Hydrophilic Polydiorganosiloxane Vinyl Crosslinking Agent

Abstract

The present invention provides a class of hydrophilized polydiorganosiloxane vinyl crosslinkers. Each of the hydrophilized polydiorganosiloxane vinyl crosslinkers of the present invention comprises: (1) a polydiorganosiloxane segment comprising a hydrophilized siloxane unit, each having a dimethylsiloxane unit and one methyl substituent and one organic substituent having a phosphorylcholine moiety; and (2) an ethylenically unsaturated group. The present invention also provides a silicone hydrogel contact lens comprising a crosslinked polymeric material comprising at least one repeat unit of such a class of hydrophilized polydiorganosiloxane vinyl crosslinkers. The present invention further provides a method of producing a hydrophilized contact lens from a polymerizable composition comprising at least one of such a class of hydrophilized polydiorganosiloxane vinyl crosslinkers.

Description

Technical Field

[0001] The present invention relates to a hydrophilic polydiorganosiloxane vinyl crosslinking agent having one or more hydrophilic siloxane units each having one organic substituent having one methyl substituent and one phosphorylcholine moiety, and their use in the preparation of silicone hydrogel contact lenses.

Background Art

[0002] Recently, soft silicone hydrogel contact lenses have become increasingly popular due to their high oxygen permeability and comfort. "Soft" contact lenses can fit snugly to the shape of the eye, and thus oxygen cannot easily pass through the lens. Since the cornea does not receive oxygen from a blood supply like other tissues, soft contact lenses must allow oxygen (i.e., oxygen) from the surrounding air to reach the cornea. If sufficient oxygen does not reach the cornea, corneal swelling occurs. Prolonged oxygen deprivation causes unwanted growth of blood vessels in the cornea. By having high oxygen permeability, silicone hydrogel contact lenses allow sufficient oxygen to permeate through the lens to the cornea and minimize adverse effects on corneal health.

[0003] One of the lens-forming materials widely used in making silicone hydrogel contact lenses is a polydiorganosiloxane (e.g., polydimethylsiloxane) vinyl crosslinker, which can impart high oxygen permeability to the resulting contact lens. However, polydimethylsiloxane vinyl crosslinkers can affect the mechanical properties of the resulting contact lens, such as the elastic modulus. For example, low molecular weight polydimethylsiloxane vinyl crosslinkers (<2,000 g / mol) can impart a relatively high elastic modulus to the resulting contact lens to achieve the desired oxygen permeability. Relatively high molecular weight polydimethylsiloxane vinyl crosslinkers are typically used to achieve both high oxygen permeability and low elastic modulus. However, due to its hydrophobicity, polydimethylsiloxane vinyl crosslinkers, especially those of high molecular weight, are not compatible with hydrophilic components in the lens formulation, such as, for example, N,N-dimethylacrylamide (DMA), N-vinylpyrrolidone (NVP), N-vinyl-N-methylacetamide (VMA), or internal wetting agents. It would be difficult to obtain a uniform lens formulation (i.e., a clear lens formulation) from the use of such polydimethylsiloxane vinyl crosslinkers.

[0004] Silicone is hydrophobic and has a strong tendency to migrate to the lens surface exposed to air, so the incorporation of silicone into contact lens materials also has an undesirable effect on the biocompatibility of contact lenses. As a result, silicone hydrogel contact lenses generally require a surface modification process to eliminate or minimize the exposure of silicone in the contact lens and to maintain a biocompatible surface.

[0005] Therefore, there is a need for a novel hydrophilic polydiorganosiloxane vinyl crosslinker suitable for manufacturing silicone hydrogel contact lenses.

[0006] U.S. Patent Nos. 4,260,725; 5,034,461; 5,346,946; 5,416,132; 5,449,729; 5,486,579; 5,512,205; 5,760,100; 5,994,488; 6,858,218; 6,867,245; 7,671,156; 7,744,785; 8,129,442; 8,163,206; 8,501,833; 8,513,325; 8,524,850; 8,835,525; 8,993,651; 9,187,601; 10,081,697; 10,449,740; 10,866,344; and 10,875,967, among other documents, disclose that various lens formulations, either solvent-containing formulations or solvent-free formulations, containing one or more hydrophilic polysiloxane crosslinking agents can be used to make silicone hydrogel contact lenses. SUMMARY OF THE INVENTION MEANS FOR SOLVING THE PROBLEM

[0007] In one aspect, the present invention provides a polysiloxane vinyl crosslinking agent. The polydiorganosiloxane vinyl crosslinking agent of the present invention includes a polydiorganosiloxane segment containing dimethylsiloxane units and a hydrophilic siloxane unit having one methyl substituent and one organic substituent having a phosphorylcholine moiety; and an ethylenically unsaturated group.

[0008] In another aspect, the present invention provides a soft contact lens comprising a crosslinked polymer material containing units (as described above) of the polydiorganosiloxane vinyl crosslinking agent of the present invention.

[0009] The present invention provides the foregoing and other features, and the advantages of the present invention will become more apparent from the following detailed description of the preferred embodiments, read in conjunction with the accompanying drawings. The detailed description and drawings are merely illustrative of the present invention, which is defined by the appended claims and their equivalents, and do not limit the scope of the present invention.

Best Mode for Carrying Out the Invention

[0010] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In general, the nomenclature and experimental procedures used herein are well known and commonly used in the art. Conventional methods, such as those provided in the art and various general references, are used for these procedures. When a term is given in the singular, the inventors also contemplate the plural of that term. The nomenclature used herein and the experimental procedures described below are well known and commonly used in the art.

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

[0012] "Contact lens" refers to a structure that can be placed on or in the wearer's eye. A contact lens can correct, improve, or alter the wearer's vision, but it need not do so.

[0013] "Silicone hydrogel contact lens" refers to a contact lens that contains a silicone hydrogel material as the bulk material.

[0014] "Hydrogel" or "hydrogel material" refers to a crosslinked polymer material that has a three-dimensional polymer network (i.e., a polymer matrix), is insoluble in water, but can retain at least 10% by weight of water in its polymer matrix when fully hydrated (or equilibrated).

[0015] "Silicone hydrogel" refers to a silicone-containing hydrogel that contains repeating units of at least one silicone-containing monomer and / or a silicone-containing vinyl crosslinker, and repeating units of at least a hydrophilic vinyl monomer. It is typically formed by copolymerization of a polymerizable composition containing at least one silicone-containing monomer and / or a silicone-containing vinyl crosslinker and at least one hydrophilic vinyl monomer.

[0016] As used in this application, the term "non-silicone hydrogel" refers to a hydrogel that theoretically does not contain silicon.

[0017] "Hydrophilic", as used herein, refers to a material or a part thereof that would more readily associate with water than with lipids.

[0018] "Vinyl monomer" refers to a compound that has one and only one ethylenically unsaturated group, is soluble in a solvent, and can be polymerized by actinic radiation or thermally.

[0019] In relation to a compound or material in a solvent, the term "soluble" means that the compound or material can dissolve in the solvent at room temperature (i.e., a temperature of about 21°C to about 27°C) to give a solution with a concentration of at least about 0.5% by weight.

[0020] In relation to a compound or material in a solvent, the term "insoluble" means that the compound or material can dissolve in the solvent at room temperature (as defined above) to give a solution with a concentration of less than about 0.01% by weight.

[0021] The term "ethylenically unsaturated group" is used herein in a broad sense and is intended to include any group containing at least one >C=C< group. Exemplary ethylenically unsaturated groups include, without limitation, (meth)acryloyl (

Chem.

[0022] As used herein, "photochemically" in connection with the curing, crosslinking, or polymerization of a polymerizable composition, prepolymer, or material means that the curing (e.g., crosslinking and / or polymerization) is effected by photochemical irradiation such as, for example, UV irradiation, ionizing radiation (e.g., gamma ray or X-ray irradiation), microwave irradiation, etc. Thermal curing or photochemical curing methods are well known to those skilled in the art.

[0023] "Acrylic monomer" refers to a vinyl monomer having a single (meth)acryloyl group. Examples of acrylic monomers include (meth)acryloxy [or (meth)acryloyloxy] monomers and (meth)acrylamide monomers.

[0024] "(Meth)acryloxy monomer" or "(meth)acryloyloxy monomer" refers to

Chem.

[0025] "(Meth)acrylamide monomer" refers to

Chem.

[0026] The term "(meth)acrylamide" refers to methacrylamide and / or acrylamide.

[0027] The term "(meth)acrylate" refers to methacrylate and / or acrylate.

[0028] "N-vinylamide monomer" refers to an amide compound having a vinyl group (-CH=CH 2 ) directly bonded to the nitrogen atom of the amide group.

[0029] The term "ene group" refers to a monovalent group of CH 2 =CH- or CH 2 =CCH 3 - that is not covalently bonded to an oxygen or nitrogen atom or a carbonyl group.

[0030] "Ene monomer" refers to a vinyl monomer having one and only one ene group.

[0031] "Hydrophilic vinyl monomer", "hydrophilic acrylic monomer", "hydrophilic (meth)acryloxy monomer", or "hydrophilic (meth)acrylamide monomer", as used herein, refers to a vinyl monomer, an acrylic monomer, a (meth)acryloxy monomer, or a (meth)acrylamide monomer, respectively, that typically results in a homopolymer that is water-soluble or can absorb at least 10 weight percent of water.

[0032] "Hydrophobic vinyl monomer", "hydrophobic acrylic monomer", "hydrophobic (meth)acryloxy monomer", or "hydrophobic (meth)acrylamide monomer", as used herein, refers to a vinyl monomer, an acrylic monomer, a (meth)acryloxy monomer, or a (meth)acrylamide monomer, respectively, that typically results in a homopolymer that is water-insoluble and can absorb less than 10 weight percent of water.

[0033] As used in this application, the term "vinyl crosslinking agent" refers to an organic compound having at least two ethylenically unsaturated groups. "Vinyl crosslinking agent" refers to a vinyl crosslinking agent having a molecular weight of 700 Daltons or less.

[0034] Siloxane, often also described as silicone, refers to a molecule having at least one moiety of -Si-O-Si- in which each Si atom has two organic groups as substituents.

[0035] "Silicone-containing vinyl monomer or crosslinking agent" or "siloxane-containing vinyl monomer or crosslinking agent" has the same meaning and refers to a vinyl monomer or crosslinking agent having at least one moiety of -Si-O-Si- (where each Si atom has at least two substituents (organic groups)).

[0036] "Polysiloxane segment" or "polydiorganosiloxane segment" has the same meaning. [Chemical formula] [wherein, SN is an integer of 3 or more, and R S1 and R S2 each, independently of one another, is C 1 ~C 10 alkyl; phenyl; C 1 ~C 4 alkyl-substituted phenyl; C 1 ~C 4 alkoxy-substituted phenyl; phenyl-C 1 ~C 6 alkyl; C 1 ~C 10 fluoroalkyl; C 1 ~C 10 fluoroether; aryl; arylC 1 ~C 18 alkyl; -alk-(OC 2 H 4 ) γ1 -OR o (where alk is C 1 ~C 6an alkylene group, and R o is H or C 1 ~C 4 alkyl, and γ1 is an integer from 1 to 10); a hydroxyl group (-OH), a carboxyl group (-COOH), an amino group (-NR N1 R N1 ’), -NR N1 - amino bond, -CONR N1 - amide bond, -CONR N1 R N1 ’ amide, -OCONH- urethane bond, and C 1 ~C 4 an organic group having at least one functional group selected from the group consisting of alkoxy groups, or a linear hydrophilic polymer chain, where R 2 ~C 40 is selected from the group consisting of an organic group having a phosphorylcholine moiety; and here, R N1 and R N1 ’ are, independently of each other, hydrogen or C 1 ~C 15 alkyl; and refers to a polymer chain segment (i.e., a divalent group) that is an organic group having a phosphorylcholine moiety].

[0037] The term "polydiorganosiloxane vinyl crosslinking agent" or "polysiloxane vinyl crosslinking agent" has the same meaning and refers to a compound containing at least one polysiloxane segment and at least two ethylenically unsaturated groups.

[0038] When used in this application, the term "phosphorylcholine moiety"

Chemical formula

[0039] As used herein, the term "fluid" indicates that the material can flow like a liquid.

[0040] As used in this application, the term "transparent" in relation to a polymerizable composition means a transparent solution or liquid mixture in which the polymerizable composition has a light transmittance of 85% or more (preferably 90% or more) in the range of 400 to 700 nm.

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

[0042] "Macromer" or "prepolymer" refers to a compound or polymer containing ethylenically unsaturated groups and having a number average molecular weight of more than 700 daltons.

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

[0044] The term "monovalent group" refers to an organic group that is obtained by removing a hydrogen atom from an organic compound and that forms one bond with one other group in the organic compound. Examples include, without limitation, alkyl (by removal of a hydrogen atom from an alkane), alkoxy (or alkoxyl) (by removal of one hydrogen atom from the hydroxyl group of an alkyl alcohol), thioyl (by removal of one hydrogen atom from the thiol group of an alkyl thiol), cycloalkyl (by removal of a hydrogen atom from a cycloalkane), cycloheteroalkyl (by removal of a hydrogen atom from a cycloheteroalkane), aryl (by removal of a hydrogen atom from an aromatic ring of an aromatic hydrocarbon), heteroaryl (by removal of a hydrogen atom from any ring atom), amino (by removal of one hydrogen atom from an amine), and the like.

[0045] The term "divalent group" refers to an organic group that is obtained by removing two hydrogen atoms from an organic compound and that forms two bonds with two other groups in the organic compound. For example, an alkylene divalent group (i.e., alkenylenyl) is obtained by removing two hydrogen atoms from an alkane, and a cycloalkylene divalent group (i.e., cycloalkenylenyl) is obtained by removing two hydrogen atoms from a cyclic ring.

[0046] In the present application, the term "substituted" in relation to alkyl or alkenylenyl means that the alkyl or alkenylenyl is replaced with one hydrogen atom of the alkyl or alkenylenyl and is also -OH (hydroxyl), -COOH (carboxyl), -NH 2 , -SH (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 4It means containing at least one substituent selected from the group consisting of alkylamino and combinations thereof.

