RU2820814C2 - Hydrophilised polydiorganosiloxane vinyl cross-linking agents and methods of use thereof - Google Patents

Abstract

FIELD: physics; chemistry.

SUBSTANCE: invention relates to silicone hydrogel contact lenses. Disclosed is a silicone-hydrogel contact lens comprising a cross-linked polymer material, which contains links of a polydiorganosiloxane vinyl cross-linking agent of formula (1), in which υ1 is integer from 30 to 500 and ω1 is integer from 1 to 75 provided that ω1/υ1 ranges from approximately 0.035 to approximately 0.15; X₀ is O; R₁ is hydrogen or methyl; R₂ and R₃ independently represent unsubstituted C₁-C₁₀ alkylene divalent radical or a divalent radical -R₅-O-R₆-, in which R₅ and R₆ independently represent unsubstituted C₁-C₁₀ alkylene divalent radical; R₄ is a monovalent radical of formula (6), q1 is zero or 1; n1 is integer from 2 to 4; R₇ is hydrogen or methyl; wherein the polydiorganosiloxane vinyl cross-linking agent is characterized by a number-average molecular weight of about 3000 Da to about 80,000 Da.

EFFECT: disclosed silicone hydrogel contact lens enables penetration of a sufficient amount of oxygen through the contact lens to the cornea with minimal negative effects on the normal state of the cornea.

21 cl, 4 tbl, 9 ex

Description

The present invention relates to a hydrophilized polydiorganosiloxane vinyl crosslinker, silicone hydrogel contact lenses containing repeat units of such a hydrophilized polydiorganosiloxane vinyl crosslinker, and a method for producing silicone hydrogel contact lenses from such a hydrophilized polydiorganosiloxane vinyl crosslinker.

BACKGROUND OF THE ART

In recent years, soft silicone hydrogel contact lenses have become more and more popular due to their high oxygen permeability and ease of use. “Soft” contact lenses may fit tightly enough to the shape of the eyeball that oxygen cannot easily pass through the lens. Soft contact lenses must allow oxygen from the environment (i.e., air) to reach the cornea because the cornea does not receive oxygen from the blood like other tissues. If enough oxygen does not reach the cornea, corneal edema occurs. Prolonged periods of oxygen deprivation lead to unwanted growth of blood vessels in the cornea. Due to its high oxygen permeability, the silicone hydrogel contact lens allows sufficient oxygen to pass through the contact lens to the cornea with minimal negative effects on the normal condition of the cornea.

One lens molding material that is widely used in the production of silicone hydrogel contact lenses is a polydiorganosiloxane (eg, polydimethylsiloxane) vinyl crosslinker, which can provide high oxygen permeability to the resulting contact lenses. But the polydimethylsiloxane vinyl crosslinker can affect the mechanical properties, such as elastic modulus, of the resulting contact lenses. For example, a low molecular weight (<2000 g/mol) polydimethylsiloxane vinyl crosslinker can provide the resulting contact lens with a relatively high modulus to achieve the desired oxygen permeability. To achieve both high oxygen permeability and low modulus, a polydimethylsiloxane vinyl crosslinker with a relatively high molecular weight is usually required. However, due to its hydrophobic nature, polydimethylsiloxane vinyl crosslinker, particularly high molecular weight ones, is incompatible with hydrophilic components in the lens formulation, including, for example, N,N-dimethylacrylamide, N-vinylpyrrolidone, N-vinyl- N-methylacetamide or internal wetting agent. It would be difficult to obtain uniform lens formulations (ie, clear lens formulations) using such a polydimethylsiloxane vinyl crosslinker.

It would be even more difficult to obtain a uniform, solvent-free lens formulation using such a polydimethylsiloxane vinyl crosslinker. The use of organic solvents in the preparation of silicone hydrogel contact lenses can be expensive and not environmentally friendly.

Therefore, there is a need for new hydrophilized polydiorganosiloxane vinyl crosslinkers suitable for producing a solvent-free lens formulation that can be used to produce silicone hydrogel contact lenses with long-term thermal stability.

In documents, including US patents Nos. 4260725, 5034461, 5346946, 5416132, 5449729, 5486579, 5512205, 5760100, 5994488, 6858218, 6867245, 7671156, 7 744785, 8129442, 8163206, 8501833, 8513325, 8524850, 8835525, 8993651 and 9187601 and US Patent Application Publication No. 2016/0090432 A1, disclose that various lens formulations (which are either solvent-containing or solvent-free formulations) containing one or more hydrophilized polysiloxane crosslinkers.

BRIEF DESCRIPTION OF THE INVENTION

In one aspect, the present invention provides a hydrophilized polydiorganosiloxane vinyl crosslinker. The hydrophilized polydiorganosiloxane vinyl crosslinker of the present invention contains: (1) a polydiorganosiloxane polymer chain containing dimethylsiloxane units and hydrophilized siloxane units, each of them having one methyl substituent and one substituent representing a monovalent organic C ₄ -C ₄₀ radical, containing from 2 to 6 hydroxyl groups, with the molar ratio of hydrophilized siloxane units and dimethylsiloxane units being from about 0.035 to about 0.15; (2) two terminal (meth)acryloyl groups, wherein the hydrophilized polydiorganosiloxane vinyl crosslinker has a number average molecular weight of about 3,000 daltons to about 80,000 daltons.

In another aspect, the present invention provides a silicone hydrogel contact lens comprising a crosslinked polymeric material comprising: units of a hydrophilized polydiorganosiloxane vinyl crosslinker of the present invention (described above), units of a siloxane-containing vinyl monomer, units of at least one hydrophilic vinyl monomer, wherein The silicone hydrogel contact lens, when fully hydrated, has an oxygen permeability (Dk) of at least about 70 bbl, a moisture content of about 25% to about 70% by weight, and an elastic modulus of about 0.2 MPa to about 1.2 MPa.

In a further aspect, the present invention provides a method for producing silicone hydrogel contact lenses. The method includes the steps of: obtaining a lens molding composition that is clear at room temperature and optionally, but preferably, at a temperature of from about 0 to about 4°C, wherein the lens molding composition contains (a) from about 5% to about 35% by weight of a hydrophilized polydiorganosiloxane vinyl crosslinker of the present invention, (b) a siloxane-containing vinyl monomer, (c) from about 30% to about 60 % by weight of at least one hydrophilic vinyl monomer, (d) at least one free radical polymerization initiator, provided that the polymerizable components listed above and any additional polymerizable components add up to 100% by weight; introducing a composition for molding a lens into a mold, wherein the mold has a first half-mold with a first molding surface defining the front surface of the contact lens, and a second half-mold with a second molding surface defining the back surface of the contact lens, where said first and second halves are made capable of being aligned with each other so that a cavity is formed between said first and second forming surfaces; curing, thermally or by actinic radiation, a lens molding composition in a lens mold to form a silicone hydrogel contact lens, wherein the silicone hydrogel contact lens has an oxygen permeability (Dk) of at least about 70 bbl, a moisture content of from about 25% to about 70% by weight, and a modulus of elasticity from about 0.2 MPa to about 1.2 MPa.

DETAILED DESCRIPTION OF EMBODIMENTS OF THE PRESENT INVENTION

Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by one skilled in the art to which the present invention belongs. In general, the terminology used herein and laboratory procedures are well known and standard in the art. These procedures use conventional methods such as those provided in the art, as well as various general references. In the event that a term is given in the singular, the inventors also intend the plural for this term. The terminology used herein and the laboratory procedures described below are well known and standard in the art.

When used herein, “approximately” means that the number to which “approximately” refers is the stated number plus or minus 1-10% of that stated number.

The term “contact lens” refers to a structure that can be placed on the surface of the eye or inside the eye of a wearer. A contact lens can correct, improve, or change the wearer's vision, but it is not required to do so. The contact lens may be made of any suitable material known in the art or newly developed material, and may be a soft lens, a hard lens, or a combination lens. The term “silicone hydrogel contact lens” refers to a contact lens containing a silicone hydrogel material.

The term "hydrogel" or "hydrogel material" refers to a cross-linked polymeric material that is insoluble in water but can absorb at least 10 percent by weight of water.

The term “silicone hydrogel” refers to a silicone-containing hydrogel obtained by copolymerizing a polymerizable composition containing at least one silicone-containing vinyl monomer, or at least one silicone-containing vinyl macromer, or at least one silicone-containing prepolymer crosslinkable under the influence of actinic radiation.

As used herein, the term “hydrophilic” describes a material or portion thereof that will bind more easily to water than to lipids.

“Vinyl monomer” refers to a compound that has only one ethylenically unsaturated group and is soluble in a solvent.

The term “soluble” with respect to a compound or material in a solvent means that the compound or material can be dissolved in a solvent to produce a solution at a concentration of at least about 0.5% by weight at room temperature (i.e., at a temperature from about 20°C to approx. 30°C).

The term “insoluble” with respect to a compound or material in a solvent means that the compound or material can be dissolved in a solvent to form a solution at a concentration of less than 0.005% by weight at room temperature (as defined above).

The term "olefinically unsaturated group" or "ethylenically unsaturated group" is used herein in a broad sense and is intended to cover any groups containing at least one >C=C< group. Exemplary ethylenically unsaturated groups include, but are not limited to (meth)acryloyl ( and/or ), allyl, vinyl, styrene or other groups containing C=C.

The term “double bond group” refers to a monovalent radical containing CH ₂ =CH- that is not covalently attached to an oxygen or nitrogen atom or to a carbonyl group.

As used herein, the expression "actinic" with respect to the curing, cross-linking or polymerization of a polymerizable composition, prepolymer or material means that the curing (e.g., cross-linking and/or polymerization) is accomplished by actinic irradiation, such as, for example, UV/visible irradiation, ionizing radiation (eg, gamma rays or x-rays), microwave irradiation, etc. Thermal curing or actinic radiation curing methods are known to those skilled in the art.

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

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

The term "(meth)acryloxy" refers to the group and/or .

The term "(meth)acrylamido" refers to the group and/or where R' represents hydrogen or C ₁ -C ₁₀ alkyl.

As used herein, the term “hydrophilic vinyl monomer” refers to a vinyl monomer that is typically produced as a homopolymer into a polymer that is water soluble or can absorb at least 10 percent by weight of water.

As used herein, the term “hydrophobic vinyl monomer” refers to a vinyl monomer that is typically produced as a homopolymer into a polymer that is insoluble in water and can absorb less than 10 percent by weight of water.

The term "miscible vinyl monomer" refers to a vinyl monomer capable of dissolving both hydrophilic and hydrophobic components of the polymerizable composition to form a solution.

The term "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.

“Polymer” means a material formed by polymerization/cross-linking of one or more vinyl monomers, macromers and/or prepolymers.

As used herein, the term “molecular weight” of a polymeric material (including monomeric or macromeric materials) refers to the number average molecular weight unless specifically stated otherwise or unless test conditions indicate otherwise.

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

The term "alkylene" refers to a divalent radical obtained by removing one hydrogen atom from an alkyl. An alkylene group (or radical) forms two bonds with other groups in an organic compound.

As used herein, the term “substituted” with respect to an alkylene divalent radical or alkyl radical means that the alkylene divalent radical or alkyl radical contains at least one substituent which replaces one hydrogen atom of the alkylene or alkyl radical and which is selected from the group consisting of hydroxyl, carboxyl , -NH ₂ , sulfhydryl, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkylthio (alkyl sulfide), C ₁ -C ₄ acylamino, C ₁ -C ₄ alkylamino, di-C ₁ - C ₄ alkylamino, halogen atom (Br or Cl) and combinations thereof.

As used herein, the term “ ^siloxane unit” refers to a divalent radical -Si( ^1R2R )-O- having only two substituents, ¹ R and ² R, which are independently monovalent organic radicals and are directly linked through a single single bond with the silicon atom of the siloxane unit.

The term "monovalent organic radical" refers to a monovalent radical obtained by removing a hydrogen atom from an organic compound.

As used herein, the term “methyl substituent” in relation to a siloxane unit refers to a methyl radical directly bonded to the silicon atom of the siloxane unit; The term “monovalent organic C ₄ -C ₄₀ radical substituent” in relation to a siloxane unit refers to a monovalent organic radical containing from 4 to 40 carbon atoms and directly bonded to the silicon atom of the siloxane unit.

As used herein, the term “hydrophilized siloxane unit” refers to a siloxane unit in which one of the two substituents on the silicon atom of the siloxane unit is a monovalent organic C ₄ -C ₄₀ radical having at least one hydrophilic group or moiety (such as hydroxyl, methoxy -, carboxyl or amino group, or amide or amine bond).

As used herein, the term “hydrophilized polydiorganosiloxane vinyl crosslinker” refers to a polydiorganosiloxane vinyl crosslinker containing at least one hydrophilized siloxane unit.

As used herein, the term “multiple” means three or more.

“Vinyl crosslinker” refers to a compound with at least two ethylenically unsaturated groups. “Vinyl crosslinker” refers to a compound with two or more ethylenically unsaturated groups and a molecular weight of less than 700 daltons.

The free radical polymerization initiator can be either a photoinitiator or a thermal initiator. The term “photoinitiator” refers to a chemical that initiates a free radical cross-linking/free radical polymerization reaction using light. “Thermal initiator” refers to a chemical substance that initiates a radical cross-linking/polymerization reaction by using thermal energy.

The term “polymerizable UV absorbing agent” or “UV absorbing vinyl monomer” refers to a compound containing an ethylenically unsaturated group and a UV absorbing moiety.

“UV absorbing moiety” refers to an organic functional group that can absorb or shield UV radiation in the range of 200 nm to 400 nm, as understood by one skilled in the art.

