Multifocal diffractive silicone hydrogel contact lens

Abstract

A contact lens in which the diffractive structure does not contact the cornea or the surface of the eye, thereby improving the wearing comfort and simultaneously reducing the risk of adverse events.SOLUTION: To provide an embedded silicone hydrogel contact lens having an insert embedded in a silicone hydrogel bulk material and having abrasion resistance. The insert is made of a cross-linked polymeric material having a refractive index at least 0.07 higher than the silicone hydrogel bulk material and comprises a diffractive structure disposed on one of the front curve surface and the back curve surface of the insert to provide a diffractive power that contributes to the overall refractive power of the contact lens.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to an implantable silicone hydrogel contact lens having an embedded insert that includes a diffractive structure disposed on one of the anterior and posterior surfaces of the insert to impart diffractive power, and to a method for making such a diffractive contact lens. [Background technology]

[0002] Presbyopia is a well-known disorder in which the eye loses its ability to focus at near distances, affecting over 2 billion people worldwide. Extensive research efforts have been made to develop multifocal ophthalmic lenses (intraocular lenses or contact lenses) to correct presbyopia. One area of ​​extensive research is the development of multifocal diffractive ophthalmic lenses.For example, U.S. Patent Nos. 4,210,391, 4,338,005, 4,340,283, 4,637,697, 4,641,934, 4,642,112, 4,655,565, 4,830,481, 4,881,804, 4,881,805, 4,936,666, 4,995,714, 4,995,715, 5,054,905, 5,056,908, 5,076 684 specification, 5100226 specification, 5104212 specification, 5114220 specification, 5116111 specification, 5117306 specification, 5120120 specification, 5121979 specification, 512 Specification No. 1980, Specification No. 5229797, Specification No. 5748282, Specification No. 5760871, Specification No. 5982543, Specification No. 6120148, Specification No. 6364483, Specification No. 6536899, Specification No. 695 Specification No. 1391, Specification No. 6957891, Specification No. 7025456, Specification No. 7073906, Specification No. 7093938, Specification No. 7156516, Specification No. 7188949, Specification No. 7232218, Specification No. 78 91810 specification, 8038293 specification, 8128222 specification, 8142016 specification, 8382281 specification, 8480228 specification, 8556416 specification, 8573775 specification, 86 See Nos. 78583, 8755117, 9033494, 9310624, 9320594, 9370416, 10197815, 10209533, 10426599, 10463474, 10524899, 10675146, 10725320, 10932901, and 10945834. Multifocal diffractive intraocular lenses are now commercially available for correcting presbyopia.

[0003] However, multifocal diffractive contact lenses are not yet commercially available for correcting presbyopia, likely due to the inherent problems associated with contact lenses (see Perez-Prados, et al., "Soft Multifocal Simultaneous Image Contact Lenses: Review," Clin. Exp. Optom. 2017, 100:107-127). For example, standard lens materials have a refractive index of approximately 1.42 or less, or approximately 0.04 higher than the refractive index of the tear film. Such a small refractive index difference requires a higher diffraction grating height on one of the anterior and posterior surfaces of the contact lens. However, for comfortable wear, the contact lens must have smooth anterior and posterior surfaces. Such a diffraction grating may cause discomfort to the patient. Summary of the Invention [Problem to be solved by the invention]

[0004] Therefore, there is a need for multifocal diffractive contact lenses. [Means for solving the problem]

[0005] In one aspect, the present invention provides an implantable silicone hydrogel contact lens comprising a silicone hydrogel bulk material and an insert embedded therein, the insert being made of a crosslinked polymeric material having a first refractive index, the silicone hydrogel bulk material having a second refractive index, the first refractive index being at least 0.07 higher than the second refractive index, the insert having a front curve surface, an opposing back curve surface, and a diameter of less than 13.0 mm, the insert being located in a central portion of the implantable hydrogel contact lens and including a diffractive structure disposed on one of the front curve surface and the back curve surface to impart a diffractive power that contributes to the overall optical power of the contact lens, the diffractive structure being embedded within the silicone hydrogel bulk material, the implantable silicone hydrogel contact lens exhibiting resistance to delamination after being autoclaved in a packaging solution in a sealed package at 121° C. for about 45 minutes, as indicated by the absence of air bubbles upon microscopic examination of the interface between the insert and the bulk material within the implantable silicone hydrogel contact lens, the packaging solution being phosphate buffered saline having a pH of 7.1±0.2.

[0006] In another aspect, the present invention provides a method for making an implantable silicone hydrogel contact lens having a diffractive insert of the present invention therein.

[0007] The present invention provides the foregoing and other features, the advantages of which will become more apparent from the following detailed description of the presently preferred embodiment, read in conjunction with the accompanying drawings. The detailed description and drawings are merely illustrative of the invention and do not limit the scope of the invention, as defined by the appended claims and equivalents thereof. [Brief explanation of the drawings]

[0008] [Figure 1]1 shows a simulated diffraction profile placed on the back (or front) curve surface of an insert with an RI of 1.55 embedded in a silicone hydrogel material with an RI of 1.43 for a +2.5D add power. [Figure 2] 1 shows a simulated diffraction profile placed on the back (or front) curve surface of an insert with an RI of 1.47 embedded in a silicone hydrogel material with an RI of 1.43 for a +2.5D add power. DETAILED DESCRIPTION OF THE INVENTION

[0009] 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. Generally, the nomenclature and experimental procedures used herein are well known and commonly used in the art. Conventional methods, such as those provided in the art and various general references, are used for these procedures. Where a term is given in the singular, the inventors also contemplate the plural form of that term. The nomenclature used herein and the experimental procedures described below are well known and commonly used in the art.

[0010] "About" as used herein in this application means that a number referred to as "about" includes the recited number plus or minus 1 to 10% of the recited number.

[0011] "Contact lens" refers to a structure that can be placed on or in the eye of a wearer. A contact lens can, but need not, correct, improve, or alter the user's vision.

[0012] "Hydrogel contact lens" refers to a contact lens that includes a hydrogel bulk (core) material. The hydrogel bulk material can be a non-silicone hydrogel material, or preferably a silicone hydrogel material.

[0013] "Hydrogel" or "hydrogel material" refers to a crosslinked polymeric material having a three-dimensional polymer network (i.e., a polymeric matrix) that is insoluble in water but can retain at least 10% by weight of water within its polymeric matrix when fully hydrated (or equilibrated).

[0014] "Silicone hydrogel" or "SiHy" are interchangeable and refer to a silicone-containing hydrogel that includes repeat units of at least one silicone-containing monomer and / or silicone-containing vinyl crosslinker and repeat units of at least one hydrophilic vinyl monomer.

[0015] Siloxane, often also referred to as silicone, refers to a molecule having at least one moiety of -Si-O-Si-, where each Si atom has two organic groups as substituents.

[0016] As used in this application, the term "non-silicone hydrogel" refers to a hydrogel that is theoretically free of silicon.

[0017] An "implantable silicone hydrogel contact lens" refers to a hydrogel contact lens that includes at least one insert embedded within the bulk hydrogel material of the implantable silicone hydrogel contact lens to the extent that at most one of the front curve and back curve surfaces of the insert can be fully or partially exposed. It is understood that the material of the insert is different from the bulk hydrogel material of the implantable hydrogel contact lens.

[0018] "Insert" refers to any three-dimensional article having dimensions of at least 5 microns but small enough to be embedded in the bulk material of an implantable hydrogel contact lens, and made from a material different from the bulk hydrogel material (preferably a non-hydrogel material).

[0019] According to the present invention, a non-hydrogel material can be any material that can absorb less than 10% by weight of water when fully hydrated (preferably about 7.5% by weight or less, more preferably about 5% by weight or less, and even more preferably about 2.5% by weight or less).

[0020] "Hydrophilic," as used herein, describes a material or portion thereof that associates more readily with water than with lipids.

[0021] "Vinyl monomer" refers to a compound that has one and only one ethylenically unsaturated group, is soluble in a solvent, and can be polymerized actinically or thermally.

[0022] The term "soluble," in reference to a compound or material in a solvent, means that the compound or material can be dissolved in the solvent at room temperature (i.e., a temperature of about 21°C to about 27°C) to provide a solution with a concentration of at least about 0.5% by weight.

[0023] The term "insoluble," in reference to a compound or material in a solvent, means that the compound or material can be dissolved in the solvent at room temperature (as defined above) to provide a solution with a concentration of less than about 0.01% by weight.

[0024] The term "ethylenically unsaturated group" is used broadly herein and is intended to encompass any group containing at least one >C=CH group. Exemplary ethylenically unsaturated groups include, but are not limited to, (meth)acryloyl [ka] , allyl, vinyl, styrenyl, or other C=C containing groups.

[0025] As used herein, "actinically," in reference to curing, crosslinking, or polymerization of a polymerizable composition, prepolymer, or material, means that the curing (e.g., crosslinking and / or polymerization) is effected by actinic radiation, such as, for example, UV radiation, ionizing radiation (e.g., gamma or X-ray radiation), microwave radiation, etc. Thermal curing or actinic curing methods are well known to those skilled in the art.

[0026] "Acrylic monomer" refers to a vinyl monomer having one and only one (meth)acryloyl group. Examples of acrylic monomers include (meth)acryloxy [or (meth)acryloyloxy] monomers and (meth)acrylamide monomers.

[0027] "(Meth)acryloxy monomer" or "(meth)acryloyloxy monomer" means one and only one [ka] It refers to a vinyl monomer having the group:

[0028] "(Meth)acrylamide monomer" is [ka] (In the formula, R o refers to a vinyl monomer having one and only one group (which is H or C1-C4 alkyl).

[0029] The terms "aryl vinyl monomer" or "aryl-containing vinyl monomer" are interchangeable and refer to vinyl monomers that contain at least one aromatic ring.

[0030] The terms "aryl acrylic monomer" or "aryl-containing acrylic monomer" are interchangeable and refer to acrylic monomers that contain at least one aromatic ring.

[0031] The term "(meth)acrylamide" refers to methacrylamide and / or acrylamide.

[0032] The term "(meth)acrylate" refers to methacrylate and / or acrylate.

[0033] "N-vinyl amide monomer" refers to an amide compound having a vinyl group (-CH=CH2) attached directly to the nitrogen atom of the amide group.

[0034] The term "ene group" refers to a monovalent radical of CH2=CH- or CH2=CCH3- that is not covalently bonded to an oxygen or nitrogen atom or a carbonyl group.

[0035] "Ene monomer" refers to a vinyl monomer having one and only one ene group.

[0036] "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, which typically results in a homopolymer that is water-soluble or can absorb at least 10 weight percent water.

[0037] "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, which typically results in a homopolymer that is insoluble in water and can absorb less than 10% by weight of water.

[0038] As used in this application, the term "vinyl crosslinker" refers to an organic compound having at least two ethylenically unsaturated groups. "Vinyl crosslinker" refers to a vinyl crosslinker having a molecular weight of 700 Daltons or less.

[0039] The terms "aryl vinyl crosslinker" or "aryl-containing vinyl crosslinker" are interchangeable and refer to vinyl crosslinkers that contain at least one aromatic ring.

[0040] "Acrylic crosslinker" refers to a vinyl crosslinker having at least two (meth)acryloyl groups.

[0041] The terms "aryl acrylic crosslinker" or "aryl-containing aryl crosslinker" are interchangeable and refer to an acrylic crosslinker that has at least one aromatic ring.

[0042] The term "acrylic repeat unit" refers to a repeat unit of a polymeric material that is each derived from an acrylic monomer or crosslinker in a free radical polymerization to form the polymeric material.

[0043] The term "terminal (meth)acryloyl group," as known to those skilled in the art, refers to one (meth)acryloyl group at one of the two ends of the main chain (or backbone) of an organic compound.

[0044] The terms "silicone-containing vinyl monomer or crosslinker" or "siloxane-containing vinyl monomer or crosslinker" are interchangeable and refer to a vinyl monomer or crosslinker having at least one moiety of -Si-O-Si-, where each Si atom has at least two substituents (organic groups).

[0045] The terms "polysiloxane segment" and "polydiorganosiloxane segment" are interchangeable, [ka] where SN is an integer equal to or greater than 3, and R S1 and R S2 Each of C1 to C 10 Alkyl;Phenyl;C1-C4 alkyl-substituted phenyl;C1-C4 alkoxy-substituted phenyl;Phenyl-C1-C6 alkyl;C1-C 10 Fluoroalkyl; C1-C 10 Fluoroether;Aryl;Aryl C1-C 18 Alkyl;-alk-(OC2H4) γ1 -OR o (wherein alk is a C1-C6 alkylene diradical, R o is H or C1-C4 alkyl, and γ1 is an integer of 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 C2-C alkoxy group having at least one functional group selected from the group consisting of an amide of -OCONH-, a urethane bond of -OCONH-, and a C1-C4 alkoxy group 40 an organic radical, or a linear hydrophilic polymer chain, wherein R N1 and R N1 ' are each independently hydrogen or C1-C 15 alkyl; and organic radicals having up to 45 carbon atoms.

[0046] The terms "polydiorganosiloxane vinyl crosslinker" or "polysiloxane vinyl crosslinker" are interchangeable and refer to a compound that contains at least one polysiloxane segment and at least two ethylenically unsaturated groups.

[0047] The term "fluid" as used herein indicates that the material is capable of flowing like a liquid.

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

[0049] 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.

[0050] "Macromer" or "prepolymer" refers to a compound or polymer that contains ethylenically unsaturated groups and has a number average molecular weight greater than 700 Daltons.

[0051] As used in this application, the term "molecular weight" of a polymeric material (including a monomeric or macromeric material) refers to the number average molecular weight unless otherwise specified or unless the test conditions dictate otherwise. Those skilled in the art will readily appreciate that molecular weight can be measured by known methods, such as GPC (gel permeation chromatography) 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 viscometry detector, a UV detector, and an infrared (IR) detector; MALDI-TOF MS (matrix-assisted laser desorption / ionization time-of-flight mass spectrometry); 1 Know how to determine the molecular weight of polymers according to H NMR (proton nuclear magnetic resonance) spectroscopy etc.

[0052] The term "monovalent radical" refers to an organic radical obtained by removing a hydrogen atom from an organic compound and forming one bond with one other group in the organic compound. Examples include, without limitation, alkyl (by removing a hydrogen atom from an alkane), alkoxy (or alkoxyl) (by removing one hydrogen atom from the hydroxyl group of an alkyl alcohol), thiyl (by removing one hydrogen atom from the thiol group of an alkylthiol), cycloalkyl (by removing a hydrogen atom from a cycloalkane), cycloheteroalkyl (by removing a hydrogen atom from a cycloheteroalkane), aryl (by removing a hydrogen atom from the aromatic ring of an aromatic hydrocarbon), heteroaryl (by removing a hydrogen atom from any ring atom), amino (by removing one hydrogen atom from an amine), and the like.

[0053] The term "divalent radical" refers to an organic radical 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 radical (i.e., alkylenyl) is obtained by removing two hydrogen atoms from an alkane, and a cycloalkylene divalent radical (i.e., cycloalkylenyl) is obtained by removing two hydrogen atoms from a cyclic ring.

[0054] In this application, the term "substituted" with reference to an alkyl or alkylenyl means that the alkyl or alkylenyl replaces one hydrogen atom of the alkyl or alkylenyl and includes at least one substituent selected from the group consisting of hydroxyl (-OH), carboxyl (-COOH), -NH, sulfhydryl (-SH), C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkylthio (alkylsulfido), C1-C4 acylamino, C1-C4 alkylamino, di-C1-C4 alkylamino, and combinations thereof.

[0055] The term "terminal ethylenically unsaturated group," as known to those skilled in the art, refers to an ethylenically unsaturated group at one of the two ends of the main chain (or backbone) of an organic compound.

[0056] "Blending vinyl monomer" refers to a vinyl monomer that is capable of dissolving both the hydrophilic and hydrophobic components of the polymerizable composition to form a solution.

[0057] A free radical initiator can be either a photoinitiator or a thermal initiator. A "photoinitiator" refers to a chemical that initiates a free radical crosslinking / polymerization reaction with the use of light. A "thermal initiator" refers to a chemical that initiates a radical crosslinking / polymerization reaction with the use of heat energy.

[0058] In the context of silicone hydrogel bulk materials or SiHy contact lenses, "post-cure surface treatment" refers to a surface treatment process that occurs after the silicone hydrogel bulk material or SiHy contact lens is formed by curing (i.e., thermally or actinically polymerizing) the SiHy lens formulation.

[0059] The terms "silicone hydrogel lens formulation" or "SiHy lens formulation" are interchangeable and refer to a polymerizable composition that contains all the necessary polymerizable components to produce a silicone hydrogel (SiHy) contact lens or SiHy lens bulk material, as is well known to those skilled in the art.

[0060] The material's inherent "oxygen permeability" Dk i is the rate at which oxygen passes through a material. Oxygen permeability is usually expressed in units of barrers, where "barrer" is the number of bars per square meter (cm 3 oxygen)(mm) / (cm 2 )(sec)(mmHg)]×10 -10 is defined as:

[0061] The "oxygen permeability" of an insert or material, Dk / t, is the rate at which oxygen passes through a particular insert or material of average thickness t [in mm] over the area being measured. Oxygen permeability is usually expressed in units of barrer / mm, where "barrer / mm" is the number of bars per square meter (cm 3 oxygen) / (cm2 )(sec)(mmHg)]×10 -9 is defined as:

[0062] The "ion permeability" through the lens correlates with the ionoflux diffusion coefficient. The ionoflux diffusion coefficient D ([mm 2 The time (units of time / minute) is determined by applying Fick's law: D=-n' / (A×dc / dx) (where n' = ion transport rate [mol / min]; A = exposed lens area [mm 2 ]; dc = concentration difference [mol / L]; dx = lens thickness [mm]).

[0063] The term "modulus" or "elastic modulus" with respect to a contact lens or material means the tensile modulus, i.e., Young's modulus, which is a measure of the embedding of the contact lens or material. The modulus can be measured according to the procedure described in Example 1.

[0064] "Unprocessed state" refers to an insert or contact lens obtained by casting a polymerizable composition in a mold and which has not been subjected to an extraction and / or hydration post-molding process (i.e., has not been in contact with water or any organic solvent or any liquid after molding).

[0065] "Male mold half" or "base curve mold half" are interchangeable and refer to a mold half that is substantially convex and has a molding surface that defines the posterior surface of a contact lens or insert.

[0066] "Female mold half" or "front curve mold half" are interchangeable and refer to a mold half that is substantially concave and has a molding surface that defines the front surface of a contact lens or insert.

[0067] As used in this application, the terms "front surface," "front surface," "front curve surface," or "FC surface" in reference to a contact lens or insert are interchangeable and refer to the surface of the contact lens or insert that faces away from the eye during wear. The front surface (FC surface) is typically convex.

[0068] As used in this application, the terms "posterior surface," "back surface," "back curve surface," or "BC surface" in reference to a contact lens or insert are interchangeable and refer to the surface of the contact lens or insert that faces the eye during wear. The posterior surface (BC surface) is typically concave.

[0069] As used in this application, the term "diameter" in reference to a contact lens or insert means the width from edge to edge of the contact lens or insert.

[0070] Generally, the present invention relates to a peel-resistant diffractive contact lens having an insert embedded in a silicone hydrogel bulk material, the insert being made of a crosslinked polymeric material having a refractive index at least 0.07 higher than that of the silicone hydrogel bulk material, and including a diffractive structure disposed on one of the front curve and back curve surfaces of the insert to impart diffractive power that contributes to the overall optical power of the contact lens. The present invention is based, in part, on the discovery that such an insert having a relatively high oxygen permeability and a relatively high refractive index (≥ 1.49) can be prepared from a polymerizable composition containing at least about 50 mole % of one or more acrylic monomers and / or crosslinkers, and at least one polymerizable component selected from the group consisting of silicone-containing vinyl monomers, aryl vinyl monomers, aryl silicone-containing vinyl monomers, and polysiloxane vinyl crosslinkers each containing siloxane units having at least one aryl-containing vinyl substituent. Such an insert having a relatively high oxygen permeability will minimize adverse effects on the oxygen permeability of the contact lens and, therefore, ocular health. At relatively high refractive indices, the diffractive structures, which are essentially diffraction gratings and which are located on one of the front and back curve surfaces of each insert, can have a low grating height (e.g., ≦5 μm).The present invention is also based, in part, on the discovery that peel-resistant implantable silicone hydrogel contact lenses can be obtained by fully or partially encapsulating an insert comprising at least 50 mole % repeat units of one or more acrylic monomers and / or crosslinkers within a silicone hydrogel bulk material comprising repeat units of at least one silicone-containing vinyl crosslinker and / or monomer having an H-bond donor.

