HK1189011B - Amphiphilic polysiloxane prepolymers and uses thereof - Google Patents

Description

Amphiphilic polysiloxane prepolymers and their use

The present invention relates to a class of amphiphilic polysiloxane prepolymers suitable for use in the preparation of hydrogel contact lenses. The invention also relates to hydrogel contact lenses made from the amphiphilic polysiloxane prepolymers of the invention and to methods of making the amphiphilic polysiloxane prepolymers of the invention and of making silicone hydrogel contact lenses.

Background

Currently, commercially available silicone hydrogel contact lenses are produced according to conventional cast molding techniques, which include the use of disposable plastic molds and monomer mixtures, with or without the presence of macromers. However, disposable plastic molds themselves have unavoidable dimensional variations because, during injection molding of the plastic mold, fluctuations in the mold dimensions may occur due to fluctuations in the production process (temperature, pressure, material properties), and because the final mold may undergo uneven shrinkage after injection molding. Dimensional changes in the mold can lead to fluctuations in the contact lens parameters (peak refractive index, diameter, base curve, center thickness, etc.) to be produced and low fidelity in replicating complex lens designs.

The above-mentioned disadvantages encountered in conventional cast molding techniques can be overcome by using the so-called lightstream technology as explained in U.S. Pat. nos. 5,508,317, 5,789,464, 5,849,810 and 6,800,225^TM(CIBAVision) was overcome and the above patent documents are incorporated by reference in their entirety. Lightstream technology^TMIncluding reusable molds for high precision production and curing under spatial constraints of actinic radiation (e.g., UV). According to LightstreamTechnology, because of the use of reusable high-precision moulds^TMThe lenses produced may have high consistency and high retention of the original lens design. In addition, contact lenses having high quality can be produced at relatively low cost due to short curing times and high yield.

In order to use LightstreamTechnology in the preparation of silicone hydrogel contact lenses^TMSilicone-containing prepolymers have been developed, such as those described in U.S. patents 6,039,913, 6,043,328, 7,091,283, 7,268,189 and 7,238,750, 7,521,519; U.S. patent publication applications US2008-0015315a1, US2008-0143958a1, US2008-0143003a1, US2008-0234457a1, US2008-0231798a1 to the same owner and U.S. patent applications 12/313,546, 12/616,166 and 12/616169 to the same owner, which are incorporated by reference in their entirety. However, prepolymers of the types disclosed in the above patents and patent applications are useful inFor use in light stream technology^TMThere may be some practical limitations in the process of making silicone hydrogel contact lenses.

Co-pending U.S. patent application 12/456,364 (incorporated herein by reference in its entirety) discloses a method according to lightstream technology^TMMethods of making silicone hydrogel contact lenses from a monomer mixture (i.e., a lens-forming composition). However, it has been found herein that in addition to relatively long cure times, relatively significant shrinkage can occur during curing of the monomer mixture within the mold, which can greatly impede the use of lightstream technology in the preparation of silicone hydrogel contact lenses^TM。

Thus, there still exists a need for a method suitable for use in accordance with lightstream technology^TMThere is a need for new prepolymers for making silicone hydrogel contact lenses.

Summary of The Invention

The invention provides a method suitable for use in light stream technology^TMAmphiphilic branched polysiloxane prepolymers for making silicone hydrogel contact lenses. The polysiloxane prepolymer comprises hydrophilic monomer units derived from at least one hydrophilic vinyl monomer, polysiloxane crosslinking units derived from at least one polysiloxane crosslinker having at least two terminal ethylenically unsaturated groups, each side chain polysiloxane chain of the polysiloxane crosslinker being terminated with an ethylenically unsaturated group, and chain transfer units derived from a chain transfer agent other than a RAFT agent.

The invention also provides a method of making a silicone hydrogel contact lens. The method comprises the following steps: (i) obtaining an amphiphilic branched polysiloxane prepolymer of the invention (as described above), (ii) preparing a lens-forming composition using the amphiphilic branched polysiloxane prepolymer, said composition additionally comprising a free radical initiator and optionally at least one polymerizable component selected from the group consisting of hydrophilic vinyl monomers, silicone-containing vinyl monomers or macromers, hydrophobic vinyl monomers, linear polysiloxane crosslinkers end-capped with two ethylenically unsaturated groups, crosslinkers having a molecular weight of less than 700 daltons, and mixtures thereof; (ii) adding a lens-forming composition to a mold having a first mold half having a first molding surface defining an anterior surface of a contact lens and a second mold half having a second molding surface defining a posterior surface of a contact lens, wherein said first and second mold halves are configured to be received in one another so as to form a cavity between said first and second molding surfaces for receiving a lens-forming material; and (iii) polymerizing the lens-forming material within the cavity to form the silicone hydrogel contact lens.

The present invention further provides a process for producing the amphiphilic branched polysiloxane prepolymers of the present invention.

The present invention additionally provides silicone hydrogel contact lenses comprising a polymeric material polymerized from a lens-forming composition comprising the amphiphilic branched polysiloxane prepolymer of the present invention.

These and other aspects of the present invention will become apparent from the following description of the presently preferred embodiments. The detailed description is to be construed as merely illustrative of the invention and not limitative of the scope thereof, which is defined by the appended claims and their equivalents. It will be obvious to those skilled in the art that many changes and modifications may be made without departing from the spirit and scope of the novel concepts of the specification.

Detailed description of embodiments of the invention

Unless defined otherwise, 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 used herein and the laboratory research methods are well known and commonly employed in the art. Conventional methods are used for the above-described research methods, such as those provided in the art and various general references. Where a term is provided in the singular, the invention also includes the plural of that term. The nomenclature used herein and the laboratory research procedures described below are those well known and commonly employed in the art.

"contact lens" refers to a device that can be placed on or in the eye of a wearer. Contact lenses can correct, improve or alter a user's vision, but this need not be the case. By "silicone hydrogel contact lens" is meant a contact lens comprising a silicone hydrogel material.

"hydrogel" or "hydrogel material" refers to a polymeric material that can absorb at least 10% by weight water when it is fully hydrated.

"silicone hydrogel" refers to a silicone-containing hydrogel obtained by copolymerization of a polymerizable composition comprising at least one silicone-containing vinyl monomer or macromer, a silicone-containing crosslinker, and/or at least one crosslinkable silicone-containing prepolymer.

"vinyl monomer" refers to a low molecular weight compound having one sole ethylenically unsaturated group. Low molecular weight generally means an average molecular weight of less than 700 daltons.

Vinyl macromers refer to neutralized high molecular weight compounds containing one sole ethylenically unsaturated group. By neutralized high molecular weight is generally meant an average molecular weight greater than 700 daltons.

The term "ethylenically unsaturated group" or "ethylenically unsaturated group" is used in a broad sense and is meant to include a compound containing at least one>C＝C<Any one of the groups. Exemplary ethylenically unsaturated groups include, but are not limited to, (meth) acryloyl: (meth)And/or) Allyl, vinylStyryl or other groups containing C ═ C.

As used herein, "actinically" with respect to curing, crosslinking, or polymerizing a polymerizable composition, prepolymer, or material means that curing (e.g., crosslinking and/or polymerization) is performed by actinic radiation, such as UV/visible light radiation, ionic radiation (e.g., gamma ray or X-ray radiation), microwave radiation, and the like. Thermal or actinic curing methods are well known to those skilled in the art.

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

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

As used herein, "hydrophilic vinyl monomer" refers to a vinyl monomer that can polymerize to form a homopolymer that is water soluble or can absorb at least 10 weight percent water.

"hydrophobic vinyl monomer" refers to a vinyl monomer that can polymerize to form a homopolymer that is insoluble in water and can absorb less than 10 weight percent water.

As used herein, the term "amino" refers to a functional group that is-NHR ', where R' is hydrogen or C₁-C₂₀Unsubstituted or substituted, straight-chain or branched alkyl groups.

As used herein, the term "azlactone (azlactone) group" refers to a compound having the formulaWherein r is 0 or 1; r₁And R₂May independently be an alkyl group having 1 to 14 carbon atoms, a cycloalkyl group having 3 to 14 carbon atoms, an aryl group having 5 to 12 ring atoms, an aryl (aryl) group having 6 to 26 carbons and 0 to 3 sulfur, nitrogen and/or oxygen atoms, or R₁And R₂Together with the carbon to which they are attached may form a carbocyclic ring containing from 4 to 12 ring atoms.

As used herein, "polysiloxane" refers to a polysiloxane comprising at least one divalent groupA compound or segment of (a), wherein R₃、R₄、R₅、R₆、R₇、R₈、R₉And R₁₀Independently of one another are C₁-C₁₀Alkyl radical, C₁-C₁₀Aminoalkyl radical, C₁-C₁₀Hydroxyalkyl radical, C₁-C₁₀Ether, C₁-C₄Alkyl-or C₁-C₄-alkoxy-substituted phenyl, C₁-C₁₀Fluoroalkyl, C₁-C₁₀Fluoroether, C₆-C₁₈Aryl radical, cyano radical (C)₁-C₁₂-alkyl), -alk- (OCH)₂CH₂)_n-OR₁₁Wherein alk is C₁-C₆Alkylene divalent radical, R₁₁Is hydrogen or C₁-C₆Alkyl and n is an integer from 1 to 10; m and p are each independently an integer from 0 to 350 and (m + p) is from 1 to 700.

"crosslinker" refers to a compound having at least two ethylenically unsaturated groups.

"crosslinker" refers to a compound having two or more ethylenically unsaturated groups and a molecular weight of less than 700 daltons. Crosslinkers can be used to improve structural integrity and mechanical strength. The amount of crosslinking agent used is expressed in terms of content relative to the weight of the total polymer and is preferably from about 0.05% to about 4%, and more preferably from about 0.1% to about 2%. Examples of preferred crosslinking agents include, but are not limited to, tetraethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, trimethylolpropane trimethacrylate, pentaerythritol tetramethacrylate, bisphenol a dimethacrylate, vinyl methacrylate, allyl (meth) acrylate, ethylenediamine di (meth) acrylamide, glycerol dimethacrylate, N ' -methylenedi (meth) acrylamide, N ' -ethylenedi (meth) acrylamide, N ' -dihydroxyethylenedi (meth) acrylamide, triallylisocyanate, triallyl cyanate, allyl (meth) acrylate, 1, 3-bis (methacrylamidopropyl) -1,1,3, 3-tetrakis (trimethylsiloxy) disiloxane, 1, 3-bis (N- (meth) acrylamidopropyl) -1,1,3, 3-tetrakis (trimethylsiloxy) disiloxane, 1, 3-bis (methacrylamidobutyl) -1,1,3, 3-tetrakis (trimethylsiloxy) -disiloxane, 1, 3-bis (methacryloyloxyethylureidopropyl) -1,1,3, 3-tetrakis (trimethylsiloxy) disiloxane, and combinations thereof. More preferred crosslinkers are hydrophilic crosslinkers such as tetra (ethylene glycol) diacrylate, tri (ethylene glycol) diacrylate, ethylene glycol diacrylate, di (ethylene glycol) diacrylate, glycerol dimethacrylate, N ' -methylenebis (meth) acrylamide, N ' -ethylenebis (meth) acrylamide, N ' -dihydroxyethylenebis (meth) acrylamide, triallyl isocyanate, triallyl cyanate, and combinations thereof.

As used herein, the term "fluid" means that a material is capable of flowing like a liquid.

"prepolymer" refers to a starting polymer that contains two or more ethylenically unsaturated groups and is actinically curable (e.g., crosslinked or polymerized) to yield a crosslinked polymer having a much higher molecular weight than the starting polymer.

"Silicone-containing prepolymer" refers to a silicone-containing prepolymer.

As used herein, "molecular weight" of a polymeric material (including monomeric or macromer materials) refers to weight average molecular weight, if not otherwise specified or if test conditions are not otherwise specified.

By "polymer" is meant a material formed by polymerizing one or more monomers.

The term "RAFT" refers to free radical addition-fragmentation transfer or reversible addition fragmentation chain transfer, as understood by those skilled in the art.

"RAFT agent" refers to a dithioester compoundWherein R is_LIs a leaving group and has the conventional meaning as understood by those skilled in the art; r_ZAre activating groups and have conventional meanings as understood by those skilled in the art.

As used herein, the term "alkene-functional" with respect to a copolymer or compound is meant to describe that one or more alkene groups have been covalently attached to the copolymer or compound through a pendant or terminal reactive functional group of the copolymer or compound according to a coupling process.

"ethylenically functionalized vinyl monomer" refers to vinyl monomers known to those skilled in the art having one reactive functional group capable of participating in a coupling (or crosslinking) reaction.

"coupling reaction" is meant to describe any reaction between a matching pair of functional groups that forms a covalent bond or linkage in the presence or absence of a coupling agent under a variety of reaction conditions well known to those skilled in the art, such as oxidation-reduction conditions, dehydrocondensation conditions, addition conditions, substitution (or displacement) conditions, Diels-Alder reaction conditions, cationic crosslinking conditions, ring opening conditions, epoxy hardening conditions, and combinations thereof.

Given below are the groups which are preferably selected from amino groups (-NHR' as defined above), hydroxyl groups, carboxylic acid groups, acid halide groups (-COX, X ═ Cl, Br or I), anhydride groups, aldehyde groups, azlactone groups, isocyanate groups, epoxide groups, aziridine groups, thiol groups and amide groups (-CONH) under various reaction conditions₂) By way of illustration, non-limiting examples of coupling reactions between a matched pair of co-reactive functional groups. The amino group reacts with the aldehyde group to form a Schiff base, which can be further reduced; reaction of an amino group-NHR' with an acid chloride or bromide group or an anhydride group to form an amide linkage (-CO-NR)' -; the amino group-NHR 'reacts with the isocyanate group to form a urea linkage (-NR' -c (o) -NH-); amino group-NHR 'reacts with an epoxy or aziridine group to form an amine bond (C-NR'); reaction (ring opening) of the amino group with an azlactone group to form a linkage (-C (O) NH-CR₁R₂-(CH₂)_r-C (O) -NR' -; the amino group-NHR 'reacts with the carboxylic acid group in the presence of a coupling agent-carbodiimide (e.g., 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide (EDC), N' -Dicyclohexylcarbodiimide (DCC), 1-cyclohexyl-3- (2-morpholinoethyl) carbodiimide, diisopropylcarbodiimide, or mixtures thereof) to form an amide linkage; the hydroxyl groups react with the isocyanate to form urethane linkages; the hydroxyl group reacts with the epoxy or azlactone to form an ether linkage (-O-); the hydroxyl group reacts with acyl chloride or acyl bromide group or with anhydride group to form ester connection; reaction of a hydroxyl group with an aziridine group in the presence of a catalyst to form a linkage (-C (O) NH-CR₁R₂-(CH₂)_r-c (O) -O-); the carboxyl group reacts with the epoxy group to form an ester bond; the reaction of a thiol group (-SH) with an isocyanate to form a thiocarbamate linkage (-N-C (O) -S-); the reaction of a thiol group with an epoxy or azlactone to form a thioether linkage (-S-); the thiol group reacts with an acid chloride or bromide or with an anhydride group to form a thiolate (thiol) linkage; reacting a thiol group with an aziridine group in the presence of a catalyst to form a linkage (-C (O) NH-alkylene-C (O) -S-); the thiol group reacts with the vinyl group based on a thiol-ene reaction under thiol-ene reaction conditions to form a thioether linkage (-S-); and a thiol group reacts with an acryloyl or methacryloyl group based on Michael addition under suitable reaction conditions to form a thioether linkage.

It will also be appreciated that coupling agents having two reactive functional groups may be used in the coupling reaction. For example, diisocyanates, dicarboxylic acid halides, dicarboxylic acids, diaziridines or diepoxides can be used in the coupling of two hydroxyl groups, two amino groups, two carboxyl groups, two epoxy groups or combinations thereof; diamines or dihydroxy compounds may be used in the coupling of two isocyanates, two epoxies, two azlactones, two carboxyl groups, two acid halides, or two aziridine groups, or combinations thereof.

The reaction conditions for the above-described coupling reactions are taught in textbooks and are well known to those skilled in the art.

As used herein, the term "partially ethylenically-functionalized polysiloxane" means a molar equivalent ratio R between an ethylenically-functionalized vinyl monomer having one first reactive functional group and a functionalized polysiloxane compound having two or more second reactive functional groups_{Equivalent weight}(i.e., [ functionalized vinyl monomer ]_eq]V. Linear polysiloxane monomer_eq]) A product mixture obtained from a functionalization reaction of about 0.95 (or 95%) or less alkenes, wherein a first reactive functional group can react with a second reactive functional group in the presence or absence of a coupling agent according to a known coupling reaction discussed later to form a covalent bond. As used herein, the term "xx% ethylenically functional polysiloxane" means a polysiloxane wherein the ratio of ethylenically functional vinyl monomer to functional polysiloxane compound is in molar equivalent ratio, R_{Equivalent weight}The product mixture obtained for "xx%" (i.e., a value of from about 40% to about 97%, preferably from about 50% to about 95%, more preferably from about 60% to about 92%, and still more preferably from about 70% to about 90%).

As an illustrative example, if the functionalized polysiloxane compound to be alkene-functionalized is a linear polysiloxane compound having two terminal reactive functional groups and the molar equivalent ratio R of alkene-functionalized vinyl monomer to polysiloxane compound_{Equivalent weight}About 80%, then 80% of the ethylenically functional polysiloxane is a mixture of (a) a linear polysiloxane crosslinker having two terminal ethylenically unsaturated groups, (b) a polysiloxane vinyl monomer or macromer terminated with one ethylenically unsaturated group and one second reactive functional group, and (c) an unreacted linear polysiloxane compound terminated with two second reactive functional groups. The percentage of components (a) to (c) of 80% ethylenically functionalized polysiloxane (after substantial completion of the reaction) can be estimated according to the following formula:

[ component (a)]％＝R_{Equivalent weight}×R_{Equivalent weight}＝64％

[ component (b)]％＝2×R_{Equivalent weight}×(1-R_{Equivalent weight})＝32％

[ component (c)]％＝(1-R_{Equivalent weight})×(1-R_{Equivalent weight})＝4％

It is to be understood that the functional silicone compound to be alkene-functionalized may be a star compound having "n" (e.g., 3-5) polysiloxane arms each terminated with one reactive functional group capable of participating in the coupling reaction. The amount of alkene-functional reaction product in the final mixture is (n +1) and the percentages are (R)_{Equivalent weight})ⁿ、(R_{Equivalent weight})^n-1x(1-R_{Equivalent weight})×n、(R_{Equivalent weight})^n-2×(1-R_{Equivalent weight})²×n、……、(R_{When in use Measurement of})x(1-R_{Equivalent weight})^n-1×n、(1-R_{Equivalent weight})ⁿ。

The term "plurality," as used herein, refers to two or more.

