second and fourth units of repetition in total.

[000142] 5. The silicone hydrogel contact lens of any one of embodiments 1 to 4, wherein the silicone hydrogel bulk material comprises at least 0.15 meqs of all first, second, third and fourth H-donating chemical portions in total per gram of the third repeating units.

[000143] 6. The silicone hydrogel contact lens of any one of embodiments 1 to 4, wherein the silicone hydrogel bulk material comprises at least 0.20 meqs of all first, second, third and fourth H-donating chemical portions in total per gram of the third repeating units.

[000144] 7. The silicone hydrogel contact lens of any one of embodiments 1 to 4, wherein the silicone hydrogel bulk material comprises at least 0.25 meqs of all first, second, third and fourth H-donating chemical portions in total per gram of the third repeating units.

[000145] 8. The silicone hydrogel contact lens of any one of embodiments 1 to 7, wherein the silicone hydrogel contact lens has a water break-up time of at least 15 seconds without being subjected to any post-cure surface treatment.

[000146] 9. The silicone hydrogel contact lens of any one of embodiments 1 to 7, wherein the silicone hydrogel contact lens has a water break-up time of at least 20 seconds without being subjected to any post-cure surface treatment.

[000147] 10. The silicone hydrogel contact lens of any one of embodiments 1 to 9, wherein the silicone hydrogel contact lens has a captive bubble water contact angle of about 75 degrees or less without be subjected to any post-cure surface treatment.

[000148] 11. The silicone hydrogel contact lens of any one of embodiments 1 to 9, wherein the silicone hydrogel contact lens has a captive bubble water contact angle of about 70 degrees or less without be subjected to any post-cure surface treatment.

[000149] 12. The silicone hydrogel contact lens of any one of embodiments 1 to 9, wherein the silicone hydrogel contact lens has a captive bubble water contact angle of about 65 degrees or less without be subjected to any post-cure surface treatment.

[000150] 13. The silicone hydrogel contact lens of any one of embodiments 1 to 12, wherein the silicone hydrogel contact lens has an oxygen permeability of at least about 60 bars.

[000151] 14. The silicone hydrogel contact lens of any one of embodiments 1 to 12, wherein the silicone hydrogel contact lens has an oxygen permeability of at least about 70 bars.

[000152] 15. The silicone hydrogel contact lens of any one of embodiments 1 to 12, wherein the silicone hydrogel contact lens has an oxygen permeability of at least about 80 bars.

[000153] 16. The silicone hydrogel contact lens of any one of embodiments 1 to 12, wherein the silicone hydrogel contact lens has an oxygen permeability of at least about 100 bars.

[000154] 17. The silicone hydrogel contact lens of any one of embodiments 1 to 16, wherein the silicone hydrogel contact lens has an equilibrium water content of about 43% to about 65% in Weight.

[000155] 18. The silicone hydrogel contact lens of any one of embodiments 1 to 16, wherein the silicone hydrogel contact lens has an equilibrium water content of about 45% to about 60% in Weight.

[000156] 19. The silicone hydrogel contact lens of any one of embodiments 1 to 18, wherein the silicone hydrogel contact lens has an elastic modulus of about 0.3 MPa to about 1.2 MPa or less.

[000157] 20. The silicone hydrogel contact lens of any one of embodiments 1 to 18, wherein the silicone hydrogel contact lens has an elastic modulus of about 0.4 MPa to about 1.0 MPa or less.

[000158] 21. The silicone hydrogel contact lens of any one of embodiments 1 to 20, wherein the first vinyl polysiloxane crosslinker has a number average molecular weight of about 4,000 to about 40,000 Daltons.

[000159] 22. The silicone hydrogel contact lens of any one of embodiments 1 to 20, wherein the first vinyl polysiloxane crosslinker has a number average molecular weight of about 5,000 to about 20,000 Daltons.

[000160] 23. The silicone hydrogel contact lens of any one of embodiments 1 to 22, wherein the hydrophilized siloxane units each have a methyl substituent and a monovalent C4-C40 organic radical substituent which has 2 to 6 second H-donating chemical moieties.

[000161] 24. The silicone hydrogel contact lens of any one of embodiments 1 to 23, wherein the first polysiloxane vinyl crosslinker is a compound (i.e., a vinyl crosslinker) of Formula (1) where: t)1 is an integer from 30 to 500 and ®1 is an integer from 1 to 75, since ®1/v1 is from about 0.035 to about 0.15 (preferably from about 0.040 to about 0.12, even more preferably from about 0.045 to about 0.10); X01 is O or NRn where Rn is hydrogen or C1-C10-alkyl; Ro is hydrogen or methyl; R2 and R3, independently of each other, are a substituted or unsubstituted divalent C1-C10 alkylene radical or a divalent radical of -R5-O-R6- wherein R5 and R6 independently of each other are a divalent C1-C10 alkylene radical replaced or not replaced; R4 is a monovalent radical of any one of Formula (2) to (6) p1 is zero or 1; m1 is an integer from 2 to 4; m2 is an integer from 1 to 5; m3 is an integer from 3 to 6; m4 is an integer from 2 to 5; R7 is hydrogen or methyl; R8 is a C2-C6 hydrocarbon radical that has valences (m2+1); R9 is a C2-C6 hydrocarbon radical that has valences (m4+1); R10 is ethyl or hydroxymethyl; R11 is methyl or hydromethyl; R12 is hydroxyl or methoxy; X3 is a sulfur bond of -S- or a tertiary amino bond of -NR13- wherein R13 is C1-C1 alkyl, hydroxyethyl, hydroxypropyl, or 2,3-dihydroxypropyl; eoo

[000162] X4 is an amide bond of or where R14 is hydrogen or C1-C10 alkyl.

[000163] 25. The silicone hydrogel contact lens of embodiment 24, wherein R4 is a monovalent radical of one of Formulas (2a) to (2y) where p1 is zero or an integer 1, m1 is an integer from 2 to 4, R7 is hydrogen or methyl.

[000164] 26. The silicone hydrogel contact lens of mode 25, where p1 is 1.

[000165] 27. The silicone hydrogel contact lens of the 25 or 26 modality, where m1 is 3.

[000166] 28. The silicone hydrogel contact lens of the modality of 25, 26 or 27, where R7 is hydrogen.

[000167] 29. The silicone hydrogel contact lens of embodiment 24, wherein R4 is a monovalent radical of one of Formulas (3a) to (3y)

[000168] where X4 is an amide bond of or where R14 is hydrogen or C1-C10 alkyl.

[000169] 30. The silicone hydrogel contact lens of embodiment 24, wherein R4 is a monovalent radical of Formula (4a) or (4b)

[000170] 31. The silicone hydrogel contact lens of embodiment 24, wherein R4 is a monovalent radical of one of Formulas (5a) to (5c)

[000171] 32. The silicone hydrogel contact lens of embodiment 24, in which R4 is a radical of Formula (6) in which m1 is 3 and p1 is 1.

[000172] 33. The silicone hydrogel contact lens of any one of embodiments 1 to 32, wherein the siloxane-containing vinyl monomer is a monoalkyl-terminated polysiloxane terminated in mono-(meth) acryloyl of Formula (I)

[000173] where: Ro is H or methyl; Xo is O or NR1; L1 is a divalent radical of C3-C8 alkylene or a divalent radical of L1' is a divalent radical of C2-C8 that has zero or one hydroxyl group; L1" is divalent C3-C8 alkylene radical that has zero or one hydroxyl group; ; Rt1 is a C1-C4 alkyl; , more preferably 3 to 15, even more preferably 3 to 10).

[000174] 34. The silicone hydrogel contact lens of embodiment 33, wherein the polysiloxane terminated in monoalkyl terminated in mono-(meth)acryloyl is polydimethylsiloxane terminated in w-butyl (or w-methyl) terminated in α- (meth)acryloxypropyl, polydimethylsiloxane ending in w-butyl (or w-methyl) ending in a-(meth)acryloxy-2-hydroxypropy|oxypropy|a, α-(2-hydroxyl-methacryloxypropyloxypropyl)-w-butyl-decamethylpentasiloxane, polydimethylsiloxane ending in w-butyl (or w-methyl) ending in a-[3-(meth)acryloxyethoxy-2-hydroxypropyloxypropyl], polydimethylsiloxane ending in w-butyl (or w-methyl) ending in a-[3- (meth)acryloxypropyloxy-2-hydroxypropyloxypropyl], polydimethylsiloxane terminated in w-butyl (or w-methyl) terminated in α-[3-(meth)acryloxyisopropyloxy-2-hydroxypropyloxypropyl], polydimethylsiloxane terminated in w-butyl (or w -methyl) terminated in α-[3-(meth)acryloxy-butyloxy-2-hydroxypropyloxypropyl],polydimethylsiloxane terminated in w-butyl (or w-methyl) terminated in α-[3-(meth)acryloxyethylamino-2-hydro- xypropyloxypropyl], polydimethylsiloxane ending in w-butyl (or w-methyl) ending in α-[3-(meth)acryloxypropylamino-2-hydroxypropyloxy-propyl], polydimethylsiloxane ending in w-butyl (or w-methyl) ending in α- [3-(meth)acryloxybutylamino-2-hydroxypropyloxypropyl], polydimethylsiloxane terminated in w-butyl (or w-methyl) terminated in α-(meth)acryloxy(polyethylenoxy)-2-hydroxypropyloxypropyl], polydimethylsiloxane terminated in w-butyl (or w-methyl) ending in a-[(meth)acryloxy-2-hydroxypropyloxy-ethoxypropyl], polydimethylsiloxane ending in w-butyl (or w-methyl) ending in a-[(meth)acryloxy-2-hydroxypropyl-N -ethyl-aminopropyl], polydimethylsiloxane ending in w-butyl (or w-methyl) ending in a-[(meth)acryloxy-2-hydroxypropyl-aminopropyl], polydimethylsiloxane ending in w-butyl (or w-methyl) ending in α- [(meth)acryloxy-2-hydroxypropyloxy(polyethyleneoxy)propyl], polydimethylsiloxane ending in w-butyl (or w-methyl) ending in α-(meth)acryloylamidopropyloxypropyl, w-butyl (or w-methyl) polydimethylsiloxane ending in α-N-methyl-(meth)acryloylamidopropyloxypropyl, w-butyl (or w-methyl) polydimethylsiloxane ending in α-[3-(meth)acrylamidoethoxy-2-hydroxypropyloxypropyl], polydimethylsiloxane ending in w-butyl ( or w- methyl) ending in a-[3-(meth)acrylamidopropyloxy-2-hydroxypropyloxy-propyl], polydimethylsiloxane ending in w-butyl (or w-methyl) ending in a-[3-(meth)acrylamidoisopropyloxy-2- hydroxypropyloxypropyl], polydimethylsiloxane terminated in w-butyl (or w-methyl) terminated in α-[3-(meth)acrylamidobutyloxy-2-hydroxypropyloxypropyl], w-butyl (or w-methyl) polydimethylsiloxane terminated in α-[3 -(meth)acryloylamido-2-hydroxypropyloxypropyl], polydimethylsiloxane terminated in w-butyl (or w-methyl) terminated in α-[3-[N-methyl-(meth)acryloylamido]-2-hydroxypropyloxypropyl], N-methyl-N'-(propyltetra(dimethylsiloxy)dimethylbutylsilane) (meth)acrylamide, N-(2,3-dihydroxypropane)-N'-(propyltetra(dimethylsiloxy)dimethylbutylsilane) (meth)acrylamide, (meth)acryloylamidopropyltetra(dimethylsiloxy)dimethylbutylsilane, or a mixture thereof.

[000175] 35. The silicone hydrogel contact lens of the modality of 33 or 34, where in Formula (I) n1 is an integer from 3 to 20.

[000176] 36. The silicone hydrogel contact lens of mode 33 or 34, where in Formula (I) n1 is an integer from 3 to 15.

[000177] 37. The silicone hydrogel contact lens of the modality of 33 or 34, where in Formula (I) n1 is an integer from 3 to 10.

[000178] 38. The silicone hydrogel contact lens of any one of embodiments 1 to 37, wherein the siloxane-containing vinyl monomers is a vinyl monomer that contains a tris(trimethylsilyloxy)silyl or bis(trimethylsilyloxy)alkylsilyl group.

[000179] 39. The silicone hydrogel contact lens of embodiment 38, wherein the siloxane-containing vinyl monomer is a tris(trimethylsilyloxy)silyl or bis(trimethylsilyloxy)alkylsilyl-containing vinyl monomer of Formula ( II) where: Ro is H or methyl; Xo is O or NR1; L2 is a divalent C3C8 alkylene radical or a divalent radical of either -L2-X2-L2"-, -(C2H4O)qi- L2"-, -(C2H4θ)qi-CONH-L2"-; or -L2-NHCOO- (C2H4O)qi-L2"- L2' is a divalent C2-C8 alkylene radical having zero or one hydroxyl group; L2" is divalent C3-C8 alkylene radical that has zero or one hydroxyl group; is a C1-C4 alkyl; q1 is an integer from 1 to 20, r1 is an integer from 2 or 3.