[0071] There are several potentially unique features associated with abrasion-resistant diffractive contact lenses. First, the diffractive structures are completely embedded in the bulk silicone hydrogel material. The lack of contact with the cornea or ocular surface can improve wearer comfort while simultaneously reducing the risk of adverse events. Furthermore, visual stability due to tear film changes can be mitigated. Additionally, diffractive gratings with reduced grating heights can be more easily manufactured, for example, by cast molding.

[0072] In one aspect, the present invention provides an implantable silicone hydrogel contact lens comprising a silicone hydrogel bulk material and an insert embedded therein, the insert being made of a crosslinked polymeric material having a first refractive index, the silicone hydrogel bulk material having a second refractive index, the first refractive index being at least 0.07 (preferably at least 0.08, more preferably at least 0.09, and even more preferably at least 0.10) higher than the second refractive index, the insert having a front curve surface, an opposing back curve surface, and a diameter of less than 13.0 mm, the insert being located in a central portion of the implantable hydrogel contact lens, and the contact lens the implantable silicone hydrogel contact lens comprises a diffractive structure disposed on one of the front curve surface and the back curve surface to impart a diffractive power that contributes to the overall refractive power of the lens, the diffractive structure being embedded within a silicone hydrogel bulk material, and the implantable silicone hydrogel contact lens exhibits resistance to delamination as indicated by the absence of air bubbles upon microscopic examination of the interface between the insert and the silicone hydrogel bulk material within the implantable silicone hydrogel contact lens after being autoclaved at 121°C for approximately 45 minutes in a packaging solution within a sealed package, the packaging solution being phosphate buffered saline having a pH of 7.1±0.2.

[0073] Examination of implantable silicone hydrogel contact lenses for delamination under a microscope can be performed according to any method known to those skilled in the art, preferably according to the procedure described in Example 1 of the present application.

[0074] According to the present invention, the diffractive structure is essentially a transmission diffraction grating. As known to those skilled in the art, a transmission diffraction grating typically consists of a plurality of repeating ridges and / or grooves arranged in regularly or periodically spaced concentric rings or zones—annular zones (i.e., echelettes)—on each surface of the lens (i.e., the insert in this application). The periodic spacing or pitch of the ridges and / or grooves essentially determines the points of destructive and constructive interference on the optical axis of the lens. The shape and height of the ridges and / or grooves control the amount of incident light delivered to the points of constructive interference by diffraction. The points of constructive interference are commonly referred to as diffraction orders or focal points.

[0075] Diffractive power is related to the characteristics of these zones, such as their number, shape, size, and location. Currently used echelettes are typically defined by a primary zone, a secondary zone between the primary zone and the primary zone of an adjacent echelette, and the echelette shape. The echelette shape includes an inner and outer diameter and a shaped or sloped profile. Secondary zones can describe situations where the theoretical primary zone is a discontinuous function, resulting in a discontinuous step in the profile height. Secondary zones are sometimes introduced to solve manufacturing problems with creating sharp corners on a surface and / or to reduce the possibility of light scattering from sharp corners. The overall profile can be characterized by the echelette height, or the step height between adjacent echelettes. The relative radial spacing of the echelettes primarily determines the power of the lens, while the step height of the secondary zone primarily determines the light distribution between different add powers. Together, these echelettes define a diffractive profile, often sawtooth or stepped, on one surface of the lens.

[0076] Diffraction profile (Z diff ) (or so-called sag profile) is given by Equation 1

number

[0077] The radial position x of the diffractive transition is a function of the diffractive power or add power added to the system and the wavelength:

number

[0078] The height of the diffraction transition is then given by:

number

[0079] It will be appreciated that any phase function known to one skilled in the art can be used to create the desired diffractive profile. Exemplary phase functions can be a modulo 2pi kinoform design that acts as a Fresnel lens, an apodized bifocal design similar to ReSTOR, or a quadrifocal design similar to PanOptix that results in a trifocal lens.

[0080] Figure 1 shows

number

[0081] According to the present invention, any diffractive structure can be disposed on one of the front curve and back curve surfaces of the insert of the present invention, so long as the diffractive structure is completely embedded within the silicone hydrogel bulk material. The diffractive structure can be formed (deposited) by lathing or laser cutting one of the front curve and back curve surfaces of a preformed insert according to a design to impart the desired diffractive power, as known to those skilled in the art. Alternatively, an insert having a diffractive structure on one of the front curve and back curve surfaces can be formed by casting a polymerizable composition using a mold to form the insert with the diffractive structure thereon.

[0082] In one embodiment of the present invention, the crosslinked polymeric material of the insert has a refractive index of at least about 1.47, preferably at least about 1.49, more preferably at least about 1.51, and even more preferably at least about 1.53.

[0083] In another embodiment of the present invention, the crosslinked polymeric material of the insert has an oxygen permeability of at least about 40 barrers, preferably at least about 60 barrers, more preferably at least about 80 barrers, and even more preferably at least about 100 barrers.

[0084] In another preferred embodiment of the present invention, the crosslinked polymeric material of the insert comprises at least 50 mole percent of repeat units of one or more acrylic monomers and / or crosslinkers (acrylic repeat units), it being understood that the mole percent proportion of acrylic repeat units can be calculated based on the mole percent of all acrylic monomers and acrylic crosslinkers relative to all polymerizable components in the polymerizable composition for forming the insert, excluding the non-reactive diluent.

[0085] In another preferred embodiment, the cross-linked polymeric material of the insert comprises repeat units of at least one aryl vinyl monomer and / or at least one aryl vinyl cross-linking agent.

[0086] Examples of aryl vinyl monomers include aryl acrylic monomers and aryl-containing ene monomers.

[0087] Examples of aryl acrylic monomers include, but are not limited to, 2-ethylphenoxyacrylate; 2-ethylphenoxymethacrylate; phenylacrylate; phenylmethacrylate; benzylacrylate; benzylmethacrylate; 2-phenylethylacrylate; 2-phenylethylmethacrylate; 3-phenylpropylacrylate; 3-phenylpropylmethacrylate; 4-phenylbutylacrylate; 4-phenylbutylmethacrylate; 4-methylphenylacrylate; 4-methylphenylmethacrylate; 4 -Methylbenzyl acrylate;4-Methylbenzyl methacrylate;2-(2-Methylphenyl)ethyl acrylate;2-(2-Methylphenyl)ethyl methacrylate;2-(3-Methylphenyl)ethyl acrylate;2-(3-Methylphenyl)ethyl methacrylate;2-(4-Methylphenyl)ethyl acrylate;2-(4-Methylphenyl)ethyl methacrylate;2-(4-Propylphenyl)ethyl acrylate;2-(4-Propylphenyl)ethyl methacrylate;2-(4-(1-Methylethyl)phenyl)ethyl acrylate Acrylate;2-(4-(1-methylethyl)phenyl)ethyl methacrylate;2-(4-Methoxyphenyl)ethyl acrylate;2-(4-Methoxyphenyl)ethyl methacrylate;2-(4-Cyclohexylphenyl)ethyl acrylate;2-(4-Cyclohexylphenyl)ethyl methacrylate;2-(2-Chlorophenyl)ethyl acrylate;2-(2-Chlorophenyl)ethyl methacrylate;2-(3-Chlorophenyl)ethyl acrylate;2-(3-Chlorophenyl)ethyl methacrylate;2-(4-Chlorophenyl) Ethyl acrylate;2-(4-chlorophenyl)ethyl methacrylate;2-(4-bromophenyl)ethyl acrylate;2-(4-bromophenyl)ethyl methacrylate;2-(3-phenylphenyl)ethyl acrylate;2-(3-phenylphenyl)ethyl methacrylate;2-(4-phenylphenyl)ethyl acrylate;2-(4-phenylphenyl)ethyl methacrylate;2-(4-benzylphenyl)ethyl acrylate;2-(4-benzylphenyl)ethyl methacrylate;2-(phenylthio)ethyl acrylateExamples of suitable aryl acrylic monomers include 2-(phenylthio)ethyl methacrylate, 2-benzyloxyethyl acrylate, 3-benzyloxypropyl acrylate, 2-benzyloxyethyl methacrylate, 3-benzyloxypropyl methacrylate, 2-[2-(benzyloxy)ethoxy]ethyl acrylate, 2-[2-(benzyloxy)ethoxy]ethyl methacrylate, or combinations thereof. The aryl acrylic monomers listed above can be obtained from commercial sources or prepared by methods known in the art.

[0088] Examples of preferred aryl-containing ene monomers include, but are not limited to, styrene, 2,5-dimethylstyrene, 2-(trifluoromethyl)styrene, 2-chlorostyrene, 3,4-dimethoxystyrene, 3-chlorostyrene, 3-bromostyrene, 3-vinylanisole, 3-methylstyrene, 4-bromostyrene, 4-tert-butylstyrene, p-styryltrimethoxysilane, styrylethyltrimethoxysilane, 2,3,4,5,6-pentanefluorostyrene, 2,4-dimethylstyrene, 1-methoxystyrene, 1-methyl ... 4-vinylbenzene, 1-chloro-4-vinylbenzene, 1-methyl-4-vinylbenzene, 1-(chloromethyl)-4-vinylbenzene, 1-(bromomethyl)-4-vinylbenzene, 3-nitrostyrene, 1,2-vinylphenylbenzene, 1,3-vinylphenylbenzene, 1,4-vinylphenylbenzene, 4-vinyl-1,1'-(4'-phenyl)biphenylene, 1-vinyl-4-(phenyloxy)benzene, 1-vinyl-3-(phenyloxy)benzene, 1-vinyl-2-(phenyloxy)benzene Benzene, 1-vinyl-4-(phenylcarbonyl)benzene, 1-vinyl-3-(phenylcarboxy)benzene, 1-vinyl-2-(phenoxycarbonyl)benzene, allyl phenyl ether, 2-biphenylyl allyl ether, allyl 4-phenoxyphenyl ether, allyl 2,4,6-tribromophenyl ether, allyl phenyl carbonate, 1-allyloxy-2-trifluoromethylbenzene, allylbenzene, 1-phenyl-2-prop-2-enylbenzene, 4-phenyl-1-butene, 4-Phenyl-1-buten-4-ol, 1-(4-methylphenyl)-3-buten-1-ol, 1-(4-chlorophenyl)-3-buten-1-ol, 4-allyltoluene, 1-allyl-4-fluorobenzene, 1-allyl-2-methylbenzene, 1-allyl-3-methylbenzene, 1-allyl-3-methylbenzene, 2-allylanisole, 4-allylanisole, 1-allyl-4-(trifluoromethyl)benzene, allylpentafluorobenzene, 1-allyl-2-methoxybenzene, 4-allyl-1,2-Dimethoxybenzene, 2-allylphenol, 2-allyl-6-methylphenol, 4-allyl-2-methoxyphenol, 2-allyloxyanisole, 4-allyl-2-methoxyphenyl acetate, 2-allyl-6-methoxyphenol, 1-allyl-2-bromobenzene, α-vinylbenzyl alcohol, 1-phenyl-3-buten-1-one, allylbenzyl ether, (3-allyloxy)propyl)benzene, allylphenylethyl ether, 1-benzyloxy-4-pentene, (1-allyloxy)ethyl)benzene, 1-phenylallylethyl ether, (2-methyl-2-(2-propenyloxy)propyl)benzene, ((5-hexenyloxy)methyl)benzene, 1-allyloxy-4-propoxy Benzene, 1-phenoxy-4-(3-prop-2-enoxypropoxy)benzene, 6-(4'-hydroxyphenoxy)-1-hexene, 4-but-3-enoxyphenol, 1-allyloxy-4-butoxybenzene, 1-allyloxy-4-ethoxybenzene, 1-allyl-4-benzyloxybenzene, 1-allyl-4-(phenoxy)benzene, 1-allyl-3-(phenoxy)benzene, 1-allyl-2-(phenoxy)benzene, 1-allyl-4-(phenylcarbonyl)benzene, 1-allyl-3-(phenylcarboxy)benzene, 1-allyl-2-(phenoxycarbonyl)benzene, 1,2-allylphenylbenzene, 1,3-allylphenylbenzene, 1,4-allylphenylbenzene, 4-vinyl-1,1'-(4'-phenyl)biphenylene, 1-allyl-4-(phenyloxy)benzene, 1-allyl-3-(phenyloxy)benzene, 1-allyl-2-(phenyloxy)benzene, 1-allyl-4-(phenylcarbonyl)benzene, 1-allyl-3-(phenylcarboxy)benzene, and 1-allyl-2-(phenoxycarbonyl)benzene, 1-vinylnaphthylene, 2-vinylnaphthylene, 1-allylnaphthalene, 2-allylnaphthalene, allyl-2-naphthyl ether, 2-(2-methylprop-2-ene), (nyl)naphthalene, 2-prop-2-enylnaphthalene, 4-(2-naphthyl)-1-butene, 1-(3-butenyl)naphthalene, 1-allylnaphthalene, 2-allylnaphthalene, 1-allyl-4-naphthylnaphthalene, 2-(allyloxy)-1-bromonaphthalene, 2-bromo-6-allyloxynaphthalene, 1,2-vinyl(1-naphthyl)benzene, 1,2-vinyl(2-naphthyl)benzene, 1,3-vinyl(1-naphthyl)benzene, 1,3-vinyl(2-naphthyl)benzene, 1,4-vinyl(1-naphthyl) )benzene, 1,4-vinyl(2-naphthyl)benzene, 1-naphthyl-4-vinylnaphthalene, 1-allylnaphthalene, 2-allylnaphthalene, 1,2-allyl(1-naphthyl)benzene, 1,2-allyl(2-naphthyl)benzene, 1,3-allyl(1-naphthyl)benzene, 1,3-allyl(2-naphthyl)benzene, 1,4-allyl(1-naphthyl)benzene, 1,4-allyl(2-naphthyl)benzene, 1-allyl-4-naphthylnaphthalene, 1-vinylanthracene, 2-vinylanthracene, 9-vinylanthracene Examples of suitable aryl anthracene include 1-allylanthracene, 1-allylanthracene, 2-allylanthracene, 9-allylanthracene, 9-pent-4-enylanthracene, 9-allyl-1,2,3,4-tetrachloroanthracene, 1-vinylphenanthrene, 2-vinylphenanthrene, 3-vinylphenanthrene, 4-vinylphenanthrene, 9-vinylphenanthrene, 1-allylphenanthrene, 2-allylphenanthrene, 3-allylphenanthrene, 4-allylphenanthrene, 9-allylphenanthrene, and combinations thereof.

[0089] Examples of aryl vinyl crosslinkers include, but are not limited to, divinylbenzene, 2-methyl-1,4-divinylbenzene, bis(4-vinylphenyl)methane, 1,2-bis(4-vinylphenyl)ethane, 1,4-diisopropenylbenzene, 1,2-bis(4-vinylphenyl)-1,2-ethanediol, 1,3-bis-methacryloyloxy-benzene, 1,4-phenylene dimethacrylate, bisphenol A dimethacrylate, bisphenol A glycerolate dimethacrylate, 2,5-bis{[2-(methacryloyloxy)ethoxy]carbonyl}terephthalic acid, 4-(methacryloyloxy)styrene, 2-[2-(benzyloxy)ethoxy]ethyl acrylate; 2-[2-(benzyloxy)ethoxy]ethyl methacrylate, and combinations thereof.

[0090] In a preferred embodiment, the crosslinked polymeric material of the insert comprises repeating units of: (1) polydiorganosiloxane segments comprising aryl-containing siloxane units, each having an organic substituent having up to 45 carbon atoms and at least one aryl moiety (preferably linked to a silicon atom via a linking group having at least two, more preferably three, carbon atoms); and (2) a high RI polydiorganosiloxane vinyl crosslinker comprising an ethylenically unsaturated group (preferably a (meth)acryloyl group).

[0091] In a preferred embodiment, the polydiorganosiloxane segments of the high RI polydiorganosiloxane vinyl crosslinker comprise at least 30 mol % (preferably at least 40 mol %, more preferably at least 50 mol %, even more preferably at least 60 mol %, and especially preferably at least 70 mol %) of aryl-containing siloxane units.

[0092] In another preferred embodiment, the high RI polydiorganosiloxane vinyl crosslinker can have a number average molecular weight of at least 1000 Daltons (preferably 1500 Daltons to 100,000 Daltons, more preferably 2,000 to 80,000 Daltons, and even more preferably 2,500 to 60,000 Daltons).

[0093] According to the present invention, the high RI polydiorganosiloxane vinyl crosslinker is preferably defined by formula (1): [ka] (In the formula: υ1 is an integer of 1 to 400 (preferably 3 to 350, more preferably 5 to 300, and even more preferably 10 to 250); ω1 is an integer of 1 to 800 (preferably 5 to 700, more preferably 10 to 600, and even more preferably 15 to 500); E1 is [ka] is a monovalent radical of; R0 is hydrogen or methyl; a1 is zero or 1; X0 is O or NR N1 and; R N1 is hydrogen or C1-C6 alkyl; L0 is a C2-C8 alkylene divalent radical or -L0'-X1-L0''-, [ka] is a divalent radical of; L0' is a C2-C8 alkylene divalent radical; L0″ is a C3-C8 alkylene divalent radical; X1 is -O-, -NR N1 -, -NHCOO-, -OCONH-, -CONR N1 -or-NRN1 CO-; q1 is an integer from 1 to 10; AR is an aryl radical; L AR teeth, [ka] is a divalent radical of; L e -CH2-CH2-, -CH2-CHR0-R1-, -CH2-CHR0-R1-O-, -CH2-CHR0-R1-O-R2-, -C3H6-O-R2-, -C3H6-O-R2-O-, [ka] is a divalent radical of; a2 is zero, one, or two; a3 is zero or one; R1 is a linear or branched C1-C alkyl group optionally substituted with a C1-C4 alkoxy group, a hydroxyl group, a carboxyl group, an amino group, an oxo group, or a combination thereof. 10 is an alkylene divalent radical; R2 is a linear or branched C3-C 10 is an alkylene divalent radical, R3 is a direct bond or a linear or branched C1-C4 alkylene divalent radical; X AR and each X2 independently represents a covalent bond, or -O-, -S-, [ka] , -NR N2 -, -NHCOO-, -OCONH-, -NHCONR N2 -, -NR N2 CONH-, [ka] , -CONRN2 -, -NR N2 CO-, [ka] , -NHCOS-, -SCONH-, -COO-, or -OCO- covalent bond; R N2 is hydrogen, linear or branched C1-C6 alkyl, cyclohexyl, cyclopentyl, substituted or unsubstituted phenyl, or substituted or unsubstituted phenyl-C1-C6 alkyl; Each L x are independently linear or branched C1-C alkyl groups which may optionally carry one or more hydroxyl or C1-C4 alkoxy or C1-C4 acylamino groups; 10 alkenylene divalent radical, -CH2-CHOH-CH2-O-R4-O-CH2-CHOH-CH2-; [ka] or a divalent radical obtained by removing two hydrogen atoms from two different atoms of a hydrocarbon having up to 20 carbon atoms, optionally bearing one or more hydroxyl or 1-C4 alkoxy groups, and comprising at least one divalent radical selected from the group consisting of a cycloalkylene radical, a substituted cycloalkylene radical, a phenylene radical, a substituted phenylene radical, a cycloheteroalkylene radical, and a substituted cycloheteroalkylene radical; Each R4, R5 and R6, independently of one another, is a linear or branched C1-C hydroxyl group having zero or one hydroxyl group. 10 (an alkylene divalent radical).

[0094] In a preferred embodiment, in formula (1), a1 is zero, and then E1 is [ka] is a monovalent radical.

[0095] In another preferred embodiment, ω1 / (υ1+ω1) is about 0.30 to about 0.95 (preferably about 0.40 to about 0.90, more preferably about 0.50 to about 0.90, and even more preferably about 0.60 to about 0.85).

[0096] In another preferred embodiment, AR is a phenyl group, a substituted phenyl group, a naphthyl group, a substituted naphthyl group, an anthracenyl group, a substituted anthracenyl group, a phenanthryl group, or a substituted phenanthryl group.