The free radical initiator may be a photoinitiator or a thermal initiator. "photoinitiator" refers to a chemical agent that initiates a free radical crosslinking/polymerization reaction through the use of light. Suitable photoinitiators include, but are not limited to, benzoin methyl ether, diethoxyacetophenone, benzoylphosphine oxide, 1-hydroxycyclohexyl phenyl ketone, and,Photoinitiators of the type andtype of photoinitiator, preferably1173 and2959. oxidation of benzoylphosphineExamples of the photoinitiator include 2,4, 6-trimethylbenzoyldiphenylphosphine oxide (TPO); bis (2, 6-dichlorobenzoyl) -4-N-propylphenylphosphine oxide; and bis (2, 6-dichlorobenzoyl) -4-N-butylphenyl phosphine oxide. Reactive photoinitiators which can, for example, be added to the macromonomer or can be used as special monomers are also suitable. Examples of reactive photoinitiators are those disclosed in EP632329, which is incorporated herein by reference in its entirety. The polymerization can be initiated by actinic radiation, for example light, in particular special UV light of suitable wavelength. The spectral requirements can thus be controlled by adding suitable photosensitizers, if appropriate.

"thermal initiator" refers to a chemical agent that initiates a free radical crosslinking/polymerization reaction by the use of thermal energy. Examples of suitable thermal initiators include, but are not limited to, 2,2 ' -azobis (2, 4-dimethylvaleronitrile), 2,2 ' -azobis (2-methylpropanenitrile), 2,2 ' -azobis (2-methylbutyronitrile), peroxides such as benzoyl peroxide, and the like. The preferred thermal initiator is 2, 2' -azobis (isobutyronitrile) (AIBN).

"polymerizable UV-absorbers" refer to compounds that contain an ethylenically unsaturated group and a UV-absorbing moiety or latent UV-absorbing moiety.

"UV-absorbing moiety" refers to an organofunctional group that absorbs or blocks UV radiation from 200nm to 400nm, as understood by those skilled in the art

By "polymerizable latent UV-absorber" is meant a compound comprising an ethylenically unsaturated group and a UV-absorbing moiety that has been protected by a labile functional group such that its absorption efficiency of UV radiation in the wavelength range of 200nm to 400nm is about 50% or less, preferably 70% or less, more preferably about 90% or less of the UV-absorbing moiety in the absence of the protected labile functional group.

The term "labile functional group" means a protective functional group that can be removed (cleaved) from another functional group protected by the labile functional group.

"spatial confinement of actinic radiation" refers to an action or process in which energy radiation in the form of radiation is directed through, for example, a mask or shutter or a combination thereof for projection in a spatially confined manner onto an area having a well-defined peripheral boundary. Spatial confinement of UV/visible radiation is achieved by using a mask or shield having a radiation (e.g., UV/visible) transmissive region, a radiation (e.g., UV/visible) opaque region surrounding the radiation transmissive region, and a projection profile, which is the boundary between the radiation opaque region and the radiation transmissive region, as illustrated in the drawings of U.S. patents 6,800,225 (fig. 1-11) and 6,627,124 (fig. 1-9), 7,384,590 (fig. 1-6) and 7,387,759 (fig. 1-6), all of which are incorporated herein by reference in their entirety. The mask or shield allows a beam of radiation (e.g., UV/visible radiation) to be spatially projected, the radiation having a cross-section defined by a projection profile of the mask or shield. The projection beam of radiation (e.g., UV/visible radiation) defines a projection of the radiation (e.g., UV/visible radiation) onto lens-forming material located in a projection beam path from the first molding surface to the second molding surface of the mold. The final contact lens includes a front face defined by the first molding surface, an opposite rear face defined by the second molding surface, and a lens edge defined by the cross-section of the projected UV/visible light beam (i.e., the spatial limitation of the radiation). The radiation used for crosslinking is radiation energy, in particular UV/visible radiation, gamma radiation, electron radiation or thermal radiation, preferably in the form of substantially parallel beams in order to achieve good confinement on the one hand and efficient use of the energy on the other hand.

In a conventional cast molding process, the first and second molding surfaces of the mold are pressed against each other to form a circumferential line of contact that defines the edge of the final contact lens. The mold cannot be reused because the close contact of the molding surface may destroy the optical properties of the molding surface. In contrast, in lightstream technology^TMThe edge of the final contact lens is not defined by the contact of the molding surfaces of the mold, but is replaced by a spatial limitation of the radiation. In a moldWithout any contact between the molding surfaces of (a), the mold can be reused to produce high quality contact lenses with high reproducibility.

The term "polysiloxane side chain" in relation to an amphiphilic branched polysiloxane copolymer or prepolymer is meant to describe that the copolymer or prepolymer comprises linear polysiloxane chains, each of which comprises one or more polysiloxane segments and is fixed to the backbone of the copolymer or prepolymer at one of the two ends of the polysiloxane chain by only one covalent linkage.

By "dye" is meant a substance that is soluble in the fluid material forming the lens and that is used to impart color. Dyes are generally translucent and absorb light without scattering it.

By "pigment" is meant a powdered substance (particle) suspended in the lens-forming composition in which it is insoluble.

As used herein, "surface modification" or "surface treatment" means that the article has been treated with a surface treatment process (or surface modification process) prior to or after the article is formed, wherein (1) a coating is applied to the surface of the article, (2) a chemical species is adsorbed onto the surface of the article, (3) the chemical nature (e.g., electrostatic charge) of chemical groups on the surface of the article is altered, or (4) the surface properties of the article are otherwise modified. Exemplary surface treatment processes include, but are not limited to, surface treatment by energy (e.g., plasma, electrostatic charge, radiation, or other energy source), chemical treatment, grafting of hydrophilic vinylic monomers or macromers onto the surface of the article, mold transfer application processes disclosed in U.S. patent 6,719,929 (incorporated herein by reference in its entirety), the addition of wetting agents to the lens formulation to prepare contact lenses as suggested in U.S. patents 6,367,929 and 6,822,016 (incorporated herein by reference in its entirety), the enhanced mold transfer application disclosed in U.S. patent application 60/811,949 (incorporated herein by reference in its entirety), and hydrophilic applications consisting of covalent linking or physical deposition of one or more layers of one or more hydrophilic polymers onto the surface of a contact lens.

"post-cure surface treatment" with respect to a silicone hydrogel material or a soft contact lens means a surface treatment process that is performed after formation (curing) of the hydrogel material or soft contact lens within a mold.

By "hydrophilic surface" with respect to a silicone hydrogel material or a soft contact lens is meant that the silicone hydrogel material or the contact lens has a surface hydrophilicity characterized by an average water contact angle of about 90 degrees or less, preferably about 80 degrees or less, more preferably about 70 degrees or less, and more preferably about 60 degrees or less.

"average contact angle" refers to the water contact angle (angle measured by the SessileDrop method) obtained by averaging the measurements of at least 3 individual contact lenses.

As used herein, "antimicrobial agent" refers to a chemical substance that is capable of reducing or eliminating or inhibiting the growth of microorganisms such as those terms known in the art. Preferred examples of the antibacterial agent include, but are not limited to, silver salts, silver complexes, silver nanoparticles, silver-containing zeolites, and the like.

"silver nanoparticles" refers to particles made primarily of silver metal and having a size of less than 1 micron.

The inherent "oxygen permeability," Dk, of a material is the rate at which oxygen gas passes through the material. According to the invention, the term "oxygen permeability (Dk)" in relation to a contact lens means the apparent oxygen permeability measured according to known methods with a sample (film or lens) of average thickness over the area to be measured. Oxygen permeability is generally expressed in units of barrer, where "barrer" is defined as [ (cm)³Oxygen) (mm)/(cm²)(sec)(mmHg)]×10^-10。

The "oxygen transmission rate" of a lens or material, Dk/t, is the rate of oxygen passing through a particular lens or material of average thickness t (in mm) over the area to be measured. Oxygen transmission rate is generally expressed in units of barrer/mm, where "barrer/mm" is defined as [ (cm)³Oxygen)/(cm²)(sec)(mmHg)]×10^-9。

The "particle permeability" through the lens is related to the lonoflux diffusion coefficient. Lonoflux diffusion coefficient, D (in [ mm ]²/min]In units) is determined by applying Fick's law as follows:

D＝-n’/(A×dc/dx)

where n' is the rate of particle transport [ mol/min [ ]](ii) a A is the area of the exposed lens [ mm²](ii) a dc-concentration difference [ mol/L](ii) a dx-lens thickness [ mm]。

In general, the present invention is directed to a class of amphiphilic branched polysiloxane prepolymers of the present invention, methods of making silicone hydrogel contact lenses from prepolymers of the present invention, and silicone hydrogel contact lenses made from prepolymers of the present invention.

In a first aspect, the invention provides a method adapted for being performed according to lightstream technology^TMAmphiphilic branched polysiloxane prepolymers for making silicone hydrogel contact lenses. The polysiloxane prepolymers of the present invention comprise (1) from about 5% to about 75%, preferably from about 10% to about 65%, more preferably from about 15% to about 55%, and still more preferably from about 20% to about 45%, by weight of hydrophilic monomer units derived from at least one hydrophilic vinyl monomer, (2) from about 1% to about 85%, preferably from about 2.5% to about 75%, and more preferably from about 5% to about 65%, by weight of polysiloxane crosslinking units derived from at least one polysiloxane crosslinker having two or more terminal ethylenically unsaturated groups, (3) from about 2% to about 48%, preferably from about 3% to about 38%, and more preferably from about 4% to about 28%, by weight of polysiloxane side chains each capped with an ethylenically unsaturated group, (4) from about 0.25% to about 5%, preferably from about 0.5% to about 4%, more preferably from about 0.75% to about 3%, and still more preferably from about 1% to about 2%, of chain transfer units derived from a chain transfer agent other than a RAFT agent.

According to the present invention, the amphiphilic branched polysiloxane prepolymer is dissolved in a solvent or a mixture of two or more solvents at room temperature so that a lens-forming composition containing from about 5% to about 90% by weight of the amphiphilic branched polysiloxane prepolymer can be obtained.

Examples of suitable solvents include, but are not limited to, water, tetrahydrofuran, tripropylene glycol methyl ether, dipropylene glycol methyl ether, ethylene glycol n-butyl ether, ketones (e.g., acetone, methyl ethyl ketone, etc.), diethylene glycol n-butyl ether, diethylene glycol methyl ether, ethylene glycol phenyl ether, propylene glycol methyl ether acetate, dipropylene glycol methyl ether acetate, propylene glycol n-propyl ether, dipropylene glycol n-propyl ether, tripropylene glycol n-butyl ether, propylene glycol n-butyl ether, dipropylene glycol n-butyl ether, tripropylene glycol n-butyl ether, propylene glycol phenyl ether dipropylene glycol dimethyl ether, polyethylene glycol, polypropylene glycol, ethyl acetate, butyl acetate, pentyl acetate, methyl lactate, ethyl lactate, isopropyl lactate, methylene chloride, 2-butanol, 1-propanol, 2-propanol, methanol, cyclohexanol, cyclopentanol, and exobornyl alcohol (exonorbomol), 2-pentanol, 3-pentanol, 2-hexanol, 3-methyl-2-butanol, 2-heptanol, 2-octanol, 2-nonanol, 2-decanol, 3-octanol, norbornyl alcohol, tert-butanol, tert-pentanol, 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-pentanol, 2-octanol, and 2-methyl-, 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, 3-hexanol, 4-methyl-4-heptanol, 4-isopropyl-4-heptanol, 2, 4-dimethyl-2-pentanol, 1-methylcyclopentanol, 1-ethylcyclopentanol, 3-methyl, 1-ethylcyclopentanol, 3-hydroxy-3-methyl-1-butene, 4-hydroxy-4-methyl-1-cyclopentanol, 2-phenyl-2-propanol, 2-methoxy-2-methyl-2-propanol, 2,3, 4-trimethyl-3-pentanol, 3, 7-dimethyl-3-octanol, 2-phenyl-2-butanol, 2-methyl-1-phenyl-2-propanol and 3-ethyl-3-pentanol, 1-ethoxy-2-propanol, 1-methyl-2-propanol, tert-pentanol, isopropanol, 1-methyl-2-pyrrolidone, methyl-2-propanol, tert-pentanol, isopropanol, methyl-2-pentanol, ethyl-2, N, N-dimethylpropionamide, dimethylformamide, dimethylacetamide, dimethylpropionamide, N-methylpyrrolidone, and mixtures thereof.

The amphiphilic branched polysiloxane prepolymer of the present invention is obtained by the steps of: (i) polymerizing a polymerizable composition to obtain an amphiphilic branched polysiloxane copolymer, wherein the polymerizable composition comprises (a) a portion of an ethylenically-functionalized polysiloxane, wherein the portion of the ethylenically-functionalized polysiloxane is prepared by reacting a first ethylenically-functionalized vinyl monomer having a first reactive functional group with a functionalized polysiloxane compound having two or more second reactive functional groups in a molar equivalent ratio, R_{Equivalent weight}From about 40% to about 95%, preferably from about 50% to about 95%, more preferably from about 60% to about 92%, still more preferably from about 70% to about 90% (ethylenically functionalized vinyl monomer/functionalized polysiloxane compound), wherein each first reactive functional group reacts with one second reactive functional group in the presence or absence of a coupling agent to form a covalent bond or linkage, wherein the mixture of reaction products comprises at least one polysiloxane crosslinker having at least two ethylenically unsaturated groups and at least one polysiloxane vinyl monomer or macromer having at least one second reactive functional group and at least one ethylenically unsaturated group; (b) at least one hydrophilic vinyl monomer; (c) optionally, but preferably, a hydrophobic vinyl monomer, more preferably a bulky hydrophobic vinyl monomer (i.e., a hydrophobic vinyl monomer having a bulky substituent group); (d) a chain transfer agent other than a RAFT agent, wherein the chain transfer agent optionally but preferably comprises a third reactive functional group; and (e) a free radical initiator (photoinitiator or thermal initiator, preferably thermal initiator); and (ii) the amphiphilic branched polysiloxane copolymer is alkene-functionalized by reacting it with a second alkene-functionalized vinyl monomer having a fourth reactive functional group that forms a covalent bond with one of the second or third reactive functional groups in the presence or absence of a coupling agent, thereby forming an amphiphilic branched polysiloxane prepolymer.

Preferably, the functionalized polysiloxane compound in the polymerizable composition is defined by formula (1) or (2)

FG-G₁-PDMS-G₂-FG(1)

CR(-G₁-PDMS-G₂-FG)_a1(2)

Wherein G is₁And G₂Independently of one another, a direct bond, a linear or branched C₁-C₁₀An alkylene divalent group,Wherein q is an integer of 1 to 5 and alk' are independently of each other C₁-C₆Alkylene divalent group or-R'₁-X₁-E-X₂-R’₂-a divalent radical of (A), wherein R'₁And R'₂Independently of one another, a direct bond, a linear or branched C₁-C₁₀Alkylene diradicals or as defined aboveA divalent radical of (2), X₁And X₂Independently of one another, are selected from the group consisting of-O-),Wherein R' is H or C₁-C₈Alkyl, E is an alkyl, cycloalkyl, alkylcycloalkyl, alkylaryl or aryl diradical having up to 40 carbon atoms, which may have ether, thio or amine linkages in the backbone;

PDMS is a polysiloxane divalent radical of formula (4)

Wherein nu is 0 or 1, omega is an integer of 0-5, U₁And U₂Independently of one another represents-R 'as defined above'₁-X₁-E-X₂-R’₂A divalent radical of (A) or (B) as defined aboveA divalent radical of (2), D₁、D₂And D₃Independently of one another, is a divalent radical selected from the group consisting of₂CH₂O)_t-CH₂CH₂-, where t is an integer from 3 to 40, -CF₂-(OCF₂)_a-(OCF₂CF₂)_b-OCF₂-, wherein a and b are, independently of one another, integers from 0 to 10, with the proviso that a + b is a number from 10 to 30, and divalent radicals of the formula (4)

Wherein R is₃、R₄、R₅、R₆、R₇、R₈、R₉And R₁₀Independently of one another are C₁-C₁₀Alkyl radical, C₁-C₁₀Aminoalkyl radical, C₁-C₁₀Hydroxyalkyl radical, C₁-C₁₀Ether, C₁-C₄Alkyl-or C₁-C₄Phenyl substituted by alkoxy, C₁-C₁₀Fluoroalkyl, C₁-C₁₀Fluoroether, C₆-C₁₈Aryl radical, cyano radical (C)₁-C₁₂-alkyl), -alk- (OCH)₂CH₂)_n-OR₁₁Wherein alk is C₁-C₆Alkylene divalent radical, R₁₁Is hydrogen or C₁-C₆Alkyl, and n is an integer from 1 to 10; m and p are each independently an integer from 0 to 350 and (m + p) is from 1 to 700, with the proviso that D₁、D₂And D₃At least one of (a) is represented by formula (3);

CR is a polyvalent organic group having a valence of a 1;

a1 is an integer of 3,4 or 5; and

FG is selected from the group consisting of an amino group (-NHR as defined above), a hydroxyl group, a carboxylic acid group, an acid halide group (-COX, X ═ Cl, Br or I), an anhydride (acid anhydride) group, an aldehyde group, an azlactone group, an isocyanate group, an epoxy group, an aziridine group, a thiol (-SH) and an amide group (-CONH)₂)。

Preferably, in formula (1) or (2), PDMS is a polysiloxane divalent group of formula (3), wherein ν is 0 or 1, preferably 1, ω is an integer from 0 to 3, preferably 1, U₁And U₂As defined above, D₁、D₂And D₃Independently of one another, are divalent radicals of the formula (4) in which R₃-R₁₀Independently of one another, a methyl group, fluoro (C)₁-C₁₈-alkyl) and/or-alk- (OCH)₂CH₂)_n-OR₁₁Wherein alk is C₁-C₆-alkylene divalent radical and R₁₁Is C₁-C₆Alkyl, and n is an integer from 1 to 10, m and p are, independently of one another, an integer from 1 to 698 and (m + p) is from 2 to 700.

Various difunctional (reactive) terminated polysiloxanes (i.e., having only one polysiloxane segment of formula (4)) are available from commercial suppliers (e.g., from Gelest, Inc, or Fluorochem). In addition, those skilled in the art know how to prepare the difunctional-terminated polysiloxanes according to methods known in the art and described in journal of Polymer science-Chemistry, 33, 1773(1995), the entire contents of which are incorporated herein by reference.