[000180] 40. The silicone hydrogel contact lens of embodiment 38 or 39, in which the vinyl monomer containing tris(trimethylsilyloxy) silyl contains or containing bis(trimethylsilyloxy)alkylsilyl is selected from the group consisting in tris(trimethyl-silyloxy)silylpropyl (meth)acrylate, [3-(meth)acryloxy-2-hydroxypropyloxy]propylbis(trimethylsiloxy) methylsilane, [3-(meth)acryloxy-2-hydroxypropyloxy]propylbis(trimethylsiloxy) xi) butylsilane, 3-(meth)acryloxy-2-(2-hydroxyethoxy)-propyloxy)propylbis(trimethylsiloxy)methylsilane, 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-methyl acrylamide, N-(2-hydroxy-3-(3-(tris( trimethylsilyloxy)silyl)propyloxy) propyl) (meth)acrylamide, and mixtures thereof.

[000181] 41. The silicone hydrogel contact lens of any one of embodiments 1 to 40, wherein the hydrophilic N-vinyl amide monomer is N-vinylpyrrolidone, N-vinyl piperidone, N-vinyl caprolactam, N-vinyl -N-methyl acetamide, N-vinyl formamide, N-vinyl acetamide, N-vinyl isopropylamide, N-vinyl-N-methyl acetamide, N-vinyl-N-ethyl acetamide, N-vinyl-N-ethyl formamide and mixtures thereof same.

[000182] 42. The silicone hydrogel contact lens of any one of embodiments 1 to 40, wherein the hydrophilic N-vinyl amide monomer is N-vinylpyrrolidone, N-vinyl-N-methyl acetamide or combinations thereof.

[000183] 43. The silicone hydrogel contact lens of any one of embodiments 1 to 42, wherein the silicone hydrogel contact lens additionally comprises repeating units of one or more non-silicone vinyl crosslinking agents.

[000184] 44. The silicone hydrogel contact lens of embodiment 43, wherein said one or more non-silicone vinyl crosslinking agents are selected from the group consisting of ethylene glycol di(meth)acrylate, di -diethylene glycol (meth)acrylate, triethylene glycol di-(meth)acrylate, tetraethylene glycol di-(meth)acrylate, glycerol di-(meth)acrylate, 1,3-propanediol di-(meth)acrylate, di- 1,3-butanediol (meth)acrylate, 1,4-butanediol di(meth)acrylate, glycerol 1,3-diglycerolate di-(meth)acrylate, ethylenebis[oxy(2-)di(meth)acrylate hydroxypropane-1,3-diyl)], bis[2-(meth)acryloxyethyl phosphate], trimethylolpropane di-(meth)acrylate, and 3,4-bis[(meth)acryloyl]tetrahydrofuran, diacrylamide, dimethacrylamide , N,N-di(meth)acryloyl-N-methylamine, N,N-di(meth)acryloyl-N-ethylamine, N,N'-methylene bis(meth)acrylamide, N,N'- ethylene bis(meth )acrylamide, N,N'-dihydroxyethylene bis(meth)acrylamide, N,N'-propylene bis(meth)acrylamide, N,N'-2-hydroxypropylene bis(meth) acrylamide, N,N'-2, 3-dihydroxybutylene bis(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 ether divinyl, triallyl isocyanurate, triallyl cyanurate, trimethylpropane trimethacrylate, pentaerythritol tetramethacrylate, bisphenol A dimethacrylate, and combinations thereof.

[000185] 45. The silicone hydrogel contact lens of embodiment 44, wherein said one or more non-silicone vinyl crosslinking agents are selected from the group consisting of tetra(ethylene glycol di-(meth)acrylate ), tri(ethylene glycol di-(meth)acrylate), ethylene glycol di-(meth)acrylate, di(ethylene glycol di-(meth)acrylate), tetraethylene glycol divinyl ether, triethylene glycol divinyl ether, diethylene glycol divinyl ether, ether divinyl ethylene glycol, triallyl isocyanurate and triallyl cyanurate.

[000186] 46. The silicone hydrogel contact lens of any one of embodiments 43 to 45, wherein the silicone hydrogel contact lens comprises about 1.0% or less by weight of repeat units of said one or more non-silicone vinyl crosslinking agents, in relation to the dry weight of the silicone hydrogel contact lens.

[000187] 47. The silicone hydrogel contact lens of any one of embodiments 43 to 45, wherein the silicone hydrogel contact lens comprises about 0.8% or less by weight of repeat units of said one or more non-silicone vinyl crosslinking agents, in relation to the dry weight of the silicone hydrogel contact lens.

[000188] 48. The silicone hydrogel contact lens of any one of embodiments 43 to 45, wherein the silicone hydrogel contact lens comprises from about 0.05% to about 0.6% by weight of repeating units of said one or more non-silicone vinyl crosslinking agents, relative to the dry weight of the silicone hydrogel contact lens.

[000189] 49. The silicone hydrogel contact lens of any one of embodiments 1 to 48, wherein the silicone hydrogel contact lens additionally comprises repeating units of a blending vinyl monomer.

[000190] 50. The silicone hydrogel contact lens of the modality of 49, in which the blending vinyl monomer is a C1-C10 alkyl (meth)acrylate, cyclopentylacrylate, cyclohexylmethacrylate, cyclohexylacrylate, (met) isobornyl acrylate, styrene, 4,6-trimethylstyrene (TMS), t-butyl styrene (TBS), trifluoroethyl (meth)acrylate, hexafluoro-isopropyl (meth)acrylate, hexafluorobutyl (meth)acrylate or combinations thereof.

[000191] 51. The silicone hydrogel contact lens of the 49 modality, in which the blending vinyl monomer is methyl methacrylate.

[000192] 52. The silicone hydrogel contact lens of any one of embodiments 49 to 51, wherein the silicone hydrogel contact lens comprises about 25% or less by weight of repeating units of the blending vinyl monomer , in relation to the dry weight of the silicone hydrogel contact lens.

[000193] 53. The silicone hydrogel contact lens of any one of embodiments 49 to 51, wherein the silicone hydrogel contact lens comprises about 20% or less by weight of repeating units of the blending vinyl monomer , in relation to the dry weight of the silicone hydrogel contact lens.

[000194] 54. The silicone hydrogel contact lens of any one of embodiments 49 to 51, wherein the silicone hydrogel contact lens comprises about 15% or less by weight of repeating units of the blending vinyl monomer , in relation to the dry weight of the silicone hydrogel contact lens.

[000195] 55. The silicone hydrogel contact lens of any one of embodiments 1 to 54, wherein the silicone hydrogel contact lens additionally comprises repeating units of at least one UV-absorbing vinyl monomer.

[000196] 56. The silicone hydrogel contact lens of embodiment 55, wherein the silicone hydrogel contact lens additionally comprises repeating units of at least one UV/HEVL absorbing vinyl monomer.

[000197] 57. The silicone hydrogel contact lens of any one of embodiments 1 to 56, wherein the silicone hydrogel contact lens additionally comprises the repeating units of 2-[2'-hydroxy-5'- (2-methacryloxyethyl)phenyl)]-2H-benzotriazole (Norbloc) and repeating units of at least one UV/HEVL absorbing vinyl monomer selected from the group consisting of 2-{2'-hydroxy-3'-tert -butyl-5'-[3'-methacryloyloxypropoxy]phenyl}-2H-benzotriazole, 2-{2'-hydroxy-3'-tert-butyl-5'-[3'-methacryloyloxypropoxy]phenyl}-5-methoxy- 2H-benzotriazole (UV13), 2-{2'-hydroxy-3'-tert-butyl-5'-[3'-methacryloyloxypropoxy] phenyl}-5-chloro-2H-benzotriazole (UV28), 2-[ 2'-hydroxy-3'-tert-butyl-5'-(3'-acryloyloxypropoxy)phenyl]-5-trifluoromethyl-2H-benzotriazole (UV23), and combinations thereof.

[000198] 58. The silicone hydrogel contact lens of any one of embodiments 1 to 57, wherein the silicone hydrogel contact lens is characterized by having a UVB transmittance of about 10% or less between 280 nm and 315 nm and a UVA transmittance of about 30% or less between 315 nm and 380 nm and a Violet transmittance of about 70% or less between 380 nm and 440 nm.

[000199] 59. The silicone hydrogel contact lens of embodiment 58, wherein the silicone hydrogel contact lens is characterized by having a UVB transmittance of about 5% or less between 280 nm and 315 nm.

[000200] 60. The silicone hydrogel contact lens of embodiment 58, wherein the silicone hydrogel contact lens is characterized by having UVB transmittance of about 2.5% or less between 280 nm and 315 nm .

[000201] 61. The silicone hydrogel contact lens of embodiment 58, wherein the silicone hydrogel contact lens is characterized by having a UVB transmittance of about 1% or less between 280 nm and 315 nm.

[000202] 62. The silicone hydrogel contact lens of any one of embodiments 58 to 61, wherein the silicone hydrogel contact lens is characterized by having UVA transmittance of about 20% or less between 315 nm and 380 nm of any of embodiments 58 to 61.

[000203] 63. The silicone hydrogel contact lens of any one of embodiments 58 to 61, wherein the silicone hydrogel contact lens is characterized by having UVA transmittance of about 10% or less between 315 nm and 380nm.

[000204] 64. The silicone hydrogel contact lens of any one of embodiments 58 to 61, wherein the silicone hydrogel contact lens is characterized by having UVA transmittance of about 5% or less between 315 nm and 380nm.

[000205] 65. The silicone hydrogel contact lens of any one of embodiments 58 to 64, wherein the silicone hydrogel contact lens is characterized by having Violet transmittance of about 60% or less between 380 nm and 440nm.

[000206] 66. The silicone hydrogel contact lens of any one of embodiments 58 to 64, wherein the silicone hydrogel contact lens is characterized by having Violet transmittance of about 50% or less, even more preferably about 40% or less) between 380 nm and 440 nm.

[000207] 67. The silicone hydrogel contact lens of any one of embodiments 58 to 64, wherein the silicone hydrogel contact lens is characterized by having Violet transmittance of about 40% or less between 380 nm and 440nm.

[000208] 68. The silicone hydrogel contact lens of any one of embodiments 1 to 67, wherein the silicone hydrogel contact lens additionally comprises repeating units of one or more hydrophilic acrylic monomers selected from the group consisting in N,N-dimethyl (meth)acrylamide, (meth)acrylamide, N-hydroxylethyl (meth)acrylamide, N-hydroxypropyl (meth)acrylamide, hydroxyethyl (meth)acrylate, glycerol methacrylate (GMA), polyethylene glycol ( meth)acrylate having a number average molecular weight of up to 1,500, C1-C4-alkyl polyethylene glycol ether (meth)acrylate having a number average molecular weight of up to 1,500, N-[tris(hydroxymethyl)methyl]-acrylamide, (meth)acrylic acid, ethylacrylic acid, and combinations thereof.

[000209] 69. The silicone hydrogel contact lens of any one of embodiments 1 to 68, wherein the silicone hydrogel contact lens additionally comprises repeating units of one or more hydrophilic acrylic monomers selected from the group consisting in N,N-dimethyl (meth)acrylamide, hydroxyethyl (meth)acrylate, N-hydroxylethyl (meth)acrylamide, glycerol methacrylate (GMA), and combinations thereof.

[000210] 70. The silicone hydrogel contact lens of embodiment 68 or 69, wherein the silicone hydrogel contact lens comprises about 10% or less by weight of repeating units of said one or more acrylic monomers hydrophilic, in relation to the dry weight of the silicone hydrogel contact lens.

[000211] 71. The silicone hydrogel contact lens of embodiment 68 or 69, wherein the silicone hydrogel contact lens comprises about 8% or less by weight of repeating units of said one or more acrylic monomers hydrophilic, in relation to the dry weight of the silicone hydrogel contact lens.

[000212] 72. The silicone hydrogel contact lens of embodiment 68 or 69, wherein the silicone hydrogel contact lens comprises about 5% or less by weight of repeating units of said one or more acrylic monomers hydrophilic, in relation to the dry weight of the silicone hydrogel contact lens.

[000213] 73. The silicone hydrogel contact lens of any one of embodiments 1 to 72, wherein the silicone hydrogel contact lens comprises about 60% or more by weight of the first, second and third repeat units together, in relation to the dry weight of the silicone hydrogel contact lens.

[000214] 74. The silicone hydrogel contact lens of any one of embodiments 1 to 72, wherein the silicone hydrogel contact lens comprises about 65% or more by weight of the first, second and third repeat units together, in relation to the dry weight of the silicone hydrogel contact lens.

[000215] 75. The silicone hydrogel contact lens of any one of embodiments 1 to 72, wherein the silicone hydrogel contact lens comprises about 70% or more by weight of the first, second and third repeat units together, in relation to the dry weight of the silicone hydrogel contact lens.