[0097] In another preferred embodiment, AR is [ka] where R7, R8, R9, R 10 , R 11 , R 12 , and R 13 are each independently H, Cl, Br, F, CF3, CCl3, C1-C5 alkyl, C1-C5 alkoxy, C2-C5 acyloxy, OH, phenyl, phenoxy, benzyloxy, phenylcarbonyl, phenoxycarbonyl, phenylcarboxy (phenylcarbonyloxy), or naphthyl.

[0098] The polydiorganosiloxane vinyl crosslinker of formula (1) can be prepared in a two-step process as follows: In the first step, a hydrosiloxane-containing polydiorganosiloxane of formula (2) is obtained according to any known procedure. [ka] (where E1, υ1, and ω1 are as defined above for Formula (1).) For example, the hydrosiloxane-containing polydiorganosiloxane of Formula (2) can be prepared by polymerizing a mixture of octamethylcyclotetrasiloxane (D4) and 1,3,5,7-tetramethylcyclotetrasiloxane (H4) in the presence of a catalyst and in the presence of a 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. 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 tetramethyldisiloxanes can be prepared from 1,3-bis(hydroxyalkyl)tetramethyldisiloxanes (e.g., 1,3-bis(hydroxypropyl)tetramethyldisiloxane) or 1,3-bis(aminoalkyl)tetramethyldisiloxanes (e.g., 1,3-bis(aminopropyl)tetramethyldisiloxane), for example, by reacting one of these with (meth)acryloyl chloride or vinyl isocyanate (or isopropenyl isocyanate).

[0099] In a second step, the hydrosiloxane-containing polydiorganosiloxane of formula (2) can be reacted with an aryl-containing ene monomer (i.e., an ene monomer containing a phenyl group, a substituted phenyl group, a naphthyl group, or a substituted naphthyl group) in a platinum-catalyzed hydrosilylation reaction known to those skilled in the art to form a polydiorganosiloxane vinyl crosslinker of formula (1).

[0100] Any aryl-containing ene monomer can be used in preparing the polydiorganosiloxane vinyl crosslinker of formula (1), so long as the aryl-containing ene monomer contains a phenyl group, a substituted phenyl group, a naphthyl group, a substituted naphthyl group, an anthracenyl group, a substituted anthracenyl group, a phenanthryl group, or a substituted phenanthryl group. Various aryl-containing ene monomers are described above, and they can be obtained from commercial sources or prepared according to known methods.

[0101] In another preferred embodiment, the crosslinked polymeric material of the insert comprises repeat units of at least one silicone-containing vinyl monomer (any of those described hereinafter in this application) and / or at least one silicone-containing vinyl crosslinker (a high RI polysiloxane vinyl crosslinker described above and / or any of those described hereinafter in this application).

[0102] According to the present invention, the crosslinked polymeric material of the insert may further comprise: (a) repeating units of at least one hydrophobic non-silicone vinyl monomer (any of those described hereinafter in this application); (b) repeating units of at least one non-silicone vinyl crosslinker other than an aryl-based vinyl crosslinker (any of those described hereinafter in this application); (c) repeating units of at least one polymerizable material selected from the group consisting of UV-absorbing vinyl monomers (any of those described hereinafter in this application), UV / high-energy-ultraviolet light ("HEVL") absorbing vinyl monomers (any of those described hereinafter in this application), polymerizable photochromic compounds (any of those described hereinafter in this application), polymerizable colorants (polymerizable dyes) (any of those known to those skilled in the art), and combinations thereof; or (d) combinations thereof.

[0103] According to another embodiment of the present invention, a silicone hydrogel bulk material comprises (1) repeating units of at least one silicone-containing polymerizable component comprising at least 0.5 meq / g of an H-bond donor, and (2) repeating units of at least one hydrophilic vinyl monomer. The silicone-containing polymerizable component may be a first silicone-containing vinyl monomer, a first silicone-containing vinyl crosslinker, or both. The silicone-containing component of the silicone hydrogel bulk material is located at the interface between the insert and the silicone hydrogel bulk material, and it is believed that the hydrophobic-hydrophobic interactions and hydrogen bonds formed between the insert (H-bond acceptor, such as an acrylic group) and the silicone hydrogel (H-bond donor) at the interface can be strong enough to enhance the delamination resistance of implantable silicone hydrogel contact lenses.

[0104] In a preferred embodiment, the silicone-containing polymerizable component comprising at least 0.5 meq / g of H-bond donor is a first silicone-containing vinyl monomer.

[0105] Any silicone-containing vinyl monomer can be used in the present invention as the first silicone-containing vinyl monomer, so long as it contains at least about 0.5 meq / g of H-bond donor. Examples of such silicone-containing vinyl monomers include, but are not limited to, [3-(meth)acryloxy-2-hydroxypropyloxy]propylbis(trimethylsiloxy)methylsilane, [3-(meth)acryloxy-2-hydroxypropyloxy]propylbis(trimethylsiloxy)butylsilane, 3-(meth)acryloxy-2-(2-hydroxyethoxy)-propyloxy)propylbis(trimethylsiloxy)methylsilane, 3-(meth)acryloxy-2-hydroxypropyloxy)propyltris(trimethylsiloxy)silane, N-[tris(trimethylsiloxy)silylpropyl]-(meth)acrylamide, N-(2-hydroxy-3-(3-(bis(trimethylsilyloxy)methylsilyl)propyloxy)propyl)-2-methyl(meth)acrylamide, N-(2-hydroxy-3-(3-(bis(trimethylsilyloxy)methylsilyl)propyloxy)-propyl)(meth)acrylamide, N-(2-hydroxy-3-(3-( Tris(trimethylsilyloxy)silyl)propyloxy)propyl)-2-methylacrylamide, N-(2-hydroxy-3-(3-(tris(trimethylsilyloxy)silyl)propyloxy)propyl)(meth)acrylamide, N-[tris(dimethylpropylsiloxy)silylpropyl]-(meth)acrylamide, N-[tris(dimethylphenylsiloxy)-silylpropyl](meth)acrylamide, N-[tris(dimethylethylsiloxy)-silylpropyl](meth)acrylamide N,N-bis[2-hydroxy-3-(3-(bis(trimethylsilyloxy)methylsilyl)-propyloxy)propyl]-2-methyl(meth)acrylamide, N,N-bis[2-hydroxy-3-(3-(bis(trimethylsilyloxy)methylsilyl)propyloxy)-propyl](meth)acrylamide, N,N-bis[2-hydroxy-3-(3-(tris(trimethylsilyloxy)silyl)propyloxy)-propyl]-2-methyl(meth)acrylamide, N,N-bis[2-hydroxy-3-(3-(tris(trimethylsilyloxy)silyl)-propyloxy)propyl](meth)acrylamide, N-[2-hydroxy-3-(3-(t-butyldimethylsilyl)propyloxy)propyl]-2-methyl(meth)acrylamide, N-[2-hydroxy-3-(3-(t-butyldimethylsilyl)propyloxy)propyl](meth)acrylamide, N,N-bis[2-hydroxy-3-(3-(t-butyldimethylsilyl)propyloxy)propyl]-2-methyl(meth)acrylamide allyl amide, N-2-(meth)acryloxyethyl-O-(methyl-bis-trimethylsiloxy-3-propyl)silyl carbamate, 3-[tris(trimethylsiloxy)silyl]propyl vinyl carbamate, 3-[tris(trimethylsiloxy)silyl]propyl allyl carbamate, α-(meth)acryloxy terminated ω-C1-C6-hydroxyalkyl terminated polydimethylsiloxane having a number average molecular weight of 2000 daltons or less, α-(meth)acrylamide terminated ω-C1-C6-hydroxyalkyl terminated polydimethylsiloxane having a number average molecular weight of 2000 daltons or less, 6-Hydroxyalkyl-terminated polydimethylsiloxane, α-(meth)acryloxy-2-hydroxypropyloxypropyl-terminated ω-C1-C4-alkyl-terminated polydimethylsiloxane having a number average molecular weight of 2000 Daltons or less, α-(2-hydroxyl-methacryloxypropyloxypropyl)-ω-C1-C4-alkyl-decamethylpentasiloxane, α-[3-(meth)acryloxyethoxy-2-hydroxypropyloxypropyl]-terminated ω-C1-C4-alkyl-terminated polydimethylsiloxane having a number average molecular weight of 2000 Daltons or less siloxane, α-[3-(meth)acryloxy-propyloxy-2-hydroxypropyloxypropyl]-terminated ω-C1-C4-alkyl terminated polydimethylsiloxane having a number average molecular weight of 2000 Daltons or less, α-[3-(meth)acryloxyisopropyloxy-2-hydroxypropyloxypropyl]-terminated ω-C1-C4-alkyl terminated polydimethylsiloxane having a number average molecular weight of 2000 Daltons or less, α-[3-(meth)acryloxybutyloxy-2-hydroxypropyloxypropyl]-terminated ω-C1-C4-alkyl terminated polydimethylsiloxane having a number average molecular weight of 2000 Daltons or less, α-[3-(meth)acryloxyethylamino-2-hydroxypropyloxypropyl]-terminated ω-C1-C4-alkyl terminated polydimethylsiloxane having a number average molecular weight of 2000 Daltons or less, α-[3-(meth)acryloxypropylamino-2-hydroxypropyloxypropyl]-terminated ω-C1-C4-alkyl terminated polydimethylsiloxane having a number average molecular weight of 2000 Daltons or less, α-[3-(meth)acryloxypropylamino-2-hydroxypropyloxypropyl]-terminated ω-C1-C4-alkyl terminated polydimethylsiloxane having a number average molecular weight of 2000 Daltons or less, α-[3-( [meth)acryloxy-butylamino-2-hydroxypropyloxypropyl]-terminated ω-C1-C4-alkyl-terminated polydimethylsiloxane, [alpha]-(meth)acryloxy(polyethyleneoxy)-2-hydroxypropyloxypropyl]-terminated ω-C1-C4-alkyl-terminated polydimethylsiloxane having a number average molecular weight of 2000 daltons or less, [alpha]-[(meth)acryloxy-2-hydroxypropyloxy-ethoxypropyl]-terminated ω-C1-C4-alkyl-terminated polydimethylsiloxane having a number average molecular weight of 2000 daltons or less,α-[(meth)acryloxy-2-hydroxypropyl-N-ethylaminopropyl]-terminated ω-C1-C4-alkyl terminated polydimethylsiloxane having a number average molecular weight of 2000 Daltons or less, α-[(meth)acryloxy-2-hydroxypropyl-aminopropyl]-terminated ω-C1-C4-alkyl terminated polydimethylsiloxane having a number average molecular weight of 2000 Daltons or less, α-[(meth)acryloxy-2-hydroxypropyloxy-(polyethyleneoxy)propyl]-terminated ω-C1-C4-alkyl terminated polydimethylsiloxane having a number average molecular weight of 2000 Daltons or less, 1-C4-Alkyl terminated polydimethylsiloxane, α-(meth)acrylamidopropyloxypropyl terminated ω-C1-C4-Alkyl terminated polydimethylsiloxane having a number average molecular weight of 2000 Daltons or less, α-[3-(meth)acrylamidoethoxy-2-hydroxypropyloxypropyl]-terminated ω-C1-C4-Alkyl polydimethylsiloxane having a number average molecular weight of 2000 Daltons or less, α-[3-(meth)acrylamidopropyloxy-2-hydroxypropyloxypropyl]-terminated ω-C1-C4-Alkyl polydimethylsiloxane having a number average molecular weight of 2000 Daltons or less ]-terminated ω-C1-C4-alkyl terminated polydimethylsiloxane, α-[3-(meth)acrylamidoisopropyloxy-2-hydroxypropyloxypropyl]-terminated ω-C1-C4-alkyl terminated polydimethylsiloxane having a number average molecular weight of 2000 or less, α-[3-(meth)acrylamidobutyloxy-2-hydroxypropyloxypropyl]-terminated ω-C1-C4-alkyl terminated polydimethylsiloxane having a number average molecular weight of 2000 or less, α-[3-(meth)acrylamidobutyloxy-2-hydroxypropyloxypropyl]-terminated ω-C1-C4-alkyl terminated polydimethylsiloxane having a number average molecular weight of 2000 or less, acrylamide-2-hydroxypropyloxypropyl]-terminated ω-C1 to C4-alkyl polydimethylsiloxane, α-[3-[N-methyl-(meth)acrylamido]-2-hydroxypropyloxypropyl]-terminated ω-C1 to C4-alkyl polydimethylsiloxane having a number average molecular weight of 2000 daltons or less, N-(2,3-dihydroxypropane)-N'-(propyltetra(dimethylsiloxy)-dimethylbutylsilane)(meth)acrylamide, (meth)acrylamidopropyltetra(dimethylsiloxy)dimethylbutylsilane,Examples include α-vinyl carbonate-terminated ω-C1-C4-alkyl-terminated polydimethylsiloxane, α-vinyl carbamate-terminated ω-C1-C4-alkyl-terminated polydimethylsiloxane, and combinations thereof. Preferably, the first silicone-containing vinyl monomer is one of those described above and contains one or more hydroxyl groups.

[0106] In another preferred embodiment, the silicone-containing polymerizable component comprising at least 0.5 meq / g of H-bond donor is a first polysiloxane vinyl crosslinker.

[0107] According to the present invention, any polysiloxane vinyl crosslinker can be used as the first polysiloxane vinyl crosslinker in the present invention, so long as it contains at least about 0.5 meq / g of H-bond donor. Examples of such polysiloxane vinyl crosslinkers are di-(meth)acrylamide terminated polysiloxane vinyl crosslinkers having a number average molecular weight of 4000 daltons or less, α,ω-bis[3-(meth)acryloxy-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxanes having a number average molecular weight of 4000 daltons or less, α,ω-bis[3-(meth)acryloxyethoxy-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxanes having a number average molecular weight of 4000 daltons or less, α,ω-bis[3-(meth)acryloxypropyloxy-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxanes having a number average molecular weight of 4000 daltons or less, α,ω-bis[3-(meth)acryloxy-isopropyloxy-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxanes having a number average molecular weight of 4000 daltons or less, α,ω-bis[3-(meth)acrylamideethoxy-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane having a number average molecular weight of 8000 daltons or less, α,ω-bis[3-(meth)acrylamidepropyloxy-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane having a number average molecular weight of 8000 daltons or less, α,ω-bis[3-(meth)acrylamidepropyloxy-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane having a number average molecular weight of 8000 daltons or less, α,ω-bis[3-(meth)acrylamideisopropyloxy-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane having a number average molecular weight of 4000 daltons or less, α,ω-bis[3-(meth)acrylamidebutyloxy]-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane having a number average molecular weight of 8000 daltons or less, α,ω-bis[3-(meth)acrylamidebutyloxy]-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane having a number average molecular weight of 8000 daltons or less,ω-bis[3-(meth)acryloxyethylamino-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acryloxypropylamino-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane having a number average molecular weight of 8000 daltons or less, α,ω-bis[3-(meth)acryloxybutylamino-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane having a number average molecular weight of 8000 daltons or less, α,ω-bis[(meth)acrylamidoethylamino-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane having a number average molecular weight of 12000 daltons or less, α,ω-bis[3-(meth)acrylamidopropylamino-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane having a number average molecular weight of 4000 daltons or less, α,ω-bis[3-(meth)acrylamidobutylamino-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane having a number average molecular weight of 4000 daltons or less [(meth)acryloxypropyl]-terminated polydimethylsiloxanes having a number average molecular weight of 4000 daltons or less, α,ω-bis[(meth)acryloxy-2-hydroxypropyl-N-ethylaminopropyl]-terminated polydimethylsiloxanes having a number average molecular weight of 12000 daltons or less, α,ω-bis[(meth)acryloxy-2-hydroxypropyl-aminopropyl]-polydimethylsiloxanes having a number average molecular weight of 8000 daltons or less, α,ω-bis[(meth)acryloxy-2-hydroxypropyl-(polyethyleneoxy)propyl]-terminated polydimethylsiloxanes having a number average molecular weight of 4000 daltons or less, α,ω-bis[(meth)acryloxyethyl-amino-carbonyloxy-ethoxypropyl]-terminated polydimethylsiloxanes having a number average molecular weight of 4000 daltons or less, α,ω-bis[(meth)acryloxyethyl-amino-carbonyloxy-ethoxypropyl]-terminated polydimethylsiloxanes having a number average molecular weight of 4000 daltons or less, α,ω-bis[(meth)acryloxyethyl-amino-carbonyloxy-ethoxypropyl]-terminated polydimethylsiloxanes having a number average molecular weight of 4000 daltons or less,ω-bis[(meth)acryloxyethylamino-carbonyloxy-(polyethyleneoxy)propyl]-terminated polydimethylsiloxane; di-(meth)acryloyloxy-terminated or di-(meth)acrylamide-terminated chain extended polysiloxane vinyl crosslinkers, each of which contains at least two polysiloxane segments and a bond between each pair of polysiloxane segments and between one (meth)acryloyloxy group and one polysiloxane segment, each bond having at least one H-bond donor; polysiloxane vinyl crosslinkers having dimethylsiloxane units and hydrophilized siloxane units, each of which contains one monovalent C4-C hydroxyl group having one methyl substituent and at least one H-bond donor (preferably 2-6 hydroxyl groups); 40 those having organic radical substituents (e.g., polysiloxane vinyl crosslinkers of formula (G), which are described later in this specification and can be prepared according to the procedures disclosed in U.S. Pat. No. 10,081,697), as well as combinations thereof. Preferably, the first polysiloxane vinyl crosslinker contains at least two urethane linkages (-O-CO-NH-), at least two urea linkages (-NH-CO-NH-), at least two hydroxyl groups, or a combination thereof.

[0108] Any hydrophilic vinyl monomer can be used in the present invention. Examples of preferred hydrophilic vinyl monomers are alkyl(meth)acrylamides (as described later in this application), hydroxyl-containing acrylic monomers (as described below), amino-containing acrylic monomers (as described later in this application), carboxyl-containing acrylic monomers (as described later in this application), N-vinylamide monomers (as described later in this application), methylene-containing pyrrolidone monomers (i.e., pyrrolidone derivatives each having a methylene group attached to the pyrrolidone ring at the 3- or 5-position) (as described later in this application), acrylic monomers having a C1-C4 alkoxyethoxy group (as described later in this application), vinyl ether monomers (as described later in this application), allyl ether monomers (as described later in this application), phosphorylcholine-containing vinyl monomers (as described later in this application), N-2-hydroxyethyl vinyl carbamate, N-carboxyvinyl-β-alanine (VINAL), N-carboxyvinyl-α-alanine, and combinations thereof.

[0109] Examples of alkyl(meth)acrylamides include, but are not limited to, (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.

[0110] Examples of hydroxyl-containing acrylic monomers include, but are not limited to, N-2-hydroxylethyl(meth)acrylamide, N,N-bis(hydroxyethyl)(meth)acrylamide, N-3-hydroxypropyl(meth)acrylamide, N-2-hydroxypropyl(meth)acrylamide, N-2,3-dihydroxypropyl(meth)acrylamide, N-tris(hydroxymethyl)methyl(meth)acrylamide, 2-hydroxyethyl(meth)acrylate, 3-hydroxypropyl(meth)acrylate, 2-hydroxypropyl(meth)acrylate, glycerol methacrylate (GMA), di(ethylene glycol)(meth)acrylate, tri(ethylene glycol)(meth)acrylate, tetra(ethylene glycol)(meth)acrylate, poly(ethylene glycol)(meth)acrylate having a number average molecular weight of up to 1500, poly(ethylene glycol)ethyl(meth)acrylamide having a number average molecular weight of up to 1500, and combinations thereof.

[0111] Examples of carboxyl-containing acrylic monomers include, but are not limited to, 2-(meth)acrylamidoglycolic acid, (meth)acrylic acid, ethylacrylic acid, 3-(meth)acrylamido-propionic 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.

[0112] Examples of amino-containing acrylic monomers include, but are not limited to, 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.

[0113] Examples of N-vinylamide monomers include, but are not limited to, 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, and 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 mixtures thereof.

[0114] Examples of methylene-containing pyrrolidone monomers include, but are not limited to, 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.