[0047] As is known to those skilled in the art, the term "terminal ethylenically unsaturated group" refers to one ethylenically unsaturated group at one of the two ends of the main chain (or skeleton) of an organic compound.

[0048] "Blending vinyl monomer" refers to a vinyl monomer that can dissolve both the hydrophilic and hydrophobic components of a polymerizable composition to form a solution.

[0049] The free radical initiator can be either a photoinitiator or a thermal initiator. A "photoinitiator" refers to a chemical substance that initiates a free radical crosslinking / polymerization reaction by the use of light. A "thermal initiator" refers to a chemical substance that initiates a radical crosslinking / polymerization reaction by the use of thermal energy.

[0050] In relation to a silicone hydrogel bulk material or a SiHy contact lens, "post-cure surface treatment" means a surface treatment process that is carried out after a silicone hydrogel bulk material or a SiHy contact lens is formed by curing (i.e., polymerizing thermally or by actinic radiation) a SiHy lens formulation.

[0051] The term "silicone hydrogel lens formulation" or "SiHy lens formulation" has the same meaning and refers to a polymerizable composition containing all the necessary polymerizable components for manufacturing a silicone hydrogel (SiHy) contact lens or a SiHy lens bulk material, as is well known to those skilled in the art.

[0052] Generally, the present invention is directed to a class of hydrophilic polydiorganosiloxane vinyl crosslinkers comprising (1) a polydiorganosiloxane segment containing a hydrophilic siloxane unit having a dimethylsiloxane unit and one organic substituent having one methyl substituent and a phosphorylcholine moiety, and (2) an ethylenically unsaturated group.

[0053] There are several potentially unique features associated with the use of the hydrophilic polydiorganosiloxane vinyl crosslinking agent of the present invention in the production of silicone hydrogel contact lenses.

[0054] First, the hydrophilic polydiorganosiloxane vinyl crosslinking agent of the present invention has a higher compatibility with other polymerizable components in a typical polymerizable composition (i.e., lens formulation) because the hydrophilic ionic phosphorylcholine moiety is incorporated as one of the two substituents of each hydrophilic siloxane unit of the polydiorganosiloxane vinyl crosslinking agent. It is suitable for preparing various solvent-containing or solvent-free lens formulations.

[0055] Second, since the hydrophilic polydiorganosiloxane vinyl crosslinking agent of the present invention still contains dimethylsiloxane units, it can impart relatively high oxygen permeability to the resulting contact lenses, like other polydimethylsiloxane vinyl crosslinking agents currently used to make silicone hydrogel contact lenses. To achieve higher oxygen permeability, it is considered that the polydiorganosiloxane should have at least five consecutive dimethylsiloxane units. By sufficiently controlling the ratio of the hydrophilic siloxane units to the dimethylsiloxane units in the hydrophilic polydiorganosiloxane vinyl crosslinking agent of the present invention, it can be ensured that the resulting polydiorganosiloxane vinyl crosslinking agent can have a sufficient siloxane segment consisting of more than five consecutive dimethylsiloxane units. Such a polydiorganosiloxane vinyl crosslinking agent can be used to efficiently impart relatively high oxygen permeability per siloxane unit without adversely affecting its compatibility with other polymerizable components.

[0056] Thirdly, the hydrophilic polydiorganosiloxane vinyl crosslinking agent of the present invention can be used to produce silicone hydrogel contact lenses with improved surface properties. Since the phosphorylcholine moieties are part of the polydiorganosiloxane segments, they will migrate to the surface of the resulting silicone hydrogel contact lens made from the lens formulation containing the hydrophilic polydiorganosiloxane vinyl crosslinking agent of the present invention as the silicone migrates to the lens surface. As a result, the resulting silicone hydrogel contact lens can have a phosphorylcholine-rich moiety at the lens surface.

[0057] Phosphorylcholine is commonly used in medical devices to improve biocompatibility, reduce protein adsorption, and reduce the inflammatory response. Surfaces containing phospholipids have been shown to have anti-fouling properties (see Goda, T.; Ishihara, K.; Expert Review of Medical Devices 2006, 3(2), 167-174). In contact lenses, phosphorylcholine also helps to maintain hydration while preventing the deposition of lipids and proteins. Because of these observations, monomers or polymers containing phosphorylcholine groups have been added to contact lens formulations (see, for example, Liu, Y. Polymerizable contact lens formulations and contact lenses obtained therefrom. U.S. Patent Application Publication No. 2009 / 0182067 A1, July 16, 2009), lubricating eye drops (see, for example, Sakurai, S.; Miyamoto, K.; Shimamura, Y.; Takahashi, M.; Matsuoka, Y.; Yamamoto, N. Eye drops. International Publication No. 2016 / 140242 Pamphlet, September 9, 2016), contact lens surfaces (see, for example, Takahashi, M.; Sato, K.; Sakurai, T.; Nakajima, M.; Matsuoka, Yamamoto, N. Contact lens having phosphorylcholine group-containing hydrophilic polymer on surface thereof. Japanese Patent Application Laid-Open No. 2017-146334, August 24, 2017), and packaging saline solutions (see Sakura, T.; Sato, K.; Takahashi, M.; Nakajima, M.; Matsuoka, Y.; Shimamura, Y.; Miyamoto, K.; Yamamoto, N. Solutions for soft contact lenses. Japanese Patent Application Laid-Open No. 2017-151437, August 31, 2017) to improve contact lens on-eye performance.

[0058] As a result, the obtained silicone hydrogel contact lens can be more biocompatible and resistant to lipid deposition.

[0059] In one aspect, the present invention provides a hydrophilic polyorganosiloxane vinyl crosslinking agent. The hydrophilic polyorganosiloxane vinyl crosslinking agent of the present invention comprises: (1) a polydiorganosiloxane segment containing at least one hydrophilic siloxane unit having a dimethylsiloxane unit and one organic substituent having one methyl substituent and a phosphorylcholine moiety; and (2) an ethylenically unsaturated group (preferably a (meth)acryloyl group).

[0060] In a preferred embodiment, the polydiorganosiloxane segment comprises 6 to 500 (preferably 10 to 450, more preferably 15 to 400, still more preferably 20 to 350) dimethylsiloxane units and 3 to 80 (preferably 5 to 70, more preferably 7 to 60, still more preferably 9 to 50) hydrophilic siloxane units.

[0061] In a preferred embodiment, the molar ratio of hydrophilic siloxane units to dimethylsiloxane units is from about 0.002 to about 0.50 (preferably from about 0.002 to about 0.20, more preferably from about 0.004 to about 0.1, still more preferably from about 0.004 to about 0.05).

[0062] In another preferred embodiment, the hydrophilic polyorganosiloxane vinyl crosslinking agent of the present invention can have a number average molecular weight of at least 1000 daltons (preferably from 1500 daltons to 80000 daltons, more preferably from 2000 to 50000 daltons, still more preferably from 2500 to 25000 daltons).

[0063] According to the present invention, the hydrophilic polyorganosiloxane vinyl crosslinking agent preferably has the formula (1) or (2)

Chemical formula

Chem.

Chem.

Chem.

[0064] In a preferred embodiment, in formula (1), a1 is zero, and then E 1 is

Chemical formula

[0065] In another preferred embodiment, ω1 / υ1 is from about 0.002 to about 0.50 (preferably from about 0.002 to about 0.20, more preferably from about 0.004 to about 0.1, even more preferably from about 0.004 to about 0.05).

[0066] The hydrophilic polyorganosiloxane vinyl crosslinking agent of formula (1) can be prepared in a three-step process.

[0067] In the first step, the hydrosiloxane-containing polyorganosiloxane of formula (3) is reacted with a hydroxy group-containing en monomer in a hydrosilylation reaction with a platinum catalyst known to those skilled in the art to form a polyorganosiloxane vinyl crosslinking agent having pendant reactive functional groups as represented by formula (4)

Chemical formula

[0068] The hydrosiloxane-containing polyorganosiloxane of formula (3) can be prepared according to any method known to those skilled in the art.

[0069] As an illustrative example, the hydrosiloxane-containing polydiorganosiloxane of formula (3) can be prepared from the polymerization of a mixture of octamethylcyclotetrasiloxane (D4) and 1,3,5,7-tetramethylcyclotetrasiloxane (H4) in the presence of 1,3-bis(E1 group)-terminated tetramethyldisiloxane (e.g., 1,3-bis[3-(meth)acryloxypropyl]tetramethyldisiloxane, 1,3-bis[3-(meth)acrylamidopropyl]tetramethyldisiloxane, etc.) as a chain-end block and in the presence of a catalyst. By controlling the molar ratio of D4 to H4, the desired value of υ1 / ω1 can be obtained. It is understood that 1,3-bis(E1 group)-terminated tetramethyldisiloxane can be prepared from 1,3-bis(hydroxyalkyl)tetramethyldisiloxane (e.g., 1,3-bis(hydroxypropyl)tetramethyldisiloxane) or 1,3-bis(aminoalkyl)tetramethyldisiloxane (e.g., 1,3-bis(aminopropyl)tetramethyldisiloxane).

[0070] As long as the en monomer contains only one hydroxyl group, any en monomer can be used in the preparation of the polydiorganosiloxane vinyl crosslinker of formula (4). Various en monomers having only one hydroxyl group can be obtained from commercial suppliers or prepared according to known methods.

[0071] Examples of commercially available hydroxyl-containing en monomers include, without limitation, allyl alcohol, 2-methyl-2-propen-1-ol, 3-buten-1-ol, 3-buten-2-ol, 3-methyl-3-buten-1-ol, 2-methyl-3-buten-2-ol, 2-methyl-3-buten-1-ol, 1-penten-3-ol, 4-penten-1-ol, 4-penten-2-ol, 1-hexen-3-ol, 5-hexen-1-ol, 5-hexen-2-ol, 3-methyl-1-hexen-3-ol, 5-methyl-1-hexen-3-ol, 1-hepten-3-ol, allyloxyethanol, di(ethylene glycol) monoallyl ether, poly(ethylene glycol) monoallyl ether, poly(propylene glycol) monoallyl ether, allyloxypropanol, 1-allyloxy-2-propanol, 4-allyloxy-1-butanol, 1-vinylcyclohexanol, 2-vinylcyclohexanol, 4-vinylcyclohexanol, 1-allylcyclohexanol, 2-allylcyclohexanol, 4-allylcyclohexanol, 4-vinylphenol, (4-vinylphenyl)methanol, (4-vinylphenyl)ethanol, 3-(4-vinylphenyl)-1-propanol, 1-(4-vinylphenyl)-2-methyl-2-propanol, and the like.

[0072] In the second step, the polydiorganosiloxane vinyl crosslinking agent of formula (4) has a pendant group L of the polydiorganosiloxane vinyl crosslinking agent of formula (4) e onto each of which an ethylene phosphate group [Chemical formula] (i.e., 2-oxo-1,3,2-dioxaphospholane) is reacted with ethylene phosphorochloride (i.e., 2-chloro-2-oxo-1,3,2-dioxaphospholane) in the presence of a base (e.g., triethylamine) to attach it.

[0073] Alternatively, the polydiorganosiloxane vinyl crosslinking agent of formula (4) has a pendant group L of the polydiorganosiloxane vinyl crosslinking agent of formula (4) e with one or more bromoalkyl phosphate groups attached thereto [Chemical formula] To attach, in the presence of a base (e.g., triethylamine), a bromoalkyl phosphoryl chloride (which can be obtained by reacting phosphorus oxychloride with a bromoalcohol, HO-(CH2) n Br), and this can be followed by acid hydrolysis.

[0074] In a third step, the resulting polydiorganosiloxane vinyl crosslinking agent containing a pendant ethylene phosphate group or a bromoalkyl phosphate group is successively converted to a phosphorylcholine group, i.e., to form a hydrophilic polydiorganosiloxane vinyl crosslinking agent of formula (1), with a tertiary amine, NR 1 ’R 2 ’R 3 ’.

[0075] Similarly, the hydrophilic polydiorganosiloxane vinyl crosslinking agent of formula (2) can be prepared in a 3-step process.

[0076] In a first step, a hydrosiloxane-containing polydiorganosiloxane of formula (5) is of formula (5) [Chemical formula] (wherein E 1 , υ1, ω1, and L e are as defined above for formula (2)) To form a polydiorganosiloxane vinyl crosslinking agent having pendant reactive functional groups as represented by , it is reacted with an en monomer containing a hydroxy group in a hydrosilylation reaction with a platinum catalyst, as is known to those skilled in the art.

[0077] The hydrosiloxane-containing polydiorganosiloxane of formula (5) can be prepared according to any method known to those skilled in the art.

[0078] As an illustrative example, the hydrosiloxane-containing polydiorganosiloxane of formula (5) is prepared from the polymerization of a mixture of octamethylcyclotetrasiloxane (D4) and 1,3,5,7-tetramethylcyclotetrasiloxane (H4) in the presence of 1,3-bis(T 2 group) terminal tetramethyldisiloxane (e.g., 1,3-bis(3-hydroxyethoxypropyl)tetramethyldisiloxane, etc.) as a chain end block and in the presence of a catalyst. By controlling the molar ratio of D4 to H4, the desired value of υ1 / ω1 can be obtained.

[0079] In the second step. The polydiorganosiloxane vinyl crosslinking agent of formula (6) is reacted with ethylene phosphorochloride (i.e., 2-chloro-2-oxo-1,3,2-dioxaphospholane) in the presence of a base (e.g., triethylamine) to attach an ethylene phosphate group e to each of the pendant groups L of the polydiorganosiloxane vinyl crosslinking agent of formula (6)

Chemical formula

[0080] Alternatively, the polydiorganosiloxane vinyl crosslinking agent of formula (6) can also have one or more bromoalkyl phosphate groups e attached to each of the pendant groups L of the polydiorganosiloxane vinyl crosslinking agent of formula (6)

Chemical formula

[0081] In a third step, the resulting polydiorganosiloxane vinyl crosslinker containing pendant ethylene phosphate groups or bromoalkyl phosphate groups is successively treated with a tertiary amine, NR 1 ’R 2 ’R 3 ’ to convert to phosphorylcholine groups, i.e., to form a hydrophilized polydiorganosiloxane vinyl crosslinker of formula (2).