“Spatial confinement of actinic radiation” refers to the action or manner in which radiation energy in the form of beams is directed, for example, by a protective coating or protective screen or combinations thereof, and in such a spatially confined manner falls into an area having a well-defined peripheral boundary. Spatial limitation of UV/visible radiation is achieved by using a protective coating or shield that has a radiation-permeable (eg, UV/visible) area, a radiation-impervious (eg, UV/visible) area surrounding the radiation-permeable area, and a projection contour , which is the boundary between areas impenetrable to radiation and permeable to radiation, which is schematically shown in the figures of US patents No. 6800225 (Fig. 1-11) and 6627124 (Fig. 1-9), 7384590 (Fig. 1-6) and 7,387,759 (FIGS. 1-6), all of which are incorporated herein by reference in their entirety. The protective coating or shield allows the spatial projection of a beam of radiation (eg, UV/visible radiation) that is characterized by a cross-sectional profile defined by the projection contour of the protective coating or shield. The projected beam of radiation (eg, UV/visible radiation) limits the radiation (eg, UV/visible radiation) incident on the lens molding material located along the path of the projected beam from the first molding surface to the second molding surface of the mold. The resulting contact lens includes a front surface defined by a first shaping surface, an opposing rear surface defined by a second shaping surface, and a lens edge defined by a longitudinal profile of the projected UV/visible beam (i.e., spatial radiation confinement). The radiation that is used for cross-linking is any radiation energy, in particular UV/visible radiation, gamma radiation, electron radiation or thermal radiation, the radiation energy being preferably used in the form of a beam of predominantly parallel rays with the aim, on the one hand, to achieve proper limitation, and on the other hand, use energy efficiently.

In a conventional injection molding process, the first and second forming surfaces of the mold are aligned with each other to form a circumferential contact line that defines the edge of the resulting contact lens. Since close contact of the molding surfaces may damage the optical quality of the molding surfaces, the mold cannot be reused. In contrast, according to Lightstream Technology ^™ , the edge of the resulting contact lens is determined not by the contact of the molding surfaces of the mold, but by the spatial confinement of radiation. Without any contact between the molding surfaces of the mold, this mold can be reused to produce high quality contact lenses with high repeatability.

The term “dye” means a substance that is soluble in the flowable lens molding material and that is used to impart color. Typically, dyes transmit and absorb light, but do not scatter it.

The term “pigment” means a powdery substance (particles) that is suspended in a lens composition in which it does not dissolve.

As used herein, the terms “surface modification” or “surface treatment” mean that the article has been treated in a surface treatment/modification process before or after molding of the article, in which (1) a coating is applied to the surface of the article, (2) chemicals are adsorbed onto the surface of the article, ( 3) the chemical nature (for example, electrostatic charge) of chemical groups on the surface of the product changes, or (4) other properties of the surface of the product are modified. Examples of surface treatment methods include, but are not limited to, energy-induced surface treatment (e.g., plasma, static electric charge, irradiation, or other energy source), chemical treatments, graft copolymerization of hydrophilic vinyl monomers or macromers onto the surface of an article, a mold coating method disclosed in US Pat. No. 6,719,929 (incorporated herein by reference in its entirety), the inclusion of wetting agents in a contact lens formulation proposed in US Patent Nos. 6,367,929 and 6,822,016 (incorporated herein by reference in its entirety), mold coating, disclosed in US Pat. No. 7,858,000 (incorporated herein by reference in its entirety), and hydrophilic coating, which involves covalently attaching or physically depositing one or more layers of one or more hydrophilic polymers onto the surface of a contact lens, disclosed in US Patent Nos. 8147897 and 8409599 and US Patent Application Nos. 2011/0134387, 2012/0026457 and 2013/0118127 (incorporated herein by reference in their entirety).

“Post-curing surface treatment,” with respect to a silicone hydrogel material or soft contact lens, means a surface treatment method that is carried out after molding (curing) the hydrogel material or soft contact lenses in a mold.

The term “hydrophilic surface” in relation to a silicone hydrogel material or contact lens means that the silicone hydrogel material or contact lens has a surface hydrophilicity that is characterized by an average water contact angle of about 90 degrees or less, preferably about 80 degrees or less, more preferably about 70 degrees or less, even more preferably about 60 degrees or less.

The term “average contact angle” means the water contact angle (measured using the sessile drop technique) which is obtained by averaging the measured values for at least 3 individual contact lenses.

The intrinsic “oxygen permeability”, Dk, of a material refers to the rate at which oxygen will pass through the material. As used herein, the term “oxygen permeability (Dk)” in relation to a hydrogel (silicone or non-silicone) or contact lens means the measured oxygen permeability (Dk) that is corrected for the surface resistance to oxygen flow due to boundary layer effects, according to the procedures described in the examples below. Oxygen permeability is usually expressed in units of barrer, where barrer is defined as [(cm ³ oxygen)(mm)/(cm ² )(s)(mmHg)] x 10 ^-10 .

The term oxygen transmittance, Dk/t, of a lens or material means the rate at which oxygen will pass through a particular lens or material, which is characterized by the average thickness t [in units of mm] over a measured area. Oxygen transmittance is usually expressed in units of bbl/mm, where bbl/mm is defined as [(cm ³ oxygen)/(cm ² )(s)(mm Hg)] x 10 ^-9 .

The term “heat stability” in relation to a silicone hydrogel contact lens means that the silicone hydrogel contact lens can be subjected to a maximum of 19 autoclave cycles (each lasting 30 minutes at 121°C) in phosphate-buffered saline (7.2 ± 0.2) without significant autoclave-induced change (i.e., increase or decrease of about 10% or less, preferably about 5% or less) of at least one property lens selected from the group consisting of: modulus of elasticity E' (MPa), moisture content (WC%), lens diameter D_lenses (mm) and combinations thereof, relative to the corresponding lens property of a silicone hydrogel contact lens subjected to one autoclave treatment for 30 minutes at 121°C) in phosphate-buffered saline (7.2 ± 0.2). For example, a change in lens properties caused by autoclaving () is calculated based on the following equation,

,

in which is the average lens property value after a single autoclave of a soft contact lens and is obtained by averaging the lens property values of 15 soft contact lenses measured after a single autoclave for 30 minutes at 121°C in phosphate buffered saline at pH 7.2±0.2, and is the average lens property value after autoclaving n times of a soft contact lens, and is obtained by averaging the lens property values of 15 soft contact lenses measured after storage and n autoclave cycles (times) each for 30 minutes at 121°C in phosphate-buffered saline at pH 7.2±0.2. It is believed that testing for autoclaving-induced changes in the elastic modulus of silicone hydrogel contact lenses can be used to replace traditional accelerated shelf life studies at elevated temperatures (e.g. 65°C up to 95°C) in order to significantly reduce the time required to determine the equivalent shelf life at room temperature.

As used herein, the term “clear” with respect to a lens molding composition means that the lens molding composition is a clear solution or liquid mixture (i.e., having a light transmittance of 85% or greater, preferably 90% or greater, in the range between 400 and 700 nm).

In general, the invention is directed to a class of hydrophilized polydiorganosiloxane vinyl crosslinkers, each of which contains (1) a polydiorganosiloxane polymer chain containing dimethylsiloxane units and hydrophilized siloxane units, each having one methyl substituent and one monovalent organic C substituent ₄ -C ₄₀ -radical containing from two to six hydroxyl groups, with the molar ratio of hydrophilized siloxane units and dimethylsiloxane units being from about 0.035 to about 0.15; (2) two terminal (meth)acryloyl groups, wherein the hydrophilized polydiorganosiloxane vinyl crosslinker has a number average molecular weight of about 3,000 daltons to about 80,000 daltons.

The present invention is based in part on the discovery that the hydrophilized polydiorganosiloxane vinyl crosslinker of the present invention is suitable for the preparation of various solvent-containing or solvent-free lens formulations that can contain a large amount of hydrophilic polymerizable component and remain clear at room temperature or even at low temperature storage from approx. 0°C to approx. 4°C. It is believed that the hydrophilized polydiorganosiloxane vinyl crosslinker of the present invention may contain a relatively high number of hydroxyl groups per molecule and therefore should be more compatible with other hydrophilic polymerizable components (e.g., hydrophilic vinyl monomer, hydrophilic crosslinker and/or hydrophilic prepolymer) due to the ability of hydroxyl groups to form hydrogen bonds. Given its suitability for storage at low storage temperatures from approx. 0°C to approx. 4°C, such a lens composition can advantageously be prepared in advance upon receipt.

The present invention is also based in part on the discovery that the polydiorganosiloxane vinyl crosslinker of the present invention (i.e., having a unique combination of a selected molar ratio of hydrophilized siloxane units to dimethylsiloxane units and a selected number average molecular weight) can be used in a lens formulation containing a relatively high amount hydrophilic polymerizable components to obtain a silicone hydrogel contact lens, which can have a relatively high oxygen permeability and a relatively low elastic modulus. It is believed that to achieve higher oxygen permeability, polydiorganosiloxane must have at least 5 dimethylsiloxane units in a row. By tightly packing the hydroxyl groups into a limited number of siloxane units, the hydrophilized polydiorganosiloxane vinyl crosslinker of the present invention can have a relatively low molar ratio of hydrophilized siloxane units to dimethylsiloxane units, which ensures that the siloxane segments consist of more than 5 dimethylsiloxane units in a row. By selecting a combination of the molar ratio of hydrophilized siloxane units to dimethylsiloxane units and molecular weight, the polydiorganosiloxane vinyl crosslinking agent of the present invention can have a relatively high contribution to oxygen permeability per siloxane unit, relatively high compatibility with hydrophilic polymerizable components due to the large number of hydroxyl groups per molecule, and relatively low contribution to the elastic modulus due to the relatively high molecular weight.

When the hydrophilized polydiorganosiloxane vinyl crosslinker of the present invention is used in a silicone hydrogel lens composition, the silicone hydrogel contact lenses obtained from the lens composition can exhibit greater stability due to the stable backbones of the polydiorganosiloxane polymer chains and the monovalent organic C ₄ - substituent. C ₄₀ radical, hydrophilized siloxane units. The hydrophilized polydiorganosiloxane vinyl crosslinker of the present invention is designed to have stable backbones and side chains free from unstable linkages (such as urea linkage, urethane linkage, polyethylene glycol segment) that are susceptible to degradation due to hydrolysis, photolysis, low thermal stability and /or oxidation.

In one aspect, the present invention provides a polydiorganosiloxane vinyl crosslinker. The polydiorganosiloxane vinyl crosslinking agent of the present invention contains: (1) a polydiorganosiloxane polymer chain containing dimethylsiloxane units and hydrophilized siloxane units, each having one methyl substituent and one substituent representing a monovalent organic C ₄ -C ₄₀ radical containing from two up to six hydroxyl groups, wherein the molar ratio of hydrophilized siloxane units to dimethylsiloxane units is from about 0.035 to about 0.15; (2) two terminal (meth)acryloyl groups, wherein the polydiorganosiloxane vinyl crosslinker has a number average molecular weight of from about 3,000 daltons to about 80,000 daltons (preferably from about 4,000 daltons to about 50,000 daltons, more preferably from about 5,000 daltons to about 25,000 daltons , even more preferably from about 6000 daltons to about 18000 daltons).

According to a preferred embodiment, the polydiorganosiloxane vinyl crosslinker of the present invention is a polymer of formula (1),

,

wherein

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

X ₀ represents O or NR', in which R' represents hydrogen or C ₁ -C ₁₀ alkyl;

R ₁ represents hydrogen or methyl;

R ₂ and R ₃ independently represent a substituted or unsubstituted C ₁ -C ₁₀ alkylene divalent radical or a divalent radical -R ₅ -OR ₆ - in which R ₅ and R ₆ independently represent a substituted or unsubstituted C ₁ -C ₁₀ alkylene divalent radical;

R ₄ represents a monovalent radical of any formula (2)-(6),

,

,

,

,

,

q1 equals zero or 1;

n1 is an integer from 2 to 4;

n2 is an integer from 1 to 5;

n3 is an integer from 3 to 6;

n4 is an integer from 2 to 5;

R ₇ represents hydrogen or methyl;

R ₈ and R ₉ independently of each other represent a C ₂ -C ₆ hydrocarbon radical having valencies (n2+1);

R ₁₀ is ethyl or hydroxymethyl;

R ₁₁ represents methyl or hydroxymethyl;

R ₁₂ represents hydroxyl or methoxy;

X ₁ represents a sulfur bridge -S- or a tertiary amine bridge -NR ₁₃ -, in which R ₁₃ represents C ₁ -C ₁ alkyl, hydroxyethyl, hydroxypropyl or 2,3-dihydroxypropyl;

X ₂ represents an amide bridge or , in which R ₁₄ represents hydrogen or C ₁ -C ₁₀ alkyl.

In a preferred embodiment, R ₄ is a monovalent radical of one of formulas (2a)-(2y),

,

wherein q1 is zero or 1 (preferably 1), n1 is an integer from 2 to 4 (preferably 3), R ₇ is hydrogen or methyl (preferably hydrogen).

In another preferred embodiment, R ₄ is a monovalent radical of one of formulas (3a)-(3y),

, in which X ₂ represents an amide bridge or , in which R ₁₄ represents hydrogen or C ₁ -C ₁₀ alkyl.

In another preferred embodiment, R ₄ is a monovalent radical of formula (4a) or (4b),

In another preferred embodiment, R ₄ is a monovalent radical of one of formulas (5a)-(5c),

.

In another preferred embodiment, R ₄ is a monovalent radical of formula (6) in which n1 is 3 and q1 is 1.

The polydiorganosiloxane vinyl crosslinker of formula (1) can be prepared by introducing a hydrosiloxane-containing polydiorganosiloxane of formula (7) with a double bond monomer containing 2 to 5 hydroxyl groups,

,

in which X ₀ , R ₁ , R ₂ , R ₃ , υ 1 and ω 1 are defined above, in a platinum-catalyzed hydrosilylation reaction known to one skilled in the art.

The hydrosiloxane-containing polysiloxane of formula (7) can be prepared according to any methods known to one skilled in the art. As an illustrative example, the hydrosiloxane-containing polysiloxane of formula (7) can be prepared by polymerizing a mixture of octamethylcyclotetrasiloxane (D4) and 1,3,5,7-tetramethylcyclotetrasiloxane (H4) in the presence of 1,3-bis[3-(meth)acryloxypropyl]tetramethyldisiloxane in as the end block of the chain and in the presence of a catalyst. By adjusting the molar ratio of D4 and H4, the required value of the ratio υ1/ω1 can be achieved.