Where the functionalized polysiloxane compound of formula (1) is a functionalized extended polysiloxane compound, i.e. having 2 to 5 polysiloxane segments of formula (4), the functionalized extended polysiloxane compound may be a difunctional (reactive) terminated poly (Si-O) by having only one polysiloxane segment of formula (4) and two third reactive functional groupsA siloxane compound is prepared by reaction of a coupling agent having two fourth reactive functional groups, wherein the third and fourth reactive functional groups are different from each other but are reactive with each other and are selected from the group consisting of an amino group (as defined above-NHR), a hydroxyl group, a thiol group, a carboxylic acid group, an acid halide group (-COX, X ═ Cl, Br or I), an acid anhydride group, an aldehyde group, an azlactone group, an isocyanate group, an epoxy group, an aziridine group, a thiol (-SH) and an amide group (-CONH)₂). The coupling agent having two fourth reactive functional groups may be a diisocyanate, a dicarboxylic acid halide, a dicarboxylic acid compound, a dicarboxylic acid halide compound, a diazactone compound, a diepoxide, a diamine, or a diol. The selection of a coupling reaction (e.g., any of those described herein above) and conditions thereof to prepare the functionalized chain-extended polysiloxane compound is well known to those skilled in the art.

Any suitable C may be used in the present invention₄-C₂₄A diisocyanate. Examples of preferred diisocyanates include, but are not limited to, isophorone diisocyanate, hexamethyl-1, 6-diisocyanate, 4 ' -dicyclohexylmethane diisocyanate, toluene diisocyanate, 4 ' -diphenyl diisocyanate, 4 ' -diphenylmethane diisocyanate, p-phenylene diisocyanate, 1, 4-phenylene 4,4 ' -diphenyl diisocyanate, 1, 3-bis- (4,4 ' -isocyanatomethyl) cyclohexane, cyclohexane diisocyanate, and combinations thereof.

Any suitable diamine may be used in the present invention. The organic diamine may be linear or branched C₂-C₂₄Aliphatic diamine, C₅-C₂₄Cycloaliphatic or aliphatic-cycloaliphatic diamines or C₆-C₂₄Aromatic or alkyl-aromatic diamines. Preferred organic diamines are N, N '-bis (hydroxyethyl) ethylenediamine, N' -dimethylethylenediamine, ethylenediamine, N '-dimethyl-1, 3-propylenediamine, N' -diethyl-1, 3-propylenediamine, propane-1, 3-diamine, butane-1, 4-diamine, pentane-1, 5-diamine, hexamethylenediamine and isophoronediamine.

Any suitable diacid halide may be used in the present invention. Examples of preferred diacid halides include, but are not limited to, fumaroyl chloride, suberoyl chloride, succinyl chloride, phthaloyl chloride, isophthaloyl chloride, terephthaloyl chloride, sebacoyl chloride, adipoyl chloride, trimethyl adipoyl chloride, azelaioyl chloride, dodecanedioic acid chloride, succinyl chloride, glutaroyl chloride, oxalyl chloride, and dimeric acid chloride.

Any suitable diepoxy compound may be used in the present invention. Examples of preferred diepoxy compounds are neopentyl glycol glycidyl ether, butanediol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, glycerol diglycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, and dipropylene glycol diglycidyl ether. The diepoxy compounds are commercially available (e.g., those DENACOL series diepoxy compounds available from nagasechemtex corporation).

Any suitable C may be used in the present invention₂-C₂₄Diols (i.e., compounds having two hydroxyl groups). Examples of preferred diols include, but are not limited to, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, 1, 4-butanediol, various pentanediols, various hexanediols, and various cyclohexanediols.

Any suitable C may be used in the present invention₃-C₂₄A dicarboxylic acid compound. Examples of preferred dicarboxylic acid compounds include, but are not limited to, straight or branched C₃-C₂₄Aliphatic dicarboxylic acids, C₅-C₂₄Cycloaliphatic or aliphatic-cycloaliphatic dicarboxylic acids, C₆-C₂₄Aromatic or araliphatic dicarboxylic acids, or dicarboxylic acids containing amino or amide groups or N-heterocyclic rings. Examples of suitable aliphatic dicarboxylic acids are: oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, dimethylmalonic acid, octadecylsuccinic acid, trimethyladipic acid and dimer acid (dimerization product of unsaturated aliphatic carboxylic acid such as oleic acid). Examples of suitable cycloaliphatic dicarboxylic acids are: 1, 3-cyclobutanedicarboxylic acid, 1, 3-cyclopentanedicarboxylic acid, 1, 3-and 1, 4-cyclohexanedicarboxylic acidAcids, 1, 3-and 1, 4-dicarboxymethylcyclohexane, 4' -dicyclohexyldicarboxylic acid. Examples of suitable aromatic dicarboxylic acids are: terephthalic acid, isophthalic acid, phthalic acid, 1,3-, 1,4-, 2, 6-or 2, 7-naphthalenedicarboxylic acid, 4 ' -diphenyldicarboxylic acid, 4 ' -diphenylsulfone-dicarboxylic acid, 1, 3-trimethyl-5-carboxy-3- (p-carboxyphenyl) -indane, 4 ' -diphenyl ether-dicarboxylic acid, di-p- (carboxyphenyl) -methane.

Any suitable C may be used in the present invention₁₀-C₂₄A diazlactone compound. Examples of such diazlactone compounds are those azlactone compounds disclosed in U.S. Pat. No. 4,485,236, which is incorporated herein by reference in its entirety.

Any suitable dithiol may be used in the present invention. Examples of the dithiols include, but are not limited to, C₂-C₁₂Alkyldithiols (e.g., ethyldithiol, propyldithiol, butyldithiol, pentamethylenedithiol, hexamethylenedithiol, heptamethylenedithiol, octamethylenedithiol, nonamethylenedithiol, decamethylenedithiol, or combinations thereof), ethylcyclohexyldithiol, dipentene dithiol, benzenedithiol, methyl-substituted benzenedithiol, benzenedimethanethiol, ethyleneglycol dimercaptoacetate, ethyl ether dithiol (diethylene glycol dithiol), triethylene glycol dithiol, tetraethylene glycol dithiol, dimercaptopropanol, dimercaptobutanol, dimercaptopentanol, dimercaptopropionic acid, dihydrolipoic acid, dithiothreitol, dimercaptosuccinic acid, and combinations thereof.

In formula (2), CR is the core of the functionalized multi-arm star polysiloxane and is derived from a branching agent, i.e., a compound having 3 to 5, preferably 3, fifth reactive functional groups that can participate in any known coupling reaction and are selected from the group consisting of amine groups, hydroxyl groups, carboxyl groups, isocyanate groups, thiol groups, (meth) acryloyl groups, vinyl groups (i.e., where each carbon-carbon double bond is not directly connected to a carbonyl group or to an oxygen or nitrogen atom), acid halide groups, epoxy groups, and combinations thereof. Examples of preferred branching agents include, but are not limited to, glycerol, diglycerol, triglycerol, arabitol, 1,1, 1-trimethylolethane, 1,1, 1-trimethylolpropane, 1,2, 4-butanetriol, 1,2, 6-hexanetriol, erythrose alcohol, pentaerythritol, diethylenetriamine, N-2 '-aminoethyl-1, 3-propylenediamine, N-bis (3-aminopropyl) -amine, N-bis (6-aminohexyl) amine, triethylenetetramine, the isocyanate trimer of hexamethylene diisocyanate, 2,4, 6-toluene triisocyanate, p', p "-triphenylmethane triisocyanate and isophorone diisocyanate, trimesoyl chloride, cyclohexane-1, 3, 5-tricarbonyl chloride, trimer acid chloride, triglycidyl isocyanurate (TGIC), trimethylolpropane trimethacrylate, pentaerythritol tetramethacrylate, triallylisocyanurate, triallylcyanurate, aconitic acid, citric acid, 1,3, 5-cyclohexanetricarboxylic acid, 1,3, 5-trimethyl-1, 3, 5-cyclohexanetricarboxylic acid, 1,2, 3-benzenetricarboxylic acid, 1,2, 4-benzenetricarboxylic acid, 1,3, 5-pentanetritiol.

It is well known to those skilled in the art how to prepare functionalized multi-arm star polysiloxanes of formula (2) according to any known coupling reaction. For example, the polysiloxane of formula (2) may be prepared by reacting a branching agent with an excess molar equivalent of difunctional polydisiloxane according to any known coupling reaction including those described above to form a functionalized multi-arm star-shaped polydisiloxane having three or four arms each with a terminal reactive functional group for further reaction. If each arm contains more than 1 polysiloxane segment, the functionalized chain-extended polysiloxane prepared above may be used to react with the branching agent.

According to the invention, any suitable ethylenically functionalized vinyl monomer may be used in the present invention to prepare part of the ethylenically functionalized polysiloxane and/or to prepare the amphiphilic branched polysiloxane of the present invention. It is to be understood that the second ethylenically functional vinyl monomer is different from but preferably the same as the first ethylenically functional vinyl monomer (used in making part of the ethylenically functional polysiloxane). Examples of ethylenically functional vinyl monomers include, but are not limited to, C (meth) acrylic acid₂-C₆Hydroxyalkyl ester, C₂-C₆Hydroxyalkyl (meth) acrylamides, allyl alcohols, allyl amines, amino-C (meth) acrylates₂-C₆Alkyl esters, (meth) acrylic acid C₂-C₆alkylamino-C₂-C₆Alkyl esters, vinylamines, amino-C₂-C₆Alkyl (meth) acrylamides, C₁-C₆alkylamino-C₂-C₆Alkyl (meth) acrylamides, acrylic acids, C₁-C₄Alkyl acrylic acids (e.g. methacrylic acid, ethacrylic acid, propylacrylic acid, butylacrylic acid), N- [ tris (hydroxymethyl) -methyl]Acrylamide, N-2-acrylamidoglycolic acid (N, N-2-acrylamidoglycolic acid), beta-methyl-acrylic acid (crotonic acid), alpha-phenylacrylic acid, beta-acryloxypropionic acid, sorbic acid, angelic acid, cinnamic acid, 1-carboxy-4-phenylbutadiene-1, 3, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, aconitic acid, maleic acid, fumaric acid, aziridinyl C (meth) acrylate₁-C₁₂Alkyl esters (e.g. 2- (1-aziridinyl) ethyl (meth) acrylate, 3- (1-aziridinyl) propyl (meth) acrylate, 4- (1-aziridinyl) butyl (meth) acrylate, 6- (1-aziridinyl) hexyl (meth) acrylate or 8- (1-aziridinyl) octyl (meth) acrylate), glycidyl (meth) acrylate, vinyl glycidyl ether, allyl glycidyl ether, halide groups (-COX, X ═ Cl, Br or I) of (meth) acrylate, C (meth) acrylate₁-C₆Isocyanatoalkyl esters, azlactone-containing vinyl monomers (e.g., 2-vinyl-4, 4-dimethyl-1, 3-oxazolin-5-one, 2-isopropenyl-4, 4-dimethyl-1, 3-oxazolin-5-one, 2-vinyl-4-methyl-4-ethyl-1, 3-oxazolin-5-one, 2-isopropenyl-4-methyl-4-butyl-1, 3-oxazolin-5-one, 2-vinyl-4, 4-dibutyl-1, 3-oxazolin-5-one, 2-isopropenyl-4-methyl-4-dodecyl-1, 3-oxazoline-5-one, 2-isopropenyl-4, 4-diphenyl-1, 3-oxazoline-5-one, 2-isopropenyl-4, 4-pentamethylene-1, 3-oxazoline-5-one, 2-isopropenyl-4, 4-tetramethylene-1, 3-oxazoline-5-one, 2-vinyl-4, 4-diethyl-1, 3-oxazoline-5-one, 2-vinyl-4-methyl-4-nonyl-1, 3-oxazoline-5-one, 2-isopropenyl-4-methyl-oxazoline-4-phenyl-1, 3-oxazoline-5-one, 2-isopropenyl-4-methyl-4-benzyl-1, 3-oxazoline-5-one, 2-vinyl-4, 4-pentamethylene-1, 3-oxazoline-5-one and 2-vinyl-4, 4-dimethyl-1, 3-oxazoline-6-one, 2-vinyl-4, 4-dimethyl-1, 3-oxazolin-5-one (VDMO) and 2-isopropenyl-4, 4-dimethyl-1, 3-oxazolin-5-one (IPDMO) as preferred azlactone-containing vinyl monomers) and combinations thereof.

Preferably, the first reactive functional group of the first alkene-functional vinyl monomer, the fourth reactive functional group of the second alkene-functional vinyl monomer, the second reactive functional group of the functional polysiloxane compound, and the third reactive functional group of the chain transfer agent are independently selected from an amino group (e.g., -NHR' as defined above), a hydroxyl group, a carboxylic acid group, an acid halide group (-COX, X ═ Cl, Br, or I), an acid anhydride group, an aldehyde group, an azlactone group, an isocyanate group, an epoxy group, an aziridine group, an amide group (-CONH), and mixtures thereof₂) And combinations thereof, more preferably selected from amino groups (-NHR' as defined above), hydroxyl groups, carboxylic acid groups, acyl halide groups (-COX, X ═ Cl, Br, or I), azlactone groups, isocyanate groups, epoxy groups, aziridine groups, and combinations thereof, provided that a first or fourth reactive functional group can react with a second or third reactive functional group in the presence or absence of a coupling agent to form a covalent linkage.

It is understood that a portion of the ethylenically functionalized polysiloxane comprises at least one polysiloxane vinyl monomer or macromer having at least one ethylenically unsaturated group and at least one reactive functional group. The polysiloxane vinyl monomer or macromer having at least one reactive functional group results in the formation of polysiloxane side chains in the amphiphilic branched polysiloxane copolymer, each of which is terminated with one reactive functional group, and ultimately in the amphiphilic branched polysiloxane prepolymer of the present invention, polysiloxane side chains, each of which is terminated with one ethylenically unsaturated group. In the case where the silicone vinyl monomer or macromer has two or more ethylenically unsaturated groups and at least one reactive functional group, it may also serve as a silicone crosslinker.

The functionalized polysiloxanes preferably used for preparing the partially ethylenically functionalized polysiloxanes are represented by formula (1). More preferably, the ethylenically functional vinyl monomer is reacted with the functional polysiloxane of formula (1) at a molar equivalent of from 70% to about 90% to obtain a portion of the ethylenically functional polysiloxane.

Any suitable hydrophilic vinyl monomer may be used in preparing the amphiphilic branched polysiloxane prepolymers of the present invention according to this aspect of the present invention. Suitable hydrophilic vinyl monomers are, by way of non-exhaustive example, hydroxy-substituted C (meth) acrylates₁-C₆Alkyl ester, hydroxy substituted C₁-C₆Alkyl (meth) acrylamides, hydroxy-substituted C₁-C₆Alkyl vinyl ether, C₁-C₆Alkyl (meth) acrylamides, di-C₁-C₆Alkyl (meth) acrylamides, N-vinylpyrroles, N-vinyl-2-pyrrolidone, 2-vinyloxazoline, 2-vinyl-4, 4' -dialkyloxazoline-5-one, 2-and 4-vinylpyridine, ethylenically unsaturated carboxylic acids having a total of 3 to 6 carbon atoms, amino-substituted C₁-C₆Alkyl- (wherein the term "amino" also includes quaternary ammonium), mono (C)₁-C₆Alkylamino) (C₁-C₆Alkyl) and di (C)₁-C₆Alkylamino) (C₁-C₆Alkyl) (meth) acrylates or (meth) acrylamides, allyl alcohol, vinylamine, N-vinyl C₁-C₆Alkylamides, N-vinyl-N-C₁-C₆Alkyl amides and combinations thereof.

Preferred hydrophilic vinyl monomers are, for example, N-Dimethylacrylamide (DMA), N-Dimethylmethacrylamide (DMMA), 2-acrylamidoglycolic acid, 3-acrylamido-1-propanol, N-hydroxyethylacrylamide, N- [ tris (hydroxymethyl) methyl ] acrylamide]Acrylamide, N-methyl-3-methylene-2-pyrrolidone, 1-ethyl-3-methylene-2-pyrrolidone, 1-methyl-5-methylene-2-pyrrolidone, 1-ethyl-5-methylene-2-pyrrolidone, 5-methyl-3-methylene-2-pyrrolidone, and mixtures thereof,5-ethyl-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, 2-hydroxyethyl methacrylate (HEMA), 2-hydroxyethyl acrylate (HEA), hydroxypropyl acrylate, hydroxypropyl methacrylate (HPMA), Trimethylammonium 2-hydroxypropyl methacrylate hydrochloride, aminopropyl methacrylate hydrochloride, dimethylaminoethyl methacrylate (DMAEMA), Glycerol Methacrylate (GMA), N-vinyl-2-pyrrolidone (NVP), allyl alcohol, vinylpyridine, C (meth) acrylate having a weight average molecular weight of up to 1500₁-C₄-alkoxy polyethylene glycol esters, methacrylic acid, N-vinyl formamide, N-vinyl acetamide, N-vinyl isopropylamide, N-vinyl-N-methyl acetamide, N-vinyl caprolactam and mixtures thereof. Among those preferred hydrophilic vinyl monomers, those that are free of any reactive functional groups are particularly preferred for addition to the polymerizable composition for preparing the amphiphilic branched polysiloxane copolymer.