[0082] The hydrophilized polydiorganosiloxane vinyl crosslinkers of the present invention (of formulas (1) and (2) as defined above) can find particular use in the preparation of polymers, preferably silicone hydrogel polymer materials, which is another aspect of the present invention. Those skilled in the art know how to prepare polymers or silicone hydrogel polymer materials from polymerizable compositions according to any known polymerization mechanism.

[0083] In another aspect, the present invention provides a silicone hydrogel contact lens (as described above) comprising a crosslinked polymer material containing repeating units of the hydrophilized polydiorganosiloxane vinyl crosslinker of the present invention.

[0084] In a preferred embodiment, when fully hydrated, the silicone hydrogel contact lens of the present invention has an oxygen permeability coefficient (Dk) of at least about 40 barr (preferably at least about 60 barr, more preferably at least about 70 barr, even more preferably at least about 80 barr), a water content of about 15 wt% to about 70 wt% (preferably about 20 wt% to about 70 wt%, more preferably about 25% to about 65%, even more preferably about 30 wt% to 60%), and an elastic modulus of about 0.20 MPa to about 1.8 MPa (preferably about 0.25 MPa to about 1.5 MPa, more preferably about 0.3 MPa to about 1.2 MPa, even more preferably about 0.4 MPa to about 1.0 MPa).

[0085] Those skilled in the art are well aware of the methods for measuring the oxygen permeability, oxygen transmissibility, water content, and elastic modulus of silicone hydrogel contact lenses. These lens properties are reported by all manufacturers for their silicone hydrogel contact lens products.

[0086] The silicone hydrogel contact lens of the present invention also contains units of at least one silicone-containing polymerizable component and units of at least one hydrophilic vinyl monomer.

[0087] According to the present invention, the silicone-containing polymerizable component other than the hydrophilic polyorganosiloxane vinyl crosslinking agent of the present invention can be a silicone-containing vinyl monomer, a polysiloxane vinyl crosslinking agent, or a combination thereof.

[0088] According to the present invention, the silicone-containing vinyl monomer can be any silicone-containing vinyl monomer known to those skilled in the art. Examples of preferred silicone-containing vinyl monomers include, without limitation, vinyl monomers each having a bis(trialkylsilyloxy)alkylsilyl group or a tris(trialkylsilyloxy)silyl group, polysiloxane vinyl monomers, 3-methacryloxypropylpentamethyldisiloxane, t-butyldimethyl-siloxyethyl vinyl carbonate, trimethylsilylethyl vinyl carbonate, and trimethylsilylmethyl vinyl carbonate, and combinations thereof.

[0089] Preferred polysiloxane vinyl monomers, including those of formula (M1), are described hereinafter in this application and can be obtained from commercial suppliers (e.g., Shin-Etsu Chemical, Gelest, etc.); for example, they can be prepared according to the procedures described in U.S. Patent Nos. 5,070,215, 6,166,236, 6,867,245, 8,415,405, 8,475,529, 8,614,261, and 9,217,813; they can be prepared by reacting hydroxyalkyl (meth)acrylate or (meth)acrylamide or (meth)acryloxypolyethylene glycol with monoepoxypropyl-oxypropyl-terminated polydimethylsiloxane; they can be prepared by reacting glycidyl (meth)acrylate with monocarbinol-terminated polydimethylsiloxane, monoaminopropyl-terminated polydimethylsiloxane, or monoethylaminopropyl-terminated polydimethylsiloxane; or they can be prepared by reacting isocyanatoethyl (meth)acrylate with monocarbinol-terminated polydimethylsiloxane according to coupling reactions well known to those skilled in the art.

[0090] Preferred silicone-containing vinyl monomers each having a bis(trialkylsilyloxy)alkylsilyl group or a tris(trialkylsilyloxy)silyl group, including those of formula (M2), are described later in this application and can be obtained from commercial suppliers (e.g., Shin-Etsu Chemical, Gelest, etc.) or can be prepared according to the procedures described in U.S. Patent Nos. 5,070,215; 6,166,236; 7,214,809; 8,475,529; 8,658,748; 9,097,840; 9,103,965; and 9,475,827.

[0091] Any suitable polysiloxane vinyl crosslinking agent can be used in the present invention. Examples of preferred polysiloxane vinyl crosslinking agents include di-(meth)acryloyl-terminated polydimethylsiloxane; divinyl carbonate-terminated polydimethylsiloxane; divinyl carbamate-terminated polydimethylsiloxane; N,N,N’,N’-tetrakis(3-methacryloxy-2-hydroxypropyl)-alpha,omega-bis-3-aminopropyl-polydimethylsiloxane; polysiloxane-containing macromers selected from the group consisting of macromer A, macromer B, macromer C, and macromer D described in U.S. Patent No. 5,760,100; polysiloxane-containing macromers disclosed in U.S. Patent Nos. 4,136,250, 4,153,641, 4,182,822, 4,189,546, 4,343,927, 4,254,248, 4,355,147, 4,276,402, 4,327,203, 4,341,889, 4,486,577, 4,543,398, 4,605,712, 4,661,575, 4,684,538, 4,703,097, 4,833,218, 4,837,289, 4,954,586, 4,954,587, 5,010,141, 5,034,461, 5,070,170, 5,079,319, 5,039,761, 5,346,946, 5,358,995, 5,387,632, 5,416,132, 5,451,617, 5,486,579, 5,962,548, 5,981,675, 6,039,913, and 6,762,264; polysiloxane-containing macromers disclosed in U.S. Patent Nos. 4,259,467, 4,260,725, and 4,261,875.

[0092] One class of preferred polysiloxane vinyl crosslinking agents has dimethylsiloxane units and one monovalent C having one methyl substituent and 2 to 6 hydroxyl groups 4 ~C40 A di-(meth)acryloyloxy-terminated polysiloxane vinyl crosslinking agent having a hydrophilic siloxane unit each having an organic radical substituent, more preferably a polysiloxane vinyl crosslinking agent of formula (I); It can be prepared according to the procedures described hereinafter in this application and disclosed in US Patent No. 10081697.

[0093] Another class of preferred polysiloxane vinyl crosslinking agents are vinyl crosslinking agents each of which contains one unique polydiorganosiloxane segment and two terminal (meth)acryloyl groups, which can be obtained from commercial suppliers; It can be prepared by reacting glycidyl (meth)acrylate (meth)acryloyl chloride with diamino-terminated polydimethylsiloxane or dihydroxyl-terminated polydimethylsiloxane; It can be prepared by reacting isocyanatoethyl (meth)acrylate with dihydroxyl-terminated polydimethylsiloxane; It can be prepared by reacting an amino-containing acrylic monomer with a dicarboxyl-terminated polydimethylsiloxane in the presence of a coupling agent (carbodiimide); It can be prepared by reacting a carboxyl-containing acrylic monomer with a diamino-terminated polydimethylsiloxane in the presence of a coupling agent (carbodiimide); or It can be prepared by reacting a hydroxyl-containing acrylic monomer with a dihydroxy-terminated polysiloxane in the presence of a diisocyanate or diepoxy coupling agent.

[0094] Other preferred polysiloxane vinyl crosslinking agents are chain-extended polysiloxane vinyl crosslinking agents each having at least two polydiorganosiloxane segments linked by a linker between each pair of polydiorganosiloxane segments and two terminal ethylenically unsaturated groups; it can be prepared according to the procedures described in U.S. Patent Nos. 5,034,461; 5,416,132; 5,449,729; 5,760,100; 7,423,074; 8,529,057; 8,835,525; 8,993,651; 10,301,451; and 10,465,047.

[0095] Any hydrophilic vinyl monomer can be used in the present invention. Examples of preferred hydrophilic vinyl monomers are alkyl (meth)acrylamides (as described hereinafter in this application), hydroxyl-containing acrylic monomers (as described hereinafter), amino-containing acrylic monomers (as described hereinafter in this application), carboxyl-containing acrylic monomers (as described hereinafter in this application), N-vinylamide monomers (as described hereinafter in this application), methylene-containing pyrrolidone monomers (i.e., pyrrolidone derivatives each having a methylene group bonded to the pyrrolidone ring at the 3- or 5-position) (as described hereinafter in this application), C 1 ~C 4 acrylic monomers having an alkoxyethoxy group (as described hereinafter in this application), vinyl ether monomers (as described hereinafter in this application), allyl ether monomers (as described hereinafter in this application), phosphorylcholine-containing vinyl monomers (as described hereinafter in this application), N-2-hydroxyethyl vinyl carbamate, N-carboxyvinyl-β-alanine (VINAL), N-carboxyvinyl-α-alanine, and combinations thereof.

[0096] The silicone hydrogel contact lens of the present invention can also further include units of at least one hydrophobic vinyl monomer, at least one non-silicone vinyl crosslinking agent, or combinations thereof.

[0097] According to the present invention, any hydrophobic vinyl monomer can be within the scope of the present invention. Examples of preferred hydrophobic vinyl monomers include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl valerate, styrene, chloroprene, vinyl chloride, vinylidene chloride, (meth)acrylonitrile, 1-butene, butadiene, vinyltoluene, vinyl ethyl ether, perfluorohexylethyl-thio-carbonyl-aminoethyl-methacrylate, isobornyl (meth)acrylate, trifluoroethyl (meth)acrylate, hexafluoroisopropyl (meth)acrylate, hexafluorobutyl (meth)acrylate, and combinations thereof.

[0098] According to the present invention, any non-silicone vinyl crosslinking agent can be within the scope of the present invention. Examples of preferred non-silicone vinyl crosslinking agents are described later in this application.

[0099] According to the present invention, the silicone hydrogel (SiHy) contact lenses of the present invention can be manufactured according to any lens manufacturing process. Those skilled in the art are well aware of how to make SiHy contact lenses. For example, SiHy contact lenses can be made in a conventional "spin casting" as described in, for example, U.S. Patent No. 3,408,429, or in a static full cast molding process as described in U.S. Patent Nos. 4,347,198, 5,508,317, 5,583,463, 5,789,464, and 5,849,810, or by lathe cutting of a polymer material button as used in the manufacture of customized contact lenses. In cast molding, the polymerizable composition (i.e., the SiHy lens formulation) is typically dispensed into a mold and cured (i.e., polymerized and / or crosslinked) in the mold to make the SiHy contact lens.

[0100] Molds for manufacturing contact lenses such as SiHy contact lenses are well known to those skilled in the art and are used, for example, in injection molding or spin casting. For example, a mold (for injection molding) generally includes at least two mold pieces (or parts) or mold halves, namely, a first and a second mold half. The first mold half defines a first molding (or optical) surface, and the second mold half defines a second molding (or optical) surface. The first and second mold halves are configured to receive each other such that a lens-forming cavity is formed between the first molding surface and the second molding surface. The molding surface of the mold half is the cavity-forming surface of the mold and is in direct contact with the polymerizable composition.

[0101] Methods for manufacturing mold parts for casting contact lenses are generally well known to those skilled in the art. The process of the present invention is not limited to any particular method of forming the mold. In fact, any method of forming the mold can be used in the present invention. The first and second mold halves can be formed by various techniques such as injection molding or turning. Examples of suitable processes for forming the mold halves are disclosed in U.S. Patent Nos. 4,444,711, 4,460,534, 5,843,346, and 5,894,002.

[0102] Virtually all materials known in the art for manufacturing molds can be used to manufacture molds for manufacturing contact lenses. For example, polymer materials such as polyethylene, polypropylene, polystyrene, PMMA, Topas® COC grade 8007-S10 (a transparent amorphous copolymer of ethylene and norbornene manufactured by Ticona GmbH, Frankfurt, Germany and Summit, New Jersey) etc. can be used. Other materials that allow UV light transmission such as quartz glass and sapphire can also be used.

[0103] According to the present invention, the polymerizable composition can be introduced (dispensed) into a cavity formed by a mold according to any known method.

[0104] After the polymerizable composition is dispensed into the mold, it is polymerized to produce a SiHy contact lens. Crosslinking can be initiated thermally or by actinic radiation, preferably by exposing the polymerizable composition in the mold to spatial confinement of actinic radiation to crosslink the polymerizable components in the polymerizable composition.

[0105] Opening the mold so that the formed SiHy contact lens can be removed from the mold can be done by methods known per se.

[0106] The formed SiHy contact lens can be subjected to lens extraction in a liquid extraction medium to remove unpolymerized polymerizable components and formed oligomers. According to the present invention, the extraction liquid medium is any solvent capable of dissolving the organic solvent, unpolymerized polymerizable material, and oligomers in the dry contact lens. Water, any organic solvent known to those skilled in the art, or mixtures thereof can be used in the present invention. Preferably, the organic solvent used in the extraction liquid medium is water, buffered saline, C 1 ~C 3 alkyl alcohol, 1,2-propylene glycol, polyethylene glycol having a number average molecular weight of about 400 daltons or less, C 1 ~C 6 alkyl alcohol, or combinations thereof.

[0107] After extraction, the silicone hydrogel contact lens can be hydrated in water or an aqueous solution to replace the liquid extraction medium according to any method known to those skilled in the art.

[0108] The hydrated silicone hydrogel contact lens can be further subjected to additional processes such as surface treatment, packaging in a packaging solution well known to those skilled in the art; sterilization such as autoclaving at 118 to 124 °C for at least about 30 minutes, etc.

[0109] Lens packages (or containers) are well known to those skilled in the art with respect to autoclaving and storing soft contact lenses. Any lens package can be used in the present invention. Preferably, the lens package is a blister package including a base and a cover; here, the cover is sealed to be detachable from the base, and here, the base includes a cavity for receiving a sterilizing packaging solution and a contact lens.