When in formula (1) R ₄ represents a monovalent radical of formula (4), (5) or (6), the preferred double bond monomer is 3-allyloxy-1,2-propanediol, 2-allyloxymethyl-2-(hydroxymethyl )-1,3-propanediol, 2-allyloxymethyl-2-ethyl-1,3-propanediol (i.e. trimethylolpropanallyl ether), allyl-α-D-mannopyranoside, allyl-α-D-galactopyranoside, allyl-6- deoxyhexopyranoside, allyl-6-deoxy-2-O-methylhexopyranoside, or the fully hydrolyzed (i.e., ring-opened) product of the epoxy-containing double bond monomer, which is the allyloxyglycidyl ether, 1,2-epoxy-5-hexene, 3 ,4-epoxy-1-butene or 2-methyl-2-vinyloxirane. The double bond monomers listed above are commercially available.

If in formula (1) R ₄ represents a monovalent radical of formula (2), the preferred double bond monomer is the reaction product of an epoxy-containing double bond monomer with a mercaptan containing 2 to 5 hydroxyl groups or a secondary amine containing 2 to 5 hydroxyl groups. Examples of commercially available epoxy-containing double bond monomers include, but are not limited to, allyloxyglycidyl ether, 1,2-epoxy-5-hexene, 3,4-epoxy-1-butene, and 2-methyl-2-vinyloxirane. Examples of commercially available mercaptans containing 2 to 4 hydroxyl groups include, but are not limited to, 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-methyloltetrahydropyran-3,4,5-triol. Examples of commercially available secondary amines containing 2 to 4 hydroxyl groups include, but are not limited to, 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-methyloltetrahydropyranetriol, 3-(ethylamino)-6-methyloltetrahydropyranetriol, 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-tetrahydroxypentylamine, N-methyl-2,3,4,5,6-pentahydroxyhexylamine. The reactions between an epoxide and a mercaptan (to form a thiol ether bridge) and between an epoxide and a secondary amine (to form an amine bridge) are well known to one skilled in the art and have been described in the literature.

When R ₄ in formula (1) is a monovalent radical of formula (3), the preferred double bond monomer is the product of the reaction of either (1) a carboxy-containing double bond monomer with a primary or secondary amine containing 2 to 5 hydroxyl groups, or (2) a primary amine-containing or secondary amine-containing monomer with a double bond with an alkanoic acid containing 2 to 5 hydroxyl groups, according to the well-known coupling reaction between one carboxylic acid group and one amine (primary or secondary) group in the presence of 1 -ethyl-3-(3-dimethylaminopropyl) carbodiimide (EDC) and N-hydroxysuccinimide (HO-NHS) to produce a double bond monomer containing 2 to 5 hydroxyl groups and an amide bridge. Examples of commercially available carboxy-containing double bond monomers include, but are not limited to, 3-butenoic acid, 4-pentenoic acid, 5-hexenoic acid, and 6-heptenoic acid. Examples of commercially available primary or secondary amine containing double bond monomers include, but are not limited to, 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 containing 2 to 5 hydroxyl groups include, but are not limited to, 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-trihydroxy-2-methoxypentanoic acid, xylonic acid (2,3,4,5-tetrahydroxypentanoic acid), 3,4,5-trihydroxyhexanoic acid, 3,5,6-trihydroxyhexanoic acid, 4,5,6-trihydroxyhexanoic acid, 2,4,5,6-tetrahydroxyhexanoic acid, 2,3,4,5-tetrahydroxyhexanoic acid, 2 ,3,4,5,6-pentahydroxyhexanoic acid. Examples of commercially available primary amines containing 2 to 5 hydroxyl groups include, but are not limited to, dihydroxyethylamine, 2,3-dihydroxypropylamine, 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-hydroxymethyltetrahydropyran -2,4,5-triol. The commercially available secondary amines listed above containing 2 to 5 hydroxyl groups can be used in reaction with a carboxy-containing double bond monomer to produce a double bond monomer having multiple hydroxyl groups and an amide bridge. The reaction between a carboxylic acid group and a primary or secondary amino group to form an amide bridge is well known to one skilled in the art and has been widely described in the literature.

The polydiorganosiloxane vinyl crosslinking agent of the present invention (formula (1) defined above) may find particular use in the production of a polymer, preferably a silicone hydrogel polymer material, which is another aspect of the present invention. One skilled in the art will know how to prepare a polymer or silicone hydrogel polymer material from a polymerizable composition in accordance with any known polymerization mechanisms.

In another aspect, the present invention provides a silicone hydrogel contact lens comprising a crosslinked polymeric material comprising: units of a polydiorganosiloxane vinyl crosslinker of formula (1) (defined above), units of a siloxane-containing vinyl monomer, units of at least one hydrophilic vinyl monomer, wherein The silicone hydrogel contact lens, when fully hydrated, has an oxygen permeability (Dk) of at least about 70 bbl (preferably at least about 80 bbl, more preferably at least about 90 bbl, even more preferably at least about 100 bbl), moisture content from about 25% to about 70% by weight (preferably from about 30% to about 65% by weight, more preferably from about 35% to about 60% by weight, even more preferably from about 40% to about 55% by weight ), and a modulus of elasticity from about 0.20 MPa to about 1.2 MPa (preferably from about 0.25 MPa to about 1.0 MPa, more preferably from about 0.3 MPa to about 0.9 MPa, even more preferably from about 0.4 MPa to about 0.8 MPa). Preferably, the silicone hydrogel contact lens has thermal stability, which is characterized by the presence of an autoclave-induced change , being about 10% or less (preferably about 8% or less, more preferably about 6% or less, even more preferably about 4% or less) of at least one lens property (LP) selected from the group consisting of elastic modulus , moisture content, lens diameter and their combinations, where is the average lens property value after a single autoclave and is obtained by averaging the lens property values of 15 soft contact lenses measured after a single autoclave for 30 minutes at 121°C in phosphate buffered saline at pH 7.2±0.2, and represents the average lens property values after autoclaving 19 times, and is obtained by averaging the lens property values of 15 soft contact lenses measured after storage and autoclaving 19 times, each for 30 minutes at 121°C in phosphate-buffered saline at pH 7.2±0.2.

One skilled in the art is well aware of how to measure oxygen permeability, oxygen transmittance, moisture content, elastic modulus, and lens diameter of silicone hydrogel contact lenses. These lens properties have been published by all manufacturers for their silicone hydrogel contact lens products.

Various embodiments of the polydiorganosiloxane vinyl crosslinker of formula (1) (defined above) are to be included in this aspect of the present invention.

Any suitable siloxane-containing vinyl monomers can be used in the present invention. A class of preferred siloxane-containing vinyl monomers are those that contain a tris(trialkylsiloxy)silyl group or a bis(trialkylsilyloxy)alkylsilyl group. Examples of such preferred silicone-containing vinyl monomers include, but are not limited to, 3-acrylamidopropyl-bis(trimethylsiloxy)methylsilane, 3-N-methylacrylamidopropyl-bis(trimethylsiloxy)methylsilane, N-[tris(trimethylsiloxy)silylpropyl](meth)acrylamide, N-[tris( dimethylpropylsiloxy)silylpropyl](meth)acrylamide, N-[tris(dimethylphenylsiloxy)silylpropyl](meth)acrylamide, N-[tris(dimethylethylsiloxy)silylpropyl](meth)acrylamide, N-(2-hydroxy-3-(3-( bis(trimethylsilyloxy)methylsilyl)propyloxy)propyl)-2-methylacrylamide; N-(2-hydroxy-3-(3-(bis(trimethylsilyloxy)methylsilyl)propyloxy)propyl)acrylamide; N,N-bis[2-hydroxy-3-(3-(bis(trimethylsilyloxy)methylsilyl)propyloxy)propyl]-2-methylacrylamide; N,N-bis[2-hydroxy-3-(3-(bis(trimethylsilyloxy)methylsilyl)propyloxy)propyl]acrylamide; N-(2-hydroxy-3-(3-(tris(trimethylsilyloxy)silyl)propyloxy)propyl)-2-methylacrylamide; N-(2-hydroxy-3-(3-(tris(trimethylsilyloxy)silyl)propyloxy)propyl)acrylamide; N,N-bis[2-hydroxy-3-(3-(tris(trimethylsilyloxy)silyl)propyloxy)propyl]-2-methylacrylamide; N,N-bis[2-hydroxy-3-(3-(tris(trimethylsilyloxy)silyl)propyloxy)propyl]acrylamide; N-[2-hydroxy-3-(3-(tert-butyldimethylsilyl)propyloxy)propyl]-2-methylacrylamide; N-[2-hydroxy-3-(3-(tert-butyldimethylsilyl)propyloxy)propyl]acrylamide; N,N-bis[2-hydroxy-3-(3-(tert-butyldimethylsilyl)propyloxy)propyl]-2-methylacrylamide; N,N-bis[2-hydroxy-3-(3-(tert-butyldimethylsilyl)propyloxy)propyl]acrylamide; 3-methacryloxypropylpentamethyldisiloxane, tris(trimethylsilyloxy)silylpropyl methacrylate (TRIS), (3-methacryloxy-2-hydroxypropyloxy)propyl-bis(trimethylsiloxy)methylsilane), (3-methacryloxy-2-hydroxypropyloxy)propyl-tris(trimethylsiloxy)silane, 3- methacryloxyethoxypropyloxypropyl-bis(trimethylsiloxy)methylsilane, N-2-methacryloxyethyl-O-(methyl-bis-trimethylsiloxy-3-propyl)silylcarbamate, 3-(trimethylsilyl)propylvinylcarbonate, 3-(vinyloxycarbonylthio)propyl-tris(trimethylsiloxy)silane, 3 -[tris(trimethylsiloxy)silyl]propylvinylcarbamate, 3-[tris(trimethylsiloxy)silyl]propylallylcarbamate, 3-[tris(trimethylsiloxy)silyl]propylvinylcarbonate, tert-butyldimethylsiloxyethylvinylcarbonate, trimethylsilylethylvinylcarbonate, trimethylsilylmethylvinylcarbonate and hydrophilized siloxane-containing vinyl monomers , disclosed in US Pat. No. No. 9103965, 9475827 and 9097840 (incorporated herein by reference in their entirety) containing at least one hydrophilic bridge and/or at least one hydrophilic chain.

Another class of preferred siloxane-containing vinyl monomers are polycarbosiloxane vinyl monomers (or carbosiloxane vinyl monomers). Examples of such polycarbosiloxane vinyl monomers or macromers are those described in U.S. Patent Nos. 7,915,323 and 8,420,711, U.S. Patent Application Publications Nos. 2012/244088, 2012/245249, 2015/0309211, and 2015/0309210 (incorporated herein by reference in their entirety). completeness).

An additional class of preferred siloxane-containing vinyl monomers are polydimethylsiloxane-containing vinyl monomers. Examples of such polydimethylsiloxane-containing vinyl monomers are polydimethylsiloxanes with a single terminal (meth)acryloxy group of various molecular weights (for example, polydimethylsiloxane with a single terminal 3-methacryloxypropyl group, with a single terminal butyl group or polydimethylsiloxane with a single terminal (3-methacryloxy-2-hydroxypropyloxy)propyl group , with one terminal butyl group), polydimethylsiloxanes with one terminal (meth)acrylamide group of different molecular weights or combinations thereof.

According to the present invention, the siloxane-containing vinyl monomer is preferably 3-(meth)acryloxy-2-hydroxypropyloxy)propyl-bis(trimethylsiloxy)methylsilane, 3-(meth)acryloxyethoxypropyloxypropyl-bis(trimethylsiloxy)methylsilane, 3-(meth)acrylamidopropyl -bis(trimethylsiloxy)methylsilane, 3-N-methyl-(meth)acrylamidopropyl-bis(trimethylsiloxy)methylsilane, polydimethylsiloxanes with one terminal (meth)acryloxy group of different molecular weight, polydimethylsiloxanes with one terminal (meth)acrylamide group with different molecular weight or a combination thereof.

It should be understood that the crosslinked polymeric silicone hydrogel contact lens material of the present invention may optionally contain a polydimethylsiloxane vinyl crosslinker as long as it is compatible with the hydrophilic polymerizable components in the lens molding composition for making the silicone hydrogel contact lens.

Examples of preferred hydrophilic vinyl monomers include, but are not limited to, N-vinylpyrrolidone, N,N-dimethyl(meth)acrylamide, (meth)acrylamide, hydroxyethyl(meth)acrylamide, N-hydroxypropyl(meth)acrylamide, hydroxyethyl(meth)acrylate, glycerol methacrylate (GMA) ), polyethylene glycol (meth)acrylate, characterized by a number average molecular weight of not more than 1500, C ₁ -C ₄ alkyl ether (meth)acrylate of polyethylene glycol, characterized by a number average molecular weight of up to 1500, N - [tris(hydroxymethyl)methyl]acrylamide, N- vinylformamide, N-vinylacetamide, N-vinylisopropylamide, N-vinyl-N-methylacetamide, N-methyl-3-methylene-2-pyrrolidone, 1-ethyl-3-methylene-2-pyrrolidone, 1-methyl-5-methylene- 2-pyrrolidone, 1-ethyl-5-methylene-2-pyrrolidone, 5-methyl-3-methylene-2-pyrrolidone, 5-ethyl-3-methylene-2-pyrrolidone, (meth)acrylic acid, ethyl acrylic acid and their combinations. Preferably, the hydrophilic vinyl monomer is a hydrophilic N-vinyl monomer such as N-vinylpyrrolidone, N-vinyl-N-methylacetamide, N-vinylformamide, N-vinylacetamide, N-vinyl isopropylamide, or combinations thereof. Even more preferably, the hydrophilic vinyl monomer is N-vinylpyrrolidone, N-vinyl-N-methylacetamide, or combinations thereof.

In accordance with the present invention, the crosslinked polymeric silicone hydrogel contact lens material of the present invention may further comprise non-silicone hydrophobic vinyl monomer units, non-silicone vinyl crosslinker units, UV absorbing vinyl monomer units, or a combination thereof.

Examples of preferred hydrophobic vinyl monomers include methyl acrylate, ethyl acrylate, propyl acrylate, isopropylacrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl valerate, styrene, chloroprene, vinyl chloride, vinylidene chloride, , 1-butene, butadiene, methacrylonitrile, vinyltoluene, vinylethyl ether, perfluorohexylethylthiocarbonylaminoethyl methacrylate, isobornyl methacrylate, trifluoroethyl methacrylate, hexafluoroisopropyl methacrylate, hexafluorobutyl methacrylate.