Any suitable hydrophobic vinyl monomer may be used in preparing the amphiphilic branched polysiloxane prepolymers of the present invention according to this aspect of the present invention. Examples of preferred hydrophobic vinyl monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, sec-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl valerate, styrene, chloroprene, vinyl chloride, vinylidene chloride, acrylonitrile, 1-butene, butadiene, methacrylonitrile, vinyltoluene, vinyl ethyl ether, perfluorohexylethyl-thio-carbonyl-aminoethyl methacrylate, isobornyl methacrylate, trifluoroethyl methacrylate, hexafluoroisopropyl methacrylate, isopropyl methacrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, butyl (meth) acrylate, Hexafluorobutyl methacrylate, silicone-containing vinyl monomers, and mixtures thereof. More preferably, the polymerizable composition comprises a bulky hydrophobic vinyl monomer. Preferred bulky hydrophobic vinyl monomers include, but are not limited to, N- [ tris (trimethylsiloxy) silylpropyl ] (meth) acrylamide; n- [ tris (dimethylpropylsiloxy) silylpropyl ] (meth) acrylamide; n- [ tris (dimethylphenylsiloxy) silylpropyl ] (meth) acrylamide; n- [ tris (dimethylethylsiloxy) silylpropyl ] (meth) acrylamide; n- (2-hydroxy-3- (3- (bis (trimethylsiloxy) methylsilyl) propoxy) propyl) -2-methacrylamide; n- (2-hydroxy-3- (3- (bis (trimethylsiloxy) methylsilyl) propoxy) propyl) acrylamide; n, N-bis [ 2-hydroxy-3- (3- (bis (trimethylsiloxy) methylsilyl) propoxy) propyl ] -2-methacrylamide; n, N-bis [ 2-hydroxy-3- (3- (bis (trimethylsiloxy) methylsilyl) propoxy) propyl ] acrylamide; n- (2-hydroxy-3- (3- (tris (trimethylsiloxy) silyl) propoxy) propyl) -2-methacrylamide; n- (2-hydroxy-3- (3- (tris (trimethylsiloxy) silyl) propoxy) propyl) acrylamide; n, N-bis [ 2-hydroxy-3- (3- (tris (trimethylsiloxy) silyl) propoxy) propyl ] -2-methacrylamide; n, N-bis [ 2-hydroxy-3- (3- (tris (trimethylsiloxy) silyl) propoxy) propyl ] acrylamide; n- [ 2-hydroxy-3- (3- (tert-butyldimethylsilyl) propoxy) propyl ] -2-methacrylamide; n- [ 2-hydroxy-3- (3- (tert-butyldimethylsilyl) propoxy) propyl ] acrylamide; n, N-bis [ 2-hydroxy-3- (3- (tert-butyldimethylsilyl) propoxy) propyl ] -2-methacrylamide; n, N-bis [ 2-hydroxy-3- (3- (tert-butyldimethylsilyl) propoxy) propyl ] acrylamide; 3-methacryloxypropyl pentamethyldisiloxane; TRIS (trimethylsiloxy) silylpropyl methacrylate (TRIS); (3-methacryloxy-2-hydroxypropoxy) propylbis (trimethylsiloxy) methylsilane); (3-methacryloxy-2-hydroxypropoxy) propyltris (trimethylsiloxy) silane; 3-methacryloxy-2- (2-hydroxyethoxy) -propoxy) propylbis (trimethylsiloxy) methylsilane; carbamic acid N-2-methacryloyloxyethyl-O- (methyl-bis-trimethylsiloxy-3-propyl) silyl ester; 3- (trimethylsilyl) propyl vinyl carbonate; 3- (vinyloxycarbonylthio) propyl-tris (trimethyl-siloxy) silane; 3- [ tris (trimethylsiloxy) silyl ] propyl vinyl carbamate; 3- [ tris (trimethylsiloxy) silyl ] propylallyl carbamate; 3- [ tris (trimethylsiloxy) silyl ] propyl vinyl carbonate; tert-butyldimethyl-siloxyethyl vinyl carbonate; trimethylsilylethyl vinyl carbonate; trimethylsilylmethyl vinyl carbonate; t-butyl (meth) acrylate, cyclohexyl acrylate, isobornyl methacrylate, polysiloxane-containing vinyl monomers (having 3-8 silicon atoms), and combinations thereof.

It is believed that the presence of the bulky hydrophobic vinyl monomer in the polysiloxane prepolymer may be capable of minimizing or eliminating handling-derived optical defects (permanent set) during manufacture in lenses made from lens-forming compositions containing the polysiloxane prepolymer. The distortion or optical defect refers to a permanent fold mark observed on the lens with a Contact Lens Optical Quality Analyzer (CLOQA) after manual folding of the lens as described in example 1 of pending U.S. patent application 12/456,364, incorporated herein by reference in its entirety. It is believed that when a bulky hydrophobic vinyl monomer is present, the resulting lens exhibits a "healing" effect (i.e., the fold marks become transparent and may disappear after a short time, e.g., about 15 minutes or less) that eliminates optical defects.

According to the present invention, the chain transfer agent may comprise one or more thiol groups, for example two or most preferably one thiol group. Where the chain transfer agent comprises a reactive functional group (e.g., a hydroxyl, amino, or carboxylic acid group) in addition to a thiol group, the chain transfer agent can be used to provide functionality for subsequent addition of ethylenically unsaturated groups. Suitable chain transfer agents include primary organic mercaptansOr having another reactive functional group, e.g. hydroxy, amino, N-C₁-C₆-alkylamino, carboxyl or suitable derivatives thereof. Preferred chain transfer agents are cycloaliphatic or preferably aliphatic mercaptans having from 2 to about 24 carbon atoms and having additional reactive functional groups selected from amino, hydroxyl and carboxyl groups. Thus, preferred chain transfer agents are aliphatic mercapto-containing carboxylic acids, hydroxy mercaptans or amino mercaptans. Examples of preferred chain transfer agents are 2-mercaptoethanol, 2-aminoethanethiol (cysteamine), 2-mercaptopropionic acid, thioglycolic acid, thiolactic acid, ethanedithiol, propanedithiol, and combinations thereof. In the case of amines or carboxylic acids, the chain transfer agent may be in the form of the free amine or acid, preferably in the form of a suitable salt thereof, for example the hydrochloride in the case of amines or the sodium, potassium or amine salt in the case of acids.

In a preferred embodiment, the polymerizable composition comprises a first hydrophilic vinyl monomer that does not contain any reactive functional group capable of participating in a coupling reaction using a second diene-based functionalized vinyl monomer and a second hydrophilic vinyl monomer having a reactive functional group capable of participating in a coupling reaction using a second diene-based functionalized vinyl monomer, wherein the first and second hydrophilic vinyl monomers are present in the polymerizable composition in a ratio of from about 5:1 to about 30: 1. The first hydrophilic vinyl monomer is preferably selected from the group consisting of N, N-dimethyl (meth) acrylamide, N-methyl-3-methylene-2-pyrrolidone, 1-ethyl-3-methylene-2-pyrrolidone, 1-methyl-5-methylene-2-pyrrolidone, 1-ethyl-5-methylene-2-pyrrolidone, 5-methyl-3-methylene-2-pyrrolidone, 5-ethyl-3-methylene-2-pyrrolidone, 1-N-propyl-5-methylene-2-pyrrolidone, and mixtures thereof, 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, dimethylaminoethyl (meth) acrylate, N-vinyl-2-pyrrolidone, C (meth) acrylate₁-C₄Alkoxy polyethylene glycol esters, N-vinylformamide, N-vinylacetamide, N-vinylisopropylamide, N-vinyl-N-methylacetoacetateAmines and mixtures thereof; and the second hydrophilic vinyl monomer is preferably selected from hydroxy-substituted C (meth) acrylates₁-C₄Alkyl esters, hydroxy-substituted C₁-C₄Alkyl (meth) acrylamides, amino-substituted C (meth) acrylates₁-C₄Alkyl ester, amino-substituted C₁-C₄Alkyl (meth) acrylamides, allyl alcohols, allyl amines and mixtures thereof.

In another preferred embodiment, the amphiphilic branched polysiloxane copolymer used to prepare the amphiphilic branched polysiloxane prepolymer of the present invention is obtained by polymerizing a polymerizable composition comprising: (a) from about 10% to about 94%, preferably from about 20% to about 80%, more preferably from about 40% to about 65%, by weight, of a partially (40% to about 95%, preferably from about 50% to about 95%, more preferably from about 60% to about 92%, still more preferably from about 70% to about 90%) ethylenically functional polysiloxane (i.e., a partially ethylenically functional polysiloxane); (b) from about 5% to about 75%, preferably from about 10% to about 65%, more preferably from about 15% to about 55%, and still more preferably from about 20% to about 45%, by weight, of at least one hydrophilic vinyl monomer; (c) from 0 to about 55%, preferably from about 5% to about 45%, more preferably from about 10% to about 40%, still more preferably from about 15% to about 30%, by weight of a bulky hydrophobic vinyl monomer; (d) from about 0.25% to about 5%, preferably from about 0.5% to about 4%, more preferably from about 0.75% to about 3%, still more preferably from about 1% to about 2% by weight of a chain transfer agent other than a RAFT agent, wherein the chain transfer agent optionally but preferably comprises a reactive functional group; (e) from 0 to 5%, preferably from about 0.2% to 4%, more preferably from about 0.3% to about 2.5%, still more preferably from about 0.5% to about 1.8% by weight of a polymerizable UV absorbing compound; and (f) from about 0.1% to about 5%, preferably from about 0.2% to about 4%, more preferably from about 0.3% to about 3%, still more preferably from about 0.4% to about 1.5% by weight of a free radical initiator (photoinitiator or thermal initiator, preferably thermal initiator); the weight percentages of the above components are relative to the total weight of all polymerizable components (which may include additional polymerizable components not listed here).

Preferred polymerizable UV-absorbers include, but are not limited to, 2- (2-hydroxy-5-vinylphenyl) -2H-benzotriazole, 2- (2-hydroxy-5-acryloyloxyphenyl) -2H-benzotriazole, 2- (2-hydroxy-3-methacryloylaminomethyl-5-tert-octylphenyl) benzotriazole, 2- (2 ' -hydroxy-5 ' -methacrylamidophenyl) -5-chlorobenzotriazole, 2- (2 ' -hydroxy-5 ' -methacrylamidophenyl) -5-methoxybenzotriazole, 2- (2 ' -hydroxy-5 ' -methacryloxypropyl-3 ' -tert-butyl-phenyl) -5-chlorobenzotriazole, 2- (2 '-hydroxy-5' -methacryloyloxyethylphenyl) benzotriazole, 2- (2 '-hydroxy-5' -methacryloyloxypropylphenyl) benzotriazole, 2-hydroxy-4-acryloxyalkoxybenzophenone, 2-hydroxy-4-methacryloyloxyalkoxybenzophenone, allyl-2-hydroxybenzophenone, 2-hydroxy-4-methacryloyloxybenzophenone. The polymerizable UV-absorber is typically present in the polymerizable composition to produce a polysiloxane copolymer that is vinyl functionalized to obtain the polysiloxane prepolymers of the present invention in an amount sufficient to produce a contact lens that is produced from a lens-forming material comprising the prepolymer and that absorbs at least about 80% of the UV light from about 280nm to about 370nm projected onto the lens. It will be understood by those skilled in the art that the specific amount of UV-absorber used in the polymerizable composition will depend on the molecular weight of the UV-absorber and its extinction coefficient in the range of from about 280 to about 370 nm. According to the present invention, the polymerizable composition comprises from about 0.2% to about 5.0%, preferably from about 0.3% to about 2.5%, more preferably from about 0.5% to about 1.8% by weight of the UV-absorber.

The polymerizable composition used to prepare the amphiphilic branched polysiloxane copolymer may additionally comprise a polysiloxane-containing vinyl macromonomer. The silicone-containing vinyl macromers can be prepared according to any known method, such as those described in U.S. Pat. Nos. 4,136,250, 4,486,577, 4,605,712, 5,034,461, 5,416,132, and 5,760,100, the entire contents of which are incorporated herein by reference.

Examples of preferred silicone-containing vinyl monomers or macromers include, but are not limited to, mono- (meth) acrylate-terminated polydimethylsiloxanes of various molecular weights (e.g., mono-3-methacryloxypropyl-terminated, mono-butyl-terminated polydimethylsiloxanes, mono- (3-methacryloxy-2-hydroxypropoxy) propyl-terminated, mono-butyl-terminated polydimethylsiloxanes); mono-vinyl terminated, mono-vinyl carbonate-terminated or mono-vinyl carbamate-terminated polydimethylsiloxanes of various molecular weights; a polysilalkylalkyl (meth) acrylic monomer; a hydroxyl-functionalized silicone-containing vinyl monomer or macromer; and mixtures thereof. Preferred silicone-containing cross-linking agents include, but are not limited to, di- (meth) acrylated polydimethylsiloxanes (or so-called silicone cross-linkers) of various molecular weights; di-vinyl carbonate-terminated polydimethylsiloxane (polysiloxane crosslinker); di-vinyl carbamate-terminated polydimethylsiloxane (polysiloxane crosslinker); di-vinyl terminated polydimethylsiloxanes (polysiloxane crosslinkers); di- (meth) acrylamide-terminated polydimethylsiloxane (polysiloxane crosslinker); bis 3-methacryloxy-2-hydroxypropoxypropylpolydimethylsiloxane (polysiloxane crosslinker); n, N' -tetrakis (3-methacryloxy-2-hydroxypropyl) - α, ω -bis-3-aminopropyl-polydimethylsiloxane (polysiloxane crosslinker); siloxane-containing macromers selected from the group consisting of macromer a, macromer b, macromer c, and macromer d as described in US5,760,100 (the entire contents of which are incorporated herein by reference); the reaction product of glycidyl methacrylate and amino-functionalized polydimethylsiloxane; silicone-containing crosslinkers disclosed in 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, 4,703,097, 4,833,218, 4,837,289, 4,954,586, 4,954,587, 5,010,141, 5,034,461, 5,070,170, 5,079,319, 5039,761, 5,346,946, 5,358,995, 5,387,632, 5,416,132, 5,451,617, 5,486,579, 5,962,548, 5,981,675, 6,039,913, and 6,762,264 (the entire contents of which are incorporated herein by reference); silicone-containing crosslinkers disclosed in U.S. Pat. Nos. 4,259,467, 4,260,725, and 4,261,875 (incorporated herein by reference in their entirety); di-and tri-block crosslinkers composed of polydimethylsiloxanes and polyoxyalkylenes (e.g., methacrylate end-capped polyethylene oxide-block-polydimethylsiloxane-block-polyethylene oxide)); and mixtures thereof.

Another preferred class of silicone-containing crosslinkers are silicon-containing prepolymers comprising a hydrophilic segment and a hydrophobic segment. Any suitable silicone-containing prepolymer having a hydrophilic segment and a hydrophobic segment can be used in the present invention. Examples of such silicone-containing prepolymers include those disclosed in the same owner of U.S. patents 6,039,913, 6,043,328, 7,091,283, 7,268,189 and 7,238,750, 7,521,519; silicone-containing prepolymers such as those described in U.S. patent application publications US2008-0015315a1, US2008-0143958a1, US2008-0143003a1, US2008-0234457a1, US2008-0231798a1 of the same owner, and U.S. patent applications 12/313,546, 12/616,166, and 12/616169 of the same owner; all of the above references are incorporated herein by reference in their entirety.

The polymerization of the polymerizable composition for preparing the amphiphilic branched polysiloxane copolymer is based on the well-known free radical chain growth polymerization and can be carried out according to any known method and in any vessel (reactor) suitable for polymerization. The polymerization is preferably thermally initiated. The polymerizable composition used to prepare the amphiphilic branched polysiloxane can be prepared by dissolving all the components in a suitable solvent known to those skilled in the art.

The resulting amphiphilic branched polysiloxane copolymer is then alkene-functionalized by reacting it with a second alkene-functionalized vinyl monomer having a fourth reactive functional group to obtain the amphiphilic branched polysiloxane copolymer of the present invention, provided that the fourth reactive group can react with one of the terminal second and third reactive functional groups (if available) of the amphiphilic branched polysiloxane copolymer to form a covalent linkage, with or without a coupling agent. It will be appreciated that in the above-described alkene-functionalization step, the unreacted functionalized polysiloxane inherently present in a portion of the alkene-functionalized polysiloxane is also alkene-functionalized to form a polysiloxane crosslinker, which can be used with the resulting amphiphilic branched polysiloxane prepolymer to prepare a lens formulation for use in the preparation of silicone hydrogel contact lenses.

According to the invention, the molar equivalent ratio of the second diene-based functionalized vinyl monomer to the amphiphilic polysiloxane copolymer is greater than 1, preferably from about 1 to about 1.2, more preferably from about 1 to about 1.1, and still more preferably from about 1 to 1.05. It is understood that the molar equivalent ratio calculation should account for all possible reactive functional groups of the amphiphilic branched copolymer, including those derived from a portion of the ethylenically functionalized polysiloxane, chain transfer agent, any other polymerizable component of the polymerizable composition having a reactive functional group. The calculations can be made based on the starting materials used to prepare the amphiphilic branched polysiloxane copolymer. Excess second diene-functional vinyl monomer may be (but is preferably not) removed from the resulting amphiphilic branched polysiloxane prepolymer prior to use of the prepolymer in the preparation of lens formulations for use in the preparation of silicone hydrogel contact lenses.

According to the present invention, the weight percent content of each component of the amphiphilic branched polysiloxane prepolymer is determined by the polymerizable composition or mixture based on the total weight of all polymerizable components of the composition or mixture used to prepare the amphiphilic branched polysiloxane copolymer which is ethylenically functionalized to form the prepolymer of the present invention. For example, if the polymerizable mixture used to prepare the amphiphilic branched polysiloxane copolymer that is vinyl-functionalized to form the prepolymer of the present invention comprises about 44% by weight of 80% of a vinyl-functionalized linear polydimethylsiloxane (which contains 64% of a linear polysiloxane crosslinker having two ethylenically unsaturated groups, 32% of a linear polysiloxane having one ethylenically unsaturated group and one reactive functional group for vinyl functionalization, 4% of a linear polysiloxane having two terminal reactive functional groups that are not incorporated into the amphiphilic branched prepolymer, the percentages calculated above), about 28.5% by weight of at least one hydrophilic vinyl monomer, about 26% by weight of a bulky hydrophobic vinyl monomer (e.g., TRIS, etc.), and about 1.5% of a chain transfer agent (e.g., mercaptoethanol), then the resulting amphiphilic branched prepolymer comprises about 28% by weight of polysiloxane crosslinking units (44% x 64% x100), About 14 weight percent polysiloxane side chains each capped with an ethylenically unsaturated group (44% x 32% x100), about 28.5 weight percent hydrophilic monomer units, about 26 weight percent bulky hydrophobic monomer units, and about 1.5 weight percent chain transfer units. It is well known to the person skilled in the art how to determine the percentage of the components of the amphiphilic branched prepolymer according to the method described above for the illustrative examples.

The amphiphilic branched polysiloxane prepolymers of the present invention may have particular utility as lens-forming materials for the preparation of silicone hydrogel contact lenses. It is particularly advantageous to use the amphiphilic branched polysiloxane prepolymers of the present invention together with small amounts (i.e., less than 20% by weight relative to the total amount of all polymerizable components) of one or more vinyl monomers in the preparation of lens-forming compositions for use in the preparation of silicone hydrogel contact lenses. Curing of the lens-forming composition in the mold is in fact a two-step curing process, the first being off-line curing (or pre-curing) of the lens formulation in the container and the other being on-line curing of the lens formulation in the mold. The lens-forming composition can provide the following advantages. First, the concentration of one or more vinyl monomers in the lens-forming composition can be reduced and thus shrinkage that occurs when the lens-forming composition is polymerized in a mold to produce a contact lens is greatly reduced. Second, the olefinic groups of the amphiphilic branched polysiloxane prepolymers are susceptible to free radical chain extension polymerization because they are located at the ends of the polymer chains. The curing time of the lens-forming composition in the mold is shorter compared to lens-forming compositions prepared from a monomer mixture (i.e., greater than 20 weight percent of one or more vinyl monomers relative to the total amount of all polymerizable components). Third, the viscosity of the lens-forming composition is lower compared to lens-forming compositions prepared from one or more prepolymers because of the presence of one or more vinyl monomers.