[000216] 76. The silicone hydrogel contact lens of any one of embodiments 1 to 72, wherein the silicone hydrogel contact lens comprises about 75% or more by weight of the first, second and third repeat units together, in relation to the dry weight of the silicone hydrogel contact lens.

[000217] 77. A method for producing inherently wettable silicone hydrogel contact lenses comprising the steps of: (1) preparing a polymerizable composition that is clear at room temperature, wherein the polymerizable composition comprises (a) at least one siloxane-containing vinyl monomer including 0 to 10 first H-donating chemical moieties, (b) at least one first polysiloxane vinyl crosslinker having a number average molecular weight of about 3,000 Daltons to about 80,000 Daltons and comprising (i) two terminal (meth)acryloyl groups, (ii) at least one polysiloxane segment comprising dimethylsiloxane units and hydrophilized siloxane units, each having a methyl substituent and a C4-C40 organic radical substituent monovalent having one or more second H-donating chemical moieties, and (iii) from 0 to 20 third H-donating chemical moieties that are integral parts of molecular structures outside the polysiloxane segment, (c) at least one N-monomer hydrophilic vinyl amide, (d) optionally at least one second polysiloxane vinyl crosslinker having 0 to 35 H-donating chemical moieties, and (e) at least one free radical initiator, wherein the first and second crosslinkers polysiloxane vinyls are different from each other, in that the first, second, third and fourth H-donating chemical moieties independent of each other are hydroxyl groups, carboxyl groups, amino groups of -NHR°, amino bonds of -NH-, -CONH- amide bonds, -OCONH- urethane bonds, or combinations thereof, wherein R° is H or a C1-C4 alkyl, wherein the polymerizable composition comprises at least 8.8 mmols of component (c ) per gram of all components (a), (b) and (d) in total (i.e. and at least 0.11 meqs of all first, second, third and fourth H-donating chemical moieties in total per gram of component (c) (i.e. (2) introducing the polymerizable composition into a lens mold; and (3) thermally or actinically curing the polymerizable composition in the lens mold to form a silicone hydrogel contact lens, wherein the silicone hydrogel contact lens has an oxygen permeability of at least 50 bar, a elastic modulus of about 0.2 MPa to about 1.5 MPa, and an equilibrium water content of about 40% to about 70% and is inherently wettable as characterized by having a water break-up time of at least least 10 seconds and a water contact angle per captive bubble of about 80 degrees or less without being subjected to any post-cure surface treatment.

[000218] 78. The method of embodiment 77, wherein the polymerizable composition comprises at least 9.0 mmols of component (c) per gram of all components (a), (b) and (d) in total.

[000219] 79. The method of embodiment 77, wherein the polymerizable composition comprises at least 9.2 mmols of component (c) per gram of all components (a), (b) and (d) in total.

[000220] 80. The method of embodiment 77, wherein the polymerizable composition comprises at least 9.6 mmols of component (c) per gram of all components (a), (b) and (d) in total.

[000221] 81. The method of any one of embodiments 77 to 80, wherein the polymerizable composition comprises at least 0.15 milliequivalents of all first, second, third and fourth H-donating chemical moieties in total per gram of component (c).

[000222] 82. The method of any one of embodiments 77 to 80, wherein the polymerizable composition comprises at least 0.20 milliequivalents of all first, second, third and fourth H-donating chemical moieties in total per gram of component (c).

[000223] 83. The method of any one of embodiments 77 to 80, wherein the polymerizable composition comprises at least 0.25 milliequivalents of all first, second, third and fourth H-donating chemical moieties in total per gram of component (c).

[000224] 84. The method of any one of embodiments 77 to 83, wherein the silicone hydrogel contact lens has a water break-up time of at least 15 seconds without being subjected to any post-cure surface treatment.

[000225] 85. The method of any one of embodiments 77 to 83, wherein the silicone hydrogel contact lens has a water break-up time of at least 20 seconds without being subjected to any post-cure surface treatment.

[000226] 86. The method of any one of embodiments 77 to 85, wherein the silicone hydrogel contact lens has a captive bubble water contact angle of about 75 degrees or less without being subjected to any heat treatment. post-cure surface.

[000227] 87. The method of any one of embodiments 77 to 85, wherein the silicone hydrogel contact lens has a captive bubble water contact angle of about 70 degrees or less without being subjected to any heat treatment. post-cure surface.

[000228] 88. The method of any one of embodiments 77 to 85, wherein the silicone hydrogel contact lens has a captive bubble water contact angle of about 65 degrees or less without being subjected to any heat treatment. post-cure surface.

[000229] 89. The method of any one of embodiments 77 to 88, wherein the silicone hydrogel contact lens has an oxygen permeability of at least about 60 bars.

[000230] 90. The method of any one of embodiments 77 to 88, wherein the silicone hydrogel contact lens has an oxygen permeability of at least about 70 bars.

[000231] 91. The method of any one of embodiments 77 to 88, wherein the silicone hydrogel contact lens has an oxygen permeability of at least about 80 bars.

[000232] 92. The method of any one of embodiments 77 to 88, wherein the silicone hydrogel contact lens has an oxygen permeability of at least about 100 bars.

[000233] 93. The method of any one of embodiments 77 to 92, wherein the silicone hydrogel contact lens has an equilibrium water content of about 43% to about 65% by weight.

[000234] 94. The method of any one of embodiments 77 to 92, wherein the silicone hydrogel contact lens has an equilibrium water content of about 45% to about 60% by weight.

[000235] 95. The method of any one of embodiments 77 to 94, wherein the silicone hydrogel contact lens has an elastic modulus of about 0.3 MPa to about 1.2 MPa or less.

[000236] 96. The method of any one of embodiments 77 to 94, wherein the silicone hydrogel contact lens has an elastic modulus of about 0.4 MPa to about 1.0 MPa or less.

[000237] 97. The method of any one of embodiments 77 to 96, wherein the first vinyl polysiloxane crosslinker has a number average molecular weight of about 4,000 to about 40,000 Daltons.

[000238] 98. The method of any one of embodiments 77 to 96, wherein the first vinyl polysiloxane crosslinker has a number average molecular weight of about 5,000 to about 20,000 Daltons.

[000239] 99. The method of any one of embodiments 77 to 96, wherein the hydrophilized siloxane units each have a methyl substituent and a monovalent C4-C40 organic radical substituent that is 2 to 6 seconds H-donating chemical moieties.

[000240] 100. The method of any one of embodiments 77 to 99, wherein the first polysiloxane vinyl crosslinker is a compound (i.e., a vinyl crosslinker) of Formula (1) on what:

[000241] υ1 is an integer from 30 to 500 and ω1 is an integer from 1 to 75, since ®1/v1 is from about 0.035 to about 0.15 (preferably from about 0.040 to about 0 .12, even more preferably from about 0.045 to about 0.10);

[000242] X01 is O or NRn where Rn is hydrogen or C1-C10-alkyl;

[000243] Ro is hydrogen or methyl;

[000244] R2 and R3, independently of each other, are a substituted or unsubstituted C1-C10 alkylene divalent radical or a divalent radical of -R5-O-R6- in which R5 and R6 independently of each other are a C1 divalent radical -C10 substituted or unsubstituted alkylene;

[000245] R4 is a monovalent radical of any one of Formula (2) to (6)

[000246] p1 is zero or 1; m1 is an integer from 2 to 4; m2 is an integer from 1 to 5; m3 is an integer from 3 to 6; m4 is an integer from 2 to 5;

[000247] R7 is hydrogen or methyl;

[000248] R8 is a C2-C6 hydrocarbon radical that has valences (m2+1);

[000249] R9 is a C2-C6 hydrocarbon radical that has valences (m4+1);

[000250] R10 is ethyl or hydroxymethyl;

[000251] R11 is methyl or hydromethyl;

[000252] R12 is hydroxyl or methoxy;

[000253] and the the

[000254] X4 is an amide bond of or where R14 is hydrogen or C1-C10 alkyl.

[000255] 101. The method of modality 100, wherein R4 is a monovalent radical of one of Formula (2a) to (2y) where p1 is zero or an integer 1, m1 is an integer from 2 to 4, R7 is hydrogen or methyl.

[000256] 102. The method of embodiment 101, where p1 is 1.

[000257] 103. The method of modality 101 or 102, where m1 is 3.

[000258] 104. The method of embodiment 101, 102 or 103, wherein R7 is hydrogen.

[000259] 105. The method of modality 96, wherein R4 is a monovalent radical of one of Formula (3a) to (3y)

[000260] where X4 is an amide bond of or where R14 is hydrogen or C1-C10 C-NR14- where R14 is hydrogen or C1-C10 alkyl.

[000261] 106. The method of modality 100, wherein R4 is a monovalent radical of Formula (4a) or (4b)

[000262] 107. The method of modality 100, wherein R4 is a monovalent radical of one of Formula (5a) to (5c)

[000263] 108. The method of modality 100, in which R4 is a radical of Formula (6) in which m1 is 3 and p1 is 1.

[000264] 109. The method of any one of embodiments 77 to 108, wherein the siloxane-containing vinyl monomer is a monoalkyl-terminated mono-(meth)acryloyl-terminated polysiloxane of Formula (I)

[000265] where: Ro is H or methyl; Xo is O or NR1; L1 is a divalent radical of C3-C8 alkylene or a divalent radical of L1' is a sick radical of C2-C8 having zero or one hydroxyl group; L1" is divalent C3-C8 alkylene radical that has zero or one hydroxyl group; ; Rt1 is a C1-C4 alkyl; X1' is O or NR1; q1 is an integer from 1 to 20; q2 is an integer from 0 to 20; n1 is an integer from 3 to 25.

[000266] 110. The method of modality 109, in which the monoalkyl-terminated polysiloxane terminated in mono-(meth)acryloyl is polydimethylsiloxane terminated in w-butyl (or w-methyl) terminated in α-(meth)acryloxypropyl, polydimethylsiloxane ending in w-butyl (or w-methyl) ending in a-(meth)acryloxy-2-hydroxypropyloxypropyl, α-(2-hydroxyl-methacryloxypropyloxypropyl)-w-butyl-decamethylpentasiloxane, polydimethylsiloxane ending in w-butyl ( or w-methyl) terminated in α-[3-(meth)acryloxyethoxy-2-hydroxypropyloxypropyl], polydimethylsiloxane terminated in w-butyl (or w-methyl) terminated in α-[3-(meth)acryloxypropyloxy-2- hydroxypropyloxypropyl], polydimethylsiloxane ending in w-butyl (or w-methyl) ending in a-[3-(meth)acryloxyisopropyloxy-2-hydroxypropyloxypropyl], polydimethylsiloxane ending in w-butyl (or w-methyl) ending in a-[3 -(meth)acryloxybutyloxy-2-hydroxypropyloxypropyl], polydimethylsiloxane terminated in w-butyl (or w-methyl) terminated in α-[3-(meth)acryloxyethylamino-2-hydroxypropyloxypropyl], polydimethylsiloxane terminated in w-butyl (or w-methyl) terminated in α-[3-(meth)acryloxypropylamino-2-hydroxypropyloxypropyl], polydimethylsiloxane terminated in w-butyl (or w-methyl) terminated in α-[3-(meth)acryloxybutylamino-2 -hydroxypropyloxypropyl], polydimethylsiloxane ending in w-butyl (or w-methyl) ending in α-(meth) acrylo- oxy(polyethyleneoxy)-2-hydroxypropyloxypropyl], polydimethylsiloxane ending in w-butyl (or w-methyl) ending in a -[(meth)acryloxy-2-hydroxypropyloxy-ethoxypropyl], polydimethylsiloxane ending in w-butyl (or w-methyl) ending in a-[(meth)acryloxy-2-hydroxypropyl-N-ethylamino-propyl], polydimethylsiloxane terminated in w-butyl (or w-methyl) terminated in a-[(meth)acryloxy-2-hydroxypropyl-aminopropyl], polydimethylsiloxane terminated in w-butyl (or w-methyl) terminated in α-[(met) acryloxy-2-hydroxypropyloxy(polyethyleneoxy)propyl], polydimethylsiloxane terminated in w-butyl (or w-methyl) terminated in α-(meth) acryloylamidopropyloxypropyl, w-butyl (or w-methyl) polydimethylsiloxane terminated in α- N-methyl-(meth)acryloylamidopropyloxypropyl, w-butyl (or w-methyl) polydimethylsiloxane terminated in a-[3-(meth)acrylamidoethoxy-2-hydroxypropyloxypropyl], polydimethylsiloxane terminated in w-butyl (or w- methyl) ending in a-[3-(meth)acrylamidopropyloxy-2-hydroxypropyloxypropyl], polydimethylsiloxane ending in w-butyl (or w-methyl) ending in a-[3-(meth)acrylamidoisopropyloxy-2-hydroxypropyloxypropyl], polydimethyl- siloxane terminated in w-butyl (or w-methyl) terminated in α-[3-(meth)acrylamidobutyloxy-2-hydroxypropyloxypropyl], w-butyl (or w-methyl) polydimethylsiloxane terminated in α-[3-(meth)acryloylamido -2-hydroxypropyloxypropyl], polydimethylsiloxane terminated in w-butyl (or w-methyl) terminated in α-[3-[N-methyl-(meth)acryloylamido]-2-hydroxypropyloxypropyl], N-methyl-N '-(propyltetra(dimethylsiloxy)dimethylbutylsilane) (meth)acrylamide, N-(2,3-dihydroxypropane)-N'-(propyltetra(dimethylsiloxy)dimethylbutylsilane) (meth)acrylamide, (meth)acryloylamidopropyltetra( dimethylsiloxy) dimethylbutylsilane, or a mixture thereof.