Examples of preferred non-silicone cross-linking agents include, but are not limited to, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, glycerol di(meth)acrylate, 1. 3-propanediol-di(meth)acrylate, 1,3-butanediol-di(meth)acrylate, 1,4-butanediol-di(meth)acrylate, glycerol-1,3-diglycerinate-di(meth)acrylate, ethylene- bis[oxy(2-hydroxypropane-1,3-diyl)]-di(meth)acrylate, bis[2-(meth)acryloxyethyl]phosphate, trimethylolpropane-di(meth)acrylate and 3,4-bis[(meth) acryloyl]tetrahydrofuran, diacrylamide (i.e. N-(1-oxo-2-propenyl)-2-propenamide), dimethacrylamide (i.e. N-(1-oxo-2-methyl-2-propenyl)-2 -methyl-2-propenamide), 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)acrylamidepropan-2-yldihydrogen phosphate (i.e. e. N,N'-2-phosphonyloxypropylene-bis(meth)acrylamide), piperazine diacrylamide (or 1,4-bis(meth)acryloylpiperazine), vinyl methacrylate, allyl methacrylate, allyl acrylate, N-allyl methacrylamide, N-allylacrylamide, 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, diamine product (preferably selected from the group consisting of N,N'-bis(hydroxyethyl)ethylenediamine, N, N' -dimethylethylenediamine, ethylenediamine, N,N'-dimethyl-1,3-propanediamine, N,N'-diethyl-1,3-propanediamine, propane-1,3-diamine, butane-1,4-diamine, pentane-1 ,5-diamine, hexamethylenediamine, isophorone diamine and combinations thereof) and an epoxy-containing vinyl monomer (preferably selected from the group consisting of glycidyl (meth)acrylate, vinyl glycidyl ether, allyl glycidyl ether and combinations thereof), thereof combinations.

A more preferred vinyl crosslinker is 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, glycerin dimethacrylate, allyl (meth)acrylate, N,N'-methylene-bis(meth)acrylamide, N,N'-ethylene-bis(meth)acrylamide, N,N'-dihydroxyethylene-bis(meth)acrylamide, N,N'-2 -hydroxypropylene-bis(meth)acrylamide, N,N'-2,3-dihydroxybutylene-bis(meth)acrylamide, 1,3-bis(meth)acrylamidepropan-2-yl dihydrogen phosphate (i.e. N,N'-2 -phosphonyloxypropylene bis(meth)acrylamide), piperazine diacrylamide (or 1,4-bis(meth)acryloylpiperazine), triallyl isocyanurate, tetraethylene glycol divinyl ether, triethylene glycol divinyl ether, diethylene glycol divinyl ether, ethylene glycol divinyl ether and combinations thereof.

Examples of preferred UV absorbing vinyl monomers include, but are not limited to: 2-(2-hydroxy-5-vinylphenyl)-2H-benzotriazole, 2-(2-hydroxy-5-acrylyloxyphenyl)-2H-benzotriazole, 2-(2-hydroxy- 3-methacrylamidomethyl-5-tert-octylphenyl)benzotriazole, 2-(2'-hydroxy-5'-methacrylamidophenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-5'-methacrylamidophenyl)-5-methoxybenzotriazole, 2- (2'-hydroxy-5'-methacryloxypropyl-3'-tert-butylphenyl)-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 methacrylate (WL-2), 3-(2H-benzo[d][1,2,3]triazol-2-yl)-2-hydroxy-5-methoxybenzyl methacrylate (WL-3), 3- (5-chloro-2H-benzo[d][1,2,3]triazol-2-yl)-2-hydroxy-5-methoxybenzyl methacrylate (WL-4), 2-hydroxy-5-methoxy-3-(5 -methyl-2H-benzo[d][1,2,3]triazol-2-yl)benzyl methacrylate (WL-6), 2-hydroxy-5-methyl-3-(5-(trifluoromethyl)-2H-benzo[ d][1,2,3]triazol-2-yl)benzyl methacrylate (WL-7), 4-allyl-2-(5-chloro-2H-benzo[d][1,2,3]triazol-2- yl)-6-methoxyphenol (WL-8), 2-{2'-hydroxy-3'- tert -5'[3ʺ-(4ʺ-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'-methacryloxyethylphenyl)benzotriazole ( 2-methyl-2-[3-( 2H -benzotriazol-2-yl)-4-hydroxyphenyl]ethyl 2-propenoic acid ester, Norbloc), 2-{2'-hydroxy-3'- tert -butyl- 5'-[3'-methacryloyloxypropoxy]phenyl}-5-methoxy -2H -benzotriazole (UV13), 2-[2'-hydroxy-3'- tert- butyl-5'-(3'-acryloyloxypropoxy)phenyl]- 5-trifluoromethyl -2H -benzotriazole (CF ₃ -UV13), 2-(2'-hydroxy-5-methacrylamidophenyl)-5-methoxybenzotriazole (UV6), 2-(3-allyl-2-hydroxy-5-methylphenyl)- 2H -benzotriazole (UV9), 2-(2-hydroxy-3-metallyl-5-methylphenyl) -2H -benzotriazole (UV12), 2-3'-tert-butyl-2'-hydroxy-5'-(3ʺ- dimethylvinylsilylpropoxy)-2'-hydroxyphenyl)-5-methoxybenzotriazole (UV15), 2-(2'-hydroxy-5'-methacryloylpropyl-3'-tert-butylphenyl)-5-methoxy -2H -benzotriazole (UV16), 2- (2'-hydroxy-5'-acryloylpropyl-3'-tert-butylphenyl)-5-methoxy- 2H -benzotriazole (UV16A), 3-[3-tert-butyl-5-(5-chlorobenzotriazol-2-yl) 2-Methylacrylic acid -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)ethyl methacrylate (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 (9CI) homopolymer (CAS No. 83063-87-0).

In a preferred embodiment, the silicone hydrogel contact lens contains from about 30% to about 60% by weight of units of the at least one hydrophilic vinyl monomer, where the percentage by weight of the units of the at least one hydrophilic vinyl monomer is the percentage by weight said at least one hydrophilic vinyl monomer relative to the total weight of all polymerizable components in the polymerizable composition for the manufacture of a cross-linked polymer material.

A silicone hydrogel contact lens can be produced from a lens molding composition in accordance with the method of the present invention, which is another aspect of the present invention.

In a further aspect, the present invention provides a method for producing silicone hydrogel contact lenses. The method includes the steps of: obtaining a lens molding composition that is clear at room temperature and optionally, but preferably, at a temperature of from about 0 to about 4°C, wherein the lens molding composition contains (a) from about 5% to about 35% by weight of a polydiorganosiloxane vinyl crosslinker of formula (1) (defined above), (b) a siloxane-containing vinyl monomer, (c) from about 30 % to about 60% by weight of at least one hydrophilic vinyl monomer, (d) at least one free radical polymerization initiator, provided that the above polymerizable components and any additional polymerizable components add up to 100% by weight; introducing a composition for molding a lens into a mold, wherein the mold has a first half-mold with a first molding surface defining the front surface of the contact lens, and a second half-mold with a second molding surface defining the back surface of the contact lens, where said first and second halves are made capable of being aligned with each other so that a cavity is formed between said first and second forming surfaces; curing, thermally or by actinic radiation, a lens molding composition in a lens mold to form a silicone hydrogel contact lens, wherein the silicone hydrogel contact lens has an oxygen permeability (Dk) of at least about 70 bbl, a moisture content of from about 25% to about 70% by weight, an elastic modulus of about 0.2 MPa to about 1.2 MPa, and thermal stability that is characterized by the presence of an autoclave-induced change , being approximately 10% or less of at least one lens property (LP) selected from the group consisting of elastic modulus, moisture content, lens diameter, and combinations thereof, where is the average lens property value after a single autoclave and is obtained by averaging the lens property values of 15 soft contact lenses measured after a single autoclave for 30 minutes at 121°C in phosphate buffered saline at pH 7.2±0.2, and represents the average lens property values after autoclaving 19 times, and is obtained by averaging the lens property values of 15 soft contact lenses measured after storage and autoclaving 19 times, each for 30 minutes at 121°C in phosphate-saline buffer at pH 7.2±0.2.

The various embodiments of the polydiorganosiloxane vinyl crosslinker of formula (1) (defined above) described above are to be included in this aspect of the present invention.

The various embodiments of the siloxane-containing vinyl monomer, hydrophilic vinyl monomer described above are intended to be included in this aspect of the present invention.

In accordance with the present invention, the free radical polymerization initiator may be a thermal initiator or a photoinitiator.

Suitable thermal polymerization initiators are known to one skilled in the art and include, for example, peroxides, hydroperoxides, azo-bis(alkyl or cycloalkylnitriles), persulfates, percarbonates, or mixtures thereof. Examples are benzoyl peroxide, 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. The polymerization is typically carried out in the above-mentioned solvent at an elevated temperature, for example at a temperature of from 25 to 100°C and preferably from 40 to 80°C. The reaction time can be varied within wide limits, but is typically, for example, 1 to 24 hours, or preferably 2 to 12 hours. It is preferable to first degas the components and solvents used in the polymerization reaction and carry out said copolymerization reaction under an inert atmosphere, for example, nitrogen or argon.

Suitable photoinitiators are benzoin methyl ether, diethoxyacetophenone, benzoylphosphine oxide, 1-hydroxycyclohexylbenzophenone and the Darocur and Irgacur series, preferably Darocur 1173® and Darocur 2959®, Norrish type I photoinitiators based on germanium. 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. Also suitable are reactive photoinitiators, which can be incorporated, for example, into a macromer, or they can be used as a special monomer. Examples of such reactive photoinitiators are disclosed in EP 632329, which is incorporated herein by reference in its entirety. The polymerization can then be activated by actinic radiation, for example light, in particular UV radiation of a suitable wavelength. If necessary, spectral requirements can be controlled accordingly by adding suitable photosensitizers.

When a vinyl monomer capable of absorbing ultraviolet radiation and high energy violet light (HEVL) is used in the invention, a germanium-based Norrish Type I photoinitiator and a light source, including light in the region of about 400, are preferably used to initiate free radical polymerization. up to approximately 550 nm. Any germanium-based Norrish Type I photoinitiator may be used in the present invention, provided that it is capable of initiating free radical polymerization under irradiation from a light source, including light in the region of about 400 to about 550 nm. Examples of germanium-based Norrish type I photoinitiators are the acylgermanium-based compounds described in US Pat. No. 7,605,190 (incorporated herein by reference in its entirety). Preferably, the monomer of the lens molding materials contains at least one of the following acylgermanium compounds,

.

In a preferred embodiment, the lens molding composition contains an organic solvent.

Examples of suitable solvents include, but are not limited to, tetrahydrofuran, tripropylene glycol methyl ether, dipropylene glycol methyl ether, ethylene glycol n-butyl ether, ketones (e.g., acetone, methyl ethyl ketone, etc.), diethylene glycol n-butyl ether, diethylene glycol methyl ether , ethylene glycol phenyl ether, propylene glycol methyl ether, propylene glycol methyl ether acetate, dipropylene glycol methyl ether acetate, propylene glycol n-propyl ether, dipropylene glycol n-propyl ether, tripropylene glycol n-butyl ether, propylene glycol n-butyl ether , dipropylene glycol n-butyl ether, tripropylene glycol n-butyl ether, propylene glycol phenyl ether, dipropylene glycol dimethyl ether, polyethylene glycols, polypropylene glycols, ethyl acetate, butyl acetate, amyl acetate, methyl lactate, ethyl lactate, isopropyl lactate, methylene chloride, 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, tert- amyl alcohol, isopropanol, 1-methyl-2-pyrrolidone, N,N-dimethylpropionamide, dimethylformamide, dimethylacetamide, dimethylpropionamide, N-methylpyrrolidinone and mixtures thereof.

In another preferred embodiment, the lens molding composition is a solution of all necessary components dissolved in 1-propanol, isopropanol, tert-amyl alcohol, 1,2-propylene glycol, polyethylene glycol, which has a molecular weight of about 400 daltons or less, or their mixtures.

In another preferred embodiment, the lens molding composition is a solvent-free liquid mixture and contains a miscible vinyl monomer selected from the group consisting of C ₁ -C ₁₀ alkyl methacrylate, isobornyl methacrylate, isobornyl acrylate, cyclopentyl methacrylate, cyclopentyl acrylate, cyclohexyl methacrylate, cyclohexyl acrylate, styrene, 2. 4,6-trimethylstyrene (TMS) and tert-butylstyrene (TBS) and combinations thereof. Preferably, the miscible vinyl monomer is methyl methacrylate.

In another preferred embodiment, the total amount of all silicone-containing polymerizable components present in the lens molding composition is approximately 65% or less.

In another preferred embodiment, the hydrophilic vinyl monomer is a hydrophilic N-vinyl monomer, preferably N-vinylpyrrolidone, N-vinyl-N-methylacetamide, N-vinylformamide, N-vinylacetamide, N-vinylisopropylamide or combinations thereof, even more preferably is N-vinylpyrrolidone, N-vinyl-N-methylacetamide, or combinations thereof.

In another preferred embodiment, the lens molding composition further comprises a non-silicone vinyl crosslinking agent. The various embodiments of the siloxane-containing vinyl monomer, hydrophilic vinyl monomer described above are intended to be included in this aspect of the present invention. The amount of non-silicone vinyl crosslinker used is expressed by weight relative to all polymerizable components and is preferably in the range of from about 0.05% to about 2%, and more preferably in the range from about 0.1% to about 1.5%, even more preferably in the range of from about 0.15% to about 1.0%.

In accordance with the present invention, the lens molding composition may further contain other components, such as a visual tint agent (for example, dyes, pigments or mixtures thereof), antimicrobial agents (for example, preferably silver nanoparticles), a biologically active agent, leachable lubricants substances, leachables that impart tear resistance, and mixtures thereof known to one skilled in the art.

Lens molds for producing contact lenses are well known to one skilled in the art and are, for example, used in injection molding or centrifugal casting. For example, a mold (for injection molding) typically includes at least two mold flaps (or parts) or mold halves, i.e., a first and a second mold halves. The first half-mold defines a first forming (or optical) surface, and the second half-mold defines a second forming (or optical) surface. The first and second mold halves are configured to be aligned with each other so that a cavity for molding the lens is formed between the first molding surface and the second molding surface. The molding surface of the half-mold is the surface of the mold that forms the cavity and comes into direct contact with the material to form the lens.