It will be appreciated that although various preferred embodiments of the invention have been described separately above, they may be combined in any desired manner to obtain different preferred embodiments of the invention.

In a second aspect, the present invention provides a method of making a silicone hydrogel contact lens. The method comprises the following steps: (i) obtaining an amphiphilic branched polysiloxane prepolymer, wherein the amphiphilic branched polysiloxane prepolymer comprises (a)) from about 5% to about 75%, preferably from about 10% to about 65%, more preferably from about 15% to about 55%, and still more preferably from about 20% to about 45%, by weight, of hydrophilic monomer units derived from at least one hydrophilic vinyl monomer, (b) from about 1% to about 85%, preferably from about 2.5% to about 75%, more preferably from about 5% to about 65%, by weight, of polysiloxane crosslinking units derived from at least one polysiloxane crosslinker having two or more terminal ethylenically unsaturated groups, (c) from about 2% to about 48%, preferably from about 3% to about 38%, more preferably from about 4% to about 28%, of polysiloxane side chains each capped with an ethylenically unsaturated group, and (d) by weight, from about 0.25% to about 5%, preferably from about 0.5% to about 4%, more preferably from about 0.75% to about 3%, still more preferably from about 1% to about 2%, of chain transfer units derived from a chain transfer agent other than a RAFT agent; (ii) use of an amphiphilic branched polysiloxane prepolymer to prepare a lens-forming composition comprising (a) from about 60% to about 99%, preferably from about 75% to about 97%, more preferably from about 85% to about 95% by weight of an amphiphilic branched polysiloxane prepolymer, (b) from about 0.1% to about 5%, preferably from about 0.3% to about 3%, more preferably from about 0.4% to about 1.5% by weight of a free radical initiator (photoinitiator or thermal initiator, preferably photoinitiator) and (c) from 0% to about 20%, preferably from about 2% to about 16%, more preferably from about 4% to about 12% by weight of a crosslinking agent selected from hydrophilic vinyl monomers, silicone-containing vinyl monomers or macromers, hydrophobic vinyl monomers, linear polysiloxane crosslinking agents terminated with two ethylenically unsaturated groups, a silicone-containing monomer, a silicone-based monomer, at least one polymerizable component of a crosslinking agent having a molecular weight of less than 700 daltons, a polymerizable UV-absorber, and mixtures thereof, wherein the weight percent of components (a) - (c) is relative to the total amount of all polymerizable components in the lens-forming composition, including those components not listed above; (iii) adding a lens-forming composition to a mold having a first mold half having a first molding surface defining an anterior surface of a contact lens and a second mold half having a second molding surface defining a posterior surface of a contact lens, wherein said first and second mold halves are configured to be received in one another so as to form a cavity between said first and second molding surfaces for receiving a lens-forming material; and (iv) polymerizing the lens-forming material within the cavity to form the silicone hydrogel contact lens.

Various embodiments of preferred embodiments including amphiphilic branched polysiloxane prepolymers, free radical initiators, chain transfer agents, hydrophilic vinyl compounds, silicone-containing vinyl monomers or macromers, hydrophobic vinyl monomers, crosslinkers having a molecular weight of less than 700 daltons, polymerizable UV-absorbers and linear polysiloxane crosslinkers terminated with two ethylenically unsaturated groups are described above and can be used in this aspect of the invention.

Preferably, the amphiphilic branched polysiloxane prepolymer is obtained according to a process comprising the steps of: (i) obtaining a partially ethylenically functionalized polysiloxane, wherein the partially ethylenically functionalized polysiloxane is a mixture of reaction products obtained by reacting a first ethylenically functionalized vinyl monomer having a first reactive functional group with a functionalized polysiloxane compound having two or more second reactive functional groups in a molar equivalent ratio of from about 40% to about 95%, preferably from about 50% to about 95%, more preferably from about 60% to about 92%, still more preferably from about 70% to about 90% (ethylenically functionalized vinyl monomer/functionalized polysiloxane compound), wherein each first reactive functional group reacts with one second reactive functional group in the presence or absence of a coupling agent to form a covalent bond or linkage, wherein the mixture of reaction products comprises at least one polysiloxane crosslinker having at least two ethylenically unsaturated groups and at least one polysiloxane crosslinker having at least one second reactive functional group and at least one ethylenic unsaturated group An unsaturated group polysiloxane vinyl monomer or macromer; (ii) preparing a polymerizable composition using an amphiphilic branched polysiloxane copolymer, wherein the polymerizable composition comprises at least one hydrophilic vinyl monomer, a chain transfer agent that is not RAFT and optionally (but preferably) comprises a third reactive functional group, and a free radical initiator; (iii) polymerizing the polymerizable composition to produce an amphiphilic branched polysiloxane copolymer comprising hydrophilic monomer units derived from at least one hydrophilic vinyl monomer, polysiloxane crosslinking units derived from a polysiloxane crosslinker, polysiloxane side chains each terminated with a second reactive functional group and derived from a polysiloxane vinyl monomer or macromer, and chain transfer units derived from a chain transfer agent with or without a third reactive functional group; (iv) reacting the branched polysiloxane copolymer with a second diene-functional vinyl monomer having a fourth reactive functional group that reacts with one of the second or third reactive functional groups of the branched polysiloxane copolymer in the presence or absence of a coupling agent to form a covalent linkage, thereby forming an amphiphilic branched polysiloxane prepolymer having polysiloxane side chains each terminated with one ethylenically unsaturated group.

Various embodiments of various preferred embodiments including polysiloxanes having reactive functional groups, alkene-functional vinyl monomers, hydrophilic vinyl monomers, hydrophobic vinyl monomers, bulky hydrophobic vinyl monomers, free radical initiators, polymerizable UV-absorbers, chain transfer agents and solvents, and polymerizable compositions for making amphiphilic branched polysiloxane copolymers are described above (e.g., with respect to the first aspect of the invention) and can be used in this aspect of the invention.

According to the present invention, the first and second vinyl-functional monomers of the alkene-functional vinyl monomer may be different from each other, but are preferably the same as each other. Preferably, the molar equivalent ratio of the second diene-based functionalized vinyl monomer to the amphiphilic polysiloxane copolymer is greater than 1, preferably from about 1 to about 1.2, more preferably from about 1 to about 1.1, and still more preferably from about 1 to 1.05. The amphiphilic branched polysiloxane copolymer may (but preferably is not) purified prior to ethylenic functionalization. Excess second-alkene-functional vinyl monomer may (but preferably is not) removed from the resulting amphiphilic branched polysiloxane prepolymer prior to using the prepolymer in the preparation of lens formulations for the preparation of silicone hydrogel contact lenses.

The resulting amphiphilic branched polysiloxane prepolymers can be used directly to prepare lens-forming compositions for use in the preparation of silicone hydrogel contact lenses. However, if the solvent used in the preparation of the amphiphilic branched polysiloxane prepolymer is not the solvent required to prepare the lens-forming composition, it is desirable to exchange the solvent according to any suitable technique known to those skilled in the art (e.g., repeating the cycle of condensing and diluting with a suitable solvent). Alternatively, the amphiphilic branched polysiloxane prepolymer obtained may be purified by any known suitable technique known to those skilled in the art.

It must be understood that the lens-forming composition may also comprise various components such as hydrophilic vinyl monomers, hydrophobic vinyl monomers, bulky hydrophobic vinyl monomers, visibility tinting agents (e.g., dyes, pigments, or mixtures thereof), polymerizable UV-absorbers, antimicrobial agents (e.g., preferably silver nanoparticles), bioactive agents, leachable lubricants, tearable stabilizers, and mixtures thereof, as are well known to those skilled in the art.

The bioactive agent incorporated into the polymeric substrate is any compound that can inhibit an ocular disease or reduce the symptoms of an ocular disease. The bioactive agent can be a drug, an amino acid (e.g., taurine, glycine, etc.), a polypeptide, a protein, a nucleic acid, or any combination thereof. Examples of drugs useful herein include, but are not limited to, rebamipide (rebamipide), ketotifen (ketotifen), olaptidine, cromoglycate (cromoglycate), cyclosporine (cyclosporine), nedocromil (nedocromil), levocabastine (levocabastine), lodoxamide (lodoxamide), ketotifen (ketotifen), or a pharmaceutically acceptable salt or ester thereof. Other examples of bioactive agents include 2-pyrrolidone-5-carboxylic acid (PCA), alpha hydroxy acids (e.g., glycolic acid, lactic acid, malic acid, tartaric acid, mandelic acid and citric acid and salts thereof, and the like), linoleic acid and gamma linoleic acid, and vitamins (e.g., B5, A, B6, and the like).

Examples of leachable lubricants include, but are not limited to, mucin-like materials (e.g., polyglycolic acid) and non-crosslinkable hydrophilic polymers (i.e., the absence of ethylenically unsaturated groups).

Any hydrophilic polymer or copolymer without any ethylenically unsaturated groups may be used as the leachable lubricant. Preferred examples of non-crosslinkable hydrophilic polymers include, but are not limited to, polyvinyl alcohol (PVA), polyamides, polyimides, polylactones, homopolymers of vinyl lactams, copolymers of at least one vinyl lactam in the presence or absence of one or more hydrophilic vinyl comonomers, homopolymers of acrylamide or methacrylamide, copolymers of acrylamide or methacrylamide with one or more hydrophilic vinyl monomers, polyethylene oxide (i.e., polyethylene glycol (PEG)), polyethylene oxide derivatives, poly-N-dimethylacrylamide, polyacrylic acid, poly-2-ethyl oxazoline, heparin polysaccharides, and mixtures thereof.

The weight average molecular weight Mn of the non-crosslinkable hydrophilic polymer is preferably 5,000-500,000, more preferably 10,000-300,000, still more preferably 20,000-100,000.

Examples of leachable tear stabilizers include, but are not limited to, phospholipids, monoglycerides, diglycerides, triglycerides, glycolipids, glyceroglycolipids, sphingolipids, glycolipids (sphingo-glycolipids), fatty alcohols, fatty acids, mineral oils, and mixtures thereof. Preferably, the tear stabilizer is a phospholipid, a monoglyceride, a diglyceride, a triglyceride, a glycolipid, a glyceroglycolipid, a sphingolipid, a neuroglycolipid (sphingo-glycolipid), a fatty acid having 8 to 36 carbon atoms, a fatty alcohol having 8 to 36 carbon atoms, or a mixture thereof.

The lens-forming composition can be prepared by dissolving all the required components in any suitable solvent known to those skilled in the art. Examples of suitable solvents are as described above and may be used in the aspects of the invention.

Lens molds for the manufacture of contact lenses are well known to those skilled in the art and are used, for example, in cast molding or spin casting. For example, a mold (for cast molding) typically comprises at least two mold sections 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 be received in one another to form a lens-forming cavity between the first molding surface and the second molding surface. The mold surface of the mold half is the cavity-forming surface of the mold and is in direct contact with the lens-forming material.

Methods of manufacturing mold sections for cast molding contact lenses are generally known to those of ordinary skill in the art. The method of the present invention is not limited to any particular method of forming a mold. In fact, any method of forming a mold may be used in the present invention. The first and second mold halves may be formed by various techniques, such as injection molding or turning. Examples of suitable methods of forming mold halves are disclosed in U.S. Pat. nos. 4,444,711 to Schad; 4,460,534 to Boehm et al; 5,843,346 to Morrill and 5,894,002 to Boneberger et al, the disclosures of which are incorporated herein by reference

Virtually all materials known in the art for making molds can be used to make molds for making contact lenses. For example, polymeric materials such as polyethylene, polypropylene, polystyrene, PMMA, may be used,COC grades 8007-S10 (transparent amorphous copolymers of ethylene and norbornene available from Frankfurt, Germany and Summit, New Jersey, Ticona GmbH), and the like. Other materials that transmit UV light may be used, such as quartz glass and sapphire.

In a preferred embodiment, a reusable mold is used and the lens-forming composition is allowed to cure actinically (i.e., polymerize) under a spatial limitation of actinic radiation to form a silicone hydrogel contact lens. Examples of preferred reusable molds are those disclosed in U.S. patent applications 08/274,942 filed 1994, 7, 14, 10/732,566 filed 2003, 12, 10, 10/721,913 filed 2003, 11, 25, and U.S. patent 6627124, which are incorporated by reference in their entirety. The reusable mold can be made of quartz, glass, sapphire, CaF₂Cyclic olefin copolymers (e.g., available from Frankfurt, Germany and Summit, NewJersey, Ticona GmbH)COC grades 8007-S10 (clear amorphous copolymer of ethylene and norbornene), available from Zeon Chemicals LP, Louisville, KYAnd) Polymethyl methacrylate (PMMA), polyoxymethylene (Delrin) from Dupont, available from g.e. plastics(polyetherimide),And so on.

According to the present invention, the lens-forming composition may be added (dispensed) into the cavity formed by the mold according to any known method.

After the lens-forming composition is dispensed into the mold, it is polymerized to produce a contact lens. Crosslinking can be initiated thermally or actinically, preferably by spatially limiting exposure of the lens-forming composition in the mold to actinic radiation to crosslink the polymerizable components in the lens-forming composition. Crosslinking according to the present invention can be carried out in a very short time, for example, in less than or equal to about 120 seconds, preferably in less than or equal to about 80 seconds, more preferably in less than or equal to about 50 seconds, still more preferably in less than or equal to about 30 seconds, and most preferably in the range of 5 to 30 seconds.

In the case where the lens-forming composition comprises an amphiphilic branched polysiloxane prepolymer having UV-absorbing moieties and/or a polymerisable UV-absorber, it is preferred in the present invention to use a benzoylphosphine oxide photoinitiator as the photoinitiator. Preferred benzoylphosphine oxide photoinitiators include, but are not limited to, 2,4, 6-trimethylbenzoyldiphenylphosphine oxide; bis (2, 6-dichlorobenzoyl) -4-n-propylphenylphosphine oxide; and bis (2, 6-dichlorobenzoyl) -4-n-butylphenyl phosphine oxide. It is to be understood that any photoinitiator other than the benzoylphosphine oxide initiator may be used in the present invention.

Opening of the mould so that the moulded lens can be removed from the mould can be carried out in a manner known per se.

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

The molded contact lenses can be further processed, such as by surface treatment (e.g., plasma treatment, chemical treatment, grafting of hydrophilic monomers or macromers to the lens surface, layer-by-layer coating, etc.); packaging the lens in a lens package using a packaging solution that may contain from about 0.005% to about 5% by weight of a wetting agent (e.g., the hydrophilic polymers described above) and/or a viscosity enhancing agent (e.g., Methylcellulose (MC), ethylcellulose, hydroxymethylcellulose, Hydroxyethylcellulose (HEC), Hydroxypropylcellulose (HPC), Hydroxypropylmethylcellulose (HPMC), or mixtures thereof); sterilizing; and so on.

Preferred surface treatments are LbL coating, such as those described in us patents 6,451,871, 6,719,929, 6,793,973, 6,811,805, 6,896,926 (incorporated by reference in their entirety) and plasma treatment. Preferred plasma treatments are those methods described in U.S. Pat. Nos. 4,312,575 and 4,632,844 (incorporated by reference in their entirety) in which an ionized gas is applied to the surface of an article.

The contact lenses of the invention have an oxygen permeability of preferably at least about 40barrer, more preferably at least about 60barrer, and still more preferably at least about 80 barrer. According to the present invention, the oxygen permeability is the apparent (directly measured when tested with a sample having a thickness of about 100 microns) oxygen permeability according to the method described in the examples.

The contact lenses of the invention have an elastic modulus of about 2.0MPa or less, preferably about 1.5MPa or less, more preferably about 1.2 or less, and still more preferably from about 0.4MPa to about 1.0 MPa.

The contact lenses of the invention additionally have a Lonoflux diffusion coefficient, D, of preferably at least about 1.5X 10^-6mm²A/min, more preferably at least about 2.6X 10^-6mm²A/min, still more preferably at least about 6.4X 10^-6mm²/min。

The contact lenses of the invention additionally have a water content, when fully hydrated, of preferably from about 15% to about 70%, more preferably from about 20% to about 50%, by weight. The water content of silicone hydrogel contact lenses can be measured according to bulktechnicque disclosed in US5,849,811.

In a third aspect, the present invention provides a silicone hydrogel contact lens obtained by the method of the invention.

In a fourth aspect, the present invention provides a process for preparing an amphiphilic branched polysiloxane prepolymer, the process comprising the steps of: (i) obtaining a partially ethylenically-functionalized polysiloxane, wherein the partially ethylenically-functionalized polysiloxane is a mixture of reaction products obtained by reacting a first ethylenically-functionalized vinyl monomer having a first reactive functional group with a functionalized polysiloxane compound having two or more second reactive functional groups in a molar equivalent ratio of from about 40% to about 95%, preferably from about 50% to about 95%, more preferably from about 60% to about 92%, still more preferably from about 70% to about 90% (functionalized vinyl monomer/linear polysiloxane compound), wherein each first reactive functional group reacts with one second reactive functional group in the presence or absence of a coupling agent to form a covalent bond or linkage, wherein the mixture of reaction products comprises one or more polysiloxane vinyl monomers or macromonomers having at least one second reactive functional group and at least one ethylenically unsaturated group, one or more polysiloxane crosslinkers having at least two ethylenically unsaturated groups; (ii) preparing a silicone composition comprising (a) a portion of an ethylenically-functionalized polysiloxane, (b) at least one hydrophilic vinyl monomer; (c) a chain transfer agent which is not a RAFT agent and optionally (but preferably) comprises a third reactive functional group) and (d) a free radical initiator; (ii) polymerizing the polymerizable composition to form an amphiphilic branched polysiloxane copolymer comprising hydrophilic monomer units derived from the at least one hydrophilic vinyl monomer, polysiloxane crosslinking units derived from a polysiloxane crosslinker, polysiloxane side chains derived from polysiloxane vinyl monomers or macromers and each terminated with one second reactive functional group, and chain transfer units with or without a third reactive functional group; (iii) reacting the branched polysiloxane copolymer with a second diene-functional vinyl monomer having a fourth reactive functional group that reacts with one of the second or third reactive functional groups of the branched polysiloxane copolymer in the presence or absence of a coupling agent to form an amphiphilic branched polysiloxane prepolymer having polysiloxane side chains each capped with one ethylenically unsaturated group.