[000267] 111. The method of modality 109 or 110, where in Formula (I) n1 is an integer from 3 to 20.

[000268] 112. The method of modality 109 or 110, wherein in Formula (I) n1 is an integer from 3 to 15.

[000269] 113. The method of modality 109 or 110, wherein in Formula (I) n1 is an integer from 3 to 10.

[000270] 114. The method of any one of embodiments 77 to 113, wherein the siloxane-containing vinyl monomers are a vinyl monomer that contains a tris (trimethylsilyloxy)silyl or bis (trimethylsilyloxy)alkylsilyl group.

[000271] 115. The method of embodiment 114, wherein the siloxane-containing vinyl monomer is a tris(trimethylsilyloxy)silyl-containing vinyl monomer or bis(trimethylsilyloxy)alkylsilyl-containing vinyl monomer of Formula (II) where: Ro is H or methyl; Xo is O or NR1; L2 is a divalent C3C8 alkylene radical or a divalent radical of either -L2-X2-L2"-, -(C2H4O)qi- L2"-, -(C2H4θ)qi-CONH-L2"-; or -L2-NHCOO- (C2H4O)qi-L2"- L2' is a divalent C2-C8 alkylene radical having zero or one hydroxyl group; L2" is divalent C3-C8 alkylene radical that has zero or one hydroxyl group; is a C1-C4 alkyl; q1 is an integer from 1 to 20, r1 is an integer from 2 or 3.

[000272] 116. The method, of modality 114 or 115, in which the vinyl monomer containing tris(trimethylsilyloxy)silyl or containing bis(trimethylsilyloxy)alkylsilyl is selected from the group consisting of tris (meth)acrylate (trimethylsilyloxy)silylpropyl, [3-(meth)acryloxy-2-hydroxypropyloxy]propylbis(trimethylsiloxy)methylsilane, [3-(meth)acryloxy-2-hydroxypropyloxy]propylbis(trimethylsiloxy)butylsilane, 3-(meth)acryloxy- 2-(2-hydroxyethoxy)-propyloxy)propylbis(trimethylsiloxy)methylsilane, N-[tris(trimethyl-siloxy)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-methyl acrylamide, N-(2-hydroxy-3-(3-(tris(trimethylsilyloxy)silyl)propyloxy)propyl ) (meth)acrylamide, and mixtures thereof.

[000273] 117. The method of any one of embodiments 77 to 116, wherein the hydrophilic N-vinyl amide monomer is N-vinylpyrrolidone, N-vinyl piperidone, N-vinyl caprolactam, N-vinyl-N-methyl acetamide, N-vinyl formamide, N-vinyl acetamide, N-vinyl isopropylamide, N-vinyl-N-methyl acetamide, N-vinyl-N-ethyl acetamide, N-vinyl-N-ethyl formamide and mixtures thereof.

[000274] 118. The method of any of embodiments 77 to 116, wherein the hydrophilic N-vinyl amide monomer is N-vinylpyrrolidone, N-vinyl-N-methyl acetamide or combinations thereof.

[000275] 119. The method of any one of embodiments 77 to 118, wherein the polymerizable composition additionally comprises one or more non-silicone vinyl crosslinking agents.

[000276] 120. The method of embodiment 119, wherein said one or more non-silicone vinyl crosslinking agents are selected from the group consisting of ethylene glycol di-(meth)acrylate, diethylene glycol di-(meth)acrylate , triethylene glycol di-(meth)acrylate, tetraethylene glycol di-(meth)acrylate, glycerol di-(meth)acrylate, 1,3-propanediol di-(meth)acrylate, 1-di(meth)acrylate, 3-butanediol, 1,4-butanediol di-(meth)acrylate, glycerol 1,3-diglycerolate di-(meth)acrylate, ethylenebis[oxy(2-hydroxypropane-1,3-diyl)] di-( meth)acrylate, bis[2-(meth)acryloxyethyl phosphate], trimethylolpropane di(meth)acrylate, 3,4-bis[(meth)acryloyl]tetrahydrofuran, diacrylamide, dimethacrylamide, N,N-di( met) acryloyl-N-methylamine, N,N-di(meth)acryloyl-N-ethylamine, N,N'-methylene bis(meth)acrylamide, N,N'-ethylene bis(meth)acrylamide, N,N' -dihydroxyethylene bis(meth)acrylamide, N,N'-propylene bis(meth)acrylamide, N,N'-2-hydroxypropylene bis(meth)acrylamide, N,N'-2,3-dihydroxybutylene bis(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, trimethylpropane trimethacrylate, pentaerythritol tetramethacrylate, bisphenol A dimethacrylate, and combinations thereof.

[000277] 121. The method of embodiment 120, wherein said one or more non-silicone vinyl crosslinking agents are selected from the group consisting of tetra(ethylene glycol) di-(meth)acrylate, di-(meth) tri(ethylene glycol) acrylate, ethylene glycol di(meth)acrylate, di(ethylene glycol di(meth)acrylate), tetraethylene glycol divinyl ether, triethylene glycol divinyl ether, diethylene glycol divinyl ether, ethylene glycol divinyl ether, triallyl isocyanurate and triallyl.

[000278] 122. The method of any one of embodiments 119 to 121, wherein the polymerizable composition comprises about 1.0% or less by weight of said one or more non-silicone vinyl crosslinking agents, relative to the total amount of all polymerizable components in the polymerizable composition.

[000279] 123. The method of any one of embodiments 119 to 121, wherein the polymerizable composition comprises about 0.8% or less by weight of said one or more non-silicone vinyl crosslinking agents, relative to the total amount of all polymerizable components in the polymerizable composition.

[000280] 124. The method of any one of embodiments 119 to 121, wherein the polymerizable composition comprises from about 0.05% to about 0.6% by weight of said one or more vinyl crosslinking agents of non-silicone, relative to the total amount of all polymerizable components in the polymerizable composition.

[000281] 125. The method of any one of embodiments 77 to 124, wherein the polymerizable composition additionally comprises a blending vinyl monomer.

[000282] 126. The method of modality 125, in which the blending vinyl monomer is a C1-C10 alkyl (meth) acrylate, cyclopentylacrylate, cyclohexyl methacrylate, cyclohexyl acrylate, isobornyl (meth) acrylate , styrene, 4,6-trimethylstyrene (TMS), t-butyl styrene (TBS), trifluoroethyl (meth) acrylate, hexafluoro-isopropyl (meth) acrylate, hexafluorobutyl (meth) acrylate or combinations thereof.

[000283] 127. The method of embodiment 125, in which the blending vinyl monomer is methyl methacrylate.

[000284] 128. The method of any one of embodiments 125 to 127, wherein the polymerizable composition comprises about 25% or less by weight of the blending vinyl monomer, relative to the total amount of all polymerizable components in the polymerizable composition.

[000285] 129. The method of any one of embodiments 125 to 127, wherein the polymerizable composition comprises about 20% or less by weight of the blending vinyl monomer, relative to the total amount of all polymerizable components in the polymerizable composition.

[000286] 130. The method of any one of embodiments 125 to 127, wherein the polymerizable composition comprises about 15% or less by weight of the blending vinyl monomer, relative to the total amount of all polymerizable components in the polymerizable composition.

[000287] 131. The method of any one of embodiments 77 to 130, wherein the polymerizable composition additionally comprises at least one UV-absorbing vinyl monomer.

[000288] 132. The method of embodiment 131, wherein the polymerizable composition additionally comprises at least one UV/HEVL absorbing vinyl monomer.

[000289] 133. The method of any one of embodiments 77 to 132, wherein the polymerizable composition further comprises 2-[2'-hydroxy-5'-(2-methacryloxyethyl)phenyl)]-2H-benzotriazole (Norbloc) and at least one UV/HEVL absorbing vinyl monomer selected from the group consisting of 2-{2'-hydroxy-3'-tert-butyl-5'-[3'-methacryloyloxypropoxy]phenyl}-2H-benzotriazole , 2-{2'-hydroxy-3'-tert-butyl-5'-[3'-methacryloyloxypropoxy]phenyl}-5-methoxy-2H-benzotriazole (UV13), 2-{2'-hydroxy-3 '- tert-butyl-5'-[3'-methacryloyloxypropoxy]phenyl}-5-chloro-2H-benzotriazole (UV28), 2-[2'-hydroxy-3'-tert-butyl-5'-(3' -acryloyloxypropoxy)phenyl]-5-trifluoromethyl-2H-benzotriazole (UV23), and combinations thereof.

[000290] 134. The method of any one of embodiments 77 to 133, wherein the silicone hydrogel contact lens is characterized by having a UVB transmittance of about 10% or less between 280 and 315 nanometers and a transmittance of UVA of about 30% or less between 315 and 380 nanometers and a Violet transmittance of about 70% or less between 380 nm and 440 nm.

[000291] 135. The method of embodiment 134, wherein the silicone hydrogel contact lens is characterized by having a UVB transmittance of about 5% or less between 280 and 315 nanometers.

[000292] 136. The method of embodiment 134, wherein the silicone hydrogel contact lens is characterized by having a UVB transmittance of about 2.5% or less between 280 and 315 nanometers.

[000293] 137. The method of embodiment 134, wherein the silicone hydrogel contact lens is characterized by having a UVB transmittance of about 1% or less between 280 and 315 nanometers.

[000294] 138. The method of any one of embodiments 134 to 137, wherein the silicone hydrogel contact lens is characterized by having UVA transmittance of about 20% or less between 315 and 380 nanometers.

[000295] 139. The method of any one of embodiments 134 to 137, wherein the silicone hydrogel contact lens is characterized by having UVA transmittance of about 10% or less between 315 and 380 nanometers.

[000296] 140. The method of any one of embodiments 134 to 137, wherein the silicone hydrogel contact lens is characterized by having UVA transmittance of about 5% or less between 315 and 380 nanometers.

[000297] 141. The method of any one of embodiments 134 to 140, wherein the silicone hydrogel contact lens is characterized by having Violet transmittance of about 60% or less between 380 nm and 440 nm.

[000298] 142. The method of any one of embodiments 134 to 140, wherein the silicone hydrogel contact lens is characterized by having Violet transmittance of about 50% or less between 380 nm and 440 nm.

[000299] 143. The method of any one of embodiments 134 to 140, wherein the silicone hydrogel contact lens is characterized by having Violet transmittance of about 40% or less between 380 nm and 440 nm.

[000300] 144. The method of any one of embodiments 77 to 143, wherein the polymerizable composition additionally comprises one or more hydrophilic acrylic monomers selected from the group consisting of N,N-dimethyl (meth) acrylamide, (meth) acrylamide , N-hydroxylethyl (meth)acrylamide, N-hydroxypropyl (meth)acrylamide, hydroxyethyl (meth)acrylate, glycerol methacrylate (GMA), polyethylene glycol (meth)acrylate which has a number average molecular weight of up to 1,500, ( C1-C4-alkyl polyethylene glycol ether meth)acrylate having a number average molecular weight of up to 1500, N-[tris(hydroxymethyl)methyl]-acrylamide, (meth)acrylic acid, ethylacrylic acid, and combinations thereof .

[000301] 145. The method of any one of embodiments 77 to 144, wherein the polymerizable composition additionally comprises one or more hydrophilic acrylic monomers selected from the group consisting of N,N-dimethyl (meth) acrylamide, (meth) acrylate hydroxyethyl, N-hydroxylethyl (meth)acrylamide, glycerol methacrylate (GMA), and combinations thereof.

[000302] 146. The method of embodiment 144 or 145, wherein the polymerizable composition comprises about 10% or less by weight of said one or more hydrophilic acrylic monomers, relative to the total amount of all polymerizable components in the polymerizable composition .

[000303] 147. The method of embodiment 144 or 145, wherein the polymerizable composition comprises about 8% or less by weight of said one or more hydrophilic acrylic monomers, relative to the total amount of all polymerizable components in the polymerizable composition .

[000304] 148. The method of embodiment 144 or 145, wherein the polymerizable composition comprises about 5% or less by weight of said one or more hydrophilic acrylic monomers, relative to the total amount of all polymerizable components in the polymerizable composition .

[000305] 149. The method of any one of embodiments 77 to 148, wherein the polymerizable composition comprises about 60% or more by weight of components (a), (b) and (c) together, relative to the amount total of all polymerizable components in the polymerizable composition.