[0115] Examples of acrylic monomers having a C1-C4 alkoxyethoxy group include, but are not limited to, ethylene glycol methyl ether (meth)acrylate, di(ethylene glycol) methyl ether (meth)acrylate, tri(ethylene glycol) methyl ether (meth)acrylate, tetra(ethylene glycol) methyl ether (meth)acrylate, C1-C4-alkoxypoly(ethylene glycol) (meth)acrylate having a number average molecular weight of up to 1500, methoxy-poly(ethylene glycol)ethyl (meth)acrylamide having a number average molecular weight of up to 1500, and combinations thereof.

[0116] Examples of vinyl ether monomers include, but are not limited to, 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.

[0117] Examples of allyl ether monomers include, but are not limited to, 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.

[0118] Examples of phosphorylcholine-containing vinyl monomers include, but are not limited to, (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-(vinyloxycarbonyl)ethyl-2'-(trimethylammonio)ethyl phosphate, 2-(allyloxycarbonyl)ethyl-2'-(trimethylammonio)ethyl phosphate, 2-(vinylcarbonylamino)ethyl-2'-(trimethylammonio)ethyl phosphate, 2-(allyloxycarbonylamino)ethyl-2'-(trimethylammonio)ethyl phosphate, 2-(butenoyloxy)ethyl-2'-(trimethylammonio)ethyl phosphate,and combinations thereof.

[0119] According to the present invention, the silicone hydrogel bulk material may further comprise repeat units of at least one second silicone-containing vinyl monomer (other than the first silicone-containing vinyl monomer) and / or second polysiloxane vinyl crosslinker (other than the first polysiloxane vinyl crosslinker); repeat units of at least one hydrophobic non-silicone vinyl monomer; repeat units of at least one non-silicone vinyl crosslinker (any of those described hereinafter in this application); repeat units of at least one polymerizable material selected from the group consisting of UV-absorbing vinyl monomers (any of those described hereinafter in this application), UV / high-energy ultraviolet light ("HEVL")-absorbing vinyl monomers (any of those described hereinafter in this application), polymerizable photochromic compounds (any of those described hereinafter in this application), polymerizable colorants (polymerizable dyes) (any of those known to those skilled in the art), and combinations thereof; or combinations thereof.

[0120] According to the present invention, the second silicone-containing vinyl monomer can be any known silicone-containing vinyl monomer other than the first silicone-containing vinyl monomer, and may or may not contain an H-bond donor. Examples of preferred silicone-containing vinyl monomers include, but are not limited to, vinyl monomers each having a bis(trialkylsilyloxy)alkylsilyl group or a tris(trialkylsilyloxy)silyl group, polysiloxane vinyl monomer, 3-methacryloxypropylpentamethyldisiloxane, t-butyldimethylsiloxyethyl vinyl carbonate, trimethylsilylethyl vinyl carbonate, and trimethylsilylmethyl vinyl carbonate, and combinations thereof. Polysiloxane vinyl monomers can be obtained from commercial sources (e.g., Shin-Etsu Chemical Co., Ltd., Gelest, etc.) or can be prepared according to procedures described, for example, in U.S. Pat. Nos. 5,070,215, 6,166,236, 6,867,245, 8,415,405, 8,475,529, 8,614,261, and 9,217,813. Preferred silicon-containing vinyl monomers having bis(trialkylsilyloxy)alkylsilyl or tris(trialkylsilyloxy)silyl groups, respectively, can be obtained from commercial sources (e.g., Shin-Etsu Chemical Co., Ltd., Gelest, etc.) or can be prepared according to the procedures described in U.S. Pat. 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.

[0121] According to the present invention, the second silicone-containing vinyl crosslinker can be any known silicone-containing vinyl crosslinker other than the first silicone-containing vinyl crosslinker, and may or may not contain an H-bond donor.Examples of preferred polysiloxane vinyl crosslinkers are polysiloxanes selected from the group consisting of 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; Macromer A, Macromer B, Macromer C, and Macromer D described in U.S. Pat. No. 5,760,100. Siloxane-containing macromers; U.S. Pat. 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, and 4,703,097 Specification, Specification No. 4833218, Specification No. 4837289, Specification No. 4954586, Specification No. 4954587, Specification No. 5010141, Specification No. 5034461, Specification No. 5070170, Specification No. 5079319, Specification No. 5 Specification No. 039761, Specification No. 5346946, Specification No. 5358995, Specification No. 5387632, Specification No. 5416132, Specification No. 5451617, Specification No. 5486579, Specification No. 5962548, Specification No. 5981675 polysiloxane-containing macromers disclosed in U.S. Patent Nos. 4,259,467, 4,260,725, and 4,261,875; di-(meth)acryloyloxy-terminated polysiloxane vinyl crosslinkers each having dimethylsiloxane units and hydrophilized siloxane units, wherein the hydrophilized siloxane unit is one monovalent C4-C hydroxyl group having one methyl substituent and two to six hydroxyl groups. 40di-(meth)acryloyloxy-terminated polysiloxane vinyl crosslinkers (which can be synthesized according to the procedures disclosed in U.S. Pat. No. 1,008,1697), each having an organic radical substituent; prepared by reacting glycidyl (meth)acrylate (meth)acryloyl chloride with a diamino-terminated polydimethylsiloxane or a dihydroxyl-terminated polydimethylsiloxane, or by reacting isocyanatoethyl (meth)acrylate with a dihydroxyl-terminated polydimethylsiloxane, or by reacting an amino-containing acrylic monomer with a dicarboxyl-terminated polydimethylsiloxane in the presence of a coupling agent (carbodiimide), or by reacting a carboxyl-containing acrylic monomer with a diamino-terminated polydimethylsiloxane in the presence of a coupling agent (carbodiimide), or by reacting a diisocyanate or diepoxy coupling agent. vinyl crosslinkers, each containing one unique polysiloxane segment and two terminal (meth)acryloyl groups, prepared by reacting a hydroxyl-containing acrylic monomer with a dihydroxy-terminated polydisiloxane in the presence of a crosslinking agent (these are available from commercial sources); at least two polydiorganosiloxanes, each connected by a linking group between each pair of polydiorganosiloxane segments and the two terminal ethylenically unsaturated groups; and a chain-extended polysiloxane vinyl crosslinker having siloxane segments (which can be prepared according to the procedures described in U.S. Pat. Nos. 5,034,461, 5,416,132, 5,449,729, 5,760,100, 7,423,074, 8,529,057, 8,835,525, 8,993,651, 10,301,451, and 10,465,047).

[0122] Preferred examples of the hydrophobic non-silicone vinyl monomer include non-silicone hydrophobic acrylic monomers (such as the following methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isobornyl (meth)acrylate, and (meth)acrylonitrile), fluorine-containing acrylic monomers (such as perfluorohexylethyl-thio-carbonyl-aminoethyl-methacrylate, perfluoro-substituted C2-C 12 alkyl(meth)acrylates, etc.), vinyl alkanoates (e.g., vinyl acetate, vinyl propionate, vinyl butyrate, vinyl valerate, etc.), vinyloxyalkanes (e.g., vinyl ethyl ether, propyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, cyclohexyl vinyl ether, t-butyl vinyl ether, etc.), styrene, vinyl toluene, vinyl chloride, vinylidene chloride, 1-butene, and combinations thereof.

[0123] Any suitable perfluoro-substituted -C2-C 12 Alkyl (meth)acrylates can also be used in the present invention. Perfluoro-substituted-C2-C 12 Examples of alkyl (meth)acrylates include, but are not limited to, 2,2,2-trifluoroethyl (meth)acrylate, tetrafluoropropyl (meth)acrylate, hexafluoro-iso-propyl (meth)acrylate, hexafluorobutyl (meth)acrylate, heptafluorobutyl (meth)acrylate, octafluoropentyl (meth)acrylate, heptadecafluorodecyl (meth)acrylate, pentafluorophenyl (meth)acrylate, and combinations thereof.

[0124] Examples of preferred non-silicone vinyl crosslinkers (containing no aryl groups) include, but are not limited to, the acrylic crosslinkers described below, allyl methacrylate, allyl acrylate, triallyl isocyanurate, 2,4,6-triallyloxy-1,3,5-triazine, 1,2,4-trivinylcyclohexane, or combinations thereof.

[0125] Examples of acrylic crosslinkers include, but are not limited to, ethylene glycol dimethacrylate; ethylene glycol diacrylate; 1,3-propanediol diacrylate; 1,3-propanediol dimethacrylate; 2,3-propanediol diacrylate; 2,3-propanediol dimethacrylate; 1,4-butanediol dimethacrylate; 1,4-butanediol diacrylate; 1,5-pentanediol dimethacrylate; 1,5-pentanediol diacrylate; 1,6-hexanediol dimethacrylate; 1,6-hexanediol diacrylate; diethylene glycol dimethacrylate; diethylene glycol diacrylate; triethylene glycol dimethacrylate; triethylene glycol diacrylate; tetraethylene glycol dimethacrylate; tetraethylene glycol diacrylate; N,N'-methylenebis(acrylamide); N,N'-methylenebis(methacrylamide); amide); N,N'-ethylenebis(acrylamide); N,N'-ethylenebis(methacrylamide); N,N'-hexamethylenebisacrylamide; N,N'-hexamethylenebismethacrylamide; pentaerythritol triacrylate, pentaerythritol trimethacrylate, trimethyloylpropane triacrylate, trimethyloylpropane trimethacrylate, tris(2-hydroxyethyl)isocyanurate triacrylate, tris(2-hydroxyethyl)isocyanurate trimethacrylate, 1,3,5-triacryloxylhexahydro-1,3,5-triazine, 1,3,5-trimethacryloxylhexahydro-1,3,5-triazine; pentaerythritol tetraacrylate; pentaerythritol tetramethacrylate, di(trimethyloylpropane)tetraacrylate, di(trimethyloylpropane)tetramethacrylate, or a combination thereof.

[0126] Any suitable UV-absorbing and UV / HEVL-absorbing vinyl monomers can be used in the polymerizable compositions to prepare the preformed SiHy contact lenses of the present invention. Examples of preferred UV-absorbing and UV / HEVL-absorbing vinyl monomers include, but are not limited to, 2-(2-hydroxy-5-vinylphenyl)-2H-benzotriazole, 2-(2-hydroxy-5-acryloyloxyphenyl)-2H-benzotriazole, 2-(2-hydroxy-3-methacrylamidomethyl-5-tert-octylphenyl)benzotriazole, 2-(2'-hydroxy-5'-methacrylamidophenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-5'-methacrylamidophenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-5'-methacrylamidophenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-5'-vinylphenyl)-2H- ... 2-(2'-hydroxy-5'-glycidoxypropyl-3'-t-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-5'-methacryloxypropylphenyl)benzotriazole, 2-hydroxy-5-methoxy-3-(5-(trifluoromethyl)-2H-benzo[d][1,2,3]triazol-2-yl)benzyl methacrylate (WL-1), 2-hydroxy -5-Methoxy-3-(5-methoxy-2H-benzo[d][1,2,3]triazol-2-yl)benzyl methacrylate (WL-5), 3-(5-fluoro-2H-benzo[d][1,2,3]triazol-2-yl)-2-hydroxy-5-methoxybenzyl methacrylate (WL-2), 3-(2H-benzo[d][1,2,3]triazol-2-yl)-2-hydroxy-5-methoxybenzyl methacrylate (WL-3), 3-(5-chloro-2H-benzo[d][1,2,3]triazol-2-yl)-2-hydroxy-5-methoxybenzyl methacrylate (WL-4), ]triazol-2-yl)-2-hydroxy-5-methoxybenzyl methacrylate (WL-4), 2-hydroxy-5-methoxy-3-(5-methyl-2H-benzo[d][1,2,3]triazol-2-yl)benzyl methacrylate (WL-6), 2-hydroxy-5-methyl-3-(5-(trifluoromethyl)-2H-benzo[d][1,2,3]triazol-2-yl)benzyl methacrylate (WL-7), 4-allyl-2-(5-chloro-2H-benzo[d][1,2,3]triazol-2-yl)-6-methoxyphenol (WL-8), 2{2'-hydroxy-3'-tert-5'[3"-(4"-vinylbenzyloxy)propoxy]phenyl}-5-methoxy-2H-benzotriazole, phenol, 2-(5-chloro-2H-benzotriazol-2-yl)-6-(1,1-dimethylethyl)-4-ethenyl-(UVAM), 2-[2'-hydroxy-5'-(2-methacryloxyethyl)phenyl)]-2H-benzotriazole (2-propenoic acid, 2-methyl-, 2-[3-(2H-benzotriazol-2-yl)-4-hydroxyphenyl]ethyl ester, Norbloc), 2{2'-hydroxy-3'-tert-butyl-5'-[3'-methacryloyloxypropoxy]phenyl}-2H-benzotriazole, 2{2'-hydroxy-3'-tert-butyl-5'-[3'- 2-{2'-hydroxy-3'-tert-butyl-5'-[3'-methacryloyloxypropoxy]phenyl}-5-methoxy-2H-benzotriazole (UV13), 2-{2'-hydroxy-3'-tert-butyl-5'-[3'-methacryloyloxypropoxy]phenyl}-5-chloro-2H-benzotriazole (UV28), 2[2'-hydroxy-3'-tert-butyl-5'-(3'-acryloyloxypropoxy)phenyl]-5-trifluoromethyl-2H-benzotriazole (UV23), 2-(2'-hydroxy-5-methacrylamidophenyl)-5 -Methoxybenzotriazole (UV6), 2-(3-allyl-2-hydroxy-5-methylphenyl)-2H-benzotriazole (UV9), 2-(2-hydroxy-3-methallyl-5-methylphenyl)-2H-benzotriazole (UV12), 2-3'-t-butyl-2'-hydroxy-5'-(3"-dimethylvinylsilylpropoxy)-2'-hydroxyphenyl)-5-methoxybenzotriazole (UV15), 2-(2'-hydroxy-5'-methacryloylpropyl-3'-tert-butylphenyl) -5-Methoxy-2H-benzotriazole (UV16), 2-(2'-hydroxy-5'-acryloylpropyl-3'-tert-butylphenyl)-5-methoxy-2H-benzotriazole (UV16A), 2-methylacrylic acid 3-[3-tert-butyl-5-(5-chlorobenzotriazol-2-yl)-4-hydroxyphenyl]-propyl ester (16-100, CAS#96478-15-8), 2-(3-(tert-butyl)-4-hydroxy-5-(5-methoxy-2H-benzo[d][1,2,Examples of suitable polymerizable compounds include 2-(5-chloro-2H-benzotriazol-2-yl)-6-methoxy-4-(2-propen-1-yl)ethyl methacrylate (16-102); phenol, 2-(5-chloro-2H-benzotriazol-2-yl)-6-methoxy-4-(2-propen-1-yl) (CAS# 1260141-20-5); 2-[2-hydroxy-5-[3-(methacryloyloxy)propyl]-3-tert-butylphenyl]-5-chloro-2H-benzotriazole; phenol, 2-(5-ethenyl-2H-benzotriazol-2-yl)-4-methyl-, homopolymer (9CI) (CAS# 83063-87-0). According to the present invention, the polymerizable composition contains from about 0.1% to about 3.0% by weight, preferably from about 0.2% to about 2.5% by weight, and more preferably from about 0.3% to about 2.0% by weight, of one or more UV-absorbing vinyl monomers, based on the total amount of polymerizable components in the polymerizable composition.

[0127] Examples of preferred polymerizable photochromic compounds include polymerizable naphthopyrans, polymerizable benzopyrans, polymerizable indenonaphthopyrans, polymerizable phenanthropyrans, polymerizable spiro(benzindoline)-naphthopyrans, polymerizable spiro(indoline)benzopyrans, polymerizable spiro(indoline)-naphthopyrans, polymerizable spiro(indoline)quinopurans, polymerizable spiro(indoline)-pyrans, polymerizable naphthoxazines, polymerizable spirobenzopyrans; polymerizable polymerizable spirobenzopyrans, polymerizable spirobenzothiopyrans, polymerizable naphthacenediones, polymerizable spirooxazines, polymerizable spiro(indoline)naphthoxazines, polymerizable spiro(indoline)pyridobenzoxazines, polymerizable spiro(benzindoline)pyridobenzoxazines, polymerizable spiro(benzindoline)naphthoxazines, polymerizable spiro(indoline)-benzoxazines, polymerizable diarylethenes, and combinations thereof. These are disclosed in U.S. Patent Nos. 4,929,693, 5,166,345, 6,017,121, 7,556,750, 7,584,630, 7,999,989, 8,158,037, 8,697,770, 8,741,188, 9,052,438, 9,097,916, 9,465,234, 9,904,074, 10,197,707, 6,019,914, 6,113,814, 6,149,841, 6,296,785 and 6,348,604.

[0128] In accordance with the present invention, the silicone hydrogel bulk material of an implantable silicone hydrogel contact lens has an equilibrium water content (i.e., in a fully hydrated state or when fully hydrated) of about 20% to about 70% by weight (preferably about 20% to about 65% by weight, more preferably about 25% to about 65% by weight, and even more preferably about 30% to about 60% by weight), an oxygen permeability of at least about 40 barrers (preferably at least about 60 barrers, more preferably at least about 80 barrers, and more preferably at least about 100 barrers), and a modulus of elasticity (i.e., Young's modulus) of about 1.5 MPa or less (preferably about 0.2 MPa to about 1.2 MPa, more preferably about 0.3 MPa to about 1.1 MPa, and even more preferably about 0.4 MPa to about 1.0 MPa).

[0129] According to the present invention, the insert or implantable silicone hydrogel (SiHy) contact lens of the present invention can be manufactured according to any lens manufacturing process. Those skilled in the art are very familiar with how to manufacture inserts or SiHy contact lenses. For example, inserts or implantable SiHy contact lenses can be manufactured in a conventional "rotomolding" process, as described in U.S. Pat. No. 3,408,429, or by a static full cast molding process, as described in U.S. Pat. Nos. 4,347,198, 5,508,317, 5,583,463, 5,789,464, and 5,849,810, or by lathe cutting of a button of polymeric material, as used to make customized contact lenses. In cast molding, a polymerizable composition (i.e., an insert formulation or SiHy lens formulation) is typically dispensed into a mold and cured (i.e., polymerized and / or crosslinked) in the mold by heat or actinic radiation to produce the insert or SiHy contact lens.

[0130] Lens molds for producing insert or SiHy contact lenses are well known to those skilled in the art and are used, for example, for cast molding or rotational molding. For example, a mold (for cast molding) generally includes at least two mold pieces (or portions) or mold halves, i.e., a first and a second mold half. The first mold half defines a first molding (or optical) surface, and the second mold half defines a second molding (or optical) surface. The first and second mold halves are configured to receive each other such that an insert molding or lens-forming cavity is formed between the first and second molding surfaces. The molding surface of the mold half is the cavity-forming surface of the mold and is in direct contact with the polymerizable composition.

[0131] Methods for manufacturing mold parts for casting contact lenses or inserts are generally well known to those skilled in the art. The process of the present invention is not limited to any particular method of forming a mold. In fact, any method of forming a mold can be used in the present invention. The first and second mold halves can be formed by a variety of techniques, such as injection molding or lathing. Examples of suitable processes for forming mold halves are disclosed in U.S. Patent Nos. 4,444,711, 4,460,534, 5,843,346, and 5,894,002.

[0132] Virtually any material known in the art for producing molds can be used to produce molds for making contact lenses or inserts. For example, polymeric 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) can be used. Other materials that can transmit UV light, such as quartz glass and sapphire, could also be used.

[0133] Numerous silicone hydrogel lens formulations have been described in numerous patents and patent applications published as of the filing date of this application and have been used in the manufacture of commercially available SiHy contact lenses. Examples of commercially available SiHy contact lenses include, but are not limited to, asmofilcon A, balafilcon A, confilcon A, derefilcon A, eflofilcon A, enfilcon A, funfilcon A, galyfilcon A, lotrafilcon A, lotrafilcon B, narafilcon A, narafilcon B, senofilcon A, senofilcon B, senofilcon C, sumafilcon A, somofilcon A, and stenfilcon A. These can be used directly as the lens-forming compositions of the present invention, or can be used to prepare the lens-forming compositions of the present invention by adding a silicon-containing polymerizable component having at least 0.5 meq / g of H-bond donor.

[0134] The lens-forming composition or insert-forming composition, as known to those skilled in the art, can be a solvent-free, clear liquid prepared by mixing all of the polymerizable components (or materials), at least one free-radical initiator (thermal or photoinitiator), and other necessary components (or materials), or it can be a solution prepared by dissolving all of the desired components (or materials) and at least one free-radical initiator 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 (any of the solvents described later in this application) that cannot participate in a free-radical polymerization reaction.