All of the various embodiments of the molds, lens-forming compositions and components thereof and spatial confinement of radiation and contact lenses of the invention described above with respect to the first and second aspects of the invention can be used in both aspects of the invention.

The foregoing disclosure will enable one of ordinary skill in the art to practice the invention. Various modifications and combinations of the features described herein are possible. For a better understanding of the specific technical solutions and their advantages, reference is suggested to the following examples. The purpose of the description and examples should be considered as exemplary.

Although various embodiments of the present invention have been described using specific terms, devices, and methods, the description is for illustrative purposes only. The words used are words of description rather than limitation. It is to be understood that variations and modifications can be effected by one skilled in the art without departing from the spirit or scope of the invention, which is set forth in the following claims. Additionally, it should be understood that aspects of the various embodiments may be interchanged both in whole or in part or may be combined and/or used together in any manner. Therefore, the spirit and scope of the appended claims should not be limited to the description of the preferred versions contained herein.

Example 1

Oxygen permeability measurements.

The apparent oxygen permeability of the lens and the oxygen transmission rate of the lens material are determined according to techniques similar to those described in U.S. Pat. No. 5,760,100 and Winterton et al, the article of the Cornea: Transactionsofthe WorldCongresson the Cornea111, H.D. Cavanaghed, ravenPress: New York, 1988, p.273-280, both of which are incorporated herein by reference in their entirety. Oxygen flow (J) was measured in a wet cell (wetcell) at 34 ℃ using a Dk1000 instrument (available from applied design and development co., Norcross, GA) or similar analytical instrument (i.e., GAs stream maintained at about 100% relative humidity). The air stream having a known percentage of oxygen (e.g., 21%) is caused to flow at a rate of about 10-20cm³Passing one side of the lens at/min while flowing a stream of nitrogen gas at about 10-20cm³The/min rate passes through the opposite side of the lens. The sample is allowed to equilibrate in the test medium (i.e., saline or distilled water) at the aforementioned test temperature for at least 30 minutes but not more than 45 minutes prior to measurement. Used as a cover (or)One test medium was equilibrated at the aforementioned test temperature for at least 30 minutes but not more than 45 minutes prior to measurement. The speed of the agitator motor was set at 1200 + -50 rpm, corresponding to the indicated setting on the stepper motor controller of 400 + -15. Measuring the air pressure, P, around the system_Measuring. The thickness (t) of the lens within the exposure area for testing is determined by measuring about 10 positions using a Mitotoya micrometer VL-50 or similar instrument and taking the average of the measurements. The concentration of oxygen in the nitrogen stream (i.e., oxygen diffused through the lens) was measured using a DK1000 instrument. Apparent oxygen permeability, Dk, of lens materials_{Apparent appearance}Determined by the following formula:

Dk_{apparent appearance}＝Jt/(P_{Oxygen gas})

Wherein J ═ oxygen flow [ microliter O ]₂/cm²-minutes]

P_{Oxygen gas}＝(P_Measuring-P_{Steam of water}) (in air stream% O)₂)[mmHg]Oxygen partial pressure in air stream

P_MeasuringAs air pressure (mmHg)

P_{Steam of water}0mmHg (in drycell) at 34 ℃ (mmHg)

P_{Steam of water}40mmHg (in wet pool) at 34 ℃ (mmHg)

t-average thickness (mm) of the lens over the exposed test area

Wherein Dk_{Apparent appearance}Expressed in units of barrer.

The apparent oxygen transmission rate (Dk/t) of the material can be determined by the oxygen permeability (Dk)_{Apparent appearance}) Divided by the average thickness (t) of the lens.

The above measurements are not corrected for the so-called boundary layer effect due to the use of water or saline baths on the contact lenses during the oxygen flow measurement. The boundary layer effect results in the reported apparent Dk (Dk) of the silicone hydrogel material_{Apparent appearance}) Lower than the actual inherent Dk value(Dk_i). Furthermore, the relative effect of the thicker lens boundary layer effect is greater for thinner lenses. The net effect is that the reported Dk appears to vary with the thickness of the lens when it should be kept constant.

The Dk value intrinsic to the lens can be evaluated based on the Dk value for the following correction of the surface obstruction to oxygen flow caused by boundary layer effects.

The same instrument was used to measure a reference lotrafilcon A (purchased from CIBAVISION CORPORATION)) Or lotrafilcon B (AirOptix available from CIBAVISION ORPORATION)^TM) Apparent oxygen permeability value of the lens (one point). The reference lens has a similar diopter (optical power) to the lens tested and is measured simultaneously with the lens tested.

According to the apparent Dk measurement method described above, the oxygen flow through a series of thicknesses of lotrafilcon a or lotrafilcon b (reference) lenses was measured using the same apparatus to obtain the intrinsic Dk value (Dk) of the reference lens_i). A range of thicknesses should cover a thickness range of approximately 100 μm or more. Preferably, the range of reference lens thicknesses includes the thickness of the lens tested. Dk of these reference lenses_{Watch (A) Watch with}Must be measured on the same device as the lens being tested and ideally should be measured simultaneously with the lens being tested. The device settings and measurement parameters should be kept constant throughout the experiment. Each sample can be measured multiple times if desired.

The residual oxygen barrier value, R, was determined from the reference lens results using equation 1 in the calculation_r。

Where t is the thickness of the reference lens under measurement and n is the number of reference lenses measured. The residual oxygen inhibition value R_rPlotting the t data and fitting a curve of the form Y ═ a + bX, where Y is for the jth lens_j＝(ΔP/J)_jAnd X ═ t_j. Residual oxygen barrier value R_rIs equal to a.

Calculating the corrected oxygen permeability Dk of the tested lens based on equation 2 using the residual oxygen barrier value determined above_c(estimated intrinsic Dk).

Dk_c＝t/[(t/Dk_a)-R_r](2)

The estimated intrinsic Dk of the tested lens can be used to calculate the apparent Dk (Dk) of a standard thickness lens in the same test environment based on equation 3_{a_std})。

Dk_{a_std}＝t_std/[(t_std/Dk_c)+R_{r_std}](3)

Ion permeability of the lenses was measured according to the method described in U.S. Pat. No. 5,760,100, which is incorporated herein by reference in its entirety. The values of ion permeability given in the following examples are relative ionoflux diffusion coefficients (D/D) with reference to Alsacon, a lens material as a reference material_ref). Alsacon has an ionoflux diffusion coefficient of 0.314 × 10^-3mm²In terms of a/minute.

Water Contact Angle (WCA) measurements were carried out by the sitting drop method using a DSA10 drop shape analysis system from Kruss GmbH, Germany with pure water (Fluka, surface tension 72.5mN/m at 20 ℃). For measurement, the contact lens was removed from the storage solution with forceps and the excess storage solution was removed by gentle shaking. The contact lens was placed on the convex portion of the lens mold and gently wiped with a dry and clean cloth. A drop of water (approximately 1 μ l) was then dropped onto the lens tip and the contact angle of the drop was monitored for change over time (wca (t), circle fitting mode). WCA is calculated by WCA (t) extrapolation of the graph for t to t-0.

The contact lens is manually placed in a specially made sample holder or the like that holds the lens in the same shape as it is placed on the eye. The holder was then immersed in a 1cm path length quartz cell containing phosphate buffered saline (PBS, pH 7.0-7.4) as a reference. A UV/visible spectrophotometer such as the varian cary3 EUV-visiblespecoptometer with labsphere-CA-302 beam splitter or the like may be used in this measurement. The percent transmission spectra were collected over the wavelength range 250-800nm and the% T values were collected at 0.5nm intervals. The data was transferred into an Excel spreadsheet and used to determine if the lens meets class 1 UV absorbance. The UV absorbance was calculated using the following equation:

UVA% T ═ average% T between 380 and 316 nm)/(luminous% T). times.100

UVB% T ═ average% T between 280 and 315 nm)/(luminous% T). times.100

Where the luminescence% T is the average% transmission between 380-780.

Contact Lens Optical Quality Analyzers (CLOQA) were developed to determine optical distortion caused by surface distortion and other defects within contact lenses, based on the principles of the Foucault edge test. Those skilled in the art understand how to select, align, and arrange the various optical elements to produce collimated light, illuminate a contact lens, and acquire an image with a device (e.g., a CCD camera). The test involves illuminating the contact lens with near parallel light, placing the Foucault blade near the focal point, moving to a position where the blade blocks most of the focused light, and obtaining an image of the contact lens using a device, such as a CCD camera, behind the Foucault blade. In the absence of optical distortion in the contact lens, all light rays passing through the contact lens are focused at the blade edge and most of the highly focused light is blocked. For areas outside the optical area that do not have a focusing function, the knife edge will block light from half of the lens to darken it while the other half brightens. If a contact lens has no optical distortion in its optical zone, the entire optical zone will be uniformly dark or light, depending on how much light is blocked by the blade. In the presence of optical distortions on the contact lens, the light passing through the region generally does not fall into the primary focal point and is blocked (darkened) or passes freely (brightened) by the blade edge. The level of contrast depends not only on the magnitude of the deformation but also on the exact position of the edge. Defective areas appear as contrast features in the CLOQA image. The edge test with CLOQA is a qualitative detection device designed for optical deformation of the optical zone.

The folding trace study was performed as follows. Three autoclave and/or non-autoclave contact lenses were used in the study. First, a contact lens was photographed using CLOQA. Second, each lens was folded twice with a finger (creating two perpendicular fold lines) and the contact lenses were immediately photographed with CLOQA. Third, each contact lens in about 15 after folding was photographed using CLOQA. Three types of CLOQA images were obtained: the original image (i.e., unfolded), the image just after folding, and the image about 15 minutes after folding. The fold trace study allows the change in appearance of the fold line over time to be determined.

Example 2

Various percentages of ethylenically functional polysiloxanes were prepared as follows. KF-6001A (α, ω -bis (2-hydroxyethoxypropyl) -polydimethylsiloxane, Mn ═ 2000 from Shin-Etsu) and KF-6002A (α, ω -bis (2-hydroxyethoxypropyl) -polydimethylsiloxane, Mn ═ 3400 from Shin-Etsu) were dried in a single-neck flask at about 60 ℃ for 12 hours (or overnight), respectively, under high vacuum. The weight of the OH molar equivalents of KF-6001A and KF-6002A was determined by titration of the hydroxyl groups and used to calculate the millimolar equivalents for synthesis.

A-1 Synthesis of partially ethylenically functionalized polysiloxanes

The 1 liter reaction vessel was evacuated overnight to remove water and the vacuum broken with dry nitrogen. 75.00g (75meq) of dried KF6001A was charged to the reactor, and then 16.68g (150meq) of freshly distilled isophorone diisocyanate (IPDI) was added to the reactor. The reactor was purged with nitrogen and heated to 45 ℃ with stirring and then 0.30g of dibutyltin dilaurate (DBTDL) was added. The reactor was sealed and a positive flow of nitrogen was maintained. An exotherm occurred after which the reaction mixture was cooled and stirred at 55 ℃ for 2 hours. After the exotherm was reached, 248.00g (150meq) of dried KF6002A was added to the reactor at 55 ℃ and then 100. mu.L of DBTDL was added. The reactor was stirred for 4 hours. The heating was stopped and the reactor was allowed to cool overnight. The nitrogen sparge was stopped and the reactor was vented to atmosphere for 30 minutes with moderate stirring. A hydroxyl-terminated polysiloxane having three polysiloxane segments, HO-PDMS-IPDI-PDMS-OH, was formed.

For 80% ethylenically functionalized polysiloxane, 18.64g (120meq) of isocyanatoethyl methacrylate (IEM) were charged to the reactor along with 100. mu.L of DBTDL. The reactor was stirred for 24 hours and then the product was decanted and stored under refrigeration. To prepare various percentages of ethylenically functionalized polysiloxanes, various amounts of IEM were used according to table 1 below.

TABLE 1

	% ethylenically functional polysiloxanes	IEM weight
			A-1.1	60％	13.98g(90meq)
A-1.2	70％	16.31g(105meq)
			A-1.3	80％	18.64g(120meq)
A-1.4	100％	23.30g(150meq)

A-2.100% (fully) ethylenically functionalized polysiloxane:

the 1 liter reaction vessel was evacuated overnight to remove water and the vacuum broken with dry nitrogen. 75.00g (75meq) of dried KF6001A was charged to the reactor and dried under high vacuum at 60 ℃ for 8 hours, and then 23.30g (150meq) of IEM was charged to the reactor under nitrogen. After stirring for 30 minutes, 0.2g of DBTDL was added to the mixture. The reactor was stirred at 25 ± 3 ℃ for about 4 hours and the product was subsequently decanted and stored under refrigeration.

Example 3

This example illustrates the effect of the percentage of olefinic functionalization of polydisiloxanes used to make prepolymers used to make lens formulations on the viscosity of the lens formulations.

B-1. Synthesis of amphiphilic branched copolymer

A1-L jacketed reactor was fitted with a 500-mL addition funnel, overhead stirring, reflux condenser with nitrogen/vacuum inlet adapter, thermometer, and sampling adapter. 48.55g of the partially ethylenically functionalized Polysiloxane (PDMS) prepared in example 2, A-1 were charged to the reactor. PDMSA-1.1 was degassed at room temperature for 30 minutes under vacuum below 1 mbar. After degassing was complete, the reactor was flushed with nitrogen for further processing. A monomer solution consisting of 26.06g of N, N-Dimethylacrylamide (DMA), 23.14g of (TRIS (trimethylsilyl)) silyloxypropyl) -acrylamide (TRIS-Am) and 350g of ethyl acetate was charged to a 500-mL addition funnel, subsequently degassed under a vacuum of 100 mbar for 10 minutes at room temperature and subsequently refilled with nitrogen gas. The monomer solution was degassed under the same conditions for two additional cycles. The monomer solution was then fed into the reactor. The reaction mixture was heated to 64 ℃ with stirring. While heating, a solution composed of 1.75g of mercaptoethanol (chain transfer agent, CTA), 0.30g of azoisobutyronitrile (initiator) and 50g of ethyl acetate was fed into an addition funnel, followed by the same degassing process as the monomer solution. When the reactor temperature reached 64 ℃, the initiator/CTA solution was also added to the reactor. The reaction was carried out at 64 ℃ for 6 hours. After completion of the copolymerization, the reactor temperature was cooled to room temperature.

B-2. Synthesis of amphiphilic branched prepolymer

The copolymer solution prepared in (B-1) above was functionalized by adding 4.52g of IEM (or the amount shown in Table 2) and 0.15g of DBTDL alkenes to form an amphiphilic branched prepolymer. The mixture was stirred at room temperature under sealed conditions for 12 hours. The prepolymer prepared was then stabilized with 100ppm of hydroxy-tetramethylacryloxy. After exchanging the reaction solvent for 1-propanol, the solution was ready for formulation. Various amphiphilic branched prepolymers were prepared using various combinations of various% ethylenically functionalized polysiloxanes, CTA levels, and IEM as shown in table 2.

TABLE 2

Amphiphilic branched prepolymers	% ethylenically functional polysiloxanes	CTA％	IEM
				B-2a	Example 2, A-1.1 (60%)	1.75％	4.52g
B-2b	Example 2, A-1.2 (70%	1.75％	4.35g
				B-2c	Example 2, A-1.3 (80%)	1.75％	4.17g
B-2d	Example 2, A-1.4 (100%)	1.75％	3.83g
				B-2e	Example 2, A-1.1 (60%)	1.25％	3.43g
B-2f	Example 2, A-1.2 (70%	1.25％	3.25g
				B-2g	Example 2, A-1.3 (80%)	1.25％	3.08g

B-3: preparation of lens formulations

Lens formulations were prepared by dissolving the amphiphilic branched prepolymers prepared above (B-2a to B-2g) shown in Table 3 and other components. The other ingredients in each formulation included 1.0% DC1173 (C;)1173) 0.75% DMPC (1, 2-dimyristoyl-sn-glycero-3-phosphocholine, 1, 2-dimyristoyl-sn-glyco-3-phosphocholine) and 23.25% 1-PrOH (1-propanol). The intensity used was 16mW/cm with a 330nm filter²The optorheology of the lens formulations prepared was investigated (measured using an eservelog) and is also listed in table 3.

TABLE 3

(TRIS (trimethylsilyl)) silyloxypropyl) -acrylamide (TRIS-Am)

Example 4

C-1: synthesis of amphiphilic branched copolymers

The 4-L jacketed reactor was equipped with overhead stirring, reflux condenser with nitrogen/vacuum inlet adapter, thermometer and sampling adapter. A mixture of 78.35g of the partially olefinically functionalized polysiloxane prepared in example 2, A-1.3 and 8.71g of example 2, A-2 was charged to a 4-L reactor and subsequently degassed at room temperature under a vacuum of less than 10 mbar for 30 minutes. After degassing, the reactor was filled with nitrogen for further processing. A monomer solution composed of 52.51g of DMA, 56.65g of TRIS-Am and 390g of cyclohexane was transferred into the reactor. The final mixture was degassed at 100 mbar for 5 minutes and then refilled with nitrogen gas. The degassing cycle was repeated 4 times. The reaction mixture was then heated to 64 ℃ with stirring, followed by addition of degassed initiator/chain transfer agent solution consisting of 0.60g of V-601 (dimethyl 2, 2' -azobis (2-methylpropionate, available from WAKO specialty Chemicals), 7.50g of mercaptoethanol (CTA), and 10g of THF copolymerization was carried out at 64 ℃ under nitrogen for a total of 6 hours.

C-2. Synthesis of amphiphilic branched prepolymers

The copolymer solution prepared in the above (C-1) was functionalized by adding 7.50g of IEM and 0.21g of DBTDL alkenes to form an amphiphilic branched prepolymer, which was then stirred at room temperature under seal dry conditions for 48 hours. The prepolymer prepared was then stabilized with 100ppm of hydroxy-tetramethylacryloxy. After performing a repeated process of evaporating the reaction solvent and adding 1-propanol to replace the reaction solvent with 1-propanol, the solution was ready for formulation.

C-3: lens formulation and optorheology

The amphiphilic branched prepolymer prepared in (C-3) above was formulated with the final composition as listed in Table 4. The intensity used was 16mW/cm with a 330nm filter²The optorheology of the prepared formulations was investigated using the eservelog measurement.