[0110] The lenses are packaged, sealed in individual packages and sterilized (e.g., by autoclaving at about 120 °C or higher for at least 30 minutes under pressure) before being dispensed to the user. Those skilled in the art will well understand the methods of sealing and sterilizing the lens packages.

[0111] The SiHy contact lens formulation can also include other necessary components known to those skilled in the art such as free radical initiators (e.g., thermal polymerization initiators, photoinitiators), UV absorbing vinyl monomers, high energy ultraviolet (「HEVL」) absorbing vinyl monomers, visibility colorants (e.g., reactive dyes, polymerizable dyes, pigments, antibacterial agents (e.g., preferably silver nanoparticles), bioactive agents, leachable polymer wetting agents (e.g., non-polymeric hydrophilic polymers, etc.), leachable tear stabilizers (e.g., phospholipids, monoglycerides, diglycerides, triglycerides, glycolipids, glyceroglycolipids, sphingolipids, sphingo-glycolipids, etc.), and mixtures thereof.

[0112] Any thermal polymerization initiator can be used in the present invention. Suitable thermal polymerization initiators are known to those skilled in the art and include, for example, peroxides, hydroperoxides, azo-bis(alkyl- or cycloalkylnitrile), persulfates, percarbonates, or mixtures thereof.Examples of preferred thermal polymerization initiators include, without limitation, benzoyl peroxide, t-butyl peroxide, t-amyl peroxybenzoate, 2,2-bis(tert-butylperoxy)butane, 1,1-bis(tert-butylperoxy)cyclohexane, 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane, 2,5-bis(tert-butylperoxy)-2,5-dimethyl-3-hexyne, bis(1-(tert-butylperoxy)-1-methylethyl)benzene, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, di-t-butyl diperoxyphthalate, t-butyl hydroperoxide, t-butyl peracetate, t-butyl peroxybenzoate, t-butyl peroxyisopropyl carbonate, acetyl peroxide, lauroyl peroxide, decanoyl peroxide, dicetyl peroxydicarbonate, di(4-t-butylcyclohexyl) peroxydicarbonate (Perkadox 16S), di(2-ethylhexyl) peroxydicarbonate, t-butyl peroxypivalate (Lupersol 11); t-butyl peroxy-2-ethylhexanoate (Trigonox 21-C50), 2,4-pentanedione peroxide, dicumyl peroxide, peracetic acid, potassium persulfate, sodium persulfate, ammonium persulfate, 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile) (VAZO 33), 2,2'-azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride (VAZO 44), 2,2'-azobis(2-amidinopropane) dihydrochloride (VAZO 50), 2,2'-azobis(2,4-dimethylvaleronitrile) (VAZO 52), 2,2'-azobis(isobutyronitrile) (VAZO 64 or AIBN), 2,2'-azobis-2-methylbutyronitrile (VAZO 67), 1,1-azobis(1-cyclohexanecarbonitrile) (VAZO 88); 2,2'-azobis(2-cyclopropylpropionitrile), 2,2'-azobis(methyl isobutyrate), 4,4'-azobis(4-cyanovaleric acid), and combinations thereof.Preferably, the thermal initiator is 2,2'-azobis(isobutyronitrile) (AIBN or VAZO 64).

[0113] Suitable photoinitiators are benzoin methyl ether, diethoxyacetophenone, benzoylphosphine oxide, 1-hydroxycyclohexyl phenyl ketone and Darocur and Irgacur types, preferably Darocur 1173® and Darocur 2959®, germanium-based Norrish type I photoinitiators (for example, those described in U.S. Patent No. 7,605,190). 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. For example, reactive photoinitiators that can be incorporated into macromers or used as special monomers are also suitable. Examples of reactive photoinitiators are those disclosed in European Patent No. 632329. Preferably, the SiHy lens formulation for making SiHy contact lenses contains at least one photoinitiator that can be initiated by visible light, such as benzoylphosphine oxide photoinitiators, germanium-based Norrish type I photoinitiators, or combinations thereof.

[0114] The polymerizable composition (SiHy lens formulation) can be a solvent-free transparent liquid prepared by mixing all the polymerizable components with other necessary components as known to those skilled in the art, or a solution prepared by dissolving all the desired components in any suitable solvent, such as a mixture of water and one or more water-miscible organic solvents, an organic solvent, or a mixture of one or more organic solvents. The term "solvent" refers to a chemical substance that cannot participate in the free radical polymerization reaction.

[0115] The solventless lens SiHy lens formulation typically includes at least one blending vinyl monomer as a reactive solvent to dissolve all other polymerizable components of the solventless SiHy lens formulation. Examples of preferred blending vinyl monomers are described later in this application. Preferably, methyl methacrylate is used as the blending vinyl monomer in preparing the solventless SiHy lens formulation.

[0116] Any solvent can be used in the present invention. Examples of preferred organic solvents include, without limitation, tetrahydrofuran, tripropylene glycol methyl ether, dipropylene glycol methyl ether, ethylene glycol n-butyl ether, ketones (e.g., acetone, methyl ethyl ketone, etc.), diethylene glycol n-butyl ether, diethylene glycol methyl ether, ethylene glycol phenyl ether, propylene glycol methyl ether, propylene glycol methyl ether acetate, dipropylene glycol methyl ether acetate, propylene glycol n-propyl ether, dipropylene glycol n-propyl ether, tripropylene glycol n-butyl ether, propylene glycol n-butyl ether, dipropylene glycol n-butyl ether, tripropylene glycol n-butyl ether, propylene glycol phenyl ether, dipropylene glycol dimethyl ether, polyethylene glycol, polypropylene glycol, ethyl acetate, butyl acetate, amyl acetate, methyl lactate, ethyl lactate, i-propyl lactate, methylene chloride, 2-butanol, 1-propanol, 2-propanol, menthol, cyclohexanol, cyclopentanol and exo-norborneol, 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-dimethyl-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-pyrrolidone, N,N-dimethylpropionamide, dimethylformamide, dimethylacetamide, dimethylpropionamide, N-methylpyrrolidone, and mixtures thereof are mentioned.,

[0117] The SiHy lens formulation (i.e., the polymerizable composition) can be cured (polymerized) thermally or by actinic rays as is known to those skilled in the art, preferably in a mold for cast molding of a contact lens.,

[0118] Thermal polymerization is conveniently carried out, for example, at a temperature of 25 to 120 °C, preferably 40 to 100 °C. The reaction time can vary within a wide range, but conveniently, for example, it is 1 to 24 hours or preferably 2 to 12 hours. It is advantageous to degas the components and solvents used in the polymerization reaction in advance and to carry out the copolymerization reaction under an inert atmosphere, for example, under an atmosphere of nitrogen or argon.,

[0119] Subsequently, the chemical cross-linking can be induced by actinic rays, such as light, particularly preferably UV light or visible light of a suitable wavelength. If necessary, the spectral requirements can be appropriately controlled by adding a suitable photosensitizer.

[0120] Although various embodiments of the present invention have been described using specific terms, devices, and methods, such descriptions are for illustrative purposes only. The terms used are rather descriptive terms than limiting terms. It should be understood that changes and variations can be made by those skilled in the art without departing from the spirit or scope of the present invention as defined in the following claims. In addition, as illustrated below, it should be understood that aspects of various embodiments can be exchanged, either wholly or partially, or combined and / or used together in any manner:

[0121] Embodiment 1. A hydrophilic polydiorganosiloxane vinyl cross-linking agent, (1) a polydiorganosiloxane segment containing at least one hydrophilic siloxane unit having a dimethylsiloxane unit and one organic substituent having one methyl substituent and one phosphorylcholine moiety; (2) an ethylenically unsaturated group and a cross-linking agent containing.

[0122] Embodiment 2. The hydrophilic polydiorganosiloxane vinyl cross-linking agent according to Embodiment 1, wherein the polydiorganosiloxane segment contains 6 to 500 dimethylsiloxane units.

[0123] Embodiment 3. The hydrophilic polydiorganosiloxane vinyl cross-linking agent according to Embodiment 1, wherein the polydiorganosiloxane segment contains 10 to 450 dimethylsiloxane units.

[0124] Embodiment 4. The hydrophilic polydiorganosiloxane vinyl cross-linking agent according to Embodiment 1, wherein the polydiorganosiloxane segment contains 15 to 400 dimethylsiloxane units.

[0125] Embodiment 5. The hydrophilized polyorganosiloxane vinyl crosslinking agent of Embodiment 1, wherein the polyorganosiloxane segment contains 20 to 350 dimethylsiloxane units.

[0126] Embodiment 6. The hydrophilized polyorganosiloxane vinyl crosslinking agent according to any one of Embodiments 1 to 5, wherein the polyorganosiloxane segment contains 3 to 80 hydrophilized siloxane units.

[0127] Embodiment 7. The hydrophilized polyorganosiloxane vinyl crosslinking agent according to any one of Embodiments 1 to 5, wherein the polyorganosiloxane segment contains 5 to 70 hydrophilized siloxane units.

[0128] Embodiment 8. The hydrophilized polyorganosiloxane vinyl crosslinking agent according to any one of Embodiments 1 to 5, wherein the polyorganosiloxane segment contains 7 to 60 hydrophilized siloxane units.

[0129] Embodiment 9. The hydrophilized polyorganosiloxane vinyl crosslinking agent according to any one of Embodiments 1 to 5, wherein the polyorganosiloxane segment contains 9 to 50 hydrophilized siloxane units.

[0130] Embodiment 10. The hydrophilized polyorganosiloxane vinyl crosslinking agent according to any one of Embodiments 1 to 9, wherein the ethylenically unsaturated group is a (meth)acryloyl group.

[0131] Embodiment 11. The hydrophilized polyorganosiloxane vinyl crosslinking agent according to any one of Embodiments 1 to 10, wherein the molar ratio of the hydrophilized siloxane units to the dimethylsiloxane units is from about 0.002 to about 0.50.

[0132] Embodiment 12. The hydrophilized polyorganosiloxane vinyl crosslinking agent according to any one of Embodiments 1 to 10, wherein the molar ratio of the hydrophilized siloxane units to the dimethylsiloxane units is from about 0.002 to about 0.20.

[0133] Embodiment 13. The hydrophilic siloxane unit to dimethylsiloxane unit molar ratio is from about 0.004 to about 0.1, and the hydrophilic polydiorganosiloxane vinyl crosslinking agent according to any one of Embodiments 1 to 10.

[0134] Embodiment 14. The hydrophilic siloxane unit to dimethylsiloxane unit molar ratio is from about 0.004 to about 0.05, and the hydrophilic polydiorganosiloxane vinyl crosslinking agent according to any one of Embodiments 1 to 10.

[0135] Embodiment 15. The hydrophilic polydiorganosiloxane vinyl crosslinking agent has a number average molecular weight of at least 1000 Daltons, and the hydrophilic polydiorganosiloxane vinyl crosslinking agent according to any one of Embodiments 1 to 14.

[0136] Embodiment 16. The hydrophilic polydiorganosiloxane vinyl crosslinking agent has a number average molecular weight of 1500 Daltons to 80000 Daltons, and the hydrophilic polydiorganosiloxane vinyl crosslinking agent according to any one of Embodiments 1 to 14.

[0137] Embodiment 17. The hydrophilic polydiorganosiloxane vinyl crosslinking agent has a number average molecular weight of 2000 to 50000 Daltons, and the hydrophilic polydiorganosiloxane vinyl crosslinking agent according to any one of Embodiments 1 to 14.

[0138] Embodiment 18. The hydrophilic polydiorganosiloxane vinyl crosslinking agent has a number average molecular weight of 2500 to 25000 Daltons, and the hydrophilic polydiorganosiloxane vinyl crosslinking agent according to any one of Embodiments 1 to 14.

[0139] Embodiment 19. The hydrophilic polydiorganosiloxane vinyl crosslinking agent is of formula (1) or (2)

Chemical formula

Chem.

Chem.

Chem.

Chem.

Chem.

[0140] Embodiment 20. The hydrophilic polyorganosiloxane vinyl crosslinking agent according to Embodiment 19, wherein in formula (1) or (2), υ1 is an integer from 10 to 450.

[0141] Embodiment 21. The hydrophilic polyorganosiloxane vinyl crosslinking agent according to Embodiment 19, wherein in formula (1) or (2), υ1 is an integer from 15 to 400.

[0142] Embodiment 22. The hydrophilic polyorganosiloxane vinyl crosslinking agent according to Embodiment 19, wherein in formula (1) or (2), υ1 is an integer from 20 to 350.

[0143] Embodiment 23. The hydrophilic polyorganosiloxane vinyl crosslinking agent according to any one of Embodiments 19 to 22, wherein in formula (1) or (2), ω1 is an integer from 5 to 70.

[0144] Embodiment 24. The hydrophilic polyorganosiloxane vinyl crosslinking agent according to any one of Embodiments 19 to 22, wherein in formula (1) or (2), ω1 is an integer from 7 to 60.

[0145] Embodiment 25. The hydrophilic polyorganosiloxane vinyl crosslinking agent according to any one of Embodiments 19 to 22, wherein in formula (1) or (2), ω1 is an integer from 9 to 50.

[0146] Embodiment 26. The hydrophilic polyorganosiloxane vinyl crosslinking agent according to any one of Embodiments 19 to 25, which is represented by formula (1).

[0147] Embodiment 27. The hydrophilic polyorganosiloxane vinyl crosslinking agent according to Embodiment 26, wherein in formula (1), a1 is zero.

[0148] Embodiment 28. In formula (1), X 0 is O, and it is the hydrophilic polyorganosiloxane vinyl crosslinking agent according to Embodiment 27.

[0149] Embodiment 29. In formula (1), X 0 is NR N1 and is the hydrophilic polydiorganosiloxane vinyl crosslinking agent of Embodiment 27.

[0150] Embodiment 30. The hydrophilic polydiorganosiloxane vinyl crosslinking agent is the hydrophilic polydiorganosiloxane vinyl crosslinking agent of any one of Embodiments 19 to 25, represented by formula (2).

[0151] Embodiment 31. In formula (2), X 0 is O, and is the hydrophilic polydiorganosiloxane vinyl crosslinking agent of Embodiment 30.