[0135] 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 cycloalkylnitriles), persulfates, percarbonates, or mixtures thereof.Examples of suitable 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)benzyl, 2,2-bis(tert-butylperoxy)butane, 1,1-bis(tert-butylperoxy)cyclo ...2,2-bis(tert-butylperoxy)butane, 2,2-bis(tert-butylperoxy)butane, 2,2-bis(tert-butylperoxy)butane, 2,2-bis(tert-butylperoxy)butane, 2,2-bis(tert-butylperoxy)butane, 2,2-bis(tert-butylperoxy)butane 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).

[0136] Suitable photoinitiators include benzoin methyl ether, diethoxyacetophenone, benzoylphosphine oxide, 1-hydroxycyclohexylphenyl ketone, and Darocur and Irgacur types, preferably Darocur 1173® and Darocur 2959®, and germanium-based Norrish Type I photoinitiators (e.g., those described in U.S. Pat. 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. Reactive photoinitiators, which can be incorporated into macromers or used as special monomers, are also suitable. Examples of reactive photoinitiators are those disclosed in EP 632329. Preferably, the SiHy lens formulation for making SiHy contact lenses includes at least one photoinitiator capable of being initiated by visible light, such as a benzoylphosphine oxide photoinitiator, a germanium-based Norrish Type I photoinitiator, or a combination thereof.

[0137] Solventless SiHy lens formulations (silicone hydrogel-lens-forming compositions) typically include 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.

[0138] Examples of suitable solvents include acetone, methanol, cyclohexane, 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 ethylene 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 exonorborneol, 2-pentanol, 3-pentanol, 2-hexanol, 3-hexanol, 3-methyl-2-butanol, 2-heptanol, 2-octanol, 2-nonanol, 2-decanol, 3-octanol, norborneol, tert-butanol, tert-amyl alcohol, 2-methyl-2-pentanol, 2,3-dimethyl-2-butanol, 3-methyl-3-pentanol, 1-methylcyclohexanol, 2-methyl-2-hexanol, 3,7-Dimethyl-3-octanol, 1-chloro-2-methyl-2-propanol, 2-methyl-2-heptanol, 2-methyl-2-octanol, 2-2-methyl-2-nonanol, 2-methyl-2-decanol, 3-methyl-3-hexanol, 3-methyl-3-heptanol, 4-methyl-4-heptanol, 3-methyl-3-octanol, 4-methyl-4-octanol, 3-methyl-3-nonanol, 4-methyl-4-nonanol, 3-methyl-3-octanol, 3-ethyl-3-hexanol, 3-methyl-3-heptanol, 4-ethyl-4-heptanol, 4-propyl-4-heptanol, 4-isopropyl-4-heptanol, 2,4-dimethyl-2-pentanol, 1-methylcyclopentanol, 1-ethylcyclopentanol alcohol, 1-ethylcyclopentanol, 3-hydroxy-3-methyl-1-butene, 4-hydroxy-4-methyl-1-cyclopentanol, 2-phenyl-2-propanol, 2-methoxy-2-methyl-2-propanol, 2,3,4-trimethyl-3-pentanol, 3,7-dimethyl-3-octanol, 2-phenyl-2-butanol, 2-methyl-1-phenyl-2-propanol and 3-ethyl-3-pentanol, 1-ethoxy-2-propanol, 1-methyl-2-propanol, t-amyl alcohol, isopropanol, 1-methyl-2-pyrrolidone, N,N-dimethylpropionamide, dimethylformamide, dimethylacetamide, dimethylpropionamide, N-methylpyrrolidone, and mixtures thereof. More preferred organic solvents include, but are not limited to, methanol, ethanol, 1-propanol, isopropanol, sec-butanol, tert-butyl alcohol, tert-amyl alcohol, acetone, methyl ethyl ketone, methyl isopropyl ketone, methyl propyl ketone, ethyl acetate, heptane, methylhexane (various isomers), methylcyclohexane, dimethylcyclopentane (various isomers), 2,2,4-trimethylpentane, and mixtures thereof.

[0139] In accordance with the present invention, the polymerizable composition (insert formulation or SiHy lens formulation) can be introduced (discharged) into the cavity formed by the male and female mold halves according to any known method.

[0140] After the polymerizable composition is dispensed into the mold, it is polymerized to produce the SiHy contact lens. Crosslinking can be initiated by heat or actinic radiation, as known to those skilled in the art.

[0141] Thermal polymerization is conveniently carried out at temperatures of, for example, 25 to 120°C, preferably 40 to 100°C. The reaction time may vary within wide limits but is conveniently, for example, 1 to 24 hours, or preferably 2 to 12 hours. It is advantageous to previously degas the components and solvents used in the polymerization reaction and to carry out the copolymerization reaction under an inert atmosphere, for example under an atmosphere of nitrogen or argon.

[0142] Actinic polymerization can then be induced by actinic radiation, such as light, especially UV or visible light of a suitable wavelength. If necessary, the spectral requirements can be appropriately controlled by the addition of a suitable photosensitizer.

[0143] Opening the mold so that the molded insert or SiHy contact lens can be removed from the mold can be done in a manner known per se.

[0144] As an illustrative example, the implantable silicone hydrogel contact lens of the present invention can be prepared as follows: A preformed insert having a diffractive structure on one of the insert's front curve and back curve surfaces is preferably placed in the central region of the molding surface of a female mold half (e.g., made of polypropylene) having three or more spikes distributed in a circle with a diameter sufficient to accommodate the preformed insert to fix the position of the preformed insert on the molding surface. An additional amount of SiHy lens formulation is placed into the female mold half to immerse the preformed insert, after which a casting mold half (e.g., made of polypropylene) is placed on top of the female mold half, and the mold is tightly closed to form a molding assembly. The SiHy lens formulation in the molding assembly is then thermally or actinically cured (polymerized) to form an implantable SiHy contact lens with a fully embedded insert including the diffractive structure.

[0145] Alternatively, a small amount of the first SiHy lens formulation is placed in the central region of the female mold half. Optionally, but preferably, the first SiHy lens formulation is partially cured to increase its viscosity. A preformed insert having a diffractive structure on one of the insert's front curve and back curve surfaces is then placed on top of the partially cured first SiHy lens formulation (or the uncured first SiHy lens formulation) in the central region of the molding surface of the female mold half and pressed into it, thereby holding the preformed insert in a desired position on the molding surface. If not partially cured, light is irradiated onto the first SiHy lens formulation with the preformed insert in the female mold half to partially cure the first SiHy lens formulation. Next, a certain amount of the second SiHy lens formulation is placed in the female mold half to immerse the preformed insert, after which a mold half (e.g., made of polypropylene) is placed on top of the female mold half and the mold is tightly closed to form a molded assembly. The first and second SiHy lens formulations in the molding assembly are thermally cured or actinically cured (polymerized) to form an implantable SiHy contact lens with a fully embedded insert containing the diffractive structure.

[0146] Another approach to producing the implantable SiHy contact lenses of the present invention may involve the use of a set of three mold halves: one female mold half having a first molding surface defining the anterior surface of the contact lens to be molded; a first male mold half having a second molding surface defining the back curve surface of the insert to be molded, including a diffractive structure disposed thereon; and a second male mold half having a third molding surface defining the posterior surface of the contact lens to be molded. The first male and female mold halves are configured to receive each other when closed to form an insert molding cavity between the first and second molding surfaces, and the second male and female mold halves are configured to receive each other when closed to form a lens molding cavity between the first and third molding surfaces. During production, a quantity of insert-molding composition is placed in a central portion of the first molding surface of the female mold half, which is then mated and closed with the first male mold half to form a first mold assembly. The insert-molding composition in the insert-molding cavity of the first mold assembly is cured (by heat or actinic radiation) to form a molded insert. The first mold assembly is then separated into first male and female mold halves, with the molded insert attached to a central region of the first molding surface. A lens-forming composition is dispensed into the female mold half with the molded insert attached thereon in an amount sufficient to fill the lens-molding cavity, which is then mated and closed with the second male mold half to form a second mold assembly. The lens-forming composition in the lens-molding cavity of the second mold assembly is cured (by heat or actinic radiation) to form an implantable SiHy contact lens with a partially embedded insert containing a diffractive structure.

[0147] Another similar approach for producing the implantable SiHy contact lenses of the present invention may be as follows, involving the use of a set of three mold halves: a first female mold half having a first molding surface defining a front curve surface including a diffractive structure disposed thereon of the insert to be molded; one male mold half having a second molding surface defining a posterior surface of the contact lens to be molded; and a second female mold half having a third molding surface defining a front surface of the contact lens to be molded. The first male and female mold halves are configured to receive one another when closed to form an insert molding cavity between the first and second molding surfaces, and the second female and male mold halves are configured to receive one another when closed to form a lens molding cavity between the second and third molding surfaces. In production, a quantity of insert-molding composition is placed in a central portion of the first molding surface of the female mold half, which is then mated and closed with the male mold half to form a first mold assembly. The insert-forming composition in the insert-molding cavity of the first mold assembly is cured (by heat or actinic radiation) to form a molded insert. The first mold assembly is then separated into a first female mold half and a male mold half, with the molded insert attached to a central region of the second molding surface. A lens-forming composition is placed into the second female mold half, which is then mated and closed with the male mold half, with the molded insert attached, to form a second mold assembly. The lens-forming composition in the lens-molding cavity of the second mold assembly is cured (by heat or actinic radiation) to form an implantable SiHy contact lens with a partially embedded insert containing a diffractive structure.

[0148] Molded insert or implantable SiHy contact lenses can be subjected to lens extraction using 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, C1-C3 alkyl alcohol, 1,2-propylene glycol, polyethylene glycol having a number average molecular weight of about 400 Daltons or less, C1-C6 alkyl alcohol, or a combination thereof.

[0149] After extraction, the implantable silicone hydrogel contact lenses 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.

[0150] The hydrated implantable silicone hydrogel contact lenses may be further processed, such as by surface treatment, packaging in a lens package using a packaging solution known to those skilled in the art, and sterilization, such as in an autoclave at 118-124°C for at least about 30 minutes.

[0151] Lens packages (or containers) are well known to those skilled in the art for autoclaving and storing soft contact lenses. Any lens package can be used in the present invention. Preferably, the lens package is a blister package comprising a base and a cover; wherein the cover is removably sealed to the base, and wherein the base comprises a cavity for receiving a sterile packaging solution and a contact lens.

[0152] The lenses are packaged in individual packages, sealed, and sterilized (e.g., by autoclaving at about 120°C or higher under pressure for at least 30 minutes) before being distributed to users. Those skilled in the art will be familiar with methods for sealing and sterilizing lens packages.