[000306] 150. The method of any one of embodiments 77 to 148, wherein the polymerizable composition comprises about 65% or more by weight of components (a), (b) and (c) together, relative to the amount total of all polymerizable components in the polymerizable composition.

[000307] 151. The method of any one of embodiments 77 to 148, wherein the polymerizable composition comprises about 70% or more by weight of components (a), (b) and (c) together, relative to the amount total of all polymerizable components in the polymerizable composition.

[000308] 152. The method of any one of embodiments 77 to 148, wherein the silicone hydrogel contact lens comprises about 75% or more by weight of components (a), (b) and (c) together , relative to the total amount of all polymerizable components in the polymerizable composition.

[000309] 153. The method of any one of embodiments 77 to 152, wherein the polymerizable composition is clear at a temperature of about 0 to about 4 °C.

[000310] The foregoing disclosure will allow one skilled in the art to practice the invention. Several modifications, variations and combinations can be made in the different modalities described in this document. In order to allow the reader to better understand the specific modalities and their advantages, reference to the following examples is suggested. It is intended that the descriptive report and examples are considered as examples.

EXAMPLE 1 OXYGEN PERMEABILITY MEASUREMENTS

[000311] Except where specified, the apparent oxygen permeability (Dkapp), the apparent oxygen transmissibility (Dk /t), the intrinsic (or edge-corrected) oxygen permeability (Dki or Dkc) of a lens and a lens material lens are determined according to the procedures described in Example 1 of U.S. Patent Application Publication No. 2012-0026457 A1.

SURFACE WETABILITY TESTS

[000312] The water contact angle (WCA) on a contact lens is a general measurement of the surface wettability of a contact lens. In particular, a low water contact angle corresponds to the most wettable surface. Captive bubble contact angles of contact lenses are measured using an FDS instrument device available from FDS Future Digital Scientific Corp. The FDS equipment is capable of measuring forward and backward contact angles. The measurement is carried out on contact lenses hydrated at room temperature. A contact lens is removed from the vial and soaked in ~40 mL of fresh phosphate-buffered saline (PBS) and shaken for at least 30 minutes, then replaced with fresh PBS, soaked and shaken for another 30 minutes. minutes, except where otherwise specified. The contact lens is then placed on lens paper and rubbed to remove surface water before being placed on top of a lens holder with the front curve upwards, and then tightening the lens holder on top. Place the clamped lens holder into the glass cell crucible filled with filtered PBS. Place the glass cell crucible on the FDS instrument platform. Adjust the height of the platform and the syringe needle to dispense the air bubble to the lens surface. Repeat 3 dispensing/withdrawing cycles for each lens to obtain advancing and receding contact angles. The receding contact angles are reported in the examples below.

WATER BREAKTHROUGH TIME TESTS (WBUT)

[000313] The hydrophilicity of the lens surface (after autoclaving) is evaluated by determining the time required for the water film to begin to break down on the surface of the lens. Lenses that exhibit WBUT > 10 seconds are considered to have a hydrophilic surface and are expected to exhibit adequate wettability (ability to support tear film) in the eye.

[000314] The lenses are prepared for water breakthrough measurement by removing the lens from its blister with soft plastic tweezers (Menicon) and placing the lens in a beaker containing phosphate-buffered saline. The beaker contains at least 20 mL of phosphate-buffered saline per lens, with up to 3 lenses per beaker. The lenses are soaked for a minimum of 30 minutes up to 24 hours before being transferred with soft plastic forceps to a 96-well plastic tray of fresh phosphate-buffered saline.

[000315] Water breakthrough time is measured at room temperature as follows: lenses are held with soft plastic tweezers as close to the edge of the lens as possible, the base curve towards the meter, taking care that the lens Do not touch the sides of the well after it is removed from the saline solution. As illustrated schematically in Figure 1, the lens (101) is shaken once to remove excess saline and a timer is started. Ideally, the water film (120) on the curved base surface of the lens will recede from the point of contact with the tips of the tweezers (111) in a uniform circular pattern (125). When approximately 30% of the hydrated area (125) has receded, the timer is stopped and this time is recorded as the water break time (WBUT). Lenses that do not exhibit the ideal recoil pattern can be placed back in the tray and measured again after rehydrating for at least 30 seconds.

WATER BALANCE CONTENT

[000316] The equilibrium water content (EWC) of contact lenses is determined as set out below.

[000317] The amount of water (expressed as a percentage by weight) present in a hydrated hydrogel contact lens, which is completely equilibrated in saline, is determined at room temperature. Quickly stack the lenses, and transfer the stack of lenses to the aluminum tray on the analytical balance after smearing the lens on a cloth. The number of lenses for each sample tray is typically five (5). Record the weight of the tray plus the hydrated weight of the lenses. Cover the tray with aluminum foil. Place the trays in a laboratory oven at 100 ± 2 °C to dry for 16 to 18 hours. Remove the baking tray from the oven and cool in a desiccator for at least 30 minutes. Remove a single tray from the desiccator, and discard the aluminum foil. Weigh the tray plus dry lens sample on an analytical balance. Repeat for all trays. The dry and wet weight of the lens samples can be calculated by subtracting the weight of the empty weight tray.

ELASTIC MODULE

[000318] The elastic modulus of a contact lens is determined using an MTS discerning instrument. The contact lens is first cut into a 3.12 mm strip using the Precision Concept two-stage cutter. Five thickness values are measured within a useful length of 6.5 mm. The strip is mounted on the instrument's jaws and submerged in PBS (phosphate buffered saline) with the temperature controlled at 21 ± 2 °C. Typically 5N load cell is used for testing. Constant force and speed is applied to the sample until the sample breaks. Force and displacement data are collected by TestWorks software. The elastic modulus value is calculated by the TestWorks software, which is the angular coefficient or tangent of the elongation by deformation curve versus almost zero tension, in the elastic deformation region.

TRANSMITTANCE

[000319] The contact lenses are manually placed in a specially manufactured sample holder or the like that can maintain the shape of the lens as it would be when placed on the eye. This holder is then submerged in a phosphate buffered saline solution containing 1 cm path length quartz cell (PBS, pH ~7.0 to 7.4) as the reference. A UV/visible spectrophotometer, such as Varian Cary 3E UV-visible spectrophotometer with a LabSphere DRA-CA-302 beam splitter or similar, can be used for this measurement. Percent transmission spectra are collected over a wavelength range of 250 to 800 nm with % T values collected at 0.5 nm intervals. This data is transposed into an Excel spreadsheet and used to determine whether the lens conforms to class 1 UV absorbance. Transmittance is calculated using the following equations:

[000320] where the luminescence % T is the average transmission % between 380 and 780.

CHEMICALS

[000321] The following abbreviations are used in the following examples: NVP represents N-vinylpyrrolidone; DMA represents N,N-dimethylacrylamide; VMA represents N-vinyl-N-methyl acetamide; MMA represents methyl methacrylate; TEGDMA stands for triethylene glycol dimethacrylate; TEGDVE stands for triethylene glycol divinyl ether; EGMA stands for ethylene glycol methyl ether methacrylate; VAZO 64 represents 2,2'-dimethyl-2,2'azodipropiononitrile; Nobloc is 2-[3-(2H-Benzotriazol-2-yl)-4-hydroxyphenyl]ethyl methacrylate available from Aldrich; UV28 represents 2-{2'-hydroxy-3'-tert-butyl-5'-[3'-methacryloyloxypropoxy]phenyl}-5-chloro-2H-benzotriazole; RB246 is Reactive Blue 246; RB247 is Reactive Blue 247; TAA represents tert-amyl alcohol; PrOH represents 1-propanol; IPA stands for isopropanol; DC 1173 represents Darocur 1173® photoinitiator; MeCN represents acetonitrile; SiGMA represents 3-(3-methacryloxy-2-hydroxypropyloxypropyl-bis(trimethylsiloxy)methylsilane; mSi1 represents polydimethylsiloxane terminated in monomethacryloxypropyl terminated in monobutyl (Mw ~ 600 to 800 g/mol available from Gelest); mSi2 represents polydimethylsiloxane terminated in monomethacryloxypropyl terminated in monobutyl (Mw ~ 1100 g/mol available from Gelest); D3 represents polydimethylsiloxane terminated in monomethacryloxypropyl terminated in monobutyl (Mw ~ 539 g/mol available from Shin-Etsu); D6 represents polydimethylsiloxane terminated in monomethacryloxypropyl terminated in monobutyl (Mw ~ 761 g/mol available from Shin-Etsu); D9 represents polydimethylsiloxane terminated in monomethacryloxypropyl terminated in monobutyl (Mw ~ 984 g/mol available from Shin-Etsu); D7 represents polydimethylsiloxane terminated in monomethacryloxypropyl terminated in monobutyl (Mw ~ 750 g/mol available from Shin-Etsu); D8 represents polydimethylsiloxane terminated in monomethacryloxypropyl terminated in monobutyl (Mw ~ 850 g/mol available from Shin-Etsu); LM-CEPDMS represents a di-methacrylate-terminated extended-chain polydimethylsiloxane (Mn ~ 6000 g/mol), which has three polydimethylsiloxane (PDMS) segments linked via diurethane bonds between two PDMS segments and two urethane bonds each located between a terminal methacrylate group and a PDMS segment, is prepared according to a method similar to that described in Example 2 of US patent 8529057; CEPDMS represents a di-methacrylate-terminated extended-chain polydimethylsiloxane (Mn ~ 9000 g/mol), which has three polydimethylsiloxane (PDMS) segments linked via diurethane bonds between two PDMS segments and two urethane bonds each. located between a terminal methacrylate group and a PDMS segment, is prepared according to a method similar to that described in Example 2 of US patent 8529057; Betacon represents an extended-chain dimethacrylate-terminated polydimethylsiloxane (Mn ~ 5000 g/mol), which has two polydimethylsiloxane (PDMS) segments separated by a perfluoropolyether (PFPE) through diurethane bonds between PDMS and PFPE segments and two urethane linkages, each located between a terminal methacrylate group and a PDMS segment, are prepared according to a method similar to that described in Example B-1 of US patent 5,760,100; "GA" macromer represents a di-methacryloyloxypropyl-terminated polysiloxane (Mn ~ 6.8K g/mol, OH content ~ 1.2 meq/g) of Formula (A) shown above; macromer "G0" represents a di-methacryloyloxypropyl-terminated polysiloxane (Mn ~ 8.0K g/mol, OH content ~ 1.8 meq/g) of Formula (A) shown above; "G1" macromer represents a dimethacryloyloxypropyl-terminated polysiloxane (Mn ~ 10.7K g/mol, OH content ~ 1.8 meq/g) of Formula (A) shown above; "G3" macromer represents a di-methacryloyloxypropyl-terminated polysiloxane (Mn ~ 16.3K g/mol, OH content ~ 1.8 meq/g) of Formula (A) shown above; "G4" macromer represents a di-methacryloyloxypropyl-terminated polysiloxane (Mn ~ 13.5K g/mol, OH content ~ 1.8 meq/g) of Formula (A) shown above; "G5" macromer represents a dimethacryloyloxypropyl-terminated polysiloxane (Mn ~ 14.8K g/mol, OH content ~ 2.2 meq/g) of Formula (A) shown above; "G6" macromer represents a di-methacryloyloxypropyl-terminated polysiloxane (Mn ~ 17.9K g/mol, OH content ~ 2.2 meq/g) of Formula (A) shown above. All di-methacryloyloxypropyl-terminated polysiloxanes of Formula (A) are prepared according to the procedures described in U.S. Patent Application Publication No. 2017-0166673 A1.

EXAMPLE 2

[000322] A lens formulation is purged with nitrogen at room temperature for 30 to 35 minutes. The N2-purged lens formulation is introduced into polypropylene molds and thermally cured in an oven under the following curing conditions: raising the ambient temperature to a first temperature and then holding at the first temperature for a first period of time. of cure; raising the first temperature to a second temperature and holding at the second temperature for a second curing period of time; optionally raising the second temperature to a third temperature and holding at the third temperature for a third period of curing time; and optionally raising the third temperature to a fourth temperature and holding at the fourth temperature for a fourth curing time period.

[000323] The lens molds are opened using a mold release machine with a pressure pin. The lenses are pushed into the base curve molds by a push pin, and then the molds are separated into base curve mold halves and front curve mold halves. Base curve mold halves with a lens therein are placed in an ultrasonic device (e.g., Dukane single-horn ultrasonic device). With a certain energetic force, a dry state lens is released from the mold. The dry state lens is loaded into a designed extraction tray. Alternatively, the lenses can be removed from the base curve mold halves by flotation (i.e., soaking in an organic solvent, e.g., IPA, without ultrasonication). The lenses removed from the molds are subjected to an extraction process using water or an organic solvent or a mixture of solvents for at least 30 minutes. For example, extracted in 50% IPA for 30 min, or in 100% IPA for 15 min, then back to 50% IPA for 30 min, DI water for 30 min, and finally in one day's PBS saline To the other. The inspected lens is packaged in lens packs containing a phosphate buffered saline solution (pH ~ 7.2) and autoclaved at 121°C for approximately 30 to 45 minutes.