[0152] Embodiment 32. In formula (2), X 0 is NR N1 and is the hydrophilic polydiorganosiloxane vinyl crosslinking agent of Embodiment 30.

[0153] Embodiment 33. A silicone hydrogel contact lens comprising a crosslinked polymer material containing units of the hydrophilic polydiorganosiloxane vinyl crosslinking agent of any one of Embodiments 1 to 32.

[0154] Embodiment 34. The silicone hydrogel contact lens has an oxygen permeability coefficient (Dk) of at least about 40 barrers, a water content of about 15 wt% to about 70 wt%, and a modulus of elasticity of about 0.20 MPa to about 1.8 MPa when fully hydrated, and is the silicone hydrogel contact lens of Embodiment 33.

[0155] Embodiment 35. The silicone hydrogel contact lens has an oxygen permeability coefficient (Dk) of at least about 60 barrers when fully hydrated, and is the silicone hydrogel contact lens of Embodiment 33 or 34.

[0156] Embodiment 36. The silicone hydrogel contact lens has an oxygen permeability coefficient (Dk) of at least about 70 barrers when fully hydrated, and is the silicone hydrogel contact lens of Embodiment 33 or 34.

[0157] Embodiment 37. The silicone hydrogel contact lens is the silicone hydrogel contact lens of Embodiment 33 or 34, which has an oxygen permeability coefficient (Dk) of at least about 80 barrers when fully hydrated.

[0158] Embodiment 38. The silicone hydrogel contact lens is the silicone hydrogel contact lens of any one of Embodiments 33 to 37, which has a water content of about 20 wt% to about 70 wt% when fully hydrated.

[0159] Embodiment 39. The silicone hydrogel contact lens is the silicone hydrogel contact lens of any one of Embodiments 33 to 38, which has a water content of about 25 wt% to about 65 wt% when fully hydrated.

[0160] Embodiment 40. The silicone hydrogel contact lens is the silicone hydrogel contact lens of any one of Embodiments 33 to 38, which has a water content of about 30 wt% to about 60 wt% when fully hydrated.

[0161] Embodiment 41. The hydrophilic silicone hydrogel contact lens is the silicone hydrogel contact lens of any one of Embodiments 33 to 40, which has a modulus of elasticity of about 0.25 MPa to about 1.5 MPa when fully hydrated.

[0162] Embodiment 42. The hydrophilic silicone hydrogel contact lens is the silicone hydrogel contact lens of any one of Embodiments 33 to 40, which has a modulus of elasticity of about 0.3 MPa to about 1.2 MPa when fully hydrated.

[0163] Embodiment 43. The hydrophilic silicone hydrogel contact lens is the silicone hydrogel contact lens of any one of Embodiments 33 to 40, which has a modulus of elasticity of about 0.4 MPa to about 1.0 MPa when fully hydrated.

[0164] Embodiment 44. The silicone hydrogel contact lens is the silicone hydrogel contact lens according to any one of Embodiments 33 to 43, which contains units of at least one silicone-containing polymerizable component and units of at least one hydrophilic vinyl monomer.

[0165] Embodiment 45. The silicone hydrogel contact material contains repeating units of at least one silicone-containing vinyl monomer selected from the group consisting of vinyl monomers having a bis(trialkylsilyloxy)alkylsilyl group, vinyl monomers having a tris(trialkylsilyloxy)silyl group, polysiloxane vinyl monomers, 3-methacryloxypropylpentamethyldisiloxane, t-butyldimethyl-siloxyethyl vinyl carbonate, trimethylsilylethyl vinyl carbonate, and trimethylsilylmethyl vinyl carbonate, and combinations thereof, and is the silicone hydrogel contact lens according to any one of Embodiments 33 to 44.

[0166] Embodiment 46. The silicone hydrogel contact material has the formula (M1) or (M2) [Chemical formula] [wherein: a M1 is zero or 1; R M0 is H or methyl; X M0 is O or NR M1 ; L M1 is a C 2 ~C 8 alkylene divalent group or [Chemical formula] divalent group; L M1 ’ is a C 2 ~C 8 alkylene divalent group having zero or one hydroxyl group; L M1 ’’ is a C 3 ~C8 is an alkylene divalent group; X M1 is O, NR M1 , NHCOO, OCONH, CONR M1 , or NR M1 CO; R M1 is H or C having 0 to 2 hydroxyl groups 1 ~C 4 alkyl; R t1 and R t2 are independently of each other C 1 ~C 6 alkyl; X M1 ’ is O or NR 1 ; v1 is an integer from 1 to 30, v2 is an integer from 0 to 30, n1 is an integer from 3 to 40; r1 is 2 or 3] A silicone hydrogel contact lens according to any one of Embodiments 33 to 44, comprising a repeating unit of at least one silicone-containing vinyl monomer of .

[0167] Embodiment 47. The at least one silicone-containing vinyl monomer is tris(trimethylsilyloxy)silylpropyl (meth)acrylate, [3-(meth)acryloxy-2-hydroxypropyl-oxy]propylbis(trimethylsiloxy)methylsilane, [3-(meth)acryloxy-2-hydroxypropyl-oxy]propylbis(trimethylsiloxy)butylsilane, 3-(meth)acryloxy-2-(2-hydroxyethoxy)-propyl-oxy)propylbis(trimethylsiloxy)methylsilane, 3-(meth)acryloxy-2-hydroxypropyl-oxy)propyltris(trimethylsiloxy)silane, N-[tris(trimethylsiloxy)silylpropyl]-(meth)acrylamide, N-(2-hydroxy-3-(3-(bis(trimethylsilyloxy)methylsilyl)propyl-oxy)propyl)-2-methyl(meth)acrylamide, N-(2-hydroxy-3-(3-(bis(trimethylsilyloxy)methylsilyl)propyl-oxy)-propyl)(meth)acrylamide, N-(2-hydroxy-3-(3-(tris(trimethylsilyloxy)silyl)propyl-oxy)propyl)-2-methylacrylamide, N-(2-hydroxy-3-(3-(tris(trimethylsilyloxy)silyl)propyl-oxy)propyl)(meth)acrylamide, N-[tris(dimethylpropylsiloxy)silylpropyl]-(meth)acrylamide, N-[tris(dimethylphenylsiloxy)-silylpropyl](meth)acrylamide, N-[tris(dimethylethylsiloxy)-silylpropyl](meth)acrylamide, N,N-bis[2-hydroxy-3-(3-(bis(trimethylsilyloxy)methylsilyl)-propyl-oxy)propyl]-2-methyl(meth)acrylamide, N,N-bis[2-hydroxy-3-(3-(bis(trimethylsilyloxy)methylsilyl)propyl-oxy)-propyl](meth)acrylamide, N,N-bis[2-hydroxy-3-(3-(tris(trimethylsilyloxy)silyl)propyl-oxy)propyl]-2-methyl(meth)acrylamide, N,N-N-bis[2-hydroxy-3-(3-(tris(trimethylsilyloxy)silyl)-propyloxy)propyl](meth)acrylamide, N-[2-hydroxy-3-(3-(t-butyldimethylsilyl)propyloxy)-propyl]-2-methyl(meth)acrylamide, N-[2-hydroxy-3-(3-(t-butyldimethylsilyl)propyloxy)propyl](meth)acrylamide, N,N-bis[2-hydroxy-3-(3-(t-butyldimethylsilyl)propyloxy)propyl]-2-methyl(meth)acrylamide, N-2-(meth)acryloxyethyl-O-(methyl-bis-trimethylsiloxy-3-propyl)silylcarbamate, 3-(trimethylsilyl)propyl vinyl carbonate, 3-(vinyloxycarbonylthio)-propyl-tris(trimethylsiloxy)silane, 3-[tris(trimethylsiloxy)silyl]propyl vinyl carbamate, 3-[tris(trimethylsiloxy)silyl]propyl allyl carbamate, 3-[tris(trimethylsiloxy)silyl]propyl vinyl carbonate, or a combination thereof, a silicone hydrogel contact lens of Embodiment 45 or 46.,

[0168] Embodiment 48. The at least one silicone-containing vinyl monomer is α-(meth)acryloxypropyl-terminated ω-C 1 ~C 4 alkyl-terminated polydimethylsiloxane, α-(meth)acryloxy-2-hydroxypropyl-oxypropyl-terminated ω-C 1 ~C 4 alkyl-terminated polydimethylsiloxane, α-(2-hydroxyl-methacryloxypropyl-oxypropyl)-ω-C 1 ~C 4 alkyl-decamethylpentasiloxane, α-[3-(meth)acryloxyethoxy-2-hydroxypropyl-oxypropyl] -terminated ω-C 1 ~C 4 alkyl-terminated polydimethylsiloxane, α-[3-(meth)acryloxy-propyloxy-2-hydroxypropyl-oxypropyl] -terminated ω-C 1 ~C 4Alkyl-terminated polydimethylsiloxane, α-[3-(meth)acryloyloxyisopropyl-oxy-2-hydroxypropyl-oxypropyl] end ω-C 1 ~C 4 Alkyl-terminated polydimethylsiloxane, α-[3-(meth)acryloyloxybutyl-oxy-2-hydroxypropyl-oxypropyl] end ω-C 1 ~C 4 Alkyl-terminated polydimethylsiloxane, α-[3-(meth)acryloyloxyethylamino-2-hydroxypropyl-oxypropyl] end ω-C 1 ~C 4 Alkyl-terminated polydimethylsiloxane, α-[3-(meth)acryloyloxypropylamino-2-hydroxypropyl-oxypropyl] end ω-C 1 ~C 4 Alkyl-terminated polydimethylsiloxane, α-[3-(meth)acryloxy-butylamino-2-hydroxypropyl-oxypropyl] end ω-C 1 ~C 4 Alkyl-terminated polydimethylsiloxane, α-(meth)acryloxy(polyethyleneoxy)-2-hydroxypropyl-oxypropyl] end ω-C 1 ~C 4 Alkyl-terminated polydimethylsiloxane, α-[(meth)acryloyloxy-2-hydroxypropyl-oxy-ethoxypropyl] end ω-C 1 ~C 4 Alkyl-terminated polydimethylsiloxane, α-[(meth)acryloyloxy-2-hydroxypropyl-N-ethylaminopropyl] end ω-C 1 ~C 4 Alkyl-terminated polydimethylsiloxane, α-[(meth)acryloyloxy-2-hydroxypropyl-amino-propyl] end ω-C 1 ~C 4 Alkyl-terminated polydimethylsiloxane, α-[(meth)acryloyloxy-2-hydroxypropyl-oxy-(polyethyleneoxy)propyl] end ω-C 1 ~C 4 Alkyl-terminated polydimethylsiloxane, α-(meth)acryloylamidopropyl-oxypropyl end ω-C 1 ~C 4Alkyl-terminated polydimethylsiloxane, α-N-methyl-(meth)acryloylamidopropyloxypropyl-terminated ω-C 1 ~C 4 Alkyl-terminated polydimethylsiloxane, α-[3-(meth)acrylamidoethoxy-2-hydroxypropyloxy-propyl]-terminated ω-C 1 ~C 4 Alkyl polydimethylsiloxane, α-[3-(meth)acrylamidopropyloxy-2-hydroxypropyloxypropyl]-terminated ω-C 1 ~C 4 Alkyl-terminated polydimethylsiloxane, α-[3-(meth)acrylamidoisopropyloxy-2-hydroxypropyloxypropyl]-terminated ω-C 1 ~C 4 Alkyl-terminated polydimethylsiloxane, α-[3-(meth)acrylamidobutyloxy-2-hydroxypropyloxypropyl]-terminated ω-C 1 ~C 4 Alkyl-terminated polydimethylsiloxane, α-[3-(meth)acryloylamido-2-hydroxypropyloxypropyl]-terminated ω-C 1 ~C 4 Alkyl polydimethylsiloxane, α-[3-[N-methyl-(meth)acryloylamido]-2-hydroxypropyloxypropyl]-terminated ω-C 1 ~C 4 Alkyl-terminated polydimethylsiloxane, N-methyl-N'-(propyltetra(dimethylsiloxy)dimethylbutylsilane)(meth)acrylamide, N-(2,3-dihydroxypropane)-N'-(propyltetra(dimethylsiloxy)dimethylbutylsilane)(meth)acrylamide, (meth)acryloylamidopropyltetra(dimethylsiloxy)dimethylbutylsilane, α-vinyl carbonate-terminated ω-C 1 ~C 4 Alkyl-terminated polydimethylsiloxane, α-vinyl carbamate-terminated ω-C 1 ~C 4 A silicone hydrogel contact lens according to any one of Embodiments 45 to 47, comprising an alkyl-terminated polydimethylsiloxane, or a mixture thereof.

[0169] Embodiment 49. The silicone hydrogel material is a silicone hydrogel contact lens according to any one of Embodiments 33 to 48, including repeating units of at least one polysiloxane vinyl crosslinking agent.

[0170] Embodiment 50. The at least one polysiloxane vinyl crosslinking agent includes di(meth)acryloyl-terminated polydimethylsiloxane, divinyl carbonate-terminated polydimethylsiloxane, divinyl carbamate-terminated polydimethylsiloxane, N,N,N’,N’-tetrakis(3-methacryloxy-2-hydroxypropyl)-alpha,omega-bis-3-aminopropyl-polydimethylsiloxane, or a combination thereof, and is a silicone hydrogel contact lens according to Embodiment 49.