[0153] Although various embodiments of the present invention have been described using specific terms, devices, and methods, such description is for illustrative purposes only. The words used are words of description rather than of limitation. It is to be understood that changes and variations may be made by those skilled in the art without departing from the spirit or scope of the present invention, as set forth in the following claims. In addition, it is to be understood that aspects of the various embodiments may be interchanged in whole or in part, or may be combined in any manner and / or used together, as set forth below: 1. An implantable silicone hydrogel contact lens comprising a silicone hydrogel bulk material and an insert embedded therein, 1. An implantable silicone hydrogel contact lens, wherein the insert is made of a crosslinked polymeric material having a first refractive index, the silicone hydrogel bulk material has a second refractive index, the first refractive index being at least 0.07 higher than the second refractive index, the insert having a front curve surface, an opposing back curve surface, and a diameter of less than 13.0 mm, the insert being located in a central portion of the implantable hydrogel contact lens and including a diffractive structure disposed on one of the front curve surface and the back curve surface to impart a diffractive power that contributes to the overall optical power of the contact lens, the diffractive structure being embedded within the silicone hydrogel bulk material, the implantable silicone hydrogel contact lens having resistance to delamination after being autoclaved in a packaging solution in a sealed package at 121° C. for about 45 minutes, as indicated by the absence of air bubbles upon microscopic examination of the interface between the insert and the silicone hydrogel bulk material within the implantable silicone hydrogel contact lens, the packaging solution being phosphate buffered saline having a pH of 7.1±0.2. 2. The implantable silicone hydrogel contact lens of embodiment 1, wherein the first refractive index is at least 0.08 higher than the second refractive index. 3. The implantable silicone hydrogel contact lens of embodiment 1, wherein the first refractive index is at least 0.09 higher than the second refractive index. 4. The implantable silicone hydrogel contact lens of embodiment 1, wherein the first refractive index is at least 0.10 higher than the second refractive index. 5. An implantable silicone hydrogel contact lens according to any one of embodiments 1 to 4, wherein the crosslinked polymeric material of the insert has a refractive index of at least about 1.47. 6. An implantable silicone hydrogel contact lens according to any one of embodiments 1 to 4, wherein the crosslinked polymeric material of the insert has a refractive index of at least about 1.49. 7. An implantable silicone hydrogel contact lens according to any one of embodiments 1 to 4, wherein the crosslinked polymeric material of the insert has a refractive index of at least about 1.51. 8. An implantable silicone hydrogel contact lens according to any one of embodiments 1 to 4, wherein the crosslinked polymeric material of the insert has a refractive index of at least about 1.53. 9. An implantable silicone hydrogel contact lens according to any one of embodiments 1 to 8, wherein the crosslinked polymeric material of the insert has an oxygen permeability of at least about 40 barrers. 10. An implantable silicone hydrogel contact lens according to any one of embodiments 1 to 8, wherein the crosslinked polymeric material of the insert has an oxygen permeability of at least about 60 barrers. 11. An implantable silicone hydrogel contact lens according to any one of embodiments 1 to 8, wherein the crosslinked polymeric material of the insert has an oxygen permeability of at least about 80 barrers. 12. An implantable silicone hydrogel contact lens according to any one of embodiments 1 to 8, wherein the crosslinked polymeric material of the insert has an oxygen permeability of at least about 100 barrers. 13. The implantable silicone hydrogel contact lens of any one of embodiments 1-12, wherein the crosslinked polymeric material of the insert comprises at least 50 mol % of repeat units (acrylic repeat units) of one or more acrylic monomers and / or crosslinkers. 14. The implantable silicone hydrogel contact lens of any one of embodiments 1-13, wherein the crosslinked polymeric material of the insert comprises repeat units of at least one aryl vinyl monomer. 15. The at least one aryl vinyl monomer is selected from the group consisting of 2-ethylphenoxyacrylate; 2-ethylphenoxymethacrylate; phenylacrylate; phenylmethacrylate; benzylacrylate; benzylmethacrylate; 2-phenylethylacrylate; 2-phenylethylmethacrylate; 3-phenylpropylacrylate; 3-phenylpropylmethacrylate; 4-phenylbutylacrylate; 4-phenylbutylmethacrylate; 4-methylphenylacrylate; 4-methylphenylmethacrylate; 4-methylbenzylacrylate; 2-(4-Methylphenyl)ethyl acrylate;2-(2-methylphenyl)ethyl methacrylate;2-(3-methylphenyl)ethyl acrylate;2-(3-methylphenyl)ethyl methacrylate;2-(4-Methylphenyl)ethyl acrylate;2-(4-Methylphenyl)ethyl methacrylate;2-(4-Propylphenyl)ethyl acrylate;2-(4-Propylphenyl)ethyl methacrylate;2-(4-(1-methylethyl)phenyl)ethyl acrylate ;2-(4-(1-methylethyl)phenyl)ethyl methacrylate;2-(4-methoxyphenyl)ethyl acrylate;2-(4-methoxyphenyl)ethyl methacrylate;2-(4-cyclohexylphenyl)ethyl acrylate;2-(4-cyclohexylphenyl)ethyl methacrylate;2-(2-chlorophenyl)ethyl acrylate;2-(2-chlorophenyl)ethyl methacrylate;2-(3-chlorophenyl)ethyl acrylate;2-(3-chlorophenyl)ethyl methacrylate Acrylate;2-(4-chlorophenyl)ethyl methacrylate;2-(4-bromophenyl)ethyl acrylate;2-(4-bromophenyl)ethyl methacrylate;2-(3-phenylphenyl)ethyl acrylate;2-(3-phenylphenyl)ethyl methacrylate;2-(4-phenylphenyl)ethyl acrylate;2-(4-phenylphenyl)ethyl methacrylate;2-(4-benzylphenyl)ethyl acrylate;2-(4-benzylphenyl)ethyl methacrylate;2-(phenylthio)ethyl acrylate15. The implantable silicone hydrogel contact lens of embodiment 14, comprising 2-(phenylthio)ethyl methacrylate; 2-benzyloxyethyl acrylate; 3-benzyloxypropyl acrylate; 2-benzyloxyethyl methacrylate; 3-benzyloxypropyl methacrylate; 2-[2-(benzyloxy)ethoxy]ethyl acrylate; 2-[2-(benzyloxy)ethoxy]ethyl methacrylate; or combinations thereof. 16. The at least one aryl vinyl monomer is selected from the group consisting of styrene, 2,5-dimethylstyrene, 2-(trifluoromethyl)styrene, 2-chlorostyrene, 3,4-dimethoxystyrene, 3-chlorostyrene, 3-bromostyrene, 3-vinylanisole, 3-methylstyrene, 4-bromostyrene, 4-tert-butylstyrene, p-styryltrimethoxysilane, styrylethyltrimethoxysilane, 2,3,4,5,6-pentanefluorostyrene, 2,4-dimethylstyrene, 1-methoxy-4-vinyl Benzene, 1-chloro-4-vinylbenzene, 1-methyl-4-vinylbenzene, 1-(chloromethyl)-4-vinylbenzene, 1-(bromomethyl)-4-vinylbenzene, 3-nitrostyrene, 1,2-vinylphenylbenzene, 1,3-vinylphenylbenzene, 1,4-vinylphenylbenzene, 4-vinyl-1,1'-(4'-phenyl)biphenylene, 1-vinyl-4-(phenyloxy)benzene, 1-vinyl-3-(phenyloxy)benzene, 1-vinyl-2-(phenyloxy)benzene , 1-vinyl-4-(phenylcarbonyl)benzene, 1-vinyl-3-(phenylcarboxy)benzene, 1-vinyl-2-(phenoxycarbonyl)benzene, allyl phenyl ether, 2-biphenylyl allyl ether, allyl 4-phenoxyphenyl ether, allyl 2,4,6-tribromophenyl ether, allyl phenyl carbonate, 1-allyloxy-2-trifluoromethylbenzene, allylbenzene, 1-phenyl-2-prop-2-enylbenzene, 4-phenyl-1-butene, 4- Phenyl-1-buten-4-ol, 1-(4-methylphenyl)-3-buten-1-ol, 1-(4-chlorophenyl)-3-buten-1-ol, 4-allyltoluene, 1-allyl-4-fluorobenzene, 1-allyl-2-methylbenzene, 1-allyl-3-methylbenzene, 1-allyl-3-methylbenzene, 2-allylanisole, 4-allylanisole, 1-allyl-4-(trifluoromethyl)benzene, allylpentafluorobenzene, 1-allyl-2-methoxybenzene, 4-allyl-1,2-Dimethoxybenzene, 2-allylphenol, 2-allyl-6-methylphenol, 4-allyl-2-methoxyphenol, 2-allyloxyanisole, 4-allyl-2-methoxyphenyl acetate, 2-allyl-6-methoxyphenol, 1-allyl-2-bromobenzene, α-vinylbenzyl alcohol, 1-phenyl-3-buten-1-one, allylbenzyl ether, (3-allyloxy)propyl)benzene, allylphenylethyl ether, 1-benzyloxy-4-pentene, (1-allyloxy)ethyl)benzene, 1-phenylallylethyl ether, (2-methyl-2-(2-propenyloxy)propyl)benzene, ((5-hexenyloxy)methyl)benzene, 1-allyloxy-4-propoxy Benzene, 1-phenoxy-4-(3-prop-2-enoxypropoxy)benzene, 6-(4'-hydroxyphenoxy)-1-hexene, 4-but-3-enoxyphenol, 1-allyloxy-4-butoxybenzene, 1-allyloxy-4-ethoxybenzene, 1-allyl-4-benzyloxybenzene, 1-allyl-4-(phenoxy)benzene, 1-allyl-3-(phenoxy)benzene, 1-allyl-2-(phenoxy)benzene, 1-allyl-4-(phenylcarbonyl)benzene, 1-allyl-3-(phenylcarboxy)benzene, 1-allyl-2-(phenoxycarbonyl)benzene, 1,2-allylphenylbenzene, 1,3-allylphenylbenzene, 1,4-allylphenylbenzene, 4-vinyl-1,1'-(4'-phenyl)biphenylene, 1-allyl-4-(phenyloxy)benzene, 1-allyl-3-(phenyloxy)benzene, 1-allyl-2-(phenyloxy)benzene, 1-allyl-4-(phenylcarbonyl)benzene, 1-allyl-3-(phenylcarboxy)benzene, and 1-allyl-2-(phenoxycarbonyl)benzene, 1-vinylnaphthylene, 2-vinylnaphthylene, 1-allylnaphthalene, 2-allylnaphthalene, allyl-2-naphthyl ether, 2-(2-methylprop-2-enyl)naphthalene , 2-prop-2-enylnaphthalene, 4-(2-naphthyl)-1-butene, 1-(3-butenyl)naphthalene, 1-allylnaphthalene, 2-allylnaphthalene, 1-allyl-4-naphthylnaphthalene, 2-(allyloxy)-1-bromonaphthalene, 2-bromo-6-allyloxynaphthalene, 1,2-vinyl(1-naphthyl)benzene, 1,2-vinyl(2-naphthyl)benzene, 1,3-vinyl(1-naphthyl)benzene, 1,3-vinyl(2-naphthyl)benzene, 1,4-vinyl(1-naphthyl)benzene, 1,4-vinyl(2- naphthyl)benzene, 1-naphthyl-4-vinylnaphthalene, 1-allylnaphthalene, 2-allylnaphthalene, 1,2-allyl(1-naphthyl)benzene, 1,2-allyl(2-naphthyl)benzene, 1,3-allyl(1-naphthyl)benzene, 1,3-allyl(2-naphthyl)benzene, 1,4-allyl(1-naphthyl)benzene, 1,4-allyl(2-naphthyl)benzene, 1-allyl-4-naphthylnaphthalene, 1-vinylanthracene, 2-vinylanthracene, 9-vinylanthracene, 1-allylanthracene, 2-allylanthracene 16. The implantable silicone hydrogel contact lens of embodiment 14 or 15, comprising 1-allyl anthracene, 9-allylanthracene, 9-pent-4-enylanthracene, 9-allyl-1,2,3,4-tetrachloroanthracene, 1-vinylphenanthrene, 2-vinylphenanthrene, 3-vinylphenanthrene, 4-vinylphenanthrene, 9-vinylphenanthrene, 1-allylphenanthrene, 2-allylphenanthrene, 3-allylphenanthrene, 4-allylphenanthrene, 9-allylphenanthrene, or combinations thereof. 17. The implantable silicone hydrogel contact lens of any one of embodiments 1-16, wherein the crosslinked polymeric material of the insert comprises repeat units of at least one aryl vinyl crosslinker. 18. The implantable silicone hydrogel contact lens of embodiment 17, wherein the at least one aryl vinyl crosslinker comprises divinylbenzene, 2-methyl-1,4-divinylbenzene, bis(4-vinylphenyl)methane, 1,2-bis(4-vinylphenyl)ethane, 1,4-diisopropenylbenzene, 1,2-bis(4-vinylphenyl)-1,2-ethanediol, 1,3-bis-methacryloyloxy-benzene, 1,4-phenylene dimethacrylate, bisphenol A dimethacrylate, bisphenol A glycerolate dimethacrylate, 2,5-bis{[2-(methacryloyloxy)ethoxy]carbonyl}terephthalic acid, 4-(methacryloyloxy)styrene, 2-[2-(benzyloxy)ethoxy]ethyl acrylate; 2-[2-(benzyloxy)ethoxy]ethyl methacrylate, or a combination thereof. 19. The implantable silicone hydrogel contact lens of any one of embodiments 1-18, wherein the crosslinked polymeric material of the insert comprises repeating units of: (1) polydiorganosiloxane segments comprising aryl-containing siloxane units, each having an organic substituent, the organic substituent having up to 45 carbon atoms and at least one aryl moiety (preferably linked to a Si atom via a linking group having at least 2, more preferably 3, carbon atoms); and (2) a high RI polydiorganosiloxane vinyl crosslinker comprising: an ethylenically unsaturated group, preferably a (meth)acryloyl group. 20. The implantable silicone hydrogel contact lens of embodiment 19, wherein said polydiorganosiloxane segments comprise at least 30 mole percent aryl-containing siloxane units. 21. The implantable silicone hydrogel contact lens of embodiment 19, wherein said polydiorganosiloxane segments comprise at least 40 mole percent aryl-containing siloxane units. 22. The implantable silicone hydrogel contact lens of embodiment 19, wherein said polydiorganosiloxane segments comprise at least 50 mole % aryl-containing siloxane units. 23. The implantable silicone hydrogel contact lens of embodiment 19, wherein said polydiorganosiloxane segments comprise at least 60 mole percent aryl-containing siloxane units. 24. The implantable silicone hydrogel contact lens of embodiment 19, wherein said polydiorganosiloxane segments comprise at least 70 mole % aryl-containing siloxane units. 25. The implantable silicone hydrogel contact lens of any one of embodiments 19-24, wherein the polysiloxane vinyl crosslinker has a number average molecular weight of at least 1000 Daltons. 26. The implantable silicone hydrogel contact lens of any one of embodiments 19-24, wherein the polydiorganosiloxane vinyl crosslinker has a number average molecular weight of from about 1,500 Daltons to about 100,000 Daltons. 27. The implantable silicone hydrogel contact lens of any one of embodiments 19-24, wherein the polydiorganosiloxane vinyl crosslinker has a number average molecular weight of 2,000 to 80,000 daltons. 28. The implantable silicone hydrogel contact lens of any one of embodiments 19-24, wherein the polydiorganosiloxane vinyl crosslinker has a number average molecular weight of 2,500 Daltons to 60,000 Daltons. 29. The implantable silicone hydrogel contact lens of any one of embodiments 19-28, wherein the polydiorganosiloxane vinyl crosslinker is defined by formula (1): [ka] (In the formula: υ1 is an integer between 1 and 400; ω1 is an integer between 1 and 800; E1 is [ka] is a monovalent radical of; R0 is hydrogen or methyl; a1 is zero or 1; X0 is O or NR N1 and; R N1 is hydrogen or C1-C6 alkyl; L0 is a C2-C8 alkylene divalent radical or -L0'-X1-L0''-, [ka] is a divalent radical of; L0' is a C2-C8 alkylene divalent radical; L0″ is a C3-C8 alkylene divalent radical; X1 is -O-, -NR N1 -, -NHCOO-, -OCONH-, -CONR N1 -or-NR N1 CO-; q1 is an integer from 1 to 10; AR is an aryl radical; L AR teeth, [ka] is a divalent radical of; L e -CH2-CH2-, -CH2-CHR0-R1-, -CH2-CHR0-R1-O-, -CH2-CHR0-R1-O-R2-, -C3H6-O-R2-, -C3H6-O-R2-O-, [ka] is a divalent radical of; a2 is zero, one, or two; a3 is zero or one; R1 is a linear or branched C1-C alkyl group optionally substituted with a C1-C4 alkoxy group, a hydroxyl group, a carboxyl group, an amino group, an oxo group, or a combination thereof. 10 is an alkylene divalent radical; R2 is a linear or branched C3-C 10 is an alkylene divalent radical, R3 is a direct bond or a linear or branched C1-C4 alkylene divalent radical; X AR and each X2 independently represents a covalent bond, or -O-, -S-, [ka] , -NR N2 -, -NHCOO-, -OCONH-, -NHCONR N2 -, -NR N2 CONH-, [ka] , -CONR N2 -, -NR N2 CO-, [ka] , -NHCOS-, -SCONH-, -COO-, or -OCO- covalent bond; R N2 is hydrogen, linear or branched C1-C6 alkyl, cyclohexyl, cyclopentyl, substituted or unsubstituted phenyl, or substituted or unsubstituted phenyl-C1-C6 alkyl; Each L x are independently linear or branched C1-C alkyl groups which may optionally carry one or more hydroxyl or C1-C4 alkoxy or C1-C4 acylamino groups; 10alkenylene divalent radical, -CH2-CHOH-CH2-O-R4-O-CH2-CHOH-CH2-; [ka] or a divalent radical obtained by removing two hydrogen atoms from two different atoms of a hydrocarbon having up to 20 carbon atoms, optionally bearing one or more hydroxyl or 1-C4 alkoxy groups, and comprising at least one divalent radical selected from the group consisting of a cycloalkylene radical, a substituted cycloalkylene radical, a phenylene radical, a substituted phenylene radical, a cycloheteroalkylene radical, and a substituted cycloheteroalkylene radical; Each R4, R5 and R6, independently of one another, is a linear or branched C1-C hydroxyl group having zero or one hydroxyl group. 10 (an alkylene divalent radical). 30. The implantable silicone hydrogel contact lens of embodiment 29, wherein in formula (1), υ1 is an integer from 3 to 350. 31. The implantable silicone hydrogel contact lens of embodiment 29, wherein in formula (1), υ1 is an integer from 5 to 300. 32. The implantable silicone hydrogel contact lens of embodiment 29, wherein in formula (1), υ1 is an integer from 10 to 250. 33. The implantable silicone hydrogel contact lens of any one of embodiments 29 to 32, wherein in formula (1), ω1 is an integer from 5 to 700. 34. The implantable silicone hydrogel contact lens of any one of embodiments 29 to 32, wherein in formula (1), ω1 is an integer from 10 to 600. 35. The implantable silicone hydrogel contact lens of any one of embodiments 29 to 32, wherein in formula (1), ω1 is an integer from 15 to 500. 36. The implantable silicone hydrogel contact lens of any one of embodiments 29 to 35, wherein in formula (1), a1 is zero. 37. The implantable silicone hydrogel contact lens of embodiment 36, wherein, in formula (1), X0 is O. 38. In equation (1), X0 is NR N1 37. The implantable silicone hydrogel contact lens of embodiment 36, wherein 39. The implantable silicone hydrogel contact lens of any one of embodiments 29 to 38, wherein, in formula (1), ω1 / (υ1+ω1) is from about 0.30 to about 0.95. 40. The implantable silicone hydrogel contact lens of any one of embodiments 29 to 38, wherein, in formula (1), ω1 / (υ1+ω1) is from about 0.40 to about 0.90. 41. The implantable silicone hydrogel contact lens of any one of embodiments 29 to 38, wherein, in formula (1), ω1 / (υ1+ω1) is from about 0.50 to about 0.90. 42. The implantable silicone hydrogel contact lens of any one of embodiments 29 to 38, wherein, in formula (1), ω1 / (υ1+ω1) is from about 0.60 to about 0.85. 43. The implantable silicone hydrogel contact lens of any one of embodiments 29-42, wherein in formula (1), AR is a phenyl group, a substituted phenyl group, a naphthyl group, a substituted naphthyl group, an anthracenyl group, a substituted anthracenyl group, a phenanthryl group, or a substituted phenanthryl group. 44. In equation (1), AR is [ka] (In the formula, R7, R8, R9, R 10 , R 11 , R 12 , and R 13are, independently of each other, H, Cl, Br, F, CF3, CCl3, C1-C5 alkyl, C1-C5 alkoxy, C2-C5 acyloxy, OH, phenyl, phenoxy, benzyloxy, phenylcarbonyl, phenoxycarbonyl, phenylcarboxy(phenylcarbonyloxy), or naphthyl), a monovalent radical. 45. The implantable silicone hydrogel contact lens of any one of embodiments 13-44, wherein the crosslinked polymeric material of the insert further comprises: (a) repeating units of at least one first hydrophobic non-silicone vinyl monomer; (b) repeating units of at least one first non-silicone vinyl crosslinker; (c) repeating units of at least one first polymerizable material selected from the group consisting of a first UV-absorbing vinyl monomer, a first UV / high-energy-ultraviolet light ("HEVL")-absorbing vinyl monomer, a first polymerizable photochromic compound, a first polymerizable colorant, and combinations thereof; or (d) combinations thereof. 46. ​​An implantable silicone hydrogel contact lens according to any one of embodiments 1 to 45, wherein the silicone hydrogel bulk material comprises (1) repeating units of at least one silicone-containing polymerizable component comprising at least 0.5 meq / g of H-bond donor, and (2) repeating units of at least one hydrophilic vinyl monomer. 47. The implantable silicone hydrogel contact lens of embodiment 46, wherein the silicone-containing polymerizable component comprises a first silicone-containing vinyl monomer, a first silicone-containing vinyl crosslinker, or both. 48. The silicone-containing polymerizable component is selected from the group consisting of [3-(meth)acryloxy-2-hydroxypropyloxy]propylbis(trimethylsiloxy)methylsilane, [3-(meth)acryloxy-2-hydroxypropyloxy]propylbis(trimethylsiloxy)butylsilane, 3-(meth)acryloxy-2-(2-hydroxyethoxy)propyloxy)propylbis(trimethylsiloxy)methylsilane, and 3-(meth)acryloxy-2-hydroxypropyloxy)propyltris(trimethylsiloxy)silane. N-[tris(trimethylsiloxy)silylpropyl]-(meth)acrylamide, N-(2-hydroxy-3-(3-(bis(trimethylsilyloxy)methylsilyl)propyloxy)propyl)-2-methyl(meth)acrylamide, N-(2-hydroxy-3-(3-(bis(trimethylsilyloxy)methylsilyl)propyloxy)propyl)(meth)acrylamide, N-(2-hydroxy-3-(3-(tris(trimethylsilyloxy)silyl)propyloxy)propyl)-2-methylacrylamide amide, N-(2-hydroxy-3-(3-(tris(trimethylsilyloxy)silyl)propyloxy)propyl)(meth)acrylamide, N-[tris(dimethylpropylsiloxy)silylpropyl]-(meth)acrylamide, N-[tris(dimethylphenylsiloxy)-silylpropyl](meth)acrylamide, N-[tris(dimethylethylsiloxy)-silylpropyl](meth)acrylamide, N,N-bis[2-hydroxy-3-(3-(bis(trimethylsilyloxy)methylsilyl)-propyl] N,N-bis[2-hydroxy-3-(3-(bis(trimethylsilyloxy)methylsilyl)propyloxy)propyl]-2-methyl(meth)acrylamide, N,N-bis[2-hydroxy-3-(3-(tris(trimethylsilyloxy)silyl)propyloxy)propyl]-2-methyl(meth)acrylamide, N,N-bis[2-hydroxy-3-(3-(tris(trimethylsilyloxy)silyl)propyloxy)propyl](meth)acrylamide,N-[2-hydroxy-3-(3-(t-butyldimethylsilyl)propyloxy)propyl]-2-methyl(meth)acrylamide, N-[2-hydroxy-3-(3-(t-butyldimethylsilyl)propyloxy)propyl](meth)acrylamide, N,N-bis[2-hydroxy-3-(3-(t-butyldimethylsilyl)propyloxy)propyl]-2-methyl(meth)acrylamide, N-2-(meth)acryloxyethyl-O-(methyl-bis-trimethylsiloxy-3-propyl)silylcarbamate , 3-[tris(trimethylsiloxy)silyl]propyl vinyl carbamate, 3-[tris(trimethylsiloxy)silyl]propyl allyl carbamate, α-(meth)acryloxy-terminated ω-C1-C6-hydroxyalkyl-terminated polydimethylsiloxane having a number average molecular weight of 2000 Daltons or less, α-(meth)acrylamide-terminated ω-C1-C6-hydroxyalkyl-terminated polydimethylsiloxane having a number average molecular weight of 2000 Daltons or less, α-(meth)acryloxy-terminated ω-C1-C6-hydroxyalkyl-terminated polydimethylsiloxane having a number average molecular weight of 2000 Daltons or less -2-hydroxypropyloxypropyl-terminated ω-C1-C4-alkyl-terminated polydimethylsiloxane, α-(2-hydroxyl-methacryloxypropyloxypropyl)-ω-C1-C4-alkyl-decamethylpentasiloxane, α-[3-(meth)acryloxyethoxy-2-hydroxypropyloxypropyl]-terminated ω-C1-C4-alkyl-terminated polydimethylsiloxane having a number average molecular weight of 2000 or less, α-[3-(meth)acryloxy-propyl]-terminated ω-C1-C4-alkyl-terminated polydimethylsiloxane having a number average molecular weight of 2000 or less α-[3-(meth)acryloxyisopropyloxy-2-hydroxypropyloxypropyl]-terminated ω-C1-C4-alkyl terminated polydimethylsiloxane having a number average molecular weight of 2000 daltons or less, α-[3-(meth)acryloxybutyloxy-2-hydroxypropyloxypropyl]-terminated ω-C1-C4-alkyl terminated polydimethylsiloxane having a number average molecular weight of 2000 daltons or less,α-[3-(meth)acryloxyethylamino-2-hydroxypropyloxypropyl]-terminated ω-C1-C4-alkyl terminated polydimethylsiloxane having a number average molecular weight of 2000 daltons or less, α-[3-(meth)acryloxypropyl ...-butylamino-2-hydroxypropyloxypropyl]-terminated ω-C1-C4-alkyl terminated polydimethylsiloxane having a number average molecular weight of 2000 daltons or less, [(meth)acryloxy(ethyleneoxy)-2-hydroxypropyloxypropyl]-terminated ω-C1-C4-alkyl terminated polydimethylsiloxane having a number average molecular weight of 2000 Daltons or less, ... α-[(meth)acryloxy-2-hydroxypropyl-N-ethylaminopropyl]-terminated ω-C1-C4-alkyl-terminated polydimethylsiloxane having a number average molecular weight of 2000 Daltons or less, α-[(meth)acryloxy-2-hydroxypropyl-aminopropyl]-terminated ω-C1-C4-alkyl-terminated polydimethylsiloxane having a number average molecular weight of 2000 Daltons or less, α-[(meth)acryloxy-2-hydroxypropyloxy-(polyethyleneoxy)propyl]-terminated ω-C1-C4-alkyl-terminated polydimethylsiloxane having a number average molecular weight of 2000 Daltons or less, α-(meth)acrylamidopropyloxypropyl-terminated ω-C1-C4-alkyl terminated polydimethylsiloxane having a number average molecular weight of 2000 Daltons or less, α-[3-(meth)acrylamidoethoxy-2-hydroxypropyloxypropyl]-terminated ω-C1-C4-alkyl terminated polydimethylsiloxane having a number average molecular weight of 2000 Daltons or less, α-[3-(meth)acrylamidopropyloxy-2-hydroxypropyloxypropyl]-terminated ω-C1-C4-alkyl terminated polydimethylsiloxane having a number average molecular weight of 2000 Daltons or less,α-[3-(meth)acrylamidoisopropyloxy-2-hydroxypropyloxypropyl]-terminated ω-C1-C4-alkyl terminated polydimethylsiloxane having a number average molecular weight of 2000 daltons or less, α-[3-(meth)acrylamidobutyloxy-2-hydroxypropyloxypropyl]-terminated ω-C1-C4-alkyl terminated polydimethylsiloxane having a number average molecular weight of 2000 daltons or less, α-[3-(meth)acrylamido ... polydimethylsiloxane having a number average molecular weight of 2000 daltons or less, α-[3-[N-methyl-(meth)acrylamidobutyloxy-2-hydroxypropyloxypropyl]-terminated ω-C1-C4-alkyl polydimethylsiloxane having a number average molecular weight of 2000 daltons or less, 48. The implantable silicone hydrogel contact lens of embodiment 47, comprising a first silicone-containing vinyl monomer selected from the group consisting of N-(2,3-dihydroxypropane)-N'-(propyltetra(dimethylsiloxy)-dimethylbutylsilane)(meth)acrylamide, (meth)acrylamidopropyltetra(dimethylsiloxy)dimethylbutylsilane, α-vinyl carbonate terminated ω-C1-C4-alkyl-terminated polydimethylsiloxane, α-vinyl carbamate terminated ω-C1-C4-alkyl-terminated polydimethylsiloxane, and combinations thereof. 49. The silicone-containing polymerizable component is selected from the group consisting of [3-(meth)acryloxy-2-hydroxypropyloxy]propylbis(trimethylsiloxy)methylsilane, [3-(meth)acryloxy-2-hydroxypropyloxy]propylbis(trimethylsiloxy)butylsilane, 3-(meth)acryloxy-2-(2-hydroxyethoxy)propyloxy)propylbis(trimethylsiloxy)methylsilane, 3-(meth)acryloxy-2-hydroxypropyloxy)propyl-tris(trimethylsiloxy)silane, N-( 2-Hydroxy-3-(3-(bis(trimethylsilyloxy)methylsilyl)propyloxy)propyl)-2-methyl(meth)acrylamide, N-(2-hydroxy-3-(3-(bis(trimethylsilyloxy)methylsilyl)propyloxy)propyl)(meth)acrylamide, N-(2-hydroxy-3-(3-(tris(trimethylsilyloxy)silyl)propyloxy)propyl)-2-methylacrylamide, N-(2-hydroxy-3-(3-(tris(trimethylsilyloxy)silyl)propyloxy)propyl) N,N-bis[2-hydroxy-3-(3-(bis(trimethylsilyloxy)methylsilyl)-propyloxy)propyl](meth)acrylamide, N,N-bis[2-hydroxy-3-(3-(bis(trimethylsilyloxy)methylsilyl)propyloxy)propyl]-2-methyl(meth)acrylamide, N,N-bis[2-hydroxy-3-(3-(tris(trimethylsilyloxy)silyl)propyloxy)propyl]-2-methyl(meth)acrylamide, N,N-bis[2 -hydroxy-3-(3-(tris(trimethylsilyloxy)silyl)-propyloxy)propyl](meth)acrylamide, N-[2-hydroxy-3-(3-(t-butyldimethylsilyl)propyloxy)-propyl]-2-methyl(meth)acrylamide, N-[2-hydroxy-3-(3-(t-butyldimethylsilyl)propyloxy)-propyl](meth)acrylamide, N,N-bis[2-hydroxy-3-(3-(t-butyldimethylsilyl)propyloxy)propyl]-2-methyl(meth)acrylamide,α-(meth)acryloxy-terminated ω-C1-C6-hydroxyalkyl-terminated polydimethylsiloxane having a number average molecular weight of 2000 Daltons or less, α-(meth)acrylamide-terminated ω-C1-C6-hydroxyalkyl-terminated polydimethylsiloxane having a number average molecular weight of 2000 Daltons or less, α-(meth)acryloxy-2-hydroxypropyloxypropyl-terminated ω-C1-C4- ... α-[3-(meth)acryloxyethoxy-2-hydroxypropyloxypropyl]-terminated ω-C1-C4-alkyl-decamethylpentasiloxane, α-[3-(meth)acryloxyethoxy-2-hydroxypropyloxypropyl]-terminated ω-C1-C4-alkyl-terminated polydimethylsiloxane having a number average molecular weight of 2000 Daltons or less, α-[3-(meth)acryloxy-propyloxy-2-hydroxypropyloxypropyl]-terminated ω-C1-C4-alkyl-terminated polydimethylsiloxane having a number average molecular weight of 2000 Daltons or less, 200 α-[3-(meth)acryloxyisopropyloxy-2-hydroxypropyloxypropyl]-terminated ω-C1-C4-alkyl terminated polydimethylsiloxane having a number average molecular weight of 0 Daltons or less, α-[3-(meth)acryloxybutyloxy-2-hydroxypropyloxypropyl]-terminated ω-C1-C4-alkyl terminated polydimethylsiloxane having a number average molecular weight of 2000 Daltons or less, α-[3-(meth)acryloxyethylamino-2-hydroxypropyloxypropyl]-terminated ω-C1-C4-alkyl terminated polydimethylsiloxane having a number average molecular weight of 2000 Daltons or less, α-[3-(meth)acryloxypropylamino-2-hydroxypropyloxypropyl]-terminated ω-C1-C4-alkyl terminated polydimethylsiloxane having a number average molecular weight of 2000 or less, α-[3-(meth)acryloxypropylamino-2-hydroxypropyloxypropyl]-terminated ω-C1-C4-alkyl terminated polydimethylsiloxane having a number average molecular weight of 2000 or less, α-[3-(meth)acryloxy-butylamino-2-hydroxypropyloxypropyl]-terminated ω-C1-C4-alkyl terminated polydimethylsiloxane having a number average molecular weight of 2000 or less,α-(meth)acryloxy(polyethyleneoxy)-2-hydroxypropyloxypropyl]-terminated ω-C1-C4-alkyl terminated polydimethylsiloxane having a number average molecular weight of 2000 daltons or less, α-[(meth)acryloxy-2-hydroxypropyloxy-eth ... α-[(meth)acryloxy-2-hydroxypropyl-aminopropyl]-terminated ω-C1-C4-alkyl terminated polydimethylsiloxane having a number average molecular weight of 2000 Daltons or less, α-[(meth)acryloxy-2-hydroxypropyloxy-(polyethyleneoxy)propyl]-terminated ω-C1-C4-alkyl terminated polydimethylsiloxane having a number average molecular weight of 2000 Daltons or less, α-[(meth)acryloxy-2-hydroxypropyloxy-(polyethyleneoxy)propyl]-terminated ω-C1-C4-alkyl terminated polydimethylsiloxane having a number average molecular weight of 2000 Daltons or less, α-[3-(meth)acrylamidoethoxy-2-hydroxypropyloxypropyl]-terminated ω-C<39591-C4-alkyl polydimethylsiloxane having a number average molecular weight of 2000 Daltons or less, α-[3-(meth)acrylamidopropyl ...isopropyl α-[3-(meth)acrylamidobutyloxy-2-hydroxypropyloxypropyl]-terminated ω-C1-C4-alkyl terminated polydimethylsiloxane having a number average molecular weight of 2000 or less, α-[3-(meth)acrylamidobutyloxy-2-hydroxypropyloxypropyl]-terminated ω-C1-C4-alkyl terminated polydimethylsiloxane having a number average molecular weight of 2000 or less, α-[3-(meth)acrylamidobutyloxy-2-hydroxypropyloxypropyl]-terminated ω-C1-C4-alkyl polydimethylsiloxane having a number average molecular weight of 2000 or less,48. The implantable silicone hydrogel contact lens of embodiment 47, wherein the first silicone-containing vinyl monomer is selected from the group consisting of α-[3-[N-methyl-(meth)acrylamido]-2-hydroxypropyloxypropyl] terminated ω-C1-C4-alkyl terminated polydimethylsiloxane having a number average molecular weight of 2000 Daltons or less, N-(2,3-dihydroxypropane)-N'-(propyltetra(dimethylsiloxy)-dimethylbutylsilane)(meth)acrylamide, and combinations thereof. 50. The silicone-containing polymerizable component is selected from the group consisting of a di-(meth)acrylamide-terminated polysiloxane vinyl crosslinker having a number average molecular weight of 4000 daltons or less, an α,ω-bis[3-(meth)acryloxy-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane having a number average molecular weight of 4000 daltons or less, an α,ω-bis[3-(meth)acryloxyeth ... α,ω-bis[3-(meth)acryloxypropyloxy-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxanes having a number average molecular weight of 4000 Daltons or less, α,ω-bis[3-(meth)acryloxybutyloxy-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxanes having a number average molecular weight of 4000 Daltons or less, α,ω-bis[3-(meth)acryloxybutyloxy-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxanes having a number average molecular weight of 8000 Daltons or less, ω-bis[3-(meth)acrylamidoethoxy-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acrylamidopropyloxy-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane having a number average molecular weight of 8000 Daltons or less, α,ω-bis[3-(meth)acrylamidoisopropyloxy-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane having a number average molecular weight of 4000 Daltons or less, α, ω-bis[3-(meth)acrylamidebutyloxy]-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane, α,ω-bis[3-(meth)acryloxyethylamino-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane having a number average molecular weight of 8000 Daltons or less, α,ω-bis[3-(meth)acryloxypropylamino-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane having a number average molecular weight of 8000 Daltons or less, α,ω-bis[3-(meth)acryloxybutylamino-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane, α,ω-bis[(meth)acrylamidoethylamino-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane having a number average molecular weight of 12,000 daltons or less, α,ω-bis[3-(meth)acrylamidopropylamino-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane having a number average molecular weight of 4,000 daltons or less, α,ω-bis[3-(meth)acrylamidobutylamino-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane having a number average molecular weight of 4,000 daltons or less, α,ω-bis[(meth)acrylamidobutylamino-2-hydroxypropyloxypropyl]-terminated polydimethylsiloxane having a number average molecular weight of 4,000 daltons or less, α,ω-bis[(meth)acryloxy-2-hydroxypropyloxyethylamino] α,ω-bis[(meth)acryloxy-2-hydroxypropyl-N-ethylaminopropyl]-terminated polydimethylsiloxanes having a number average molecular weight of 12,000 daltons or less, α,ω-bis[(meth)acryloxy-2-hydroxypropyl-aminopropyl]-polydimethylsiloxanes having a number average molecular weight of 8,000 daltons or less, α,ω-bis[(meth)acryloxy-2-hydroxypropyloxy-(polyethyleneoxy)propyl]-terminated polydimethylsiloxanes having a number average molecular weight of 4,000 daltons or less, α,ω-bis[(meth)acryloxyethyl-amino-carbonyloxy-ethoxy ...ω-bis[(meth)acryloxyethylamino-carbonyloxy-(polyethyleneoxy)propyl]-terminated polydimethylsiloxane; di-(meth)acryloyloxy-terminated or di-(meth)acrylamide-terminated chain extended polysiloxane vinyl crosslinkers, each of which contains at least two polysiloxane segments and a bond between each pair of polysiloxane segments and between one (meth)acryloyloxy group and one polysiloxane segment, each bond having at least one H-bond donor; polysiloxane vinyl crosslinkers having dimethylsiloxane units and hydrophilized siloxane units, each of which contains one monovalent C4-C hydroxyl group having one methyl substituent and at least one H-bond donor (preferably 2-6 hydroxyl groups); 40 50. The implantable silicone hydrogel contact lens of any one of embodiments 46-49, comprising a first silicone-containing vinyl crosslinker selected from the group consisting of those having organic radical substituents, and combinations thereof. 51. The implantable silicone hydrogel contact lens of any one of embodiments 46-49, wherein the silicone-containing polymerizable component comprises a first silicone-containing vinyl crosslinker comprising at least two urethane linkages (—O—CO—NH—), at least two urea linkages (—NH—CO—NH—), at least two hydroxyl groups, or a combination thereof. 52. The implantable silicone hydrogel contact lens of any one of embodiments 46-51, wherein the at least one hydrophilic vinyl monomer comprises at least one alkyl(meth)acrylamide, at least one hydroxyl-containing acrylic monomer, at least one amino-containing acrylic monomer, at least one carboxyl-containing acrylic monomer, at least one N-vinylamide monomer, at least one methylene-containing pyrrolidone monomer, at least one acrylic monomer having a C1-C4 alkoxyethoxy group, at least one vinyl ether monomer, at least one allyl ether monomer, at least one phosphorylcholine-containing vinyl monomer, N-2-hydroxyethyl vinylcarbamate, N-carboxyvinyl-β-alanine (VINAL), N-carboxyvinyl-α-alanine, or a combination thereof. 53. The implantable silicone hydrogel contact lens of embodiment 52, wherein the at least one alkyl(meth)acrylamide is 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. 54. The implantable silicone hydrogel contact lens of embodiment 52 or 53, wherein the at least one hydroxyl-containing acrylic monomer is selected from the group consisting of N-2-hydroxylethyl(meth)acrylamide, N,N-bis(hydroxyethyl)(meth)acrylamide, N-3-hydroxypropyl(meth)acrylamide, N-2-hydroxypropyl(meth)acrylamide, N-2,3-dihydroxypropyl(meth)acrylamide, N-tris(hydroxymethyl)methyl(meth)acrylamide, 2-hydroxyethyl(meth)acrylate, 3-hydroxypropyl(meth)acrylate, 2-hydroxypropyl(meth)acrylate, glycerol methacrylate (GMA), di(ethylene glycol)(meth)acrylate, tri(ethylene glycol)(meth)acrylate, tetra(ethylene glycol)(meth)acrylate, poly(ethylene glycol)(meth)acrylate having a number average molecular weight of up to 1500, poly(ethylene glycol)ethyl(meth)acrylamide having a number average molecular weight of up to 1500, and combinations thereof. 55. The implantable silicone hydrogel contact lens of embodiment 52, 53, or 54, wherein the at least one carboxyl-containing acrylic monomer is selected from the group consisting of 2-(meth)acrylamidoglycolic acid, (meth)acrylic acid, ethylacrylic acid, 3-(meth)acrylamido-propionic 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. 56. The at least one N-vinylamide monomer is selected from the group consisting of 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, and N-vinyl-5,5-dimethyl-2-pyrrolidone. N-vinyl-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 56. The implantable silicone hydrogel contact lens of any one of embodiments 52-55, wherein the vinyl copolymer is selected from the group consisting of 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 mixtures thereof. 57. 57. The implantable silicone hydrogel contact lens of any one of embodiments 52-56, wherein the at least one methylene-containing pyrrolidone monomer is 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. 58. The implantable silicone hydrogel contact lens of any one of embodiments 52 to 57, wherein the at least one acrylic monomer having a C1-C4 alkoxyethoxy group is selected from the group consisting of ethylene glycol methyl ether (meth)acrylate, di(ethylene glycol) methyl ether (meth)acrylate, tri(ethylene glycol) methyl ether (meth)acrylate, tetra(ethylene glycol) methyl ether (meth)acrylate, C1-C4-alkoxypoly(ethylene glycol) (meth)acrylates having a number average molecular weight of up to 1500, methoxy-poly(ethylene glycol)ethyl (meth)acrylamides having a number average molecular weight of up to 1500, and combinations thereof. 59. The implantable silicone hydrogel contact lens of any one of embodiments 52-58, wherein the at least one vinyl ether monomer is 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. 60. The implantable silicone hydrogel contact lens of any one of embodiments 52-59, wherein the at least one allyl ether monomer is 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. 61. The at least one phosphorylcholine-containing vinyl monomer is (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, (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,61. The implantable silicone hydrogel contact lens of any one of embodiments 52 to 60, selected from the group consisting of: 62. The implantable silicone hydrogel contact lens of any one of embodiments 46-61, wherein the silicone hydrogel bulk material further comprises repeat units of at least one second silicone-containing vinyl monomer (other than the first silicone-containing vinyl monomer) and / or second polysiloxane vinyl crosslinker (other than the first polysiloxane vinyl crosslinker); repeat units of at least one second hydrophobic non-silicone vinyl monomer; repeat units of at least one second non-silicone vinyl crosslinker; repeat units of at least one second polymerizable material selected from the group consisting of a second UV-absorbing vinyl monomer, a second UV / high-energy ultraviolet light ("HEVL")-absorbing vinyl monomer, a second polymerizable photochromic compound, a second polymerizable colorant (polymerizable dye), and combinations thereof; or combinations thereof. 63. The implantable silicone hydrogel contact lens of embodiment 45 or 62, wherein the at least one first hydrophobic non-silicone vinyl monomer and the at least one second hydrophobic non-silicone vinyl monomer are, independently of each other, selected from the group consisting of non-silicone hydrophobic acrylic monomers, fluorine-containing acrylic monomers, vinyl alkanoates, vinyloxyalkanes, styrene, vinyl toluene, vinyl chloride, vinylidene chloride, 1-butene, and combinations thereof. 64. The non-silicone hydrophobic acrylic monomer is methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isobornyl (meth)acrylate, (meth)acrylonitrile, or a combination thereof; and the fluorine-containing acrylic monomer is perfluorohexylethyl-thio-carbonyl-aminoethyl-methacrylate, perfluoro-substituted-C2-C 1264. The implantable silicone hydrogel contact lens of embodiment 63, wherein the vinyl alkanoate is vinyl acetate, vinyl propionate, vinyl butyrate, vinyl valerate, or a combination thereof; and the vinyloxyalkane is vinyl ethyl ether, propyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, cyclohexyl vinyl ether, t-butyl vinyl ether, or a combination thereof. 65. The at least one first non-silicone vinyl crosslinker and the at least one second non-silicone vinyl crosslinker are, independently of each other, selected from the group consisting of allyl methacrylate, allyl acrylate, triallyl isocyanurate, 2,4,6-triallyloxy-1,3,5-triazine, 1,2,4-trivinylcyclohexane, ethylene glycol dimethacrylate; ethylene glycol diacrylate; 1,3-propanediol diacrylate; 1,3-propanediol dimethacrylate; 2,3-propanediol diacrylate; 2,3-propanediol dimethacrylate; 1,4-butanediol dimethacrylate; 1,4-butanediol diacrylate; 1,5-pentanediol dimethacrylate; 1,5-pentanediol diacrylate; 1,6-hexanediol dimethacrylate; 1,6-hexanediol diacrylate; diethylene glycol dimethacrylate; diethylene glycol diacrylate; triethylene glycol diacrylate; Ethylene glycol dimethacrylate;Triethylene glycol diacrylate;Tetraethylene glycol dimethacrylate;Tetraethylene glycol diacrylate;N,N'-Methylenebis(acrylamide);N,N'-Methylenebis(methacrylamide);N,N'-Ethylenebis(acrylamide);N,N'-Ethylenebis(methacrylamide);N,N'-Hexamethylenebisacrylamide;N,N'-Hexamethylenebismethacrylamide;Pentaerythritol triacrylate, Pentaerythritol trimethacrylate, Trimethylolpropane triacrylate, Trimethylolpropane trimethacrylate, Tris(2-hydroxyethyl)isocyanurate triacrylate, Tris(2-hydroxyethyl)isocyanurate trimethacrylate, 1,3,5-Triacryloxylhexahydro-1,3,5-triazine, 1,3,5-Triacryloxylhexahydro-1,3,5-triazine;65. The implantable silicone hydrogel contact lens of any one of embodiments 45 and 62-64, wherein the silicone hydrogel is selected from the group consisting of pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, di(trimethyloylpropane)tetraacrylate, di(trimethyloylpropane)tetramethacrylate, or combinations thereof;