Methods for making mold flaps for injection molding a contact lens are generally well known to those skilled in the art. The method of the present invention is not limited to any particular mold manufacturing method. In fact, any mold manufacturing method can be used in the present invention. The first and second mold halves can be produced using various techniques such as injection molding or turning. Examples of suitable methods for forming mold halves are disclosed in US Pat. Nos. 4,444,711; 4460534; 5843346 and 5894002, which are incorporated herein by reference in their entirety.

Virtually all materials known in the art of making molds can be used to make molds for producing contact lenses. For example, polymeric materials such as polyethylene, polypropylene, polystyrene, PMMA, ^Topas® COC grade 8007-S10 (pure amorphous ethylene-norbornene copolymer from Ticona GmbH, Frankfurt, Germany and Summit, NJ) or the like can be used. Other materials that transmit UV radiation, such as quartz glass and sapphire, can be used.

In accordance with the present invention, the lens molding composition (or composition) can be introduced (poured) into the cavity formed by the mold in accordance with any known methods.

After the lens molding composition is poured into the mold, it is polymerized to form a contact lens. Cross-linking can be initiated thermally or actinically.

The opening of the mold is carried out in a manner known per se in such a way that it is possible to remove the molded product from the mold.

The molded contact lens can be subjected to extraction to remove uncured polymerizable components. The extraction solvent can be any solvent known to one skilled in the art. Examples of suitable extraction solvent are described above. Preferably, water or an aqueous solution is used as the extraction solvent. After extraction, the lenses can be hydrated in water or an aqueous solution of a wetting agent (eg, a hydrophilic polymer).

The molded contact lenses can then be subjected to additional processing methods, such as, for example, surface treatment, packaging the lenses in packages with a packaging solution that may contain from about 0.005% to about 5% by weight of a wetting agent (e.g., the hydrophilic polymer described above, or the like known to one skilled in the art) and/or a viscosity increasing agent (eg methylcellulose (MC), ethylcellulose, hydroxymethylcellulose, hydroxyethylcellulose (HEC), hydroxypropylcellulose (HPC), hydroxypropylmethylcellulose (HPMC) or a mixture thereof); sterilization, such as autoclaving at a temperature of 118 to 124°C for at least about 30 minutes; and the like.

In a preferred embodiment, the resulting silicone hydrogel contact lens is subjected to extraction with water or an aqueous solution.

In another preferred embodiment, the mold is a reusable mold wherein the lens molding composition is cured (ie, polymerized) by exposure to actinic radiation while spatially confining the actinic radiation to form a silicone hydrogel contact lens. Examples of preferred reusable molds are those disclosed in US Pat. Nos. 6,627,124, 6,800,225, 7,384,590, and 7,387,759, which are incorporated by reference in their entirety. Recyclable molds can be made from quartz, glass, sapphire, CaF ₂ , cyclic olefin copolymer (such as, for example, Topas ^® COC grade 8007-S10 (transparent amorphous ethylene-norbornene copolymer) from Ticona GmbH, Frankfurt , Germany and Summit, New Jersey, Zeonex® and Zeonor® from Zeon Chemicals LP, Louisville, KY), polymethyl methacrylate (PMMA), polyoxymethylene from DuPont (Delrin), Ultem® (polyetherimide) from GE Plastics, PrimoSpire® and combinations thereof .

Although various embodiments of the present invention have been described using certain terms, devices and methods, such description is provided for illustrative purposes only. The words used are words of description and not of limitation. It should be understood that changes and variations may be made by those skilled in the art without departing from the spirit or scope of the present invention as set forth in the appended claims. Additionally, it should be understood that aspects of the various embodiments may be interchangeable in whole or in part, or they may be combined in any manner and/or used together, as follows:

1. A polydiorganosiloxane vinyl crosslinking agent containing: (1) a polydiorganosiloxane polymer chain containing dimethylsiloxane units and hydrophilized siloxane units, each of them having one methyl substituent and one substituent representing a monovalent organic C ₄ -C ₄₀ radical containing two to six hydroxyl groups, wherein the molar ratio of hydrophilized siloxane units to dimethylsiloxane units is from about 0.035 to about 0.15; (2) two terminal (meth)acryloyl groups, wherein the polydiorganosiloxane vinyl crosslinker has a number average molecular weight of about 3,000 daltons to about 80,000 daltons.

2. A polydiorganosiloxane vinyl crosslinker according to the invention according to claim 1, wherein the polydiorganosiloxane vinyl crosslinker is a polymer of formula (1),

,

wherein:

υ1 is an integer from 30 to 500, and ω1 is an integer from 1 to 75, with the proviso that ω1/υ1 is from about 0.035 to about 0.15;

X ₀ represents O or NR', in which R' represents hydrogen or C ₁ -C ₁₀ alkyl;

R ₁ represents hydrogen or methyl;

R ₂ and R ₃ independently represent a substituted or unsubstituted C ₁ -C ₁₀ alkylene divalent radical or a divalent radical -R ₅ -OR ₆ - in which R ₅ and R ₆ independently represent a substituted or unsubstituted C ₁ -C ₁₀ alkylene divalent radical;

R ₄ represents a monovalent radical of any formula (2)-(6),

,

,

,

,

,

q1 equals zero or 1;

n1 is an integer from 2 to 4;

n2 is an integer from 1 to 5;

n3 is an integer from 3 to 6;

n4 is an integer from 2 to 5;

R ₇ represents hydrogen or methyl;

R ₈ and R ₉ independently of each other represent a C ₂ -C ₆ hydrocarbon radical having valencies (n2+1);

R ₁₀ is ethyl or hydroxymethyl;

R ₁₁ represents methyl or hydroxymethyl;

R ₁₂ represents hydroxyl or methoxy;

X ₁ represents a sulfur bridge -S- or a tertiary amine bridge -NR ₁₃ -, in which R ₁₃ represents C ₁ -C ₃ alkyl, hydroxyethyl, hydroxypropyl or 2,3-dihydroxypropyl; And

X ₂ represents an amide bridge or , in which R ₁₄ represents hydrogen or C ₁ -C ₁₀ alkyl.

3. The polydiorganosiloxane vinyl crosslinking agent according to the invention according to claim 2, wherein in formula (1) ω1/υ1 is from about 0.040 to about 0.12.

4. The polydiorganosiloxane vinyl crosslinking agent according to the invention according to claim 2, wherein in formula (1) ω1/υ1 is from about 0.045 to about 0.10.

5. A polydiorganosiloxane vinyl crosslinking agent according to the invention to any of items 2 to 4, wherein R ₄ is a monovalent radical of formula (2).

6. Polydiorganosiloxane vinyl crosslinking agent in accordance with the invention according to paragraph 5, where R ₄ represents a monovalent radical of any of formulas (2a)-(2y),

,

in which q1 is zero or 1, n1 is an integer from 2 to 4, R ₇ is hydrogen or methyl.

7. A polydiorganosiloxane vinyl crosslinking agent according to the invention to any of items 2 to 4, wherein R ₄ is a monovalent radical of formula (3).

8. Polydiorganosiloxane vinyl crosslinking agent in accordance with the invention according to paragraph 7, where R ₄ represents a monovalent radical of any of the formulas (3a)-(3y),

,

in which X ₂ represents an amide bridge or , in which R ₁₄ represents hydrogen or C ₁ -C ₁₀ alkyl.

9. A polydiorganosiloxane vinyl crosslinking agent according to the invention to any of items 2 to 4, wherein R ₄ is a monovalent radical of formula (4).

10. Polydiorganosiloxane vinyl crosslinking agent according to the invention according to claim 9, where R ₄ represents a monovalent radical of formula (4a) or (4b),

.

11. A polydiorganosiloxane vinyl crosslinking agent according to the invention to any of items 2 to 4, wherein R ₄ is a monovalent radical of formula (5).

12. Polydiorganosiloxane vinyl crosslinking agent in accordance with the invention according to paragraph 11, where R ₄ represents a monovalent radical of any of formulas (5a)-(5c),

.

13. A polydiorganosiloxane vinyl crosslinking agent according to the invention to any of items 2 to 4, wherein R ₄ is a monovalent radical of formula (6).

14. The polydiorganosiloxane vinyl crosslinking agent according to the invention according to claim 13, where in formula (6) n1 is 3 and q1 is 1.

15. A polydiorganosiloxane vinyl crosslinking agent according to the invention according to any one of paragraphs 2 to 11, wherein in formula (1) X ₀ represents O.

16. A polydiorganosiloxane vinyl crosslinking agent according to the invention according to any one of paragraphs 2 to 11, wherein in formula (1) X ₀ represents NR', in which R' represents hydrogen or C ₁ -C ₁₀ alkyl.

17. The polydiorganosiloxane vinyl crosslinker according to the invention according to any one of claims 1 to 16, wherein the polydiorganosiloxane vinyl crosslinker has a number average molecular weight of from about 4,000 daltons to about 50,000 daltons.

18. The polydiorganosiloxane vinyl crosslinker according to the invention according to any one of claims 1 to 16, wherein the polydiorganosiloxane vinyl crosslinker has a number average molecular weight of from about 5,000 daltons to about 25,000 daltons.

19. The polydiorganosiloxane vinyl crosslinker according to the invention according to any one of claims 1 to 16, wherein the polydiorganosiloxane vinyl crosslinker has a number average molecular weight of from about 6,000 daltons to about 18,000 daltons.

20. A silicone hydrogel contact lens containing a cross-linked polymer material that contains:

polydiorganosiloxane vinyl crosslinking units according to the invention according to any one of claims 1 to 19;

siloxane-containing vinyl monomer units;

units of at least one hydrophilic vinyl monomer,

wherein the silicone hydrogel contact lens, when fully hydrated, has an oxygen permeability (Dk) of at least about 70 bbl, a moisture content of from about 25% to about 70% by weight, and a modulus of elasticity from about 0.2 MPa to about 1.2 MPa.

21. A silicone hydrogel contact lens according to the invention of claim 20, wherein the silicone hydrogel contact lens has a thermal stability that is characterized by an autoclave-induced change , being approximately 10% or less of at least one lens property (LP) selected from the group consisting of elastic modulus, moisture content, lens diameter, and combinations thereof, where is the average lens property value after a single autoclave and is obtained by averaging the lens property values of 15 soft contact lenses measured after a single autoclave for 30 minutes at 121°C in phosphate buffered saline at pH 7.2±0.2, and represents the average lens property values after autoclaving 19 times, and is obtained by averaging the lens property values of 15 soft contact lenses measured after storage and autoclaving 19 times, each for 30 minutes at 121°C in phosphate-buffered saline at pH 7.2±0.2.

22. A silicone hydrogel contact lens according to the invention according to claim 20 or claim 21, wherein the hydrophilic vinyl monomer is N-vinylpyrrolidone, N,N-dimethyl(meth)acrylamide, (meth)acrylamide, N-hydroxyethyl(meth)acrylamide , N-hydroxypropyl(meth)acrylamide, hydroxyethyl(meth)acrylate, glycerin methacrylate (GMA), polyethylene glycol (meth)acrylate, characterized by a number average molecular weight of not more than 1500, C ₁ -C ₄ alkyl ether polyethylene glycol (meth)acrylate, characterized molecular weight up to 1500, N- [tris(hydroxymethyl)methyl]acrylamide, N-vinylformamide, N-vinylacetamide, N-vinylisopropylamide, N-vinyl-N-methylacetamide, N-methyl-3-methylene-2-pyrrolidone, 1- ethyl-3-methylene-2-pyrrolidone, 1-methyl-5-methylene-2-pyrrolidone, 1-ethyl-5-methylene-2-pyrrolidone, 5-methyl-3-methylene-2-pyrrolidone, 5-ethyl- 3-methylene-2-pyrrolidone, (meth)acrylic acid, ethyl acrylic acid or combinations thereof.

23. A silicone hydrogel contact lens according to the invention of claim 22, wherein the hydrophilic vinyl monomer is N-vinylpyrrolidone, N-vinyl-N-methylacetamide, or combinations thereof.

24. A silicone hydrogel contact lens in accordance with the invention according to any one of claims 20-23, wherein the crosslinked polymer material further comprises silicone-free hydrophobic vinyl monomer units, non-silicone vinyl crosslinker units, UV absorbing vinyl monomer units, or a combination thereof.

25. A silicone hydrogel contact lens in accordance with the invention according to any one of claims 20-24, wherein the silicone hydrogel contact lens contains from about 30% to about 60% by weight of units of said at least one hydrophilic vinyl monomer, wherein the percentage is The unit weight of said at least one hydrophilic vinyl monomer is the percentage by weight of said at least one hydrophilic vinyl monomer relative to the total weight of all polymerizable components in the polymerizable composition for making a cross-linked polymer material.

26. A method for producing silicone hydrogel contact lenses, comprising the stages:

providing a lens molding composition that is clear at room temperature and optionally, but preferably, at a temperature of from about 0 to about 4°C, wherein the lens molding composition contains (a) from about 5% to about 35% by weight of a polydiorganosiloxane vinyl crosslinker according to any one of paragraphs 1-19, (b) a siloxane-containing vinyl monomer, (c) from about 30% up to about 60% by weight of at least one hydrophilic vinyl monomer, (d) at least one free radical polymerization initiator, provided that the polymerizable components listed above and any additional polymerizable components add up to 100% by weight;

introducing a composition for molding a lens into a mold, wherein the mold has a first half-mold with a first molding surface defining the front surface of the contact lens, and a second half-mold with a second molding surface defining the back surface of the contact lens, where said first and second halves are made capable of being aligned with each other so that a cavity is formed between said first and second forming surfaces; And

curing, thermally or by actinic radiation, a lens molding composition in a lens mold to form a silicone hydrogel contact lens, wherein the silicone hydrogel contact lens has an oxygen permeability (Dk) of at least about 70 bbl, a moisture content of from about 25% to about 70% by weight, and a modulus of elasticity from about 0.2 MPa to about 1.2 MPa.