[0171] Embodiment 51. The at least one polysiloxane vinyl crosslinking agent has the formula (I) [Chemical formula] [wherein: Provided that d2 / d1 is from about 0.035 to about 0.15 (preferably from about 0.040 to about 0.12, more preferably from about 0.045 to about 0.10), d1 is an integer from 30 to 500, and d2 is an integer from 1 to 75; X 01 is O or NR IN wherein R IN is hydrogen or C 1 ~C 10 alkyl; R I0 is hydrogen or methyl; R I1 and R I2 are independently of each other a substituted or unsubstituted C 1 ~C 10 alkylene divalent group or a divalent group of -R I4 -O-R I5 -, where R I4 and R I5 are independently of each other a substituted or unsubstituted C1 ~C 10 is an alkylene divalent group; R I3 is one of the monovalent groups of formulas (Ia) to (Ie)

Chemical formula

Chemical formula

[0172] Embodiment 52. The at least one polysiloxane vinyl crosslinking agent is (1) a vinyl crosslinking agent containing one unique polydiorganosiloxane segment and two terminal ethylenically unsaturated groups selected from the group consisting of (meth)acryloyloxy group, (meth)acryloylamino group, vinyl carbonate group, and vinyl carbamate group, and / or (2) a chain-extended polysiloxane vinyl crosslinking agent containing at least two polydiorganosiloxane segments and a covalent linker between each pair of the polydiorganosiloxane segments and two terminal ethylenically unsaturated groups selected from the group consisting of (meth)acryloyloxy group, (meth)acryloylamino group, vinyl carbonate group, and vinyl carbamate group. The silicone hydrogel contact lens according to any one of Embodiments 49 to 51.

[0173] Embodiment 53. The at least one polysiloxane vinyl crosslinking agent is α,ω-bis[3-(meth)acrylamidopropyl] terminated polydimethylsiloxane, α,ω-bis[3-(meth)acryloxypropyl] terminated polydimethylsiloxane, α,ω-bis[3-(meth)acryloxy-2-hydroxypropyloxypropyl] terminated polydimethylsiloxane, α,ω-bis[3-(meth)acryloxyethoxy-2-hydroxypropyloxypropyl] terminated polydimethylsiloxane, α,ω-bis[3-(meth)acryloxypropyloxy-2-hydroxypropyloxypropyl] terminated polydimethylsiloxane, α,ω-bis[3-(meth)acryloxy-isopropyloxy-2-hydroxypropyloxypropyl] terminated polydimethylsiloxane, α,ω-bis[3-(meth)acryloxybutyloxy-2-hydroxypropyloxypropyl] terminated polydimethylsiloxane, α,ω-bis[3-(meth)acrylamideethoxy-2-hydroxypropyloxypropyl] terminated polydimethylsiloxane, α,ω-bis[3-(meth)acrylamidepropyloxy-2-hydroxypropyloxypropyl] terminated polydimethylsiloxane, α,ω-bis[3-(meth)acrylamideisopropyloxy-2-hydroxypropyloxypropyl] terminated polydimethylsiloxane, α,ω-bis[3-(meth)acrylamidebutyloxy-2-hydroxypropyloxypropyl] terminated polydimethylsiloxane, α,ω-bis[3-(meth)acryloxyethylamino-2-hydroxypropyloxypropyl] terminated polydimethylsiloxane, α,ω-bis[3-(meth)acryloxypropylamino-2-hydroxypropyloxypropyl] terminated polydimethylsiloxane, α,ω-bis[3-(meth)acryloxybutylamino-2-hydroxypropyloxypropyl] terminated polydimethylsiloxane, α,ω-bis[(meth)acrylamideethylamino-2-hydroxypropyloxy-propyl] terminated polydimethylsiloxane, α,ω-bis[3-(meth)acrylamidepropylamino-2-hydroxypropyloxypropyl] terminated polydimethylsiloxane, α,ω-bis[3-(meth)acrylamido-butylamino-2-hydroxypropyl-oxypropyl] terminated polydimethylsiloxane, α,ω-bis[(meth)acryloxy-2-hydroxypropyl-oxy-ethoxypropyl] terminated polydimethylsiloxane, α,ω-bis[(meth)acryloxy-2-hydroxypropyl-N-ethylaminopropyl] terminated polydimethylsiloxane, α,ω-bis[(meth)acryloxy-2-hydroxypropyl-amino-propyl]-polydimethylsiloxane, α,ω-bis[(meth)acryloxy-2-hydroxypropyl-oxy-(polyethyleneoxy)propyl] terminated polydimethylsiloxane, α,ω-bis[(meth)acryloxyethylamino-carbonyl-oxy-ethoxypropyl] terminated polydimethylsiloxane, α,ω-bis[(meth)acryloxyethylamino-carbonyl-oxy-(polyethyleneoxy)propyl] terminated polydimethylsiloxane, or a combination thereof, the silicone hydrogel contact lens of any one of Embodiments 49 to 52.,

[0174] Embodiment 54. The silicone hydrogel material is the silicone hydrogel contact lens of any one of Embodiments 33 to 53, which contains repeating units of at least one hydrophilic vinyl monomer.

[0175] Embodiment 55. The at least one hydrophilic vinyl monomer is (1) an alkyl (meth) acrylamide selected from the group consisting of (meth) acrylamide, N,N-dimethyl (meth) acrylamide, N-ethyl (meth) acrylamide, N,N-diethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-3-methoxypropyl (meth) acrylamide, and combinations thereof; (2) a hydroxyl-containing acrylic monomer selected from the group consisting of N-2-hydroxyethyl (meth) acrylamide, N,N-bis (hydroxyethyl) (meth) acrylamide, N-3-hydroxypropyl (meth) acrylamide, N-2-hydroxypropyl (meth) acrylamide, N-2,3-dihydroxypropyl (meth) acrylamide, N-tris (hydroxymethyl) methyl (meth) acrylamide, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, glycerol methacrylate (GMA), di (ethylene glycol) (meth) acrylate, tri (ethylene glycol) (meth) acrylate, tetra (ethylene glycol) (meth) acrylate, poly (ethylene glycol) (meth) acrylate having a number average molecular weight of 1500 or less, poly (ethylene glycol) ethyl (meth) acrylamide having a number average molecular weight of 1500 or less, and combinations thereof; (3) a carboxyl-containing acrylic monomer selected from the group consisting of 2- (meth) acrylamidoglycolic acid, (meth) acrylic acid, ethylacrylic acid, 3- (meth) acrylamidopropionic acid, 5- (meth) acrylamidopentanoic acid, 4- (meth) acrylamidobutanoic acid, 3- (meth) acrylamido-2-methylbutanoic acid, 3- (meth) acrylamido-3-methylbutanoic acid, 2- (meth) acrylamido-2-methyl-3,3-dimethylbutanoic acid, 3- (meth) acrylamidohexanoic acid, 4- (meth) acrylamido-3,3-dimethylhexanoic acid, and combinations thereof.(4) Amino-containing acrylic monomers selected from the group consisting of N-2-aminoethyl (meth) acrylamide, N-2-methylaminoethyl (meth) acrylamide, N-2-ethylaminoethyl (meth) acrylamide, N-2-dimethylaminoethyl (meth) acrylamide, N-3-aminopropyl (meth) acrylamide, N-3-methylaminopropyl (meth) acrylamide, N-3-dimethylaminopropyl (meth) acrylamide, 2-aminoethyl (meth) acrylate, 2-methylaminoethyl (meth) acrylate, 2-ethylaminoethyl (meth) acrylate, 3-aminopropyl (meth) acrylate, 3-methylaminopropyl (meth) acrylate, 3-ethylaminopropyl (meth) acrylate, 3-amino-2-hydroxypropyl (meth) acrylate, trimethylammonium 2-hydroxypropyl (meth) acrylate hydrochloride, dimethylaminoethyl (meth) acrylate, and combinations thereof;(5) N-vinylpyrrolidone (also known as N-vinyl-2-pyrrolidone), N-vinyl-3-methyl-2-pyrrolidone, N-vinyl-4-methyl-2-pyrrolidone, N-vinyl-5-methyl-2-pyrrolidone, N-vinyl-6-methyl-2-pyrrolidone, N-vinyl-3-ethyl-2-pyrrolidone, N-vinyl-4,5-dimethyl-2-pyrrolidone, N-vinyl-5,5-dimethyl-2-pyrrolidone, N-vinyl-3,3,5-trimethyl-2-pyrrolidone, N-vinylpiperidone (also known as N-vinyl-2-piperidone), N-vinyl-3-methyl-2-piperidone, N-vinyl-4-methyl-2-piperidone, N-vinyl-5-methyl-2-piperidone, N-vinyl-6-methyl-2-piperidone, N-vinyl-6-ethyl-2-piperidone, N-vinyl-3,5-dimethyl-2-piperidone, N-vinyl-4,4-dimethyl-2-piperidone, N-vinylcaprolactam (also known as N-vinyl-2-caprolactam), N-vinyl-3-methyl-2-caprolactam, N-vinyl-4-methyl-2-caprolactam, N-vinyl-7-methyl-2-caprolactam, N-vinyl-7-ethyl-2-caprolactam, N-vinyl-3,5-dimethyl-2-caprolactam, N-vinyl-4,6-dimethyl-2-caprolactam, N-vinyl-3,5,7-trimethyl-2-caprolactam, N-vinyl-N-methylacetamide, N-vinylformamide, N-vinylacetamide, N-vinylisopropylamide, N-vinyl-N-ethylacetamide, N-vinyl-N-ethylformamide, and N-vinylamide monomers selected from the group consisting of combinations thereof;(6) A methylene-containing pyrrolidone monomer selected from the group consisting of 1-methyl-3-methylene-2-pyrrolidone, 1-ethyl-3-methylene-2-pyrrolidone, 1-methyl-5-methylene-2-pyrrolidone, 1-ethyl-5-methylene-2-pyrrolidone, 5-methyl-3-methylene-2-pyrrolidone, 5-ethyl-3-methylene-2-pyrrolidone, 1-n-propyl-3-methylene-2-pyrrolidone, 1-n-propyl-5-methylene-2-pyrrolidone, 1-isopropyl-3-methylene-2-pyrrolidone, 1-isopropyl-5-methylene-2-pyrrolidone, 1-n-butyl-3-methylene-2-pyrrolidone, 1-tert-butyl-3-methylene-2-pyrrolidone, and combinations thereof; (7) C; 1 ~C 4 Having an alkoxyethoxy group and ethylene glycol methyl ether (meth)acrylate, di(ethylene glycol) methyl ether (meth)acrylate, tri(ethylene glycol) methyl ether (meth)acrylate, tetra(ethylene glycol) methyl ether (meth)acrylate, C having a number average molecular weight of 1500 or less 1 ~C 4Acrylic monomers selected from the group consisting of alkoxypoly(ethylene glycol)(meth)acrylate, methoxy-poly(ethylene glycol)ethyl(meth)acrylamide having a number average molecular weight of 1500 or less, and combinations thereof; (8) vinyl ether monomers selected from the group consisting of ethylene glycol monovinyl ether, di(ethylene glycol)monovinyl ether, tri(ethylene glycol)monovinyl ether, tetra(ethylene glycol)monovinyl ether, poly(ethylene glycol)monovinyl ether, ethylene glycol methyl vinyl ether, di(ethylene glycol)methyl vinyl ether, tri(ethylene glycol)methyl vinyl ether, tetra(ethylene glycol)methyl vinyl ether, poly(ethylene glycol)methyl vinyl ether, and combinations thereof; (9) allyl ether monomers selected from the group consisting of ethylene glycol monoallyl ether, di(ethylene glycol)monoallyl ether, tri(ethylene glycol)monoallyl ether, tetra(ethylene glycol)monoallyl ether, poly(ethylene glycol)monoallyl ether, ethylene glycol methyl allyl ether, di(ethylene glycol)methyl allyl ether, tri(ethylene glycol)methyl allyl ether, tetra(ethylene glycol)methyl allyl ether, poly(ethylene glycol)methyl allyl ether, and combinations thereof; (10) (meth)acryloyloxyethyl phosphorylcholine, (meth)acryloyloxypropyl phosphorylcholine, 4-((meth)acryloyloxy)butyl-2'-(trimethylammonio)ethyl phosphate, 2-[(meth)acryloylamino]ethyl-2'-(trimethylammonio)-ethyl phosphate, 3-[(meth)acryloylamino]propyl-2'-(trimethylammonio)ethyl phosphate, 4-[(meth)acryloylamino]butyl-2'-(trimethylammonio)ethyl phosphate, 5-((meth)acryloyloxy)pentyl-2'-(trimethylammonio)ethyl phosphate, 6-((meth)acryloyloxy)hexyl-2'-(trimethylammonio)-ethyl phosphate,2-((Meth)acryloyloxy)ethyl-2'-(triethylammonio)ethyl phosphate, 2-((meth)acryloyloxy)ethyl-2'-(tripropylammonio)ethyl phosphate, 2-((meth)acryloyloxy)ethyl-2'-(tributylammonio)ethyl phosphate, 2-((meth)acryloyloxy)propyl-2'-(trimethylammonio)-ethyl phosphate, 2-((meth)acryloyloxy)butyl-2'-(trimethylammonio)ethyl phosphate, 2-((meth)acryloyloxy)pentyl-2'-(trimethylammonio)ethyl phosphate, 2-((meth)acryloyloxy)hexyl-2'-(trimethylammonio)ethyl phosphate, 2-(vinyloxy)ethyl-2'-(trimethylammonio)ethyl phosphate, 2-(allyloxy)ethyl-2'-(trimethylammonio)ethyl phosphate, 2-(vinyloxycarbonyl)ethyl-2'-(trimethylammonio)ethyl phosphate, 2-(allyloxycarbonyl)ethyl-2'-(trimethylammonio)-ethyl phosphate, 2-(vinylcarbonylamino)ethyl-2'-(trimethylammonio)ethyl phosphate, 2-(allyloxycarbonylamino)ethyl-2'-(trimethylammonio)ethyl phosphate, 2-(butenoyloxy)ethyl-2'-(trimethylammonio)ethyl phosphate, and a phosphorylcholine-containing vinyl monomer selected from the group consisting of combinations thereof; (11) allyl alcohol; (12) N-2-hydroxyethyl vinyl carbamate; (13) N-carboxyvinyl-β-alanine (VINAL); (14) N-carboxyvinyl-α-alanine; (15) or a combination thereof, the silicone hydrogel contact lens of embodiment 54.

[0176] Embodiment 56. The at least one hydrophilic vinyl monomer comprises N-vinylpyrrolidone, N-vinyl-N-methylacetamide, or a combination thereof, the silicone hydrogel contact lens of embodiment 54 or 55.