EXAMPLE 3

[000324] A lens formulation is purged with nitrogen at room temperature for 30 to 35 minutes. The N2-purged lens formulation is introduced into polypropylene molds and cured by UV/visible light (Hamamatsu lamp) for a period of curing time. The post-molding casting procedures described in Example 2 are used in this process to produce SiHy contact lenses.

EXAMPLES 4 TO 24

[000325] In Examples 4 to 24, polymerizable compositions are prepared and listed in Tables 1 to 4. All concentrations of the components listed in the Tables are units of part, by weight. The prepared polymerizable compositions comprise 0.01 part by weight of a reactive dye (RB246 or RB247) and 0.5 part by weight of free radical initiator (VAZO 64 for heat-curable compositions or DC1173 for UV-curable compositions). ). TABLE 1 TABLE 2 * also contains 5 part units by weight of methoxy ethylene glycol methacrylate. TABLE 3 TABLE 4

[000326] SiHy contact lenses are prepared from those polymerizable compositions according to the curing processes described in Example 2 or 3. The lens properties of the resulting SiHy contact lenses are determined according to the procedure described in Example 1 and reported in Table 5. TABLE 5 NVA: N-vinyl amide monomer (or monomers); HD: H-donating chemical moieties; Si-comp: all polymerizable components that contain silicone.

[000327] As shown in Table 5, there are two limitations on the amounts of the siloxane-containing vinyl monomer, the vinyl crosslinker polysiloxane and the N-vinyl amide monomer in a polymerizable composition to form inherently wettable SiHy contact lenses.

[000328] The first limitation appears to be that there is a threshold amount of N-vinyl amide monomer in relation to the total amount of all polymerizable silicone-containing components. This threshold value of the amount of N-vinyl amide monomer is probably around 8.8 mmols per gram of all silicone-containing polymerizable components. For the purpose of forming inherently wettable SiHy contact lenses, a polymerizable composition must comprise about 8.8 mmols or more per gram of all silicone-containing polymerizable components present in the polymerizable composition.

[000329] The second limitation appears to be that there is also a threshold value for the total amount of H-donating ("H-D") chemical moieties contributed by the polysiloxane vinyl crosslinker and the siloxane-containing vinyl monomer in relation to the amount of N-vinyl amide monomer. This threshold value appears to be around 0.11 meqs of H-donating chemical moieties per gram of N-vinyl amide monomer. For the purpose of forming inherently wettable SiHy contact lenses, a polymerizable composition must comprise about 0.11 meqs or more of H-donating chemical moieties (contributed from all silicone-containing polymerizable components) per gram of the N-vinyl amide monomer.

EXAMPLES 25 TO 76

[000330] In Examples 25 to 76, polymerizable compositions are prepared and listed in Tables 6a to 6h. All concentrations of components listed in the Tables are units of part, by weight. The prepared polymerizable compositions comprise 0.01 part by weight of a reactive dye (RB246 or RB247) and 0.5 part by weight of free radical initiator (VAZO 64 for heat-curable compositions or DC1173 for UV-curable compositions). ). TABLE 6A TABLE 6B TABLE 6C TABLE 6D TABLE 6E TABLE 6F TABLE 6G TABLE 6H

[000331] SiH y contact lenses are prepared from those polymerizable compositions according to the curing processes described in Example 2 or 3. The lens properties of the resulting SiHy contact lenses are determined according to the procedure described in Example 1 and reported in Table 7. TABLE 7

[000332] Table 7 shows that when a polymerizable composition comprises at least 8.8 mmols of N-vinyl amide monomer (or monomers) (NVP and/or VMA) per gram of the sum of vinyl monomer containing siloxane and the polysiloxane vinyl crosslinker and more than 0.11 meqs of the H-donating chemical moieties (i.e., hydroxyl groups of the polysiloxane vinyl crosslinker) per gram of N-vinyl amide monomer (or monomers) ( NVP and/or VMA), the resulting SiHy contact lenses prepared from such a composition are inherently wettable.

EXAMPLE 74

[000333] The surface compositions of SiHy contact lenses are determined by characterizing vacuum-dried contact lenses with X-ray photoelectron spectroscopy (XPS). XPS is a method for measuring the surface composition of lenses with a sampling depth of about 10 nm.

[000334] XPS analysis of SiHy contact lenses of the invention (prepared according to the procedures described in Examples 21 and 56) and commercial SiHy contact lenses without plasma treatment or any coating (ACUVUE® Advance®, MyDay , CLARITITM, AVAIRA, ACUVUE® TruEyeTM, Oasys®, UltraTM, Biofinity®) is performed. All lenses are vacuum dried. Polyethylene sheets (Goodfellow, LDPE, d=0.015 mm) and DAILIES® AquaCom fortPlus (DACP) are used as controls due to the fact that they do not contain silicon. The surface compositions of SiHy contact lenses are reported in Table 8 below. TABLE 8

[000335] The low % Si value for the two control samples and the fluorine content observed in the lenses that do not contain fluorine indicate some contaminants that could be introduced during the preparation process including the vacuum drying process and analysis of XPS. Atomic Si percentage values for control samples can represent the baseline of XPS analysis.

[000336] All publications, patents and patent application publications that were cited in this document above in this application are incorporated into this document by reference, in their entirety.

Claims (40)