TABLE 4

DMPC: 1, 2-dimyristoyl-sn-glycero-3-phosphocholine;

DC1173：Darocur1173

c-4: lens preparation and characterization

Contact lenses are prepared by casting lens formulations prepared from above (C-3.1 and C-3.2) in reusable molds similar to the molds shown in FIGS. 1-6 of U.S. Pat. Nos. 7,384,590 and 7,387,759 (FIGS. 1-6). The mold comprises CaF₂A female mold half made and a male mold half made of PMMA. The UV radiation source was at an intensity of about 4mW/cm²Hamamatsu lamp with WG335+ TM297 cut-off filter (measured using eseivlog). The lens formulation in the mold was irradiated with UV radiation for about 25 seconds. The lenses prepared were extracted with isopropanol, washed in pure water, coated with polyacrylic acid (PAA) (m.w.:450kDa, available from Lubrizol) by immersing the lenses in a 1-PrOH solution of PAA (0.1 wt%, ph2.5), and then hydrated with pure water. The coated lenses were packaged in lens packages containing phosphate buffered saline and autoclaved. Oxygen permeability (Dk)_{Apparent appearance}And Dk_c) And Ion Permeability (IP) was determined according to the method described in example 1. The lens properties, dk (barrer), IP (vs Alsacon), elastic modulus (E'), elongation at break (EtB) and water content (% by weight) are listed in table 5.

TABLE 5

Lot#

E’(MPa)

EtB(％)

DkApparent appearance

Dkc #

IP

Water%

C-3.1

0.68

260％

831

136

5.1

34.0％

C-3.2

0.67

260％

862

143

4.2

31.9％

1. Average lens thickness: 113 μm.

2. Average lens center thickness: 115 μm.

Lotrafilcon B lens with an average lens center thickness of 80 μm was used as a reference lens and the inherent Dk of the reference lens was 110 barrer.

Example 5

D-1 Synthesis of amphiphilic branched copolymer

A1-L jacketed reactor was fitted with a 500-mL addition funnel, overhead stirring, reflux condenser with nitrogen/vacuum inlet adapter, thermometer, and sampling adapter. 45.60g of the partly ethylenically functionalized polysiloxane prepared in example 2, A-1.3 are charged to a reactor and subsequently degassed at room temperature for 30 minutes under a vacuum of less than 1 mbar. After degassing, the reactor was filled with nitrogen for further processing. A monomer solution consisting of 0.65g of hydroxyethyl methacrylate (HEMA), 25.80g of DMA, 27.80g of 3- [ TRIS (trimethylsiloxy) silyl ] propyl methacrylate (TRIS) and 279g of ethyl acetate was charged to a 500-mL addition funnel, subsequently degassed under a vacuum of 100 mbar for 10 minutes at room temperature and subsequently refilled with nitrogen gas. The monomer solution was degassed using the same conditions for two additional cycles. The monomer solution was then fed into the reactor. The reaction mixture was heated to 67 ℃ with stirring. While heating, a solution composed of 1.50g of mercaptoethanol (CTA), 0.26g of azoisobutyronitrile (initiator) and 39g of ethyl acetate was fed into an addition funnel, followed by the same degassing process as the monomer solution. When the reactor temperature reached 67 ℃, the initiator/CTA solution was also added to the reactor. The reaction was carried out at 67 ℃ for 8 hours. After completion of the copolymerization, the reactor temperature was cooled to room temperature.

D-2. Synthesis of amphiphilic branched prepolymers

The copolymer solution prepared in (D-1) above was functionalized by adding 4.45g of IEM (or the desired molar equivalent of isocyanatoethyl methacrylate) to form an amphiphilic branched prepolymer in the presence of 0.21g of DBTDL. The mixture was stirred at room temperature under sealed conditions for 24 hours. The prepared macromer was then stabilized with 100ppm hydroxy-tetramethylepichlorohydrin prior to concentrating the solution to 200g (-50%) and filtering through a filter paper of 1 μm pore size. The solids content was measured by removing the solvent in a vacuum oven at 80 ℃. After exchanging the reaction solvent for 1-propanol, the solution was further concentrated to the desired concentration and prepared for the preparation of lens formulations.

D-3. preparation of lens formulations and optorheology

A lens formulation was prepared to have the following composition: 72% by weight of prepolymer D2 prepared above; 6% by weight of DMA; 1% by weight of DC 1173; 0.75 wt% DMPC; and 20.25 wt% of 1-PrOH. The optorheology was studied using a Hamamatsu lamp with a 330nm long pass cut-off filter (longpasscotoffilter) placed just before the sample. Intensity measurements using ESEUVLOG with a 297nm cut-off filter (16 mW/cm)²) Long pass filters were placed before the samples to cure the formulations. The results of the optorheological studies were: a cure time of about 12 seconds, a G' of 165kPa and a viscosity of 5550 mPa.s.

D-4: lens characterization

Contact lenses were cast from lens formulation D3, extracted with isopropanol, washed with water, coated with PAA, hydrated in water, packaged/autoclaved within the lens package, and characterized according to the method described in example 4. The obtained lens has the following characteristics: e' 0.75 MPa; EtB% ═ 212; dk_{Watch (A) Watch with}95 (for lenses with an average center thickness of 119 μm); dk_c172 (using lotrafilcon b lens as reference lens, average center thickness 81 μm and intrinsic Dk of 110); IP ═ 3.6; water% ═ 29.0.

Example 6

E-1: synthesis of UV-absorbing amphiphilic branched copolymers

A1-L jacketed reactor was fitted with a 500-mL addition funnel, overhead stirring, reflux condenser with nitrogen/vacuum inlet adapter, thermometer, and sampling adapter. 45.98g of the partially ethylenically functionalized polysiloxane prepared in example 2, A-1.3 were charged to a reaction flask and subsequently degassed at room temperature for about 30 minutes under a vacuum of less than 1 mbar. A monomer solution prepared by mixing 0.51g of HEMA, 25.35g of DMA, 1.38g of Norbloc methacrylate, 26.03g of TRIS and 263g of ethyl acetate is charged to a 500-mL addition funnel, degassed at room temperature for 10 minutes under a vacuum of 100 mbar and then refilled with nitrogen gas. The monomer solution was degassed using the same conditions for two additional cycles. The monomer solution was then fed into the reactor. The reaction mixture was heated to 67 ℃ with thorough stirring. While heating, a solution composed of 1.48g of mercaptoethanol (chain transfer agent, CTA), 0.26g of azoisobutyronitrile (initiator) and 38g of ethyl acetate was fed into an addition funnel, followed by the same degassing process as the monomer solution. When the reactor temperature reached 67 ℃, the initiator/CTA solution was also added to the reactor. The reaction was carried out at 67 ℃ for 8 hours. After completion of the copolymerization, the reactor temperature was cooled to room temperature.

E-2: synthesis of UV-absorbing amphiphilic branched prepolymers

The copolymer solution prepared in (E-1) above was functionalized by adding 3.84g of IEM (or the desired molar equivalent of isocyanatoethyl methacrylate) to form an amphiphilic branched prepolymer in the presence of 0.15g of DBTDL. The mixture was stirred at room temperature under sealed conditions for 24 hours. The prepared macromer was then stabilized with 100ppm hydroxy-tetramethylepichlorohydrin prior to concentrating the solution to 200g (-50%) and filtering through a filter paper of 1 μm pore size. After exchanging the reaction solvent for 1-propanol by repeated cycles of evaporation and dilution, the solution can be used for formulation. The solids content was measured by removing the solvent in a vacuum oven at 80 ℃.

E-3: preparation of lens formulations and optorheology

A lens formulation was prepared to have the following composition: 71% by weight of the above preparationPrepolymer E2; 4% by weight of DMA; 1 wt% TPO; 0.75 wt% DMPC; and 23.25 wt% of 1-PrOH. The optorheology was studied using a Hamamatsu lamp with 330nm and 388nm long-pass cut-off filter stacks placed just before the sample. Intensity measurement Using an IL1700 Detector (4.6 mW/cm)²) The detector used a SED005 sensor with a 297nm cut-off filter from international, which was placed before the sample to cure the formulation. The results of the optorheological studies were: a curing time of about 22 seconds, a G' of 155kPa and a viscosity of 2900 mPa.s.

E-4: lens and lens assembly

Contact lenses were cast from lens formulation E3, extracted with isopropanol, washed with water, coated with PAA, hydrated in water, packaged/autoclaved within the lens package, and characterized according to the method described in example 4. The obtained lens has the following characteristics: e' is 0.72 MPa; EtB = 130; dk_{Apparent appearance}101 (for a lens with an average center thickness of 122 μm); dk_c181 (using lotrafilcon b lens as reference lens, average center thickness 80 μm and intrinsic Dk of 110); IP 2.9; 26.9 percent of water; and UVA/UVB% T4.3/0.09.

Example 7

A: synthesis of 80% of alkene-functionalized chain-extended polysiloxane

KF-6001A (α, ω -bis (2-hydroxyethoxypropyl) -polydimethylsiloxane, Mn ═ 2000 from Shin-Etsu) and KF-6002A (α, ω -bis (2-hydroxyethoxypropyl) -polydimethylsiloxane, Mn ═ 3400 from Shin-Etsu) were dried in a single-neck flask at about 60 ℃ for 12 hours (or overnight), respectively, under high vacuum. The OH molar equivalent weights of KF-6001A and KF-6002A were determined by titration of the hydroxyl groups and used to calculate the millimolar equivalents for the synthesis.

The 1 liter reaction vessel was evacuated overnight to remove water and the vacuum broken with dry nitrogen. 75.00g (75meq) of dried KF6001A was charged to the reactor, and then 16.68g (150meq) of freshly distilled IPDI was charged to the reactor. The reactor was purged with nitrogen and heated to 45 ℃ with stirring and then 0.30g of DBTDL was added. The reactor was sealed and a positive flow of nitrogen was maintained. An exotherm occurred after which the reaction mixture was cooled and stirred at 55 ℃ for 2 hours. After the exotherm was reached, 248.00g (150meq) of dried KF6002A was added to the reactor at 55 ℃ and then 100. mu.L of DBTDL was added. The reactor was stirred for 4 hours. The heating was stopped and the reactor was allowed to cool overnight. The nitrogen sparge was stopped and the reactor was vented to atmosphere for 30 minutes with moderate stirring. A hydroxyl terminated chain extended polysiloxane having three polysiloxane segments, HO-PDMS-IPDI-PDMS-OH (or HO-CE-PDMS-OH), is formed.

For 80% ethylenically functionalized polysiloxane, 18.64g (120meq) of IEM was added to the reactor along with 100. mu.L of DBTDL. The reactor was stirred for 24 hours and then the product (80% IEM-terminated CE-PDMS) was decanted and stored under refrigeration.

B: synthesis of non-UV-absorbing amphiphilic branched polysiloxane prepolymers

A1-L jacketed reactor was fitted with a 500-mL addition funnel, overhead stirring, reflux condenser with nitrogen/vacuum inlet adapter, thermometer, and sampling adapter. 45.6g of 80% IEM-terminated CE-PDMS prepared above was charged to the reactor and sealed. A solution of 0.65g of hydroxyethyl methacrylate (HEMA), 25.80g of DMA, 27.80g of (TRIS (trimethylsilyl)) -siloxypropyl) methacrylate (TRIS) in 279g of ethyl acetate was added to the addition funnel. The reactor was degassed at <1 mbar at RT for 30 min with a high vacuum pump. The monomer solution was degassed at 100 mbar and RT for 10 minutes in three cycles, and the vacuum was broken with nitrogen between degassing cycles. The monomer solution was then charged to the reactor and the reactor mixture was then stirred and heated to 67 ℃. While heating, a solution of 1.50g of mercaptoethanol (chain transfer agent, CTA) and 0.26g of azoisobutyronitrile dissolved in 39g of ethyl acetate was fed into the addition funnel and deoxygenated at 100 mbar, RT for 10 minutes. When the reactor temperature reached 67 ℃, the initiator/CTA solution was also added to the PDMS/monomer solution in the reactor. The reaction was allowed to proceed for 8 hours, and then heating was stopped and the reactor temperature was allowed to reach room temperature in 15 minutes.

The resulting reaction mixture was then siphoned into a dry single-necked flask with a sealed lid and 4.452g of IEM and 0.21g of DBTDL were added. The mixture was stirred at room temperature for 24 hours to form a non-UV-absorbing amphiphilic branched polysiloxane prepolymer. To the mixture solution was added 100. mu.L of hydroxy-tetramethyleneepoxynitrile solution in ethyl acetate (2g/20 mL). The solution was then concentrated to 200g (. about.50%) using a rotary evaporator at 30 ℃ and filtered through a filter paper of 1 μm pore size. After exchanging the solvent for 1-propanol, the solution was further concentrated to the desired concentration.

C. Synthesis of UV-absorbing amphiphilic branched polysiloxane prepolymers

A1-L jacketed reactor was fitted with a 500-mL addition funnel, overhead stirring, reflux condenser with nitrogen/vacuum inlet adapter, thermometer, and sampling adapter. 45.98g of 80% IEM-terminated CE-PDMS prepared above was charged to the reactor and sealed. A solution of 0.512g HEMA, 25.354g DMA, 1.38g Norbloc methacrylate, 26.034g TRIS in 263g ethyl acetate was charged to the addition funnel. The reactor was degassed at <1 mbar at RT for 30 min with a high vacuum pump. The monomer solution was degassed at 100 mbar and RT for 10 minutes in three cycles, and the vacuum was broken with nitrogen between degassing cycles. The monomer solution was then charged to the reactor and the reactor mixture was then stirred and heated to 67 ℃. While heating, a solution of 1.480g of mercaptoethanol (chain transfer agent, CTA) and 0.260g of azoisobutyronitrile dissolved in 38g of ethyl acetate was fed into the addition funnel and deoxygenated at 100 mbar, RT for 10 minutes. When the reactor temperature reached 67 ℃, the initiator/CTA solution was also added to the PDMS/monomer solution in the reactor. The reaction was allowed to proceed for 8 hours, and then heating was stopped and the reactor temperature was allowed to reach room temperature in 15 minutes.

The resulting reaction mixture was then siphoned into a dry single-neck flask with a sealed lid and 3.841g of isocyanatoethyl acrylate and 0.15g of DBTDL were added. The mixture was stirred at room temperature for 24 hours to form a UV-absorbing amphiphilic branched polysiloxane prepolymer. To the mixture solution was added 100. mu.L of hydroxy-tetramethyleneepoxynitrile solution in ethyl acetate (2g/20 mL). The solution was then concentrated to 200g (. about.50%) using a rotary evaporator at 30 ℃ and filtered through a filter paper of 1 μm pore size. After exchanging the solvent for 1-propanol, the solution was further concentrated to the desired concentration.

D-1: lens formulations with UV-absorbing polysiloxane prepolymers

In a 100mL amber bottle, 4.31g of macromer solution (which is 82.39% solution in 1-propanol prepared from the macromer solution prepared above by repeated dilution of the 1-propanol evaporation cycle) was added. In a 20mL vial, 0.081g of TPO and 0.045g of DMPC are dissolved in 10g of 1-propanol and then transferred to a macromer solution. After concentrating the mixture to 5.64g at 30 ℃ using a rotary evaporator, 0.36g of DMA was added and the formulation was homogenized at room temperature. 6g of transparent lens preparation D-1 was obtained.

D-2: lens formulation with UV-absorbing polysiloxane prepolymer (4% DMA)

In a 100mL amber vial, 24.250g of macromer solution (43.92% in ethyl acetate) was added. In a 50mL vial, 0.15g of TPO and 0.75g of DMPC were dissolved in 20g of 1-propanol and subsequently transferred to a macromer solution. 20g of solvent were stripped off at 30 ℃ using a rotary evaporator, after which 20g of 1-propanol were added. After two cycles, the mixture was concentrated to 14.40 g. 0.6g of DMA was added to the mixture and the formulation was homogenized at room temperature. 15g of transparent lens preparation D-2 was obtained.

D-3: lens formulation with UV-absorbing polysiloxane prepolymer (2% DMA/2% HEA)

In a 100mL amber vial, 24.250g of macromer solution (43.92% in ethyl acetate) was added. In a 50mL vial, 0.15g of TPO and 0.75g of DMPC were dissolved in 20g of 1-propanol and subsequently transferred to a macromer solution. 20g of solvent were stripped off at 30 ℃ using a rotary evaporator, after which 20g of 1-propanol were added. After two cycles, the mixture was concentrated to 14.40 g. 0.3g of DMA and 0.3g of HEA were added to the mixture and the formulation was homogenized at room temperature. 15g of transparent lens preparation D-3 was obtained.

Example 8

E: covalent attachment of modified PAE coating polymers

Monomers containing an amine group, N- (3-aminopropyl) methacrylamide hydrochloride (APMAA-HCl) or N- (2-aminoethyl) methacrylamide hydrochloride (AEMAA-HCl) were purchased from Polysciences and used as such. Poly (amidoamine epichlorohydrin) (PAE) was purchased from Ashland as an aqueous solution and used directly. Poly (acrylamide-co-acrylic acid) available from Polysciences (poly (AAm-co-AA) (90/10), mPEG-SH available from laysan bio, and poly (MPC-co-AeMA) available from NOF (i.e., a copolymer of Methacryloyloxyethyl Phosphorylcholine (MPC) and aminoethyl methacrylate (AeMA)) were used as is.

The APMAA-HCl monomer was dissolved in methanol and added to lens formulations D-1, D-2 and D-3 (prepared in example 7) to obtain a concentration of 1 wt%.

Reactive packaging brines were prepared by dissolving the components listed in table 6 in DI water along with the appropriate buffer salts. After the heated pretreatment, the brine was cooled to room temperature and then filtered using a 0.2 μm PES filter.

TABLE 6

Lens formulations D-1, D-2 and D3, prepared in example 7, were modified by the addition of APMAA-HCl monomer (a storage solution of APMMA-HCL in methanol). DSM lens was set at 16mW/cm²The LS lens was cured with a 330nm filter at 4.6mW/cm²Curing was performed with a 380nm filter.

The concave part of the polypropylene lens mold was filled with about 75 ml of the lens formulation prepared above and the mold was closed with the convex part of the polypropylene mold (base curve mold). By using a UV radiation source (at an intensity of about 16 mW/cm)²Lower Hamamatsu lamp with 330nm cut-off filter) the closed mold was cured for about 5 minutes to obtain a contact lens.