[0177] Embodiment 57. The silicone hydrogel contact lens according to any one of Embodiments 54 to 56, wherein the at least one hydrophilic vinyl monomer contains N,N-dimethyl(meth)acrylamide.

[0178] Embodiment 58. The silicone hydrogel contact lens according to any one of Embodiments 54 to 57, wherein the at least one hydrophilic vinyl monomer contains N-2-hydroxyethyl(meth)acrylamide, N,N-bis(hydroxyethyl)(meth)acrylamide, N-3-hydroxypropyl(meth)acrylamide, N-2-hydroxypropyl(meth)acrylamide, N-2,3-dihydroxypropyl(meth)acrylamide, N-tris(hydroxymethyl)methyl(meth)acrylamide, 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl(meth)acrylate, 2-hydroxypropyl(meth)acrylate, glycerol methacrylate (GMA), di(ethylene glycol)(meth)acrylate, tri(ethylene glycol)(meth)acrylate, tetra(ethylene glycol)(meth)acrylate, poly(ethylene glycol)(meth)acrylate having a number average molecular weight of up to 1500, poly(ethylene glycol)ethyl(meth)acrylamide having a number average molecular weight of up to 1500, or a combination thereof.

[0179] Embodiment 59. The silicone hydrogel contact lens according to any one of Embodiments 33 to 58, wherein the silicone hydrogel material contains repeating units of at least one non-silicone vinyl crosslinking agent.

[0180] Embodiment 60. The at least one non-silicone vinyl crosslinking agent is ethylene glycol di-(meth)acrylate, diethylene glycol di-(meth)acrylate, triethylene glycol di-(meth)acrylate, tetraethylene glycol di-(meth)acrylate, glycerol di-(meth)acrylate, 1,3-propanediol di-(meth)acrylate, 1,3-butanediol di-(meth)acrylate, 1,4-butanediol di-(meth)acrylate, glycerol 1,3-diglycerolate di-(meth)acrylate, ethylene bis[oxy(2-hydroxypropane-1,3-diyl)] di-(meth)acrylate, bis[2-(meth)acryloxyethyl] phosphate, trimethylolpropane di-(meth)acrylate, and 3,4-bis[(meth)acryloyl]tetrahydrofuran, diacrylamide, dimethacrylamide, N,N-di(meth)acryloyl-N-methylamine, N,N-di(meth)acryloyl-N-ethylamine, N,N'-methylenebis(meth)acrylamide, N,N'-ethylenebis(meth)acrylamide, N,N'-dihydroxyethylenebis(meth)acrylamide, N,N'-propylenebis(meth)acrylamide, N,N'-2-hydroxypropylenebis(meth)acrylamide, N,N'-2,3-dihydroxybutylenebis(meth)acrylamide, 1,3-bis(meth)acrylamidepropane-2-yl dihydrogen phosphate, piperazine diacrylamide, tetraethylene glycol divinyl ether, triethylene glycol divinyl ether, diethylene glycol divinyl ether, ethylene glycol divinyl ether, triallyl isocyanurate, triallyl cyanurate, trimethylolpropane trimethacrylate, pentaerythritol tetramethacrylate, bisphenol A dimethacrylate, allyl methacrylate, allyl acrylate, N-allyl-methacrylamide, N-allyl-acrylamide, or a combination thereof, a silicone hydrogel contact lens of Embodiment 59.

[0181] Embodiment 61. The silicone hydrogel material is a silicone hydrogel contact lens according to any one of Embodiments 33 to 60, including repeating units of at least one blending vinyl monomer.

[0182] Embodiment 62. The at least one blending vinyl monomer is C 1 ~C 10 alkyl (meth) acrylate, cyclopentyl acrylate, cyclohexyl methacrylate, cyclohexyl acrylate, isobornyl (meth) acrylate, styrene, 4,6-trimethylstyrene (TMS), t-butylstyrene (TBS), trifluoroethyl (meth) acrylate, hexafluoro-isopropyl (meth) acrylate, hexafluorobutyl (meth) acrylate, or a combination thereof, in the silicone hydrogel contact lens of Embodiment 61.

[0183] Embodiment 63. The at least one blending vinyl monomer includes methyl methacrylate, in the silicone hydrogel contact lens of Embodiment 61 or 62.

[0184] The above disclosure will enable those skilled in the art to practice the present invention. Various modifications, variations, and combinations can be made to the various embodiments described herein. References to the following examples are proposed to better enable the reader to understand a particular embodiment and its advantages. The specification and examples are intended to be considered illustrative.

Examples

[0185] Example 1 Measurement of Oxygen Permeability Coefficient Unless otherwise specified, the oxygen permeability coefficient (Dk / t), the intrinsic (or edge-corrected) oxygen permeability coefficient (Dk i or Dk c ) of the lens and lens material is measured according to the procedure described in ISO 18369-4.

[0186] Equilibrium water content The equilibrium water content (EWC) of the contact lens is measured as follows.

[0187] The amount of water present in the hydrated hydrogel contact lens (expressed as a weight percentage), which is completely equilibrated in physiological saline, is measured at room temperature. The lenses are quickly stacked, and after wiping the lenses on a cloth, the lens stack is transferred to an aluminum pan on an analytical balance. The number of lenses for each sample pan is typically five. Record the hydrated weight of the pan + lenses. Cover the pan with aluminum foil. Place the pan in a laboratory oven at 100 ± 2 °C and dry for 16 - 18 hours. Remove the pan + lenses from the oven and cool in a desiccator for at least 30 minutes. Remove only one pan from the desiccator and discard the aluminum foil. Weigh the pan + dry lens sample on an analytical balance. Repeat for all pans. The wet weight and dry weight of the lens sample can be calculated by subtracting the weight of the empty weighing pan.

[0188] Elastic modulus The elastic modulus of the contact lens is measured using an MTS Insight instrument. The contact lens is first cut into strips 3.12 mm wide using a Precision Concept two-stage cutter. Measure five thickness values within a 6.5 mm gauge length. Attach the strip to the instrument grip and immerse it in PBS (phosphate buffered saline) at a temperature controlled to 21 ± 2 °C. Typically, a 5 N load cell is used for the test. Apply a constant force and speed to the sample until it breaks. Collect the force and displacement data with TestWorks software. The elastic modulus value is calculated by TestWorks software, which is the slope or tangent of the stress-strain curve near zero elongation in the elastic deformation region.

[0189] Example 2 A polydiorganosiloxane vinyl crosslinker having pendant reactive functional groups (e.g., primary hydroxyl groups) is prepared according to the procedure shown in Scheme 1. [Chemical formula]

[0190] Synthesis of Precursor Weigh 275.9 g of octamethylcyclotetrasiloxane (M.W. 296.62), 12.0 g of 1,3,5,7 - tetramethylcyclotetrasiloxane (M.W. 240.51), 15.3 g of 1,3 - bis(3 - methacryloxypropyl)tetramethyldisiloxane (M.W. 386.63), and 0.9 g of trifluoromethanesulfonic acid (M.W. 150.08) into a 500 mL round - bottom flask. After reacting at 35 °C for 24 h, add 170 mL of 0.5% sodium bicarbonate. Extract the collected organic part 5 more times with deionized water (170 mL per cycle). Anhydrous MgSO 4 , followed by adding about 350 mL of additional CHCl 3 to the collected organic solution, and then stir the solution overnight. After filtration, remove the solvent by Rotovap and then under high vacuum. 102 g of the final product (precursor) is obtained.

[0191] Hydrosilylation Reaction Using Allyloxyethanol Connect a small reactor to a heater and an air condenser with a drying tube. Add 21 g of toluene, 15 g of the above - mentioned precursor, and 3.88 g of allyloxyethanol to the reactor. After the solution temperature stabilizes at 30 °C, add 152 μL of Karstedt catalyst (2% Pt in xylene). After 2 hours, 100% conversion of Si - H is achieved based on IR. Then, transfer the solution to a flask, concentrate it using Rotovop, followed by precipitation 3 times in an acetonitrile / water mixture (75 / 25). After removing the solvent by Rotovop and then under high vacuum, 10 g of a turbid liquid is obtained. The molecular weight is determined by H 1 NMR spectroscopy.

[0192] Example 3 The hydrophilic polydiorganosiloxane vinyl cross - linker is prepared according to the procedure shown in Scheme 2.

Chemical formula

[0193] The synthesis of the hydrophilic polydiorganosiloxane vinyl crosslinking agent 1 is accomplished by reacting hydroxyl group-containing PDMS 2 with commercially available 2-chloro-2-oxo-1,3,2-dioxaphospholane (COP) in THF (or a compatible solvent) at a low temperature (e.g., about -10 °C) to produce an intermediate 3, which is then successively reacted with trimethylamine in THF (or a compatible solvent) at a slightly higher temperature (e.g., 50 °C). The reaction conditions for the preparation of the hydrophilic polydiorganosiloxane vinyl crosslinking agent can be carried out according to the procedures exemplified in Example 4, except for the procedures described in the literature regarding the synthesis of 2-(methacryloyloxy)ethyl-2-(trimethylammonium)ethyl phosphate (MPC) (see Takashi Umeda, Tadao Nakaya, Minoru Imoto, Makromol. Chem., Rapid Commun. 3, 457-459 (1982) and Kazuhiko Ishihara, Tomoko Ueda, Nobuko Nakabayashi, Polymer Journal, 22, 355-360 (1990)) and those procedures involved in the reaction between ethylene cyclic phosphate-containing PDMS 3-A and dimethylaminopropylmethacrylamide.

[0194] Next, the hydrophilic polydiorganosiloxane vinyl crosslinking agent can be purified and characterized according to the experimental procedures described in Example 4.

[0195] Example 4 The reactions carried out in Example 4 are summarized in Scheme 3 below.

Chemical formula

[0196] A 500 mL jacketed reactor equipped with a mechanical stirrer, a thermocouple, a nitrogen supply port (attached to the condenser), a septum, and a condenser is cooled to -10 °C and purged with nitrogen at a rate of 100 mL / min for 60 minutes.

[0197] Hydroxyl group-containing PDMS 2-A (6.10 g, MW approximately 10,000 g / mol, x = 88, y = 23) is charged into a three-necked flask equipped with a magnetic stirrer, and the flask is covered with a rubber septum. Anhydrous THF (75 mL) is cannulated into the flask through the septum. The contents of the flask are left to stir at room temperature until all the polymer has dissolved, and then it is cannulated into the reactor. Triethylamine (1.45 g, 14.33 mmol) is added to the reactor by syringe.

[0198] 2-Chloro-2-oxo-1,3,2-dioxaphospholane (COP) (2.03 g, 14.25 mmol) is dissolved in 30 mL of THF and charged into a 500 mL Hamilton Gas Tight syringe equipped with a 20-inch stainless steel needle. The syringe is fixed to a Harvard PHD Infusion syringe pump, and the stainless steel needle is inserted into the reactor through the rubber septum.

[0199] A solution of COP in THF was added by syringe pump over 50 minutes while maintaining the temperature of the reactor at -10 °C to -8 °C during this time. After the addition of COP, the reaction mixture was further stirred at about -8 °C for 2 h to form ethylene cyclic phosphate-containing PDMS 3-A. During this time, a significant amount of triethylammonium hydrochloride precipitated. After stirring at -8 °C for 2 h, the temperature of the reaction was raised to 25 °C and dimethylaminopropylmethacrylamide (0.45 g, 2.64 mmol) in 20 mL of THF was added to the reactor. The temperature of the reaction was raised to 50 °C and left to stir for 18 h. The reaction mixture was then cooled to 0 °C and trimethylamine in THF (1.0 M in THF, 20 mL, 20 mmol) was added by syringe. It was left to stir at 50 °C for 6 h, then the temperature of the reactor was lowered to 0 °C and an additional amount of trimethylamine solution in THF was added (10 mL). The temperature of the reaction was raised to 50 °C and left to stir for an additional 23 h.

[0200] The contents of the reactor were transferred to a beaker. The triethylammonium hydrochloride that precipitated in the first step was filtered off and washed with THF. 1-Propanol was added to the filtrate and it was subjected to rotary evaporation. Evaporation and the gradual addition of 1-propanol continued until all of the THF had evaporated. The modified polymer in 1-propanol was purified by dialysis in a 1 kDa MWCO Regenerated Cellulose Membrane. Dialysis was started in a 50:50 1-propanol / water solvent system and gradually switched to pure DI water. After dialysis, 436 g of an aqueous polymer solution was collected. The solution was filtered through a Porosity 3 Schott funnel and concentrated on a rotary evaporator until a solids content of 1.8% was reached. A total of 250 g of a 1.8% solution was obtained after evaporation.

[0201] Further concentration of the 1.8% aqueous polymer solution results in precipitation of the polymer as a white rubbery mass. The addition of 1-propanol / water redissolves it, but redissolution takes a long time, and therefore it is recommended to stop concentrating the polymer when the solution begins to become slightly turbid.

[0202] The formation of the desired product is 31 confirmed by 31P NMR (peak at -0.09 ppm) and 1 1H NMR (peaks at 5.637 and 5.390 ppm (methacrylamide) and 3.126 and 3.113 ppm (-N + (CH 3 ) 3 and (-N + (CH 3 ) 2 -CH 2 -)).

[0203] All publications, patents, and published patent applications cited above in this specification are hereby incorporated by reference in their entirety.