27. The method according to the invention according to claim 26, wherein the silicone hydrogel contact lens has thermal stability which is characterized by the presence of an autoclave-induced change , being approximately 10% or less of at least one lens property (LP) selected from the group consisting of elastic modulus, moisture content, lens diameter, and combinations thereof, where is the average lens property value after a single autoclave and is obtained by averaging the lens property values of 15 soft contact lenses measured after a single autoclave for 30 minutes at 121°C in phosphate buffered saline at pH 7.2±0.2, and represents the average lens property values after autoclaving 19 times, and is obtained by averaging the lens property values of 15 soft contact lenses measured after storage and autoclaving 19 times, each for 30 minutes at 121°C in phosphate-buffered saline at pH 7.2±0.2.

28. The method in accordance with the invention according to claim 26 or claim 27, wherein the lens molding composition is a liquid mixture without a solvent and contains a miscible vinyl monomer selected from the group consisting of C ₁ -C ₁₀ alkyl methacrylate, isobornyl methacrylate, isobornyl acrylate, cyclopentyl methacrylate, cyclopentyl acrylate, cyclohexyl methacrylate, cyclohexyl acrylate, styrene, 2,4,6-trimethylstyrene (TMS) and tert-butyl styrene (TBS) and combinations thereof (preferably the miscible vinyl monomer is methyl methacrylate).

29. The method according to the invention according to claim 26 or claim 27, wherein the lens molding composition contains an organic solvent (preferably selected from the group consisting of 1-propanol, isopropanol, tert-amyl alcohol, 1,2-propylene glycol, polyethylene glycol, which characterized by a molecular weight of approximately 400 daltons or less, or mixtures thereof).

30. The method of the invention according to any one of claims 26-29, wherein the total amount of all silicone-containing polymerizable components present in the lens molding composition is approximately 65% or less.

31. The method according to the invention according to any one of claims 26 to 30, wherein the hydrophilic vinyl monomer is a hydrophilic N-vinyl monomer, preferably N-vinylpyrrolidone, N-vinyl-N-methylacetamide, N-vinylformamide, N-vinylacetamide, N-vinyl isopropylamide or combinations thereof, even more preferably N-vinylpyrrolidone, N-vinyl-N-methylacetamide or combinations thereof.

32. The method according to the invention according to any one of claims 26-31, wherein the lens molding composition further comprises a non-silicone vinyl crosslinking agent.

33. The method according to the invention according to claim 32, wherein the non-silicone vinyl crosslinking agent is selected from the group consisting of ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di( meth)acrylate, glycerol-di(meth)acrylate, 1,3-propanediol-di(meth)acrylate, 1,3-butanediol-di(meth)acrylate, 1,4-butanediol-di(meth)acrylate, glycerol- 1,3-diglycerinate-di(meth)acrylate, ethylene bis[oxy(2-hydroxypropane-1,3-diyl)]-di(meth)acrylate, bis[2-(meth)acryloxyethyl]phosphate, trimethylolpropane-di (meth)acrylate and 3,4-bis[(meth)acryloyl]tetrahydrofuran, diacrylamide (i.e. N-(1-oxo-2-propenyl)-2-propenamide), dimethacrylamide (i.e., N- (1-oxo-2-methyl-2-propenyl)-2-methyl-2-propenamide), 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)acrylamidepropan-2-yl dihydrogen phosphate (t . e. N,N'-2-phosphonyloxypropylene-bis(meth)acrylamide), piperazine diacrylamide (or 1,4-bis(meth)acryloylpiperazine), vinyl methacrylate, allyl methacrylate, allyl acrylate, N-allyl methacrylamide, N-allylacrylamide, 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, combinations thereof (preferably selected from the group consisting of tetra(ethylene glycol)-di(meth)acrylate, three(ethylene glycol) -di(meth)acrylate, ethylene glycol-di(meth)acrylate, di(ethylene glycol)-di(meth)acrylate, glycerin dimethacrylate, allyl(meth)acrylate, N,N'-methylene-bis(meth)acrylamide, N,N '-ethylene-bis(meth)acrylamide, N,N'-dihydroxyethylene-bis(meth)acrylamide, N,N'-2-hydroxypropylene-bis(meth)acrylamide, N,N'-2,3-dihydroxybutylene-bis (meth)acrylamide, 1,3-bis(meth)acrylamidepropan-2-yl dihydrogen phosphate (i.e. N,N'-2-phosphonyloxypropylene-bis(meth)acrylamide), piperazine diacrylamide (or 1,4-bis(meth) acryloylpiperazine), triallyl isocyanurate, tetraethylene glycol divinyl ether, triethylene glycol divinyl ether, diethylene glycol divinyl ether, ethylene glycol divinyl ether and combinations thereof).

34. The method according to the invention according to any one of claims 26 to 33, wherein the siloxane-containing vinyl monomer is 3-(meth)acryloxy-2-hydroxypropyloxy)propyl-bis(trimethylsiloxy)methylsilane, 3-(meth)acryloxyethoxypropyloxypropyl-bis(trimethylsiloxy )methylsilane, 3-(meth)acrylamidopropyl-bis(trimethylsiloxy)methylsilane, 3-N-methyl(meth)acrylamidopropyl-bis(trimethylsiloxy)methylsilane, polydimethylsiloxanes with one terminal (meth)acryloxy group with different molecular weights, polydimethylsiloxanes with one terminal ( meth)acrylamide group with different molecular weights or a combination thereof.

35. The method according to the invention according to any one of paragraphs 26 to 34, wherein the curing step is carried out thermally.

The above disclosure will enable one skilled in the art to practice the present invention. Various modifications, variations and combinations may be made with respect to the various embodiments described herein. To help the reader better understand specific embodiments and their advantages, examples are provided below. It is intended that this description and examples should be considered illustrative.

In the following examples, the following abbreviations are used: MCR-M07 means polydimethylsiloxane with one butyl and one methacryloxypropyl end group (MW 600-800 g/mol, from Gelest); NVP stands for N-vinylpyrrolidone; DMA means N,N-dimethylacrylamide; VMA stands for N-vinyl-N-methylacetamide; N-CH ₃ -BisAm means N-methyl-N-bis(trimethylsiloxy)methylsilylpropylacrylamide (or 3-N-methyl(meth)acrylamidopropylbis(trimethylsiloxy)methylsilane); SIGMA means 3-(3-methacryloxy-2-hydroxypropyloxypropyl-bis(trimethylsiloxy)methylsilane; MMA means methyl methacrylate; TEGDMA means triethylene glycol dimethacrylate; TEGDVE means triethylene glycol divinyl ether; EGMA means ethylene glycol methyl ether methacrylate; AMA means allyl methacrylate; VAZO 64 means 2,2'-dimethyl-2,2'-azodipropiononitrile; Nobloc is 2-[3-(2H-benzotriazol-2-yl)-4-hydroxyphenyl]ethyl methacrylate from Aldrich; RB246 is Reactive Blue 246 from Arran; -PrOH means 1-propanol; IPA means isopropanol; DC 1173 means photoinitiator Darocur 1173®;

Example 1

Oxygen permeability measurement

Unless otherwise specified, the apparent oxygen permeability (Dk _each ), apparent oxygen transmittance (Dk/t), intrinsic (or edge-adjusted) oxygen permeability (Dk _cor ) of the lens and lens material are determined according to the methods described in Example 1 US Patent Application Publication No. 2012/0026457 A1 (incorporated herein by reference in its entirety).

Ionic Permeability Measurement

The ionic permeability of the lens is measured according to the procedures described in US Pat. No. 5,760,100 (incorporated herein by reference in its entirety). The ion permeability values published in the following examples are relative ion flux diffusion coefficients (D/D _st ) relative to Alsacon lens material taken as a reference material. Alsacon has an ion flux diffusion coefficient of 0.314 X 10 ^-3 mm ² /minute.

Autoclaving

Autoclave processing is carried out at 121°C. Each autoclave cycle lasts 30 minutes. 15 lenses are subjected to 1 autoclave cycle. 15 lenses are subjected to 7 autoclave cycles. 15 lenses are subjected to 13 autoclave cycles. 15 lenses are subjected to 19 autoclave cycles. Lenses subjected to n autoclave cycles are used to determine lens properties to evaluate lens thermal stability.

Lubricity Assessment

Lens lubricity is assessed using the fingertip lubricity test, which qualitatively measures the slipperiness of the lens surface on a friction rating scale from 0 to 4. The higher the friction score, the lower the slipperiness (or lubricity).

Commercial lenses DAILIES® TOTAL1®; ACUVUE® OASYS ^TM ; ACUVUE® ADVANCE PLUS ^TM ; DAILIES® Aqua Comfort Plus® and AIR OPTIX® have assigned a friction rating (hereinafter referred to as ʺFRʺ) of 0, 1, 2, 3 and 4, respectively. They are used as standard lenses to determine the friction rating of the lens being tested.

Samples are placed in PBS for at least two rinses of 30 minutes each and then transferred to fresh PBS before evaluation. Before assessment, hands are rinsed with soap and water, rinsed thoroughly with deionized water, and then dried with KimWipe® towels. Samples are taken between the fingers and each sample is assigned a numerical value in comparison to the aforementioned standard lenses described above. For example, if a lens is determined to be only marginally better than AIR OPTIX ^® lenses, it is assigned a number of 3. The friction rating value is obtained by averaging the results of at least two contact lens friction ratings by two or more people and/or by averaging the friction ratings of two or more contact lenses (from an identical lens production batch) by one person.

Surface wettability tests

The contact lens contact angle (WCA) is a general measure of the wettability of the contact lens surface. In particular, a low contact angle value corresponds to a more wettable surface. Average contact angle (stationary drop) values of contact lenses are measured using a VCA 2500 XE contact angle meter from AST, Inc. located in Boston, MA. With this equipment it is possible to measure advancing contact angles ( _θa ) or receding contact angles (θr ₎ or stationary (static) contact angles. Unless otherwise specified, the contact angle is a fixed (static) contact angle. Measurements are taken with contact lenses in a fully hydrated state and immediately after blotting dry as follows. The contact lens is removed from the bottle and washed 3 times in ~200 ml of fresh deionized water to remove loosely bound additives from the packaging from the surface of the lens. The lens is then placed on top of a clean, lint-free cloth (Alpha Wipe TX1009), pressed firmly to remove surface water, placed on a contact angle stand, blown with dry air, and finally the sessile drop contact angle is automatically measured using software provided by the manufacturer. The deionized water used for contact angle measurements has a resistivity of >18 MΩ cm, and the drop volume used is 2 μL. Typically, uncoated silicone hydrogel lenses (after autoclaving) have a sessile drop contact angle of about 120 degrees. The tweezers and stand are thoroughly washed with isopropanol and rinsed with deionized water, and then brought into contact with the contact lenses.

Water Break Time Tests (WBUT)

The surface hydrophilicity of lenses (after autoclaving) is assessed by determining the time required for the water film on the lens surface to begin to break. Briefly, the lenses are removed from the bottle and placed in PBS (phosphate buffered saline) for at least two rinses of 30 minutes each and then transferred to fresh PBS to remove loosely bound packaging additives from the surface of the lens. The lens is removed from the solution and held against the background of a bright light source. The time required for the water film to break (droplet formation) and expose the lens material under the film is recorded visually. Uncoated lenses typically break immediately when removed from PBS and are assigned a WBUT of 0 seconds. Lenses exhibiting WBUT ≥ 10 seconds are considered to have a hydrophilic surface and are expected to exhibit adequate wettability (the ability to retain the tear film) on the eye.

Finger abrasion tests

Rub the lenses with your fingers (wearing disposable powder-free latex gloves) with PBS or RENU® Multifunctional Lens Care Solution (or other Multipurpose Lens Care Solution) for 20 seconds and then rinse with saline. The above procedure is repeated a specified number of times, for example 1 to 30 times (i.e., the number of repetitions of finger abrasion tests that simulate scrubbing and soaking cycles).

Coating integrity tests

The integrity of the coating on the surface of a contact lens can be tested according to the Sudan black stain test as follows. Coated contact lenses (LbL coating, plasma coating, or any other coating) are immersed in a solution of Sudan black dye (Sudan black in a mixture of ~80% mineral oil and ~20% vitamin E oil). Sudan black dye is hydrophobic and has a greater tendency to be adsorbed by hydrophobic material either onto a hydrophobic lens surface or hydrophobic areas on a partially coated surface of a hydrophobic lens (eg, a silicone hydrogel contact lens). If the coating on a hydrophobic lens is intact, no staining should be visible on or in the lens. All lenses tested are fully hydrated. Visible fine lines on the surface of the lens may indicate cracks in the cross-linked coatings.

Lens Surface Crack Test

Excessive cross-linking of the coating layer can result in surface cracks visible under a dark-field microscope after abrasion of the lens. The lens surface crack test is used to distinguish the degree of surface cracking resulting from exposure of the lens to conditions and forces that may occur during normal and intended lens use.

The conformation of the lens should be turned out by holding the edge of the lens between the thumb and index finger of one hand. The concave side of the lens should face the examiner's body. Using the thumb and/or index finger of the other hand, gently bend the top of the lens over the index finger, holding the lens until the conformation of the lens is turned out. Look for surface cracks at 5x to 10x magnification using a dark-field stereo microscope. If individual crack lines are clearly visible, the lenses are considered “positive” for cracks. If the lens appears to have long, cloudy, linear formations but the crack lines are not visible, the area can be examined at higher magnification if necessary. If no crack lines or long, cloudy, linear formations are visible, the lens is considered “crack negative.” Lenses exhibiting a crack-free 0 are considered superior and are expected to have a smooth and soft surface.

Lens surface test using microspheres

The microsphere lens surface test is used to evaluate the surface charges of contact lenses. The data obtained from this method represents the number of microspheres absorbed onto the surface of the lens and contains information about surface charge related properties.

Dovex 1x4 microspheres in chloride form 50-100 mesh (Lot No. 54898PJV, Sigma Aldrich, CAS 69011-19-4) are suspended in PBS. The lens is immersed in microspheres/PBS in a centrifuge tube. Then on a shaker at 300 rpm. within 2 min. the lens is rinsed with PBS. The microspheres absorbed on the surface of the lens are then observed under a dark-field microscope. Image Pro software is used to analyze the total amount of cationic microspheres. The total number of cationic microspheres is the total number of the test using microspheres.

Example 2

Synthesis of glycerol ether-containing PDMS macromer (macromer A)

Macromer A is prepared according to the procedures presented in Scheme 1 below.