[0154] Those skilled in the art will be able to practice the present invention based on the above disclosure. Various modifications, variations and combinations can be made to the various embodiments described herein. In order to enable the reader to more fully understand specific embodiments and their advantages, reference to the following examples is proposed. It is intended that the specification and examples be considered as illustrative. [Example]

[0155] Example 1 Oxygen permeability measurement Unless otherwise specified, the oxygen permeability (Dk / t) of the lens and lens material, the intrinsic (or edge-corrected) oxygen permeability (Dk i or Dk c ) is measured according to the procedure described in ISO 18369-4.

[0156] equilibrium water content The equilibrium water content (EWC) of a contact lens is measured as follows.

[0157] The amount of water (expressed as weight percent) present in hydrated hydrogel contact lenses that are fully equilibrated in saline is measured at room temperature. The lenses are quickly stacked and, after wiping them with 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. The hydrated weight of the pan + lens is recorded. The pan is covered with aluminum foil. The pan is placed in a laboratory oven at 100±2°C to dry for 16-18 hours. The pan + lens is removed from the oven and allowed to cool in a desiccator for at least 30 minutes. Only one pan is removed from the desiccator and the aluminum foil is discarded. The pan + dry lens sample is weighed on the analytical balance. Repeat for all pans. The wet and dry weights of the lens sample can be calculated by subtracting the weight of the empty weighing pan.

[0158] Elastic modulus The storage modulus (Young's modulus) of the inserts is determined using a TA RSA-G2 DMA (Dynamic Mechanical Analyzer). The inserts are cut into 3.08 mm wide strips using a Precision Concept dry lens cutter. Five thickness values ​​are measured within a 6.5 mm gauge length. The strips are attached to the instrument using metal grips. The inserts are subjected to an oscillatory temperature ramp test using a linear heating rate of 10 °C to 50 °C at 2 °C / min to monitor the material's response to increasing temperature at a constant frequency of 1 Hz, a constant amplitude of 0.5% strain, and a sampling rate of 10.0 pts / s. Storage modulus (E'), loss modulus (E"), and tan δ data are calculated using TRIOS software.

[0159] The modulus of elasticity of contact lenses is measured using an MTS Insight instrument. Contact lenses are first cut into 3.12 mm wide strips using a Precision Concept two-stage cutter. Five thickness values ​​are measured within a 6.5 mm gauge length. The strips are attached to the instrument grips and submerged in PBS (phosphate buffered saline) at a controlled temperature of 21 ± 2°C. Typically, a 5 N load cell is used for testing. A constant force and rate are applied to the sample until it breaks. Force and displacement data are collected by TestWorks software. The modulus value is calculated by the TestWorks software and is the slope or tangent of the stress versus strain curve near zero elongation in the elastic deformation region.