LS lenses were prepared by casting the lens formulations prepared above in a reusable mold similar to the molds shown in fig. 1-6 in U.S. patent nos. 7,384,590 and 7,387,759 (fig. 1-6). The mold comprises quartz (or CaF)₂) A female mold half made and a male mold half made of glass (or PMMA). The UV radiation source was at an intensity of about 4.6mW/cm²Hamamatsu lamp with 380nm cut-off filter under. The lens formulation in the mold was irradiated with UV radiation for about 30 seconds.

Lens formulation D-1 (example 7) modified with APMAA-HCl was cured according to the DSM and LS methods described above, while lens formulation D-2 or D-3 (example 7) was cured according to the LS method described above.

The molded lenses were extracted in methyl ethyl ketone, hydrated and packaged in one of the brines described in table 6. The lenses were placed in polypropylene lens packaging shells containing 0.6mL of IPC saline (half of the saline was added before insertion of the lenses). The shields (blister) were then sealed with a metal foil and autoclaved at 121 ℃ for 30 minutes.

Evaluation of the lens surfaces showed that all of the test lenses had no chip blocking. When viewed under a dark field microscope, the split line was not visible after rubbing the lens between the fingers.

Lens surface Wettability (WBUT), lubricity and contact angle were measured and the results are listed in table 7.

TABLE 7

1. The numbers are for the packaged brines shown in table 5.

An LS lens.

The lenses tested were prepared according to the DSM method, if not otherwise indicated. Lubricity is evaluated on a qualitative scale of 0 to 4, where lower numbers indicate greater lubricity. Generally, there is some improvement in lens surface properties after application of the coating in the package.

Example 9

Lenses were made using lens formulation D-2 (example 7) to which APMAA monomer was added to a concentration of 1%. LS lenses are made by casting the lens formulation prepared as above in a reusable mold similar to that shown in figures 1-6 of U.S. patents 7,384,590 and 7,387,759 (figures 1-6). The mold comprises a female mold half made of glass and a male mold half made of quartz. The UV radiation source was at an intensity of about 4.6mW/cm²Hamamatsu lamp with 380nm cut-off filter under. The lens formulation in the mold was irradiated with UV radiation for about 30 seconds.

The cast lenses were extracted with Methyl Ethyl Ketone (MEK), washed in water, coated with polyacrylic acid (PAA) by immersing the lenses in a solution of PAA in propanol (0.0044 wt%, acidified with formic acid to about ph2.5), and hydrated in water.

IPC brines were prepared from compositions containing about 0.07% PAAm-PAA and sufficient PAE at pre-reaction conditions of about 60 ℃ for 8 hours to provide an initial azetidinium content of about 8.8 milliequivalents/liter (-0.15% PAE). 10ppm hydrogen peroxide was then added to the IPC brine to inhibit the bioburden growth and the IPC brine was filtered using a 0.22 micron polyethersulfone [ PES ] membrane filter. The lenses were placed in polypropylene lens packages with 0.6ml of saline (half of the saline was added before insertion into the lenses). The shields were then sealed with metal foil and autoclaved at 121 ℃ for 30 minutes.

Evaluation of the lens surfaces showed that all of the test lenses had no chip blocking. When viewed under a dark field microscope, the split line was not visible after rubbing the lens between the fingers. Lens surface Wettability (WBUT) was greater than 10 seconds, lubricity was rated "1", and contact angle was approximately 20 °.

Example 10

Synthesis of UV-absorbing amphiphilic branched copolymers

A1-L jacketed reactor was fitted with a 500-mL addition funnel, overhead stirring, reflux condenser with nitrogen/vacuum inlet adapter, thermometer, and sampling adapter. 89.95g of the partially ethylenically functionalized polysiloxane prepared in example 2, A-1.3 were charged to the reactor and subsequently degassed at room temperature under a vacuum of less than 1 mbar for about 30 minutes. A monomer solution prepared by mixing 1.03g of HEMA, 50.73g of DMA, 2.76g of Norbloc methacrylate, 52.07g of TRIS and 526.05g of ethyl acetate was charged to a 500-mL addition funnel, followed by degassing under a vacuum of 100 mbar for 10 minutes at room temperature and then refilling with nitrogen gas. The monomer solution was degassed under the same conditions for two additional cycles. The monomer solution was then fed into the reactor. The reaction mixture was heated to 67 ℃ with moderate stirring. While heating, a solution composed of 2.96g of mercaptoethanol (chain transfer agent, CTA) and 0.72g of dimethyl 2, 2' -azobis (2-methylpropionate) (V-601-initiator) and 76.90g of ethyl acetate was fed to an addition funnel, followed by the same degassing process as the monomer solution. When the reactor temperature reached 67 ℃, the initiator/CTA solution was also added to the reactor. The reaction was carried out at 67 ℃ for 8 hours. After completion of the copolymerization, the reactor temperature was cooled to room temperature.

Synthesis of UV-absorbing amphiphilic branched prepolymers

The copolymer solution prepared above was functionalized by the addition of 8.44g of IEM (or a desired molar equivalent amount of 2-isocyanatoethyl methacrylate) alkene in the presence of 0.50g of DBTDL to form an amphiphilic branched prepolymer. The mixture was stirred at room temperature under sealed conditions for 24 hours. The prepared prepolymer was then stabilized with 100ppm hydroxy-tetramethylepichlorohydrin prior to concentrating the solution to 200g (. about.50%) and filtering through a1 μm pore size filter paper. After exchanging the reaction solvent for 1-propanol by repeated cycles of evaporation and dilution, the solution is ready for formulation. The solids content was measured by removing the solvent in a vacuum oven at 80 ℃.

Preparation of lens formulations

A lens formulation was prepared to have the following composition: 71% by weight of the prepolymer prepared above; 4% by weight of DMA; 1 wt% TPO; 1% by weight of DMPC; 1% by weight of Brij52 (from Calif.), and 22% by weight of 1-PrOH.

Lens preparation

Contact lenses are made by casting the lens formulation prepared above in a reusable mold similar to the molds shown in fig. 1-6 of U.S. patent nos. 7,384,590 and 7,387,759 (fig. 1-6) under the spatial limitations of UV radiation. The mold comprises a female mold half made of glass and a male mold half made of quartz. The UV radiation source was at an intensity of about 4.6mW/cm²Hamamatsu lamp with 380nm cut-off filter under. The lens formulation in the mold was irradiated with UV radiation for about 30 seconds.

The cast lenses were extracted with methyl ethyl ketone, washed in pure water, coated with polyacrylic acid (PAA) by immersing the lenses in a solution of PAA in propanol (0.004 wt%, acidified with formic acid to about ph2.0), and hydrated in water.

IPC brines were prepared from compositions containing about 0.07% PAAm-PAA and sufficient PAE at pre-reaction conditions of about 60 ℃ for 6 hours to provide an initial azetidinium content of about 8.8 milliequivalents/liter (-0.15% PAE). Then 5ppm hydrogen peroxide was added to the IPC brine to inhibit the bioburden growth and the IPC brine was filtered using a 0.22 micron polyethersulfone [ PES ] membrane filter. The lenses were placed in polypropylene lens packages with 0.6ml of saline (half of the saline was added before insertion into the lenses). The shields were then sealed with metal foil and autoclaved at 121 ℃ for 30 minutes.

Lens characterization

The obtained lens has the following characteristics: e' is about 0.82 MPa; dk_c159.4 (using Lotrafilcon B lens as reference lens, average center thickness 80 μm and intrinsic Dk 110); IP-2.3; water percent to 26.9; and UVA/UVB% T-4.6/0.1.

Claims (16)

1. An amphiphilic branched prepolymer comprising:

from 5% to 75% by weight of hydrophilic monomer units derived from at least one hydrophilic vinyl monomer;

from 1% to 85% by weight of polysiloxane crosslinking units derived from at least one polysiloxane crosslinker having two or more terminal ethylenically unsaturated groups;

2-48% by weight of polysiloxane side chains each end-capped with an ethylenically unsaturated group; and

from 0.25% to 5% by weight of chain transfer units derived from a chain transfer agent other than a RAFT agent,

wherein the amphiphilic branched prepolymer is an amphiphilic branched polysiloxane prepolymer obtained by:

(i) polymerizing a polymerizable composition to obtain an amphiphilic branched polysiloxane copolymer, wherein the polymerizable composition comprises

(a) A partially ene-functional polysiloxane, wherein the partially ene-functional polysiloxane is prepared by reacting a first ene-functional vinyl monomer having a first reactive functional group with a functional polysiloxane compound having two or more second reactive functional groups in a molar equivalent ratio, R_{Equivalent weight}From 40% to 95%, reacting the resulting mixture of reaction products, wherein each first reactive functional group reacts with one second reactive functional group in the presence or absence of a coupling agent to form a covalent bond or linkage, wherein the mixture of reaction products comprises at least one polysiloxane crosslinker having at least two ethylenically unsaturated groups and at least one polysiloxane vinyl monomer or macromer having at least one second reactive functional group and at least one ethylenically unsaturated group,

(b) at least one hydrophilic vinyl monomer, wherein the vinyl monomer,

(c) optionally, a hydrophobic vinyl monomer,

(d) a chain transfer agent other than a RAFT agent, wherein the chain transfer agent optionally comprises a third reactive functional group, and

(e) a free radical initiator; and

(ii) the amphiphilic branched polysiloxane copolymer is alkene-functionalized by reacting the amphiphilic branched polysiloxane copolymer with a second alkene-functionalized vinyl monomer having a fourth reactive functional group that forms a covalent linkage with one of the second or third reactive functional groups in the presence or absence of a coupling agent, thereby forming an amphiphilic branched polysiloxane prepolymer,

wherein vinyl monomer refers to a compound having one sole ethylenically unsaturated group and an average molecular weight of less than 700 daltons,

vinyl macromers refer to compounds which contain one sole ethylenically unsaturated group and have an average molecular weight of more than 700 daltons.

2. The amphiphilic branched prepolymer of claim 1, wherein the polymerizable composition comprises:

(a) 20-80% by weight of a partially ethylenically functionalized polysiloxane;

(b) 5-75% by weight of at least one hydrophilic vinyl monomer;

(c) from 0 to 55% by weight of a bulky hydrophobic vinyl monomer selected from: n- [ tris (trimethylsiloxy) silylpropyl ] (meth) acrylamide; n- [ tris (dimethylpropylsiloxy) silylpropyl ] (meth) acrylamide; n- [ tris (dimethylphenylsiloxy) silylpropyl ] (meth) acrylamide; n- [ tris (dimethylethylsiloxy) silylpropyl ] (meth) acrylamide; n- (2-hydroxy-3- (3- (bis (trimethylsiloxy) methylsilyl) propoxy) propyl) -2-methacrylamide; n- (2-hydroxy-3- (3- (bis (trimethylsiloxy) methylsilyl) propoxy) propyl) acrylamide; n, N-bis [ 2-hydroxy-3- (3- (bis (trimethylsiloxy) methylsilyl) propoxy) propyl ] -2-methacrylamide; n, N-bis [ 2-hydroxy-3- (3- (bis (trimethylsiloxy) methylsilyl) propoxy) propyl ] acrylamide; n- (2-hydroxy-3- (3- (tris (trimethylsiloxy) silyl) propoxy) propyl) -2-methacrylamide; n- (2-hydroxy-3- (3- (tris (trimethylsiloxy) silyl) propoxy) propyl) acrylamide; n, N-bis [ 2-hydroxy-3- (3- (tris (trimethylsiloxy) silyl) propoxy) propyl ] -2-methacrylamide; n, N-bis [ 2-hydroxy-3- (3- (tris (trimethylsiloxy) silyl) propoxy) propyl ] acrylamide; n- [ 2-hydroxy-3- (3- (tert-butyldimethylsilyl) propoxy) propyl ] -2-methacrylamide; n- [ 2-hydroxy-3- (3- (tert-butyldimethylsilyl) propoxy) propyl ] acrylamide; n, N-bis [ 2-hydroxy-3- (3- (tert-butyldimethylsilyl) propoxy) propyl ] -2-methacrylamide; n, N-bis [ 2-hydroxy-3- (3- (tert-butyldimethylsilyl) propoxy) propyl ] acrylamide; 3-methacryloxypropyl pentamethyldisiloxane; TRIS (trimethylsiloxy) silylpropyl methacrylate (TRIS); (3-methacryloxy-2-hydroxypropoxy) propylbis (trimethylsiloxy) methylsilane); (3-methacryloxy-2-hydroxypropoxy) propyltris (trimethylsiloxy) silane; 3-methacryloxy-2- (2-hydroxyethoxy) -propoxy) propylbis (trimethylsiloxy) methylsilane; carbamic acid N-2-methacryloyloxyethyl-O- (methyl-bis-trimethylsiloxy-3-propyl) silyl ester; 3- (trimethylsilyl) propyl vinyl carbonate; 3- (vinyloxycarbonylthio) propyl-tris (trimethyl-siloxy) silane; 3- [ tris (trimethylsiloxy) silyl ] propyl vinyl carbamate; 3- [ tris (trimethylsiloxy) silyl ] propylallyl carbamate; 3- [ tris (trimethylsiloxy) silyl ] propyl vinyl carbonate; tert-butyldimethyl-siloxyethyl vinyl carbonate; trimethylsilylethyl vinyl carbonate; trimethylsilylmethyl vinyl carbonate; t-butyl (meth) acrylate, cyclohexyl acrylate, isobornyl methacrylate, silicone-containing vinyl monomers having 3-8 silicon atoms, and combinations thereof;

(d) 0.25% to 5% by weight of a chain transfer agent other than a RAFT agent, wherein the chain transfer agent optionally comprises a reactive functional group;

(e) 0-5% by weight of a polymerizable UV absorbing compound; and

(f) from 0.1% to 5% by weight of a free radical initiator,

wherein the weight percentages of the above components are relative to the total weight of all polymerizable components.

3. The amphiphilic branched prepolymer of claim 2, wherein the hydrophilic vinyl monomer is absent a reactive functional group capable of participating in a coupling reaction with a second diene-functional vinyl monomer.

4. The amphiphilic branched prepolymer of claim 2, wherein the polymerizable composition comprises a first hydrophilic vinyl monomer free of any reactive functional group capable of participating in a coupling reaction with a second diene-functional vinyl monomer and a second hydrophilic vinyl monomer having a reactive functional group capable of participating in a coupling reaction with a second diene-functional vinyl monomer, wherein the first and second hydrophilic vinyl monomers are present in the polymerizable composition in a weight ratio of from 5:1 to 30: 1.

5. The amphiphilic branched prepolymer of claim 4, wherein the first hydrophilic vinyl monomer is selected from the group consisting of N, N-dimethyl (meth) acrylamide, N-methyl-3-methylene-2-pyrrolidone, 1-ethyl-3-methylene-2-pyrrolidone, 1-methyl-5-methylene-2-pyrrolidone, 1-ethyl-5-methylene-2-pyrrolidone, 5-methyl-3-methylene-2-pyrrolidone, 5-ethyl-3-methylene-2-pyrrolidone, 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, dimethylaminoethyl (meth) acrylate, N-vinyl-2-pyrrolidone, C (meth) acrylate₁-C₄-alkoxy polyethylene glycol esters, N-vinyl formamide, N-vinyl acetamide, N-vinyl isopropylamide, N-vinyl-N-methyl acetamide and mixtures thereof; and the second hydrophilic vinyl monomer is selected from hydroxyl-substituted C (meth) acrylic acid₁-C₄Alkyl esters, hydroxy-substituted C₁-C₄Alkyl (meth) acrylamides, amino-substituted C (meth) acrylates₁-C₄Alkyl ester, amino-substituted C₁-C₄Alkyl (meth) acrylamides, allyl alcohols, allyl amines and mixtures thereof.

6. The amphiphilic branched prepolymer according to claim 1, wherein the functionalized polysiloxane compound is defined by formula (1) or (2)

FG-G₁-PDMS-G₂-FG(1)

CR(-G₁-PDMS-G₂-FG)_a1(2)

Wherein

G₁And G₂Independently of one another, straight-chain or branched C₁-C₁₀An alkylene divalent group,Wherein q is an integer of 1 to 5 and alk' are independently of each other C₁-C₆Alkylene divalent group or-R'₁-X₁-E-X₂-R’₂-a divalent radical of (A), wherein R'₁And R'₂Independently of one another, straight-chain or branched C₁-C₁₀Alkylene diradicals or as defined aboveDivalent group of (2), X₁And X₂Independently of one another, are selected from the group consisting of-O-),-S-andwherein R' is H or C₁-C₈Alkyl, E is an alkyl, cycloalkyl, alkylcycloalkyl, alkylaryl or aryl diyl group having up to 40 carbon atoms, which may have ether, thio or amine linkages in the backbone;

PDMS is a polysiloxane divalent radical of formula (3)

Wherein nu is 0 or 1, omega is an integer of 0-5, U₁And U₂Independently of one another represents-R 'as defined above'₁-X₁-E-X₂-R’₂A divalent radical of (A) or (B) as defined aboveA divalent radical of (2), D₁、D₂And D₃Independently of one another, are divalent radicals selected from the group consisting of- (CH)₂CH₂O)_t-CH₂CH₂-, where t is an integer from 3 to 40, -CF₂-(OCF₂)_a-(OCF₂CF₂)_b-OCF₂-, wherein a and b are, independently of one another, integers from 0 to 10, with the proviso that a + b is a number from 10 to 30, and divalent radicals of the formula (4),

wherein R is₃、R₄、R₅、R₆、R₇、R₈、R₉And R₁₀Independently of one another are C₁-C₁₀Alkyl radical, C₁-C₁₀Aminoalkyl radical, C₁-C₁₀Hydroxyalkyl radical, C₁-C₁₀Ether, C₁-C₄Alkyl-or C₁-C₄Phenyl substituted by alkoxy, C₁-C₁₀Fluoroalkyl, C₁-C₁₀Fluoroether, C₆-C₁₈Aryl radical, -alk- (OCH)₂CH₂)_n-OR₁₁Wherein alk is C₁-C₆Alkylene divalent radical, R₁₁Is hydrogen or C₁-C₆Alkyl, and n is an integer from 1 to 10; m and p are each independently an integer from 0 to 350 and (m + p) is from 1 to 700, with the proviso that D₁、D₂And D₃At least one of (a) is represented by formula (4);

CR is a polyvalent organic group having a valence of a 1;

a1 is an integer of 3,4 or 5; and

FG is an amino group selected from the group consisting of-NHR', a hydroxyl group, a carboxylic acid group,Acyl halide group, acid anhydride group, aldehyde group, azlactone group, isocyanate group, epoxy group, aziridine group, thiol (-SH), and amide group (-CONH) of formula-COX₂) Wherein R' is hydrogen or C₁-C₂₀Unsubstituted or substituted, straight-chain or branched alkyl groups, X ═