Scheme 1

Precursor synthesis

Weigh out 275.9 g octamethylcyclotetrasiloxane (MW 296.62), 12.0 g 1,3,5,7-tetramethylcyclotetrasiloxane (MW 240.51), 9.7 g 1,3-bis(3-methacryloxypropyl)tetramethyldisiloxane (MW 386.63) and 0.9 g trifluoromethanesulfonic acid (MW 150.08) into a 500 ml round bottom flask. After reacting at 35°C for 24 hours, 170 ml of 0.5% sodium bicarbonate is added. The collected organic part is extracted an additional five times with deionized water (170 ml per cycle). Anhydrous MgSO ₄ was added to the collected organic solution, followed by the addition of an additional ~350 mL of CHCl ₃ , and the solution was then stirred overnight. After filtration, the solvent is removed using a rotary evaporator and then high vacuum. 102 g of the final product (precursor) are obtained.

Hydrosilylation reaction with 3-allyloxy-1,2-propanediol to form macromer A

A small reactor is connected to a heater and an air cooler with a drying tube. 21 g of toluene, 15 g of the above precursor and 5.03 g of 3-allyloxy-1,2-propanediol are added to the reactor. After the solution temperature has stabilized at 30°C, 152 μl of Karstedt catalyst (2% Pt in xylene) is added. After 2 h, a Si-H conversion of 100% based on IR was achieved. The solution is then transferred to a flask, concentrated using a rotary evaporator, followed by precipitation three times in a mixture of acetonitrile/water (75/25). After removing the solvent using a rotary evaporator and then applying high vacuum, 12 g of a cloudy liquid is obtained.

Example 3

Synthesis of glycerol ether-containing PDMS macromer (macromer B)

Macromer B is prepared according to procedures similar to those described in Example 2, except that the amount of tetramethylcyclotetrasiloxane in the first step to obtain the precursor is approximately doubled. The resulting macromer B is characterized by the structural formula

.

Example 4

Compatibility of macromers with hydrophilic vinyl monomers

Macromer A prepared in Example 2 is used in the preparation of various lens formulations, including from about 38% to about 58% by weight of at least one hydrophilic vinyl monomer (DMA and/or NVP) to evaluate their compatibility with relatively high amount of hydrophilic vinyl monomers. As control experiments, α,ω-dimethacryloxyethoxypropyl-terminated polydimethylsiloxane (M.W. 4500 g/mol) is also used as a macromer to prepare lens formulations in compatibility studies. Tables 1 and 2 present the compositions of the lens formulations. All lens formulations made from the hydrophilized polydisiloxane crosslinker (macromer), macromer A, are uniform (clear), while all lens formulations made from the non-hydrophilized polydisiloxane crosslinker (macromer), α,ω-dimethacryloxyethoxypropyl-terminated polydimethylsiloxane , are heterogeneous (turbid).

Table 1

Composition (parts) Composition number 1 2 3 4 5 6 7 Macromer 25 35 thirty thirty 28 25 25 N- _CH3 -BisAm 31 26 26 31 29 36 26 DMA 43 38 43 38 41 38 48

table 2

Composition (parts) Composition no. 8 9 10 eleven Macromer 18 6 6 10 MCR-M07 10.5 22.5 10.5 14.50 SIGMA 9 9 21 13 MMA 10 10 10 10 DMA 2 2 2 2 NVP 49.4 49.4 49.4 49.4

Macromer A, macromer B, and control macromer (polydimethylsiloxane with an α,ω-dimethacryloxyethoxypropyl end group) are used to prepare three formulations with the following compositions: macromer A or macromer B or control macromer (10 parts); MCS-M11 (20 parts); NVP (58 parts); MMA (10 parts); TEGDVE (0.1 parts); TEGDMA (0.5 parts); Vazo 64 (0.8 parts) and Norbloc (0.9 parts).

The composition containing the control macromer was found to be heterogeneous (cloudy) both at room temperature and at refrigerated temperature (2-4°C); the composition comprising macromer A is homogeneous (transparent) at room temperature, but heterogeneous (cloudy) at refrigerator temperature (2-4°C); the composition containing macromer B is homogeneous both at room temperature and at refrigerator temperature (2-4°C). These results indicate that a higher content of hydrophilic substituents (glycerol ether side chains) in the macromer can improve the compatibility of the macromer with hydrophilic vinyl monomers.

Example 5

Two lens compositions are prepared having the following compositions: macromer A or B obtained in example 2 (31.80%); N-CH ₃ -BisAm (20.71%); DMA (23.24%); DC 1173 (1.01%) and 1-PrOH (23.21%). The resulting lens composition is injected into polypropylene lens molds and cured by UV irradiation to form the contact lenses. The lenses are tested for properties according to the procedures described in Example 1. The properties (elastic modulus, E'; adjusted oxygen permeability, Dkc; ionic permeability, IP, relative to Alsacon; moisture content) of the resulting lenses are shown in Table 3.

Table 3

Lens properties Macromer A lenses Macromer B lenses Modulus, E' (MPa) 0.43 0.27 Dkc (barrera) 184 170 IP 3.5 2.5 WC% 29 29

It can be seen from Table 3 that if the y/x molar ratio of hydrophilized siloxane units to dimethylsiloxane units in the polydiorganosiloxane vinyl crosslinker used increases from about 0.054 (macromer A) to about 0.094 (macromer B), the oxygen permeability of the resulting lenses decreases from about 184 bbl. to approximately 170 barrels.

Lenses made from both macromers A and B were tested for thermal stability, which is characterized by autoclaving-induced changes in lens properties (E', WC%, and _lens D). Table 4 shows that there is no significant autoclave-induced change in lens properties for all lenses made from macromer A or B, even after exposure to 1, 7, 13, and 19 autoclave cycles, respectively, i.e., they are characterized by good thermal stability.

Table 4

Macromer A lenses Macromer B lenses E' (MPa) WC% _Lens D (mm) E' (MPa) WC% _Lens D (mm) AC (x1) 0.43±0.04 29.1±0.4 14.49±0.07 0.27±0.02 28.8±0.4 14.33±
0.09 AC (x7) n. d. n. d. n. d. 0.24±0.01 29.2±0.4 14.32±
0.16 AC (x13) 0.40±0.01 29.8±0.4 14.48±0.05 0.23±0.02 29.3±0.5 14.35±
0.28 AC (x19) 0.41±0.01 29.8±0.3 14.61±0.05 0.25 29.5±0.7 14.28±
0.12

Example 6

Precursor synthesis

Weigh out 1935.04 g of octamethylcyclotetrasiloxane (D4), 158.74 g of 1,3,5,7-tetramethylcyclotetrasiloxane (D4H) and 106.33 g of 1,3-bis(3-methacryloxypropyl)tetramethyldisiloxane and pre-mix in the flask and then charge into a 4 L jacketed reactor equipped with a mechanical motor, thermocouple and N ₂ flow. Then 4.4 g of triflate acid is injected into the reaction flask using a syringe. The reaction is then carried out at 25°C for approximately 14 hours. After completion of the reaction, the solution is diluted with 1000 ml of toluene and then neutralized with a solid base, followed by stirring for one hour. The final mixture is filtered using a 0.45 micron glass microfiber filter and then concentrated by rotary evaporation and then low vacuum to remove residual solvent in the presence of 400-500 ppm inhibitor. The resulting precursor was not purified and was determined to have a number average molecular weight of approximately 8 thousand g/mol, an average x of approximately 92.6 (NMR), and an average y of approximately 9.2 (NMR).

.

Synthesis of glycerol ether-containing PDMS macromer

A 4-liter jacketed reactor is heated to 75°C and purged with nitrogen for 0.5 hours. 3-allyloxy-1,2-propanediol ( approximately 780.4 g, i.e., in a molar ratio of 5:1) is added relative to the hydrosiloxane unit), the precursor obtained above ( about 999.5 g), potassium acetate ( about 2.5 g) and isopropanol ( about 1.2 L). The mixture is stirred for approximately 20 minutes. Approximately 1.6 ml ( approximately 30 ppm relative to the precursor) of Karstedt catalyst solution is introduced into it. The reaction mixture is stirred at 75°C for approximately one hour. The reaction mixture is then cooled to room temperature and transferred to a separatory funnel for extraction to remove excess 3-allyloxy-1,2-propanediol starting materials. The crude product after the reaction is then extracted as follows: first with 1.5 l of acetonitrile/water (9/1 vol.) for 42 hours and then with 1000 g of tetrahydrofuran (THF)/MeCN/water (450/350 /200 wt.) within 24 hours three times. The weight of the product after extraction is approximately 907.2 g.

After extraction, the silicone phase is stabilized with 100 mg (~200 ppm) of phenothiazine inhibitor (PTZ) in 10 ml of toluene. The solvent is removed using a rotary evaporator at 35°C. The weight of the product at this stage is approximately 537.0 g. The product is diluted with 1000 g of toluene and filtered through a celite coated glass fiber filter. After concentration using a rotary evaporator at 35°C, the product weighs approximately 473.6 g. The product is diluted again with 1000 g of toluene and then filtered using a 0.45 μm membrane. After concentration on a rotary evaporator at 35°C, the product weighs approximately 476.5 g. To stabilize the product, add 100 mg (~200 ppm) of 2,6-di-tert-butyl-4-methylphenol (BHT) and 100 mg (~ 200 ppm) 4-methoxyphenol (MEHQ) in 1.0 ml toluene. The product is dried under high vacuum at room temperature for 3 hours (weight = 458.62 g), and then at 60°C for 3 hours. The weight of the final macromer is approximately 432.6 g. Yield: 74.7 % based on half the silicone precursor. Solid content of macromers is determined by weight loss in high vacuum at 50. Solid content: 96.1%. x=109.0, y=9.9 (according to NMR),

.

Example 7

Precursor synthesis

Weigh out D4 (1067.04 g), D4H (86.64 g) and 1,3-bis(3-methacryloxypropyl)tetramethyldisiloxane (46.54 g) and pre-mix in a flask and then charge into a 4 L jacketed reactor, equipped with mechanical motor, thermocouple and N flow₂. Triflate acid (2.4 g) was then injected into the reaction flask using a syringe. Then the reaction is carried out at 25°C for 14 hours. After completion of the reaction, the solution is diluted with 1000 ml of toluene and then neutralized with a solid base, followed by stirring for one hour. The final mixture is filtered using a 0.45 micron glass microfiber filter and then concentrated by rotary evaporation and then low vacuum to remove residual solvent in the presence of 400-500 ppm inhibitor. The resulting precursor was not purified and was determined to have a number average molecular weight of approximately 8 thousand g/mol, an average x of approximately 99.6 (NMR), and an average y of approximately 9.4 (NMR).

.

Synthesis of glycerol ether-containing PDMS macromer

A 4-liter jacketed reactor is heated to 75°C and purged with nitrogen for 0.5 hours. 3-allyloxy-1,2-propanediol ( approximately 837.9 g, i.e., in a molar ratio of 5:1) is added relative to the hydrosiloxane unit), the precursor obtained above ( about 1075.1 g), potassium acetate ( about 1.8 g) and isopropanol ( about 0.9 L). The mixture is stirred for approximately 20 minutes. Approximately 1.6 ml ( approximately 30 ppm relative to the precursor) of Karstedt catalyst solution is introduced into it. The reaction mixture is stirred at 75°C for approximately one hour. The reaction mixture is then cooled to room temperature and transferred to a separatory funnel for extraction to remove excess 3-allyloxy-1,2-propanediol starting materials. The crude product after the reaction is then extracted as follows: first with 3.0 L of acetonitrile/water (9/1 vol.) for 24 hours, with 2.0 L of THF/MeCN/water (450/350/200 wt.) within 24 hours twice, and finally with 2.0 L of THF/MeCN/water mixture (450/350/200 wt.) for 66 hours. The weight of the product after extraction is approximately 1225.41 g.

The crude product is diluted with 2450 g of toluene and stabilized with 245.1 mg of BHT inhibitor and 245.3 mg of MEHQ inhibitor. The solution is filtered through a glass fiber filter coated with celite. After removal of the solvent by rotary evaporation, the product weighs approximately 1086.4 g. The product is diluted with 2000 g of toluene and then filtered again through a 0.45 μm membrane. After removal of the solvent by rotary evaporation at 35°C, the weight is approximately 1089.2 g. The product is dried under high vacuum at room temperature for 20 hours (weight = 1064.08 g) and then at 80°C for 3 hours. The final weight of the macromer is approximately 1049.9 g (theoretical: 846.12 g). Yield: 84.3%. Solid content of macromers is determined by weight loss in high vacuum at 50°C for 24 hours. Solid content: 98.0%. x=122.5, y=11.0 (according to NMR),

.

Example 8

A lens composition is obtained having the following composition: macromer A obtained in example 2 (10 parts); MCR-M07 (30 parts); MMA (10 parts); VMA (50 parts); TEGDMA (0.2 parts) and Vazo 64 (0.5 parts). The resulting lens formulation is uniform (clear) at both room temperature and refrigerated temperature (2-4°C), indicating that macromer A is VMA compatible to at least about 50% by weight.

Lenses cast (thermally) in polypropylene molds have the following properties: elastic modulus (0.52±0.01 MPa); elongation at break (245±128%); tensile strength (0.88±0.52 MPa); oxygen permeability (DKc=124.5±11 bbl).

Example 9

IPC saline solution

IPC saline solution is prepared by mixing approximately 0.07% by weight poly(AAm-co-AA) [(acrylamide-acrylic acid) copolymer] with approximately 0.35% by weight PAE (polyamidoamine-epichlorohydrin) in phosphate-buffered saline and pretreated at a certain temperature for the required time. Partial sodium salt poly(AAm-co-AA) (90/10), poly(AAm-co-AA) 90/10, M.W. 200000) was purchased from Polysciences, Inc. and apply as is. After thermal pretreatment, the IPC saline solution is filtered using a 0.22 micron membrane filter and cooled back to room temperature. 5 ppm hydrogen peroxide can be added to the final IPC saline solution to prevent bioburden growth, and the IPC saline solution is filtered using a 0.22 micron membrane filter.

Preparation of SiHy lenses

The lens composition is prepared by adding macromer A obtained in example 2 (6 parts), AMA (0.1 parts), TEGDMA (0.2 parts), MMA (10 parts), EGMA (10 parts), NVP (40 parts) , MCR-M07 (34 parts), Norbloc (0.9 parts), RB246 (0.01 parts) and VAZO 64 (0.5 parts) into a clean flask with a magnetic stirrer with stirring at 600 rpm for 30 min. at room temperature. After all the solids have dissolved, the composition is filtered using a GMF 2.7 µm filter.