Claims

1. (1)A polydiorganosiloxane segment containing at least one hydrophilic siloxane unit having a dimethylsiloxane unit and one organic substituent having one methyl substituent and one phosphorylcholine moiety; (2)Two or more ethylenically unsaturated groups A hydrophilic polydiorganosiloxane vinyl crosslinking agent, wherein the molar ratio of the hydrophilic siloxane unit to the dimethylsiloxane unit is 0.004 to 0.05, The hydrophilic polydiorganosiloxane vinyl crosslinking agent has the formula (1) or (2) 【Chemical 1】 [Wherein: υ1 is an integer from 20 to 350; ω1 is an integer from 9 to 50; γ1 is an integer from 7 to 48; E １ is 【Chemical 2】 Is a monovalent group; E ２ is 【Chemical Formula 3】 Is a monovalent group; R ０ is hydrogen or methyl; a1 is zero or 1; X ０ is O or NR Ｎ１ ; R Ｎ１ is hydrogen or C １ ~C ６ alkyl; L ０ is a C ２ -C ８ alkylene divalent group, or 【Chemical 4】 Is a divalent group; L ０ ‘ is C ２ ~C ８ an alkylene divalent group; L ０ ‘‘ is C ３ ~C ８ an alkylene divalent group; X １ is -O-, -NR Ｎ１ -, -NHCOO-, -OCONH-, -CONR Ｎ１ -, or -NR Ｎ１ CO-; q1 is an integer from 1 to 20; R ＰＣ is 【Chemical Formula 5】 Is a divalent group; L ｅ is 【Chemical Formula 6】 Is a divalent group; R １ is a linear or branched C １ -C １０ alkylene divalent group; R ２ is a linear or branched C ３ -C １０ alkylene divalent group; R ３ is a direct bond or a linear or branched C １ -C ４ alkylene divalent group; n is an integer from 1 to 5; R' and R'' are, independently of each other, C １ -C ８ alkyl or C １ -C ８ hydroxyalkyl; R''' is C １ ~C ８ an alkylene divalent group; T １ is hydrogen, a hydroxyl group or C １ to C ４ alkoxy; T ２ is C １ to C ８ alkyl, C １ to C ８ hydroxyalkyl, R ４ -O-R ５ -, or -R ＰＣ -T １ wherein; R ４ is C １ to C ４ alkyl; R ５ is a C ２ -C ８ alkylene divalent group] A hydrophilic polydiorganosiloxane vinyl crosslinking agent defined by.

2. The hydrophilic polydiorganosiloxane vinyl crosslinking agent according to claim 1, which is represented by the formula (1).

3. The hydrophilic polydiorganosiloxane vinyl crosslinking agent according to claim 2, wherein a1 is zero in the formula (1).

4. In formula (1), X ０ is O, and the hydrophilic polydiorganosiloxane vinyl crosslinking agent according to claim 3.

5. In formula (1), X ０ is NR Ｎ１ The hydrophilic polydiorganosiloxane vinyl crosslinking agent according to claim 3, wherein it is as described above.

6. The hydrophilic polydiorganosiloxane vinyl crosslinking agent according to claim 1, which is represented by the formula (2).

7. In formula (2), X ０ is O, and the hydrophilic polydiorganosiloxane vinyl crosslinking agent according to claim 6.

8. In formula (2), X ０ is NR Ｎ１ The hydrophilic polydiorganosiloxane vinyl crosslinking agent according to claim 6, wherein the compound is as described above.

9. A silicone hydrogel contact lens comprising a crosslinked polymer material containing the unit of the hydrophilic polydiorganosiloxane vinyl crosslinking agent according to any one of claims 1 to 8.

10. The crosslinked polymer material Units of at least one silicone-containing polymerizable component other than the units of the hydrophilic polydiorganosiloxane vinyl crosslinking agent, Units of at least one hydrophilic vinyl monomer And The hydrophilic vinyl monomer is a monomer that, when homopolymerized, yields a water-soluble homopolymer or a homopolymer capable of absorbing at least 10 weight percent of water. The silicone hydrogel contact lens according to claim 9.

11. The at least one hydrophilic vinyl monomer (1) an alkyl (meth)acrylamide selected from the group consisting of (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N-ethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-propyl(meth)acrylamide, N-isopropyl(meth)acrylamide, N-3-methoxypropyl(meth)acrylamide, and combinations thereof; (2) a hydroxyl-containing acrylic monomer selected from the group consisting of N-2-hydroxyethyl(meth)acrylamide, N,N-bis(hydroxyethyl)(meth)acrylamide, N-3-hydroxypropyl(meth)acrylamide, N-2-hydroxypropyl(meth)acrylamide, N-2,3-dihydroxypropyl(meth)acrylamide, N-tris(hydroxymethyl)methyl(meth)acrylamide, 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, glycerol methacrylate, di(ethylene glycol)(meth)acrylate, tri(ethylene glycol)(meth)acrylate, tetra(ethylene glycol)(meth)acrylate, poly(ethylene glycol)(meth)acrylate having a number average molecular weight of 1500 or less, poly(ethylene glycol)ethyl(meth)acrylamide having a number average molecular weight of 1500 or less, and combinations thereof; (3) a carboxyl-containing acrylic monomer selected from the group consisting of 2-(meth)acrylamidoglycolic acid, (meth)acrylic acid, ethylacrylic acid, 3-(meth)acrylamidepropionic acid, 5-(meth)acrylamidepentanoic acid, 4-(meth)acrylamidebutanoic acid, 3-(meth)acrylamide-2-methylbutanoic acid, 3-(meth)acrylamide-3-methylbutanoic acid, 2-(meth)acrylamide-2methyl-3,3-dimethylbutanoic acid, 3-(meth)acrylamidehexanoic acid, 4-(meth)acrylamide-3,3-dimethylhexanoic acid, and combinations thereof; (4) an amino-containing acrylic monomer selected from the group consisting of N-2-aminoethyl (meth) acrylamide, N-2-methylaminoethyl (meth) acrylamide, N-2-ethylaminoethyl (meth) acrylamide, N-2-dimethylaminoethyl (meth) acrylamide, N-3-aminopropyl (meth) acrylamide, N-3-methylaminopropyl (meth) acrylamide, N-3-dimethylaminopropyl (meth) acrylamide, 2-aminoethyl (meth) acrylate, 2-methylaminoethyl (meth) acrylate, 2-ethylaminoethyl (meth) acrylate, 3-aminopropyl (meth) acrylate, 3-methylaminopropyl (meth) acrylate, 3-ethylaminopropyl (meth) acrylate, 3-amino-2-hydroxypropyl (meth) acrylate, trimethylammonium 2-hydroxypropyl (meth) acrylate hydrochloride, dimethylaminoethyl (meth) acrylate, and combinations thereof; (5) N-vinylpyrrolidone, N-vinyl-3-methyl-2-pyrrolidone, N-vinyl-4-methyl-2-pyrrolidone, N-vinyl-5-methyl-2-pyrrolidone, N-vinyl-6-methyl-2-pyrrolidone, N-vinyl-3-ethyl-2-pyrrolidone, N-vinyl-4,5-dimethyl-2-pyrrolidone, N-vinyl-5,5-dimethyl-2-pyrrolidone, N-vinyl-3,3,5-trimethyl-2-pyrrolidone, N-vinylpiperidone, N-vinyl-3-methyl-2-piperidone, N-vinyl-4-methyl-2-piperidone, N-vinyl-5-methyl-2-piperidone, N-vinyl-6-methyl-2-piperidone, N-vinyl-6-ethyl-2-piperidone, N-vinyl-3,5-dimethyl-2-piperidone, N-vinyl-4,4-dimethyl-2-piperidone, N-vinylcaprolactam, N-vinyl-3-methyl-2-caprolactam, N-vinyl-4-methyl-2-caprolactam, N-vinyl-7-methyl-2-caprolactam, N-vinyl-7-ethyl-2-caprolactam, N-vinyl-3,5-dimethyl-2-caprolactam, N-vinyl-4,6-dimethyl-2-caprolactam, N-vinyl-3,5,7-trimethyl-2-caprolactam, N-vinyl-N-methylacetamide, N-vinylformamide, N-vinylacetamide, N-vinylisopropylamide, N-vinyl-N-ethylacetamide, N-vinyl-N-ethylformamide, and N-vinylamide monomers selected from the group consisting of combinations thereof; (6) Methylene-containing pyrrolidone monomers selected from the group consisting of 1-methyl-3-methylene-2-pyrrolidone, 1-ethyl-3-methylene-2-pyrrolidone, 1-methyl-5-methylene-2-pyrrolidone, 1-ethyl-5-methylene-2-pyrrolidone, 5-methyl-3-methylene-2-pyrrolidone, 5-ethyl-3-methylene-2-pyrrolidone, 1-n-propyl-3-methylene-2-pyrrolidone, 1-n-propyl-5-methylene-2-pyrrolidone, 1-isopropyl-3-methylene-2-pyrrolidone, 1-isopropyl-5-methylene-2-pyrrolidone, 1-n-butyl-3-methylene-2-pyrrolidone, 1-tert-butyl-3-methylene-2-pyrrolidone, and combinations thereof; (7) C １ ~ C ４ having an alkoxyethoxy group and C having a number average molecular weight of 1500 or less, such as ethylene glycol methyl ether (meth) acrylate, di (ethylene glycol) methyl ether (meth) acrylate, tri (ethylene glycol) methyl ether (meth) acrylate, tetra (ethylene glycol) methyl ether (meth) acrylate １ ~ C ４ an acrylic monomer selected from the group consisting of alkoxypoly (ethylene glycol) (meth) acrylate, methoxy-poly (ethylene glycol) ethyl (meth) acrylamide having a number average molecular weight of 1500 or less, and combinations thereof; A vinyl ether monomer selected from the group consisting of ethylene glycol monovinyl ether, di(ethylene glycol) monovinyl ether, tri(ethylene glycol) monovinyl ether, tetra(ethylene glycol) monovinyl ether, poly(ethylene glycol) monovinyl ether, ethylene glycol methyl vinyl ether, di(ethylene glycol) methyl vinyl ether, tri(ethylene glycol) methyl vinyl ether, tetra(ethylene glycol) methyl vinyl ether, poly(ethylene glycol) methyl vinyl ether, and combinations thereof; An allyl ether monomer selected from the group consisting of ethylene glycol monoallyl ether, di(ethylene glycol) monoallyl ether, tri(ethylene glycol) monoallyl ether, tetra(ethylene glycol) monoallyl ether, poly(ethylene glycol) monoallyl ether, ethylene glycol methyl allyl ether, di(ethylene glycol) methyl allyl ether, tri(ethylene glycol) methyl allyl ether, tetra(ethylene glycol) methyl allyl ether, poly(ethylene glycol) methyl allyl ether, and combinations thereof; (10) (Meth)acryloyloxyethyl phosphorylcholine, (meth)acryloyloxypropyl phosphorylcholine, 4-((meth)acryloyloxy)butyl-2'-(trimethylammonio)ethyl phosphate, 2-[(meth)acryloylamino]ethyl-2'-(trimethylammonio)-ethyl phosphate, 3-[(meth)acryloylamino]propyl-2'-(trimethylammonio)ethyl phosphate, 4-[(meth)acryloylamino]butyl-2'-(trimethylammonio)ethyl phosphate, 5-((meth)acryloyloxy)pentyl-2'-(trimethylammonio)ethyl phosphate, 6-((meth)acryloyloxy)hexyl-2'-(trimethylammonio)-ethyl phosphate, 2-((meth)acryloyloxy)ethyl-2'-(triethylammonio)ethyl phosphate, 2-((meth)acryloyloxy)ethyl-2'-(tripropylammonio)ethyl phosphate, 2-((meth)acryloyloxy)ethyl-2'-(tributylammonio)ethyl phosphate, 2-((meth)acryloyloxy)propyl-2'-(trimethylammonio)-ethyl phosphate, 2-((meth)acryloyloxy)butyl-2'-(trimethylammonio)ethyl phosphate, 2-((meth)acryloyloxy)pentyl-2'-(trimethylammonio)ethyl phosphate, 2-((meth)acryloyloxy)hexyl-2'-(trimethylammonio)ethyl phosphate, 2-(vinyloxy)ethyl-2'-(trimethylammonio)ethyl phosphate, 2-(allyloxy)ethyl-2'-(trimethylammonio)ethyl phosphate, 2-(vinyloxycarbonyl)ethyl-2'-(trimethylammonio)ethyl phosphate, 2-(allyloxycarbonyl)ethyl-2'-(trimethylammonio)-ethyl phosphate, 2-(vinylcarbonylamino)ethyl-2'-(trimethylammonio)ethyl phosphate, 2-(allyloxycarbonylamino)ethyl-2'-(trimethylammonio)ethyl phosphate, 2-(butenoyloxy)ethyl-2'-(trimethylammonio)ethyl phosphate,a phosphorylcholine-containing vinyl monomer selected from the group consisting of and combinations thereof; (11) Allyl alcohol; (12) N-2-hydroxyethyl vinyl carbamate; (13) N-carboxyvinyl-β-alanine (VINAL); (14) N-carboxyvinyl-α-alanine; or a combination thereof The silicone hydrogel contact lens according to claim 10, comprising.

12. The silicone hydrogel contact lens according to claim 10 or 11, wherein the at least one hydrophilic vinyl monomer comprises N-vinylpyrrolidone, N-vinyl-N-methylacetamide, or a combination thereof.

13. The silicone hydrogel contact lens according to any one of claims 10 to 12, wherein the at least one hydrophilic vinyl monomer comprises N,N-dimethyl(meth)acrylamide.

14. The at least one hydrophilic vinyl monomer includes N-2-hydroxyethyl (meth)acrylamide, N,N-bis(hydroxyethyl)(meth)acrylamide, N-3-hydroxypropyl (meth)acrylamide, N-2-hydroxypropyl (meth)acrylamide, N-2,3-dihydroxypropyl (meth)acrylamide, N-tris(hydroxymethyl)methyl (meth)acrylamide, 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, glycerol methacrylate (GMA), di(ethylene glycol)(meth)acrylate, tri(ethylene glycol)(meth)acrylate, tetra(ethylene glycol)(meth)acrylate, poly(ethylene glycol)(meth)acrylate having a number average molecular weight of up to 1500, poly(ethylene glycol)ethyl (meth)acrylamide having a number average molecular weight of up to 1500, or a combination thereof, the silicone hydrogel contact lens according to any one of claims 10 to 13.

15. The crosslinked polymer material includes repeating units of at least one non-silicone vinyl crosslinking agent, the silicone hydrogel contact lens according to any one of claims 10 to 14.

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