[0160] refractive index The refractive index (RI) of the inserts is determined with an Abbe transmission laboratory refractometer Reichert Abbe Mark III at 25° C. Before the measurements, the inserts are fully equilibrated in PBS saline.

[0161] The refractive index (RI) of the polysiloxane vinyl crosslinker is determined by a Rudolph Research analytical refractometer (Model J357) at 20° C. The RI of distilled water (RI of 1.33299 at 20° C.) is used as a standard and is performed before and after the measurement of the polysiloxane vinyl crosslinker.

[0162] Glass transition temperature The glass transition temperature (Tg) of the insert is defined as the peak of tan δ from a dynamic heating test by using a TA RSA-G2 DMA (Dynamic Mechanical Analyzer).

[0163] According to the present application, the glass transition temperature (Tg) of a polysiloxane vinyl crosslinker is the midpoint temperature of a differential scanning calorimetry (DSC) diagram obtained using differential scanning calorimetry. Figure 1 shows a DSC diagram obtained for a polysiloxane vinyl crosslinker of the present invention, characterized by its onset temperature, midpoint temperature, inflection temperature, and end temperature.

[0164] Peeling Implantable silicone hydrogel contact lenses are tested for potential delamination using an Optimec instrument or Optical Coherence Tomography (OCT).

[0165] Regardless of the evaluation method, the contact lenses are staged for a minimum of 12 hours at room temperature after the autoclave run and before the peeling study.

[0166] After the required staging time has been met, the fully hydrated contact lens is placed into the "V" graticule assembly of the Optimec instrument (Model JCF; OPTIMEC England). After the contact lens has set under the influence of gravity, the front surface of the contact lens is carefully examined for any signs of a circular pattern. Delamination will appear as a circular pattern on the Optimec image.

[0167] OCT (Thorlabs Spectral Domain Optical Coherence Tomography (Model-II)) can also be used to study delamination. OCT allows noninvasive imaging of contact lenses to obtain high-resolution cross-sectional images. For this purpose, after meeting minimum staging requirements, the contact lens is removed from its blister and immersed in PBS solution for a minimum of 30 minutes until equilibration occurs. A cuvette with a "V" block feature is then filled approximately three-quarters with fresh PBS solution, and the contact lens is transferred to the cuvette using a Q-tip. The lens is allowed to float freely in the "V" shape at the bottom of the cuvette, and the entire contact lens is scanned in 10-degree increments. Delamination appears in the OCT image as air pockets at the spacing surfaces of the insert and carrier.

[0168] chemicals In the following examples, the following abbreviations are used: BzA stands for benzyl acrylate; BzMA stands for benzyl methacrylate; DVBz stands for divinylbenzene; p-STTMS stands for styrenyltrimethoxysilane; PETA stands for pentaerythritol tetraacrylate; TrisMA stands for 3-[tris(trimethylsiloxy)silyl]propyl methacrylate; D6 stands for monobutyl-terminated, monomethacryloxypropyl-terminated polydimethylsiloxane (MW 600-800 g / mol, from Gelest); D MA represents N,N-dimethylacrylamide; MMA represents methyl methacrylate; TEGDMA represents triethylene glycol dimethacrylate; Vazo-67 represents 2,2'-azobis(2-methylbutyronitrile); Ominirad-1173 represents a photoinitiator made from 2-hydroxy-2-methyl-1-phenylpropanone; Nobloc is 2-[3-(2H-benzotriazol-2-yl)-4-hydroxyphenyl]ethyl methacrylate from Aldrich; RB247 is Reactive Blue 247 (2-propenoic acid, 2-methyl-,1,1'-[(9,10-dihydro-9,10-dioxo-1,4-anthracenediyl)bis(imino-2,1-ethanediyl)] ester); TAA represents tert-amyl alcohol; PrOH represents 1-propanol; IPA represents isopropanol; PPG represents poly(propylene glycol); EGBE represents ethylene glycol butyl ether; PBS has a pH of 7.2±0.2 at 25°C and contains approximately 0.044 wt% NaH2PO4·H2O, approximately 0 represents phosphate buffered saline containing 0.388 wt.% NaHPO·2H0 and about 0.79 wt.% NaCl; wt.% represents weight percent; "H4" macromer represents a di-methacryloyloxypropyl-terminated polysiloxane (Mn about 11.3-12.3 Kg / mol, OH content about 1.82-2.01 meq / g) of formula (A) shown below; "HA" macromer represents a di-methacryloyloxypropyl-terminated polysiloxane (Mn about 6.8 Kg / mol, OH content about 1.2 meq / g) of formula (A) shown below. [ka]

[0169] Example 2 Hydrosiloxane-containing polydiorganosiloxanes (precursors for producing the polysiloxane vinyl crosslinkers of the present invention) are prepared according to the procedure shown in Scheme 1. [ka]

[0170] Synthesis of hydrosiloxane-containing polydiorganosiloxane (Mn ca. 5KD) 602.05 g of octamethylcyclotetrasiloxane (D4), 510.32 g of 1,3,5,7-tetramethylcyclotetrasiloxane (D4H), and 92.81 g of 1,3-bis(3-methacryloxypropyl)tetramethyldisiloxane were weighed and premixed in a flask, then placed in a 2 L jacketed reactor equipped with a mechanical motor, thermocouple, and nitrogen flow adapter. 2.4 g of triflic acid was then added to the stirred reaction mixture via pipette. The reaction was stirred at 25°C for approximately 16 hours. After the reaction was complete, the solution was diluted with 1000 mL of toluene, then neutralized with solid base, and then stirred for 1 hour. The final mixture was filtered using a 0.45 micron glass microfiber filter. At this point, BHT and MEHQ inhibitors were added (250 ppm each). The polymer solution was concentrated on a rotary evaporator, followed by removal of residual solvent under low vacuum. The resulting precursor was not purified and had a number average molecular weight of about 5,000 g / mol and an average x of about 31 ( 1 HNMR), and the average y is about 32 ( 1 by HNMR).

[0171] Synthesis of hydrosiloxane-containing polydiorganosiloxane (Mn ca. 3KD) 100.19 g of octamethylcyclotetrasiloxane (D4), 247.39 g of 1,3,5,7-tetramethylcyclotetrasiloxane (D4H), and 51.32 g of 1,3-bis(3-methacryloxypropyl)-tetramethyldisiloxane were weighed and premixed in a flask and then placed in a 1 L jacketed reactor equipped with a mechanical motor, thermocouple, and nitrogen flow adapter. 0.8 g of triflic acid was then added to the stirred reaction mixture via pipette. The reaction was stirred at 25°C for approximately 16 hours. After the reaction was complete, the solution was diluted with 200 mL of toluene, then neutralized with solid base, and then stirred for 1 hour. The final mixture was filtered using a 0.45 micron glass microfiber filter. At this point, BHT and MEHQ inhibitors were added (250 ppm each). The polymer solution was concentrated on a rotary evaporator, followed by removal of residual solvent under low vacuum. The resulting precursor was not purified and had a number average molecular weight of about 3,000 g / mol and an average x of about 9.4 ( 1 1 H NMR), and the average y is about 28.1 ( 1 1 H NMR).

[0172] Example 3 Synthesis of high refractive index polysiloxane vinyl crosslinkers: [ka] A 500 mL jacketed reactor equipped with a mechanical stirrer, thermocouple, nitrogen inlet, septum, and condenser was heated to 80 °C and purged with nitrogen at a rate of 100 mL / min for 30 minutes. Allyl phenyl ether (approximately 158.62 g, i.e., a 2:1 molar ratio relative to the hydrosiloxane units), toluene (40 mL), and approximately 88.1 μL (approximately 25 ppm relative to the precursor) of Karstedt catalyst solution were added to the reactor. The nitrogen flow rate was reduced to 50 mL / min. Approximately 60.00 g of the hydrosiloxane-containing polydiorganosiloxane (Mn approximately 3 KD) prepared in Example 2, MEHQ inhibitor (0.0085 g), and toluene (60-80 mL) were placed in a beaker and stirred for 10 minutes until the MEHQ dissolved. The mixture was then loaded into two 100 mL Hamilton Gastight syringes equipped with plastic cannulas. Each syringe containing approximately 70 mL of polymer solution is secured to a Harvard PHD Infusion syringe pump, and the feed line is inserted into the reactor via a rubber septum. The solution of hydrosiloxane-containing polydiorganosiloxane in toluene is added via the syringe pump over 5 hours (rate of 0.2333 mL / min). The reactor temperature is maintained at 80 ± 2 °C throughout the reaction. After the addition of the polymer, the reaction mixture is stirred for an additional hour. After this time, an IR scan of the crude reaction mixture confirms complete consumption of the Si-H bonds. The reaction mixture is then cooled to room temperature, and the crude polymer is purified by thin-film distillation (the hot finger temperature reaches 100 °C via water reflux, and a vacuum of 1.3–1.9 mbar is maintained throughout the process). The collected polymer fraction is heated to a T of −48 °C. g and a refractive index of 1.51553 (at 20°C). 1 The 1 H NMR spectrum does not show the presence of allyl phenyl ether.

[0173] The hydrosiloxane-containing polydiorganosiloxane (Mn approx. 5KD) prepared in Example 2 was also used to prepare a polysiloxane vinyl crosslinker according to the above procedure. The resulting polysiloxane vinyl crosslinker had a refractive index of 1.49617 (20°C).

[0174] Example 4 Insert Compound The polymerizable composition for making the insert (insert formulation) is prepared in air at room temperature by blending all the components (materials) in their desired amounts (in parts by weight) to have the composition shown in Table 1.

[0175] [Table 1]

[0176] Cast Molded Inserts The insert formulation (polymerizable composition) is purged with nitrogen for 30-35 minutes at room temperature. The N2-purged polymerizable composition (30-40 mg) is introduced into a polypropylene mold, which is then sealed and placed in an oven. The oven is configured as follows: a nitrogen supply is connected to the oven through a high-flow volumetric controller that can control the flow rate of nitrogen through the oven; a vacuum pump is connected to the oven exhaust line to control the oven differential pressure.

[0177] The insert formulation (polymerizable composition) in the mold is thermally cured in an oven under the following conditions: 25°C, 80 scfh (standard cubic feet per hour) N2 flow, hold for approximately 30 minutes; 25°C to 55°C at a rate of approximately 7°C / min; 55°C, 40 scfh N2 flow, hold for approximately 30 minutes; 55°C to 80°C at a rate of approximately 7°C / min; 80°C, 40 scfh N2 flow, hold for approximately 30 minutes; 80°C to 100°C at a rate of approximately 7°C / min; 100°C, 40 scfh N2 flow, hold for approximately 30 minutes. The mold is opened, and the molded insert is removed from the mold.

[0178] The inserts may or may not be extracted. The following procedure is used to extract the inserts (if necessary): First, the inserts are extracted with PrOH for approximately 3 hours, rinsed twice with deionized water for approximately 10 minutes, and dried in a vacuum oven at 50°C and 26 mmHg for 1 hour. The inserts obtained from Insert Formulation #1 have an RI of approximately 1.50; the inserts obtained from Insert Formulation #2 have an RI of approximately 1.51; and the inserts obtained from Insert Formulation #3 have an RI of approximately 1.55.

[0179] SiHy Lens Formulation The two SiHy lens formulations are prepared at room temperature in air by blending all the components (materials) in their desired amounts (in parts by weight) to have the compositions shown in Table 2.

[0180] [Table 2]

[0181] Fabrication of SiHy contact lenses Thermally or actinically cast SiHy contact lenses are made as follows.

[0182] Mold Assembly: A fixed amount (approximately 50-60 mg) of the SiHy lens formulation prepared above is injected into a polypropylene female mold half, and then a polypropylene male mold half is placed on top of the female mold half and the mold is tightly closed to form a mold assembly.

[0183] Heat Curing. The molded assembly (i.e., the closed mold with the SiHy lens formulation therein) is heat cured in an oven under the following conditions: 25°C, 80 scfh N2 flow, hold for approximately 30 minutes; 25°C to 55°C at a rate of approximately 7°C / min; 55°C, 40 scfh N2 flow, hold for approximately 30 minutes; 55°C to 80°C at a rate of approximately 7°C / min; 80°C, 40 scfh N2 flow, hold for approximately 30 minutes; 80°C to 100°C at a rate of approximately 7°C / min; 100°C, 40 scfh N2 flow, hold for approximately 30 minutes.

[0184] Actinic Radiation Curing. The mold assembly (i.e., the closed mold with SiHy Lens Formulation #5 inside) was cured with approximately 1 mW / cm 2 The coating is then fully cured using a double-sided UV curing oven (Wicked Engineering, UV LED Module 9W 365nm / 405nm) with an intensity of 1000 kJ / min for 10 minutes.

[0185] Demolding and Lens Removal. The lens molds, each with a SiHy contact lens green therein, are mechanically opened. The molded SiHy contact lenses are attached to either male or female mold halves. The molded SiHy contact lenses attached to the male mold halves are removed using an ultrasonic device; the molded SiHy contact lenses attached to the female mold halves are manually removed from the female mold halves to which the lenses are attached.

[0186] Post-Lens Detachment Process: The detached raw SiHy contact lenses can be extracted using a 50:50 mixture of propylene glycol and water. Preferably, the detached raw SiHy contact lenses undergo the following extraction / hydration, coating, and autoclave processes: the raw SiHy contact lenses are immersed in a bath containing deionized water or an aqueous solution of Tween 80 (500 ppm) for about 60 minutes, then in a bath containing an aqueous solution of polyacrylic acid (PAA, Mw 450K) at a concentration of about 0.1 wt% at 40°C for about 120 minutes, and then in a bath containing PBS solution at room temperature for about 60 minutes; packaged / sealed in polypropylene lens packaging shells (or blisters) (one lens per shell) with 0.65 mL of in-package coating packaging saline prepared according to the procedure described in Example 19 of U.S. Pat. No. 8,480,227; and finally autoclaved at 121°C for about 45 minutes. The resulting SiHy contact lenses each have a hydrogel coating thereon.

[0187] The lens properties of the resulting SiHy contact lenses were determined according to the procedures described in Example 1 and are reported in Table 3.

[0188] [Table 3]

[0189] Fabrication of a fully implantable SiHy contact lens Thermally or actinically cast implantable SiHy contact lenses are made as follows.

[0190] Mold Assembly: The insert prepared above is placed in the central region of the molding surface of a (polypropylene) female mold half, preferably having three or more circularly distributed spikes of sufficient diameter to accommodate the insert to secure its position on the molding surface, a certain amount (approximately 50-60 mg) of the SiHy lens formulation prepared above is injected into the female mold half, allowing the insert to soak, and then a polypropylene male mold half is placed on top of the female mold half, and the mold is tightly closed to form a mold assembly.

[0191] Heat Curing The mold assemblies (i.e., the closed molds each containing an insert dipped in a SiHy lens formulation) are heat cured according to the procedure described above for producing SiHy contact lenses.

[0192] Actinic Radiation Curing: The mold assemblies (i.e., the closed molds each containing an insert dipped in SiHy Lens Formulation #5) are fully cured by actinic radiation according to the procedure described above for producing SiHy contact lenses.

[0193] Demolding and Lens Removal Demolding and lens removal are performed as described above for the manufacture of SiHy contact lenses.

[0194] Post-Lens Detachment Processing: The detached raw implantable SiHy contact lenses are subjected to the extraction / hydration, coating, and autoclave processes described above to produce SiHy contact lenses. The resulting implantable SiHy contact lenses each have a hydrogel coating thereon.

[0195] The resulting implantable SiHy contact lenses are examined under a microscope (i.e., using OCT according to the procedure described in Example 1) for possible delamination. No delamination is observed. The implantable SiHy contact lenses exhibit a well-defined lens shape without distortion after lens removal, extraction, coating, hydration, and autoclaving. Both the insert and bulk SiHy material have minimal swelling ratios upon hydration, which is believed to result in minimal internal stresses and therefore excellent shape stability over time. The characterization of the implantable SiHy contact lenses is reported in Table 4.

[0196] [Table 4]

[0197] By having a difference of at least about 0.07, the implantable SiHy contact lenses of the present invention can be particularly useful in the manufacture of diffractive multifocal contact lenses.

[0198] Fabrication of partially implantable SiHy contact lenses Thermally or actinically cast implantable SiHy contact lenses are made as follows.

[0199] The insert-molding composition (Insert Formulation #2) prepared above is purged with nitrogen for 30-35 minutes at room temperature. A specific volume (e.g., 30-40 mg) of the N2-purged insert-molding composition is placed at the center of the molding surface of a polypropylene female lens mold half. The molding surface defines the anterior surface of the contact lens to be molded. The female lens mold half containing the insert-molding composition is closed with a polypropylene male insert mold half designed with an overflow groove into which excess insert-molding composition is forced upon closure to form a first mold assembly. The male insert mold half has a molding surface that defines the posterior surface of the insert to be molded. The oven is configured as follows: a nitrogen supply is connected to the oven through a high-flow capacity controller capable of controlling the flow rate of nitrogen through the oven; and a vacuum pump is connected to the oven's exhaust line to control the oven's differential pressure.

[0200] The insert-forming composition in the first mold assembly is thermally cured in an oven under the following conditions: room temperature to 55°C at a rate of about 7°C / min; hold at 55°C for about 30-40 minutes; heat from 55°C to 80°C at a rate of about 7°C / min; hold at 55°C for about 30-40 minutes; heat from 80°C to 100°C at a rate of about 7°C / min; hold at 100°C for about 30-40 minutes. The first mold assembly is opened. The molded insert is attached to the central region of the molding surface of the female lens mold half.

[0201] The lens-forming composition prepared above (SiHy Lens Formulation #1) is purged with nitrogen for 30-35 minutes at room temperature. A specific volume (e.g., 50-60 mg) of the N2-purged lens-forming composition is placed on a molded insert attached to the central portion of the molding surface of a female lens mold half. The female lens mold half with the insert and lens-forming composition attached thereon is closed with a male lens mold half made of polypropylene and designed with an overflow groove into which excess insert-forming composition is forced upon closing to form a second mold assembly. The male lens mold half has a molding surface that will mold and define the posterior surface of the contact lens. The oven is configured as follows: a nitrogen supply is connected to the oven through a high-flow volumetric controller capable of controlling the flow rate of nitrogen through the oven; and a vacuum pump is connected at the oven exhaust line to control the differential pressure of the oven.

[0202] The closed second mold assemblies, each containing a mold insert immersed in the lens-forming composition within its lens-molding cavity, are heat-cured in an oven under the following conditions: room temperature to 55°C at a rate of about 7°C / min; hold at 55°C for about 30-40 minutes; 55°C to 80°C at a rate of about 7°C / min; hold at 55°C for about 30-40 minutes; 80°C to 100°C at a rate of about 7°C / min; hold at 100°C for about 30-40 minutes. The second mold assemblies, each having a molded green implantable silicone hydrogel contact lens attached thereto, are mechanically opened. The molded green implantable silicone hydrogel contact lenses are attached to either the male or female mold half. The molded, uncut implantable silicone hydrogel contact lens attached to the male mold half is removed using an ultrasonic device; the molded, uncut implantable silicone hydrogel contact lens attached to the female mold half is manually removed from the female mold half to which the lens is attached.

[0203] The removed raw implantable SiHy contact lenses are subjected to the extraction / hydration, coating, and autoclaving processes described above to produce SiHy contact lenses, each having a hydrogel coating thereon.

[0204] The resulting partially implantable SiHy contact lenses are examined for possible delamination using OCT according to the procedure described in Example 1. No delamination is observed. The implantable SiHy contact lenses exhibit a well-defined lens shape without distortion after lens removal, extraction, coating, hydration, and autoclaving. Both the insert and bulk SiHy material have minimal swelling ratios upon hydration, which is believed to result in minimal internal stresses and therefore excellent shape stability over time. Characterization of the implantable SiHy contact lenses is reported in Table 5.

[0205] [Table 5]

[0206] By having a difference of at least about 0.08, the partially implantable SiHy contact lenses of the present invention can be particularly useful in the manufacture of diffractive multifocal contact lenses.

[0207] All publications, patents, and published patent applications cited herein above are hereby incorporated by reference in their entirety.

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