The lens composition obtained above is purged with nitrogen at room temperature for 30-35 minutes. Purged with N₂ The lens composition is injected into polypropylene molds and thermally cured under the following curing conditions: rise from room temperature to 55°C with a rise rate of approx. 7°C/minute; holding at 55°C for approximately 30 minutes; rise from 55°C up to 80°C with a rise rate of approx. 7°C/minute; holding at 55°C for approximately 30 minutes; rise from 80°C up to 100°C with a rise rate of approx. 7°C/minute; and holding at 100°C for approximately 30 minutes. The molds are opened and the molded lenses are removed from the molds.

After removal from the molds, the silicone hydrogel contact lenses are subjected to a 3-step coating process to form PAA coatings (ie base coats) on the silicone hydrogel contact lenses as follows. Silicone hydrogel contact lenses are first immersed in phosphate buffered saline (PBS, approximately 0.044 wt% NaH ₂ PO ₄ H ₂ O, approximately 0.388 wt % Na ₂ HPO ₄ 2H ₂ O and approximately 0.79 wt .% NaCl) for approximately 60 minutes at room temperature, in the second step, immerse in a solution of PAA (about 0.5% by weight polyacrylic acid (MW 250000), pH 2.0) for approximately 60 minutes at room temperature, and in the third step, rinse with PBS for approximately 5 minutes at room temperature.

SiHy lenses having the PAA base coating obtained above are placed in polypropylene lens packaging shells (or blisters) (one lens per shell) with 0.6 ml IPC saline solution (half the saline solution is added before lens insertion). The blisters are then sealed with foil and autoclaved for approximately 45 minutes at approximately 121°C with the formation of SiHy contact lenses with cross-linked coatings (PAA-x-hydrophilic polymer material) on them.

The resulting SiHy lenses are characterized by an oxygen permeability (measured according to the polarographic method) of approximately 83 barres, a bulk modulus of approximately 0.67 MPa, a moisture content of approximately 50% by weight, a relative ion permeability of approximately 11.0 relative to the lens Alsacon, and a water contact angle of 29 degrees, WBUT of 14 seconds. Some crack lines are visible after the test lens has been abraded and stained with Sudan Black. However, the lenses lubricate very well in the finger rub test and have a friction rating of approximately 0.5. When testing lenses for lens surface charge using the Positive Particle Adhesion Test, less than 71 positively charged particles (Dowex ^™ Monosphere Ion Exchange Resins) adhered to cross-linked coated lenses.

Claims (33)

1. A silicone hydrogel contact lens comprising a crosslinked polymer material which contains polydiorganosiloxane vinyl crosslinker units of formula (1) , wherein: υ1 is an integer from 30 to 500, and ω1 is an integer from 1 to 75, with the proviso that ω1/υ1 is from about 0.035 to about 0.15; X ₀ represents O; R ₁ represents hydrogen or methyl; R ₂ and R ₃ independently represent an unsubstituted C ₁ -C ₁₀ alkylene divalent radical or a divalent radical -R ₅ -OR ₆ - in which R ₅ and R ₆ independently represent an unsubstituted C ₁ -C ₁₀ alkylene divalent radical; R ₄ is a monovalent radical of formula (6) , where q1 is equal to zero or 1; n1 is an integer from 2 to 4; R ₇ represents hydrogen or methyl; wherein the polydiorganosiloxane vinyl crosslinker has a number average molecular weight of from about 3,000 daltons to about 80,000 daltons. 2. The silicone hydrogel contact lens according to claim 1, wherein in formula (1), ω1/υ1 is from about 0.04 to about 0.12. 3. The silicone hydrogel contact lens according to claim 1, wherein in formula (1), ω1/υ1 is from about 0.045 to about 0.10. 4. The silicone hydrogel contact lens of claim 1, wherein the polydiorganosiloxane vinyl crosslinker has a number average molecular weight of from about 4,000 daltons to about 50,000 daltons. 5. The silicone hydrogel contact lens of claim 1, wherein the polydiorganosiloxane vinyl crosslinker has a number average molecular weight of from about 5,000 daltons to about 25,000 daltons. 6. The silicone hydrogel contact lens of claim 1, wherein the polydiorganosiloxane vinyl crosslinker has a number average molecular weight of from about 6,000 daltons to about 18,000 daltons. 7. Silicone hydrogel contact lens according to claim 6, where in formula (6) n1 is 3 and q1 is 1. 8. Silicone hydrogel contact lens according to any one of paragraphs. 1-7, wherein the crosslinked polymeric material contains units of at least one hydrophilic vinyl monomer. 9. The silicone hydrogel contact lens according to claim 8, wherein the hydrophilic vinyl monomer is selected from the group consisting of N-vinylpyrrolidone, N,N-dimethyl(meth)acrylamide, (meth)acrylamide, N-hydroxyethyl(meth)acrylamide, N -hydroxypropyl (meth)acrylamide, hydroxyethyl (meth)acrylate, glycerin methacrylate, polyethylene glycol (meth)acrylate, characterized by a number average molecular weight of not more than 1500, (meth)acrylate C ₁ -C ₄ alkyl ether of polyethylene glycol, characterized by a number average molecular weight of up to 1500, N- [tris(hydroxymethyl)methyl]acrylamide, N-vinylformamide, N-vinylacetamide, N-vinylisopropylamide, N-vinyl-N-methylacetamide, N-methyl-3-methylene-2-pyrrolidone, 1-ethyl-3-methylene -2-pyrrolidone, 1-methyl-5-methylene-2-pyrrolidone, 1-ethyl-5-methylene-2-pyrrolidone, 5-methyl-3-methylene-2-pyrrolidone, 5-ethyl-3-methylene-2 -pyrrolidone, (meth)acrylic acid, ethyl acrylic acid or combinations thereof. 10. The silicone hydrogel contact lens of claim 8, wherein the hydrophilic vinyl monomer comprises N-vinylpyrrolidone, N-vinyl-N-methylacetamide, or combinations thereof. 11. The silicone hydrogel contact lens of claim 10, wherein the hydrophilic vinyl monomer further comprises one monomer selected from the group consisting of N,N-dimethyl(meth)acrylamide, (meth)acrylamide, N-hydroxyethyl(meth)acrylamide, N-hydroxypropyl (meth)acrylamide, hydroxyethyl (meth)acrylate, glycerin methacrylate, polyethylene glycol (meth)acrylate, characterized by a number average molecular weight of not more than 1500, (meth)acrylate C ₁ -C ₄ alkyl ether of polyethylene glycol, characterized by a number average molecular weight of up to 1500 , and N-[tris(hydroxymethyl)methyl]acrylamide. 12. Silicone hydrogel contact lens according to claim 8, where the cross-linked polymer material contains units of hydrophilic vinyl monomer free of silicone. 13. The silicone hydrogel contact lens of claim 12, wherein the silicone-free hydrophilic vinyl monomer is methyl acrylate, ethyl acrylate, propyl acrylate, isopropylacrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, vinyl acetate, vinyl propionate, vinyl butyrate, valerate , styrene, chloroprene, vinyl chloride, vinylidene chloride, acrylonitrile, 1-butene, butadiene, methacrylonitrile, vinyltoluene, vinylethyl ether, perfluorohexylethylthio-carbonyl-aminoethyl methacrylate, isobornyl methacrylate, trifluoroethyl methacrylate, hexafluoroisopropyl methacrylate or hexafluorobutyl methacrylate. 14. The silicone hydrogel contact lens of claim 13, wherein the cross-linked polymer material contains non-silicone vinyl cross-linking agents selected from the group consisting of ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth) )acrylate, tetraethylene glycol di(meth)acrylate, glycerol di(meth)acrylate, 1,3-propanediol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,4-butanediol di (meth)acrylate, glycerol-1,3-diglycerinate-di(meth)acrylate, ethylene bis[oxy(2-hydroxypropane-1,3-diyl)]-di(meth)acrylate, bis[2-(meth) acrylicoxyethyl]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-yldihydrogen phosphate, piperazine diacrylamide, vinyl methacrylate, allyl methacrylate, allyl acrylate, N-allyl methacrylamide, N-allyl acrylamide, tetraethylene glycol divinyl ether, triethylene glycol divinyl ether, diethylene glycol divinyl ether, ethylene glycol divinyl ether, triethylene glycol divinyl ether, allyl cyanurate, trimethylpropane trimethacrylate, pentaerythritol tetramethacrylate, bisphenol A dimethacrylate, or a reaction product of a diamine with an epoxy-containing vinyl monomer and combinations thereof, where the diamine is selected from the group consisting of N,N'-bis(hydroxyethyl)ethylenediamine, N,N'-dimethylethylenediamine, ethylenediamine, N,N'-dimethyl-1 ,3-propanediamine, N,N'-diethyl-1,3-propanediamine, propane-1,3-diamine, butane-1,4-diamine, pentane-1,5-diamine, hexamethylenediamine, isophoronediamine and combinations thereof, and wherein the epoxy-containing vinyl monomer is selected from the group consisting of glycidyl (meth)acrylate, vinyl glycidyl ether, allyl glycidyl ether, and combinations thereof. 15. Silicone hydrogel contact lens according to claim 14, where the cross-linked polymer material contains units of vinyl monomer that absorbs UV radiation. 16. The silicone hydrogel contact lens of claim 9, wherein the silicone-free hydrophilic vinyl monomer is methyl acrylate, ethyl acrylate, propyl acrylate, isopropylacrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl val. erat , styrene, chloroprene, vinyl chloride, vinylidene chloride, acrylonitrile, 1-butene, butadiene, methacrylonitrile, vinyltoluene, vinylethyl ether, perfluorohexylethylthio-carbonyl-aminoethyl methacrylate, isobornyl methacrylate, trifluoroethyl methacrylate, hexafluoroisopropyl methacrylate or hexafluorobutyl methacrylate. 17. The silicone hydrogel contact lens of claim 16, wherein the crosslinked polymer material contains non-silicone vinyl crosslinking agents selected from the group consisting of ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth) )acrylate, tetraethylene glycol di(meth)acrylate, glycerol di(meth)acrylate, 1,3-propanediol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,4-butanediol di (meth)acrylate, glycerol-1,3-diglycerinate-di(meth)acrylate, ethylene bis[oxy(2-hydroxypropane-1,3-diyl)]-di(meth)acrylate, bis[2-(meth) acrylicoxyethyl]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-yldihydrogen phosphate, piperazine diacrylamide, vinyl methacrylate, allyl methacrylate, allyl acrylate, N-allyl methacrylamide, N-allyl acrylamide, tetraethylene glycol divinyl ether, triethylene glycol divinyl ether, diethylene glycol divinyl ether, ethylene glycol divinyl ether, triethylene glycol divinyl ether, allyl cyanurate, trimethylpropane trimethacrylate, pentaerythritol tetramethacrylate, bisphenol A dimethacrylate, or the reaction product of a diamine with an epoxy-containing vinyl monomer and combinations thereof, where the diamine is selected from the group consisting of N,N'-bis(hydroxyethyl)ethylenediamine, N,N'-dimethylethylenediamine, ethylenediamine, N,N'-dimethyl-1,3 -propanediamine, N, N'-diethyl-1,3-propanediamine, propane-1,3-diamine, butane-1,4-diamine, pentane-1,5-diamine, hexamethylenediamine, isophoronediamine and combinations thereof, and where the epoxide-containing the vinyl monomer is selected from the group consisting of glycidyl (meth)acrylate, vinyl glycidyl ether, allyl glycidyl ether, and combinations thereof. 18. Silicone hydrogel contact lens according to claim 17, where the cross-linked polymer material contains units of vinyl monomer that absorbs UV radiation. 19. The silicone hydrogel contact lens of claim 10, wherein the silicone-free hydrophilic vinyl monomer is methyl acrylate, ethyl acrylate, propyl acrylate, isopropylacrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, vinyl acetate, vinyl propionate, vinyl butyrate, valerate , styrene, chloroprene, vinyl chloride, vinylidene chloride, acrylonitrile, 1-butene, butadiene, methacrylonitrile, vinyltoluene, vinylethyl ether, perfluorohexylethylthio-carbonyl-aminoethyl methacrylate, isobornyl methacrylate, trifluoroethyl methacrylate, hexafluoroisopropyl methacrylate or hexafluorobutyl methacrylate. 20. The silicone hydrogel contact lens of claim 19, wherein the cross-linked polymer material comprises non-silicone vinyl cross-linking agents selected from the group consisting of ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth) )acrylate, tetraethylene glycol di(meth)acrylate, glycerol di(meth)acrylate, 1,3-propanediol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,4-butanediol di (meth)acrylate, glycerol-1,3-diglycerinate-di(meth)acrylate, ethylene bis[oxy(2-hydroxypropane-1,3-diyl)]-di(meth)acrylate, bis[2-(meth) acrylicoxyethyl]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-yldihydrogen phosphate, piperazine diacrylamide, vinyl methacrylate, allyl methacrylate, allyl acrylate, N-allyl methacrylamide, N-allyl acrylamide, tetraethylene glycol divinyl ether, triethylene glycol divinyl ether, diethylene glycol divinyl ether, ethylene glycol divinyl ether, triethylene glycol divinyl ether, allyl cyanurate, trimethylpropane trimethacrylate, pentaerythritol tetramethacrylate, bisphenol A dimethacrylate, or the reaction product of a diamine with an epoxy-containing vinyl monomer and combinations thereof, where the diamine is selected from the group consisting of N,N'-bis(hydroxyethyl)ethylenediamine, N,N'-dimethylethylenediamine, ethylenediamine, N,N'-dimethyl-1,3 -propanediamine, N, N'-diethyl-1,3-propanediamine, propane-1,3-diamine, butane-1,4-diamine, pentane-1,5-diamine, hexamethylenediamine, isophoronediamine and combinations thereof, and where the epoxide-containing the vinyl monomer is selected from the group consisting of glycidyl (meth)acrylate, vinyl glycidyl ether, allyl glycidyl ether, and combinations thereof. 21. The silicone hydrogel contact lens according to claim 20, where the cross-linked polymer material contains units of vinyl monomer that absorbs UV radiation.