1. Silicone hydrogel contact lens, characterized in that it comprises a silicone hydrogel bulk material, comprising: (1) first repeating units of at least one siloxane-containing vinyl monomer including 0 to 10 first per H-donating chemical compounds, (2) second repeating units of at least one first vinyl polysiloxane crosslinker that has a numerical average molecular weight of 3,000 Daltons to 80,000 Daltons and comprises (a) two terminal (meth)acryloyl groups , (b) at least one polysiloxane segment comprising dimethylsiloxane units and hydrophilized siloxane units each having a methyl substituent and a monovalent C4-C40 organic radical substituent having one or more second H-donating chemical moieties, and (c) from 0 to 20 third H-donating chemical moieties that are integral parts of molecular structures outside the polysiloxane segment, (3) third repeating units of at least one N-vinyl amide monomer hydrophilic, and (4) optionally fourth repeating units of at least one second vinyl polysiloxane crosslinker that has 0 to 35 fourth H-donating chemical moieties, wherein the first and second vinyl polysiloxane crosslinkers are different from each other, being that the first, second, third and fourth H-donating chemical moieties independent of each other are hydroxyl groups, carboxyl groups, amino groups of -NHR°, amino bonds of -NH-, amide bonds of -CONH-, bonds of -OCONH- urethane or combinations thereof, wherein R° is H or a C1-C4 alkyl, wherein the silicone hydrogel bulk material comprises at least 8.8 mmol of the third repeating units per gram of all first, second and fourth repeating units in total and at least 0.11 meq of all first, second, third and fourth H-donating chemical moieties in total per gram of the third repeating units, wherein the hydrogel contact lens silicone has an oxygen permeability of at least 50 barrer, an elastic modulus of 0.2 MPa to 1.5 MPa, and an equilibrium water content of 40% to 70% by weight and is inherently wettable as demonstrated. due to the characteristic that it presents a water breakthrough time of at least 10 seconds and a water contact angle per captive bubble of 80 degrees or less without subjecting to any post-cure surface treatment. 2. Silicone hydrogel contact lens according to claim 1, characterized by the fact that the hydrophilized siloxane units each have a methyl substituent and a monovalent C4-C40 organic radical substituent having from 2 to 6 second chemical portions of H donor. 3. Silicone hydrogel contact lens according to claim 1, characterized in that the first vinyl polysiloxane crosslinker is a compound of Formula (1): in which: v1 is an integer from 30 to 500 and ®1 is an integer from 1 to 75, as long as ®1/v1 is from 0.035 to 0.15; X01 is O or NRn where Rn is hydrogen or C1-C10-alkyl; Ro is hydrogen or methyl; R2 and R3, independently of each other, are a substituted or unsubstituted divalent C1-C10 alkylene radical or a divalent radical of -R5-O-R6- wherein R5 and R6 independently of each other are a divalent C1-C10 alkylene radical replaced or not replaced; R4 is a monovalent radical of any of Formulas (2) to (6): in which: p1 is zero or 1; m1 is an integer from 2 to 4; m2 is an integer from 1 to 5; m3 is an integer from 3 to 6; m4 is an integer from 2 to 5; R7 is hydrogen or methyl; R8 is a C2-C6 hydrocarbon radical that has valences (m2+1); R9 is a C2-C6 hydrocarbon radical that has valences (m4+1); R10 is ethyl or hydroxymethyl; R11 is methyl or hydromethyl; R12 is hydroxyl or methoxy; X3 is a sulfur bond of -S- or a tertiary amino bond of -NR13- wherein R13 is C1-C1 alkyl, hydroxyethyl, hydroxypropyl or 2,3-dihydroxypropyl; eoo X4 is an amide bond of or in which R14 is hydrogen or C1-C10 alkyl. 4. Silicone hydrogel contact lens according to claim 3, characterized by the fact that R4 is a monovalent radical of one of Formulas (2a) to (2y): in which: p1 is zero or 1, m1 is an integer from 2 to 4, and R7 is hydrogen or methyl. 5. Silicone hydrogel contact lens according to claim 3, characterized by the fact that R4 is a monovalent radical of one of Formulas (3a) to (3y): in which: X4 is an amide bond of or , where RU is hydrogen or C1-C10 alkyl. 6. Silicone hydrogel contact lens according to claim 3, characterized by the fact that R4 is a monovalent radical of Formula (4a) or (4b): 7. Silicone hydrogel contact lens according to claim 3, characterized by the fact that R4 is a monovalent radical of one of Formulas (5a) to (5c): 8. Silicone hydrogel contact lens, according to claim 3, characterized by the fact that R4 is a radical of Formula (6), in which m1 is 3, and p1 is 1. 9. Silicone hydrogel contact lens according to any one of claims 1 to 8, characterized by the fact that the vinyl monomer, which contains siloxane, is a polysiloxane terminated in mono-(meth)acryloyl, terminated in monoalkyl of Formula (I): in which: Ro is H or methyl; Xo is O or NR1; L1 is a divalent radical of C3-C8 alkylene or a divalent radical of L1' is a divalent C2-C8 alkylene radical that has zero or one hydroxyl group; L1" is a divalent C3-C8 alkylene radical that has zero or one hydroxyl group; Rt1 is a C1-C4 alkyl; X1' is O or NR1; q1 is an integer from 1 to 20; q2 is an integer from 0 to 20; and n1 is an integer from 3 to 25. 10. Silicone hydrogel contact lens according to claim 9, characterized by the fact that the polysiloxane terminated in monoalkyl terminated in mono-(meth)acryloyl is polydimethylsiloxane terminated in w-butyl (or w- methyl) ending in α- (meth)acryloxypropyl, polydimethylsiloxane ending in w-butyl (or w- methyl) ending in a-(meth)acryloxy-2-hydroxypropyloxypropyl, α-(2-hydroxyl-methacryloxypropyloxypropyl)-w-butyl- decamethylpentasiloxane, polydimethylsiloxane ending in w-butyl (or w-methyl) ending in α-[3-(meth)acryloxyethoxy-2-hydroxypropyloxypropyl], polydimethylsiloxane ending in w-butyl (or w-methyl) ending in α-[ 3-(meth)acryloxypropyloxy-2-hydroxypropyloxypropyl], polydimethylsiloxane ending in w-butyl (or w-methyl) ending in a-[3-(meth)acryloxy-isopropyloxy-2-hydroxypropyloxypropyl], polydimethylsiloxane ending in w- butyl (or w-methyl) ending in a-[3-(meth)acryloxybutyloxy-2-hydroxypropyloxypropyl], polydimethylsiloxane ending in w-butyl (or w-methyl) ending in α-[3-(meth)acryloxyethylamino- 2-hydroxypropyloxypropyl], polydimethylsiloxane ending in w-butyl (or w-methyl) ending in α-[3-(meth)acryloxypropylamino-2-hydroxypropyloxypropyl], polydimethylsiloxane ending in w-butyl (or w-methyl) ending in α-[3-(meth)acryloxy-butylamino-2-hydroxypropyloxypropyl], polydimethylsiloxane terminated in w-butyl (or w-methyl) terminated in a-(meth)acryloxy(polyethylenoxy)-2-hydroxypropyloxypropyl], polydimethylsiloxane terminated in w -butyl (or w-methyl) ending in a-[(meth)acryloxy-2-hydroxypropyloxy-ethoxypropyl], polydimethylsiloxane ending in w-butyl (or w-methyl) ending in a-[(meth)acryloxy-2-hydroxypropyl -N-ethylaminopropyl], polydimethylsiloxane ending in w-butyl (or w-methyl) ending in a-[(meth)acryloxy-2-hydroxypropyl-aminopropyl], polydimethylsiloxane ending in w-butyl (or w-methyl) ending in a -[(meth)acryloxy-2-hydroxypropyloxy (polyethyleneoxy)propyl], polydimethylsiloxane ending in w-butyl (or w-methyl) ending in α-(meth)acryloylamidopropyloxypropyl, polydimethylsiloxane ending in w-butyl (or w-methyl ) terminated in α-N-methyl- (meth)acryloylamidopropyloxypropyl, w-butyl (or w-methyl) polydimethylsiloxane terminated in a-[3-(meth)acrylamidoethoxy-2-hydroxypropyloxy-propyl], polydimethylsiloxane terminated in w- butyl (or w-methyl) terminated in a-[3-(meth)acrylamidopropyloxy-2-hydroxypropyloxypropyl], polydimethylsiloxane terminated in w-butyl (or w-methyl) terminated in α-[3-(meth) acrylamidoisopropyloxy-2-hydroxypropyloxypropyl], polydimethylsiloxane terminated in w-butyl (or w-methyl) terminated in α-[3-(meth)acrylamidobutyloxy-2-hydroxypropyloxypropyl], w-butyl (or w-methyl) polydimethylsiloxane terminated in α-[3-(meth)acryloylamido-2-hydroxypropyloxypropyl], polydimethylsiloxane terminated in w-butyl (or w-methyl) terminated in α-[3-[N-methyl-(meth)acryloylamido]-2-hydroxypropyloxypro - pila], N-methyl-N'-(propyltetra(dimethylsiloxy)dimethylbutylsilane) (meth)acrylamide, N-(2,3-dihydroxypropane)-N'-(propyltetra(dimethylsiloxy)dimethylbutylsilane) ( meth)acrylamide, (meth)acryloylamidopropyltetra(dimethylsiloxy)dimethylbutylsilane or a mixture thereof. 11. Silicone hydrogel contact lens according to any one of claims 1 and 8, characterized by the fact that the vinyl monomers, which contain siloxane, are a vinyl monomer, which contains a tris (trimethylsilyloxy)silyl group or bis(trimethylsilyloxy) alkylsilyl. 12. Silicone hydrogel contact lens or method according to claim 11, characterized by the fact that the vinyl monomer, which contains siloxane, is a vinyl monomer, which contains tris (trimethylsilyloxy)silyl or bis(trimethylsilyloxy )alkylsilyl of Formula (II): in which: Ro is H or methyl; Xo is O or NR1; L2 is a divalent C3-C8 alkylene radical or a divalent radical of either -L2-X2-L2"-, -(C2H4O)qi-L2"-, -(C2H4O)qi-CONH-L2"-; or - L2'-NHCOO-(C2H4O)qi-L2"-;L2' is a divalent C2-C8 alkylene radical that has zero or one hydroxyl group; L2" is a divalent C3-C8 alkylene radical that has zero or one hydroxyl group; Rt2 is a C1-C4 alkyl; q1 is an integer from 1 to 20; and r1 is an integer from 2 or 3. 13. Silicone hydrogel contact lens according to claim 11 or 12, characterized in that the vinyl monomer, which contains tris (trimethylsilyloxy)silyl or which contains bis (trimethylsilyloxy)alkylsilyl is selected from the group which consists of tris(trimethylsilyloxy)silylpropyl (meth)acrylate, [3-(meth)acryloxy-2-hydroxypropyloxy]propylbis(trimethylsiloxy)methylsilane, [3-(meth)acryloxy-2-hydroxypropyloxy]propylbis( trimethylsiloxy)butylsilane, 3-(meth)acryloxy-2-(2-hydroxy-ethoxy)-propyloxy)propylbis(trimethylsiloxy)methylsilane, 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-methyl acrylamide, N-(2-hydroxy-3-(3-(tris( trimethylsilyloxy)silyl)propyloxy)propyl) (meth)acrylamide and mixtures thereof. 14. Silicone hydrogel contact lens according to any one of claims 1 and 13, characterized in that the hydrophilic N-vinyl amide monomer is N-vinylpyrrolidone, N-vinyl piperidone, N-vinyl caprolactam, N -vinyl-N-methyl acetamide, N-vinyl formamide, N-vinyl acetamide, N-vinyl isopropylamide, N-vinyl-N-methyl acetamide, N-vinyl-N-ethyl acetamide, N-vinyl-N-ethyl formamide and mixtures thereof. 15. Silicone hydrogel contact lens according to any one of claims 1 to 14, characterized in that the silicone hydrogel contact lens further comprises the repeating units of one or more non-toxic vinyl crosslinking agents. silicone selected from the group consisting of ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, di(meth)acrylate glycerol, 1,3-propanediol di-(meth)acrylate, 1,3-butanediol di-(meth)acrylate, 1,4-butanediol di-(meth)acrylate, glycerol 1,3-diglycerolate di-(meth)acrylate, ethylene di-(meth)acrylate-bis(oxy(2-hydroxypropane-1,3-diyl)], bis[2-(meth)acryloxyethyl phosphate], di-(meth )trimethylolpropane 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'-methylene bis(meth)acrylamide, N,N'-ethylene bis(meth)acrylamide, N,N'-dihydroxyethylene bis(meth)acrylamide, N,N'-propylene bis (meth)acrylamide, N,N'-2-hydroxypropylene bis(meth)acrylamide, N,N'-2,3-dihydroxybutylene bis(meth)acrylamide, 1,3-bis dihydrogen phosphate (meth)acrylamidepropane-2-yl, piperazine diacrylamide, tetraethylene glycol divinyl ether, triethylene glycol divinyl ether, diethylene glycol divinyl ether, ethylene glycol divinyl ether, triallyl isocyanurate, triallyl cyanurate, trimethylpropane trimethacrylate, pentaerythritol tetramethacrylate, bisphenol Dimethacrylate and combinations thereof. 16. Silicone hydrogel contact lens according to any one of claims 1 to 15, characterized in that the silicone hydrogel contact lens further comprises repeating units of a blending vinyl monomer selected from the group which consists of a C1-C10 alkyl (meth)acrylate, cyclopentylacrylate, cyclohexyl methacrylate, cyclohexyl acrylate, isobornyl (meth)acrylate, styrene, 4,6-trimethylstyrene, t-butyl styrene, trifluoroethyl (meth)acrylate , hexafluoroisopropyl (meth)acrylate, hexafluorobutyl (meth)acrylate and combinations thereof. 17. Silicone hydrogel contact lens according to any one of claims 1 to 16, characterized in that the silicone hydrogel contact lens further comprises the repeating units of at least one UV-absorbing vinyl monomer and optionally repeating units of at least one UV/HEVL absorbing vinyl monomer. 18. Silicone hydrogel contact lens according to any one of claims 1 to 17, characterized in that the silicone hydrogel contact lens additionally comprises 2-[2'-hydroxy-5 repeat units '-(2-methacryloxyethyl) phenyl)]-2H-benzotriazole and repeating units of at least one UV/HEVL absorbing vinyl monomer selected from the group consisting of 2-{2'-hydroxy-3'- tert-butyl-5'-[3'-methacryloyl-xypropoxy]phenyl}-2H-benzotriazole, 2-{2'-hydroxy-3'-tert-butyl-5'-[3'-methacryloyloxypropoxy]phenyl} -5-methoxy-2H-benzotriazole, 2-{2'-hydroxy-3'-tert-butyl-5'-[3'-methacryloyloxypropoxy]phenyl}-5-chloro-2H-benzotriazole, 2-[2'- hydroxy-3'-tert-butyl-5'-(3'-acryloyloxypropoxy)phenyl]-5-trifluoromethyl-2H-benzotriazole and combinations thereof. 19. Silicone hydrogel contact lens according to any one of claims 1 to 18, characterized in that the silicone hydrogel contact lens has a UVB transmittance of 10% or less, between 280 and 315 nanometers and a UVA transmittance of 30% or less, between 315 and 380 nanometers and a Violet transmittance of 70% or less, between 380 nm and 440 nm. 20. Silicone hydrogel contact lens according to any one of claims 1 to 19, characterized in that it further comprises the repeating units of one or more hydrophilic acrylic monomers selected from the group consisting of N,N-dimethyl (meth)acrylamide, (meth)acrylamide, N-hydroxylethyl (meth)acrylamide, N-hydroxypropyl (meth)acrylamide, hydroxyethyl (meth)acrylate, glycerol methacrylate, polyethylene glycol (meth)acrylate which has a number-average molecular weight of up to 1,500, polyethylene glycol C1-C4-alkyl ether (meth)acrylate which has a number-average molecular weight of up to 1,500, N-[tris(hydroxymethyl)methyl]-acrylamide, acid ( meth)acrylic, ethylacrylic acid and combinations thereof. 21. Method for producing inherently wettable silicone hydrogel contact lenses, characterized in that it comprises the steps of: (1) preparing a polymerizable composition, which is clear at room temperature and optionally, but preferably, at a temperature from 0 to 4 °C, wherein the polymerizable composition comprises: (a) at least one siloxane-containing vinyl monomer including 0 to 10 first H-donating chemical moieties, (b) at least one first vinylic crosslinker of polysiloxane having a number average molecular weight of 3,000 Daltons to 80,000 Daltons and comprising (i) two terminal (meth)acryloyl groups, (ii) at least one polysiloxane segment comprising dimethylsiloxane units and hydrophilized siloxane units , in which each presents a methyl substituent and a monovalent C4-C40 organic radical substituent that presents one or more second H-donating chemical moieties, and (iii) from 0 to 20 third H-donating chemical moieties that are parts integrals of molecular structures outside the polysiloxane segment, (c) at least one hydrophilic N-vinyl amide monomer, (d) optionally at least one second vinyl polysiloxane crosslinker that has 0 to 35 fourth chemical donor moieties. H, and (e) at least one free radical initiator, the first and second vinyl polysiloxane crosslinkers being different from each other, the first, second, third and fourth H-donating chemical moieties being independent of each other are hydroxyl groups, carboxyl groups, amino groups of -NHR°, amino bonds of -NH-, amide bonds of -CONH-, urethane bonds of -OCONH- or combinations thereof, where R° is H or a C1-C4 alkyl, with the polymerizable composition comprising at least 8.8 mmols of component (c) per gram of all components (a), (b) and (d) in total and at least 0.11 meqs of all first, second, third and fourth H-donating chemical moieties in total per gram of component (c); (2) introducing the polymerizable composition into a lens mold; and (3) thermally or actinically curing the polymerizable composition in the lens mold to form a silicone hydrogel contact lens, the silicone hydrogel contact lens having an oxygen permeability of at least 50 bars. , an elastic modulus of 0.2 MPa to 1.5 MPa, and an equilibrium water content of 40% to 70% by weight and is inherently wettable as characterized by the fact that it has a water breakthrough time of at least 10 seconds and a captive bubble water contact angle of 80 degrees or less without subjecting to any post-cure surface treatment. 22. Method according to claim 21, characterized by the fact that the hydrophilized siloxane units each have a methyl substituent and a monovalent C4-C40 organic radical substituent that has 2 to 6 second chemical donor moieties. H. 23. Method, according to claim 21 or 22, characterized by the fact that the first vinyl polysiloxane crosslinker is a compound of Formula (1): in which: t)1 is an integer from 30 to 500 and ®1 is an integer from 1 to 75, since 14)1 is from 0.035 to 0.15 (preferably from 0.040 to 0.12, even more preferably from 0.045 to 0.10); X01 is O or NRn where Rn is hydrogen or C1-C10-alkyl; Ro is hydrogen or methyl; R2 and R3, independently of each other, are a substituted or unsubstituted divalent C1-C10 alkylene radical or a divalent radical of -R5-O-R6- wherein R5 and Re independently of each other are a divalent C1-C10 alkylene radical replaced or not replaced; R4 is a monovalent radical of any one of Formula (2) to (6): in which: p1 is zero or 1; m1 is an integer from 2 to 4; m2 is an integer from 1 to 5; m3 is an integer from 3 to 6; m4 is an integer from 2 to 5; R7 is hydrogen or methyl; R8 is a C2-C6 hydrocarbon radical that has valences (m2+1); R9 is a C2-C6 hydrocarbon radical that has valences (m4+1); R10 is ethyl or hydroxymethyl; R11 is methyl or hydromethyl; R12 is hydroxyl or methoxy; X3 is a sulfur bond of -S- or a tertiary amino bond of -NR13- wherein R13 is C1-C1 alkyl, hydroxyethyl, hydroxypropyl or 2,3-dihydroxypropyl; eoo X4 is an amide bond of or where R14 is hydrogen or C1-C10 alkyl. 24. Method according to claim 23, characterized by the fact that R4 is a monovalent radical of one of Formulas (2a) to (2y): in which: p1 is zero or 1 (preferably 1), m1 is an integer from 2 to 4 (preferably 3), and R7 is hydrogen or methyl (preferably hydrogen). 25. Method, according to claim 23, characterized by the fact that R4 is a monovalent radical of one of Formulas (3a) to (3y): in which: X4 is an amide bond of or , where R14 is hydrogen or C1-C10 alkyl. 26. Method, according to claim 23, characterized by the fact that R4 is a monovalent radical of Formula (4a) or (4b): 27. Method according to claim 23, characterized by the fact that R4 is a monovalent radical of one of Formulas (5a) to (5c): 28. Method, according to claim 23, characterized by the fact that R4 is a radical of Formula (6) where m1 is 3 and p1 is 1. 29. Method, according to any one of claims 21 to 28, characterized by the fact that the siloxane-containing vinyl monomer is a polysiloxane terminated in monoalkyl terminated in mono-(meth) acryloyl, of Formula (I): in which: Ro is H or methyl; Xo is O or NR1; L1 is a divalent radical of C3-C8 alkylene or a divalent radical of L1' is a divalent C2-C8 alkylene radical having zero or one hydroxyl group; L1" is divalent C3-C8 alkylene radical that has zero or one hydroxyl group; a C1-C4 alkyl; 3 to 15, even more preferably 3 to 10). 30. Method according to claim 29, characterized by the fact that the polysiloxane terminated in monoalkyl terminated in mono-(meth) acryloyl is polydimethylsiloxane terminated in w-butyl (or w-methyl) terminated in α-(meth) acryloxypropyl , polydimethylsiloxane ending in w-butyl (or w-methyl) ending in α-(meth)acryloxy-2-hydroxypropyloxypropyl, α-(2-hydroxyl-methacryloxypropyloxy-propyl)-w-butyl-decamethylpentasiloxane, polydimethylsiloxane ending in w -butyl (or w-methyl) ending in a-[3-(meth)acryloxyethoxy-2-hydroxypropyloxypropyl], polydimethylsiloxane ending in w-butyl (or w-methyl) ending in a-[3-(meth)acryloxypropyloxy-2 -hydroxypropyloxy-propyl], polydimethylsiloxane ending in w-butyl (or w-methyl) ending in a-[3-(meth)acryloxy-isopropyloxy-2-hydroxypropyloxypropyl], polydimethylsiloxane ending in w-butyl (or w-methyl ) terminated in α-[3-(meth)acryloxybutyloxy-2-hydroxypropyloxypropyl], polydimethylsiloxane terminated in w-butyl (or w-methyl) terminated in α-[3-(meth)acryloxyethylamino-2-hydroxypropyloxypropyl], polydimethylsiloxane terminated in w-butyl (or w-methyl) terminated in α-[3-(meth)acryloxypropylamino-2-hydroxypropyloxypropyl], polydimethylsiloxane terminated in w-butyl (or w-methyl) terminated in α-[3-(meth) acryloxybutylamino-2-hydroxypropyloxypropyl], polydimethylsiloxane terminated in w-butyl (or w-methyl) terminated in a-(meth)acryloxy(polyethyleneoxy)-2-hydroxypropyloxypropyl], polydimethylsiloxane terminated in w-butyl (or w-methyl) terminated in α-[(meth)acryloxy-2-hydroxypropyloxy-ethoxypropyl], polydimethylsiloxane terminated in w-butyl (or w-methyl) terminated in a-[(meth)acryloxy-2-hydroxypropyl-N -ethylaminopropyl], polydimethylsiloxane ending in w-butyl (or w-methyl) ending in a-[(meth)acryloxy-2-hydroxypropyl-aminopropyl], polydimethylsiloxane ending in w-butyl (or w-methyl) ending in a-[ (meth)acryloxy-2-hydroxypropyloxy(polyethyleneoxy)propyl], polydimethylsiloxane ending in w-butyl (or w-methyl) ending in α-(meth)acryloylamidopropyloxypropyl, polydimethylsiloxane ending in w-butyl (or w-methyl) ending in α -N-methyl-(meth)acryloylamido-propyloxypropyl, w-butyl (or w-methyl) polydimethylsiloxane terminated in a-[3-(meth)acrylamidoethoxy-2-hydroxypropyloxypropyl], polydimethylsiloxane terminated in w-butyl (or w -methyl) terminated in α-[3-(meth)acrylamidopropyloxy-2-hydroxypropyloxypropyl], polydimethylsiloxane terminated in w-butyl (or w-methyl) terminated in α-[3-(meth)acrylamidopropyloxy-2-hydroxypropyloxypropyl] , polydimethylsiloxane ending in w-butyl (or w-methyl) ending in α-[3-(meth)acrylamidobutyloxy-2-hydroxypropyloxypropyl], w-butyl (or w-methyl) polydimethylsiloxane ending in α-[3-( meth)acryloylamido-2-hydroxypropyloxypropyl], polydimethylsiloxane terminated in w-butyl (or w-methyl) terminated in α-[3-[N-methyl-(meth)acryloylamido]-2-hydroxypropyloxypropyl], N-methyl- N'-(propyltetra(dimethylsiloxy)dimethylbutylsilane) (meth)acrylamide, N-(2,3-dihydroxypropane)-N'-(propyltetra(dimethylsiloxy)dimethylbutylsilane) (meth)acrylamide, (meth)acryloylamidopropyltetra (dimethylsiloxy)dimethylbutylsilane or a mixture thereof. 31. Method according to any one of claims 21 to 28, characterized in that the siloxane-containing vinyl monomers are a vinyl monomer that contains a tris (trimethylsilyloxy)silyl or bis (trimethylsilyloxy)alkylsilyl group. 32. Method according to claim 31, characterized in that the siloxane-containing vinyl monomer is a tris(trimethylsilyloxy)silyl-containing vinyl monomer or bis(trimethylsilyloxy)alkylsilyl-containing vinyl monomer of Formula (II): in which: Ro is H or methyl; Xo is O or NR1; L2 is a divalent C3-C8 alkylene radical or a divalent radical of or -L2-X2-L2'-, -(C2H4θ)qi-L2"- -(C2H4θ)qi-CONH-L2"-; or -L2'-NHCOO-(C2H4O)qi-L2"-, L2' is a divalent C2C8 alkylene radical having zero or one hydroxyl group; L2" is divalent C3-C8 alkylene radical having zero or one hydroxyl group; X1 is O, NR1, NHCOO, OCONH, CONR1 or NR1CO; R1 is H or a C1-C4 alkyl having 0 to 2 hydroxyl groups; Rt2 is a C1-C4 alkyl; q1 is an integer from 1 to 20, r1 is an integer from 2 or 3. 33. Method according to claim 31 or 32, characterized by the fact that the vinyl monomer containing tris (trimethylsilyloxy)silyl or containing bis(trimethylsilyloxy)alkylsilyl is selected from the group consisting of (met )tris(trimethylsiloxy)silylpropyl acrylate, [3-(meth)acryloxy-2-hydroxypropyloxy]propylbis(trimethylsiloxy)methylsilane, [3-(meth)acryloxy-2-hydroxypropyloxy]propylbis(trimethylsiloxy)butylsilane, 3-( meth)acryloxy-2-(2-hydroxyethoxy)-propyloxy)propylbis(trimethylsiloxy)methylsilane, 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-methyl acrylamide, N-(2-hydroxy-3-(3-(tris(trimethylsilyloxy)silyl)propyloxy ) propyl) (meth) acrylamide and mixtures thereof. 34. Method according to any one of claims 21 to 33, characterized in that it comprises the hydrophilic N-vinyl amide monomer, which is N-vinylpyrrolidone, N-vinyl piperidone, N-vinyl caprolactam, N-vinyl- N-methyl acetamide, N-vinyl formamide, N-vinyl acetamide, N-vinyl isopropylamide, N-vinyl-N-methyl acetamide, N-vinyl-N-ethyl acetamide, N-vinyl-N-ethyl formamide and mixtures thereof (preferably N-vinylpyrrolidone, N-vinyl-N-methyl acetamide or combinations thereof. 35. Method according to any one of claims 21 to 34, characterized by the fact that the polymerizable composition additionally comprises one or more non-silicone vinyl crosslinking agents (preferably selected from the group consisting of di-(met )ethylene glycol acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, glycerol di(meth)acrylate, glycerol di(meth)acrylate 1,3-propanediol, 1,3-butanediol di-(meth)acrylate, 1,4-butanediol di-(meth)acrylate, glycerol 1,3-diglycerolate di-(meth)acrylate, di-(meth) ethylenebis(oxy(2-hydroxypropane-1,3-diyl) acrylate], bis[2-(meth)acryloxyethyl phosphate], trimethylolpropane di-(meth)acrylate, and 3,4-bis[ (meth)acryloyl]tetrahydrofuran, diacrylamide, dimethacrylamide, N,N-di(meth)acryloyl-N-methylamine, N,N-di(meth)acryloyl-N-ethylamine, N,N'-methylene bis (meth) acrylamide, N,N'-ethylene bis(meth)acrylamide, N,N'-dihydroxyethylene bis(meth)acrylamide, N,N'-propylene bis(meth)acrylamide, N,N'-2- hydroxypropylene bis(meth)acrylamide, N,N'-2,3-dihydroxybutylene bis(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, trimethylpropane trimethacrylate, pentaerythritol tetramethacrylate, bisphenol A dimethacrylate and combinations thereof, most preferably selected from the group consisting of tetra(ethylene glycol di-(meth)acrylate, tri(ethylene glycol di-(meth)acrylate), ethylene glycol di-(meth)acrylate, di(ethylene glycol di-(meth)acrylate), ether divinyl tetraethylene glycol, divinyl triethylene glycol ether, divinyl diethylene glycol ether, divinyl ethylene glycol ether, triallyl isocyanurate or triallyl cyanurate). 36. Method according to any one of claims 21 to 35, characterized by the fact that the polymerizable composition additionally comprises a blending vinyl monomer (preferably selected from the group consisting of a C1-C10 (meth) acrylate alkyl, cyclopentylacrylate, cyclohexylmethacrylate, cyclohexylacrylate, isobornyl (meth)acrylate, styrene, 4,6-trimethylstyrene, t-butyl styrene, trifluoroethyl (meth)acrylate, hexafluoroisopropyl (meth)acrylate, Hexafluorobutyl (meth)acrylate and combinations thereof, most preferably selected from methyl methacrylate). 37. Method according to any one of claims 21 to 36, characterized in that the polymerizable composition additionally comprises at least one UV-absorbing vinyl monomer and optionally at least one UV/HEVL absorbing vinyl monomer. 38. Method according to any one of claims 21 to 37, characterized by the fact that the polymerizable composition additionally comprises 2-[2'-hydroxy-5'-(2-methacryloxyethyl)phenyl)]-2H-benzotriazole (Norbloc) and at least one UV/HEVL absorbing vinyl monomer selected from the group consisting of 2-{2'-hydroxy-3'-tert-butyl-5'-[3'-methacryloyloxypropoxy]phenyl}-2H -benzotriazole, 2-{2'-hydroxy-3'-tert-butyl-5'-[3'-methacryloyloxypropoxy]phenyl}-5-methoxy-2H-benzotriazole (UV13), 2-{2'-hydroxy-3 '-tert-butyl-5'-[3'-methacryloyloxypropoxy] phenyl}-5-chloro-2H-benzotriazole (UV28), 2-[2'-hydroxy-3'-tert-butyl-5'- ( 3'-acryloyloxypropoxy)phenyl]-5-trifluoromethyl-2H-benzotriazole (UV23) and combinations thereof. 39. Method according to any one of claims 21 to 38, characterized in that it comprises the silicone hydrogel contact lens, which has a UVB transmittance of 10% or less (preferably 5% or less, more preferably 2.5% or less, even more preferably 1% or less) between 280 and 315 nanometers and a UVA transmittance of 30% or less (preferably 20% or less, more preferably 10% or less, even more preferably 5% or less) between 315 and 380 nanometers and a Violet transmittance of 70% or less, preferably 60% or less, more preferably 50% or less, even more preferably 40% or less) between 380 nm and 440 nm. 40. Method according to any one of claims 21 to 39, characterized in that the polymerizable composition additionally comprises one or more hydrophilic acrylic monomers selected from the group consisting of N,N-dimethyl (meth) acrylamide, (meth)acrylamide, N-hydroxylethyl (meth)acrylamide, N-hydroxypropyl (meth)acrylamide, hydroxyethyl (meth)acrylate, glycerol methacrylate (GMA), polyethylene glycol (meth)acrylate having a weight number-average molecular weight of up to 1500, C1-C4-alkyl polyethylene glycol ether (meth)acrylate having a number-average molecular weight of up to 1500, N-[tris(hydroxymethyl)methyl]-acrylamide, (meth)acrylic acid, acid ethylacrylic acid and combinations thereof (preferably selected from the group consisting of N,N-dimethyl (meth)acrylamide, hydroxyethyl (meth)acrylate, N-hydroxylethyl (meth)acrylamide, glycerol methacrylate (GMA) and combinations thereof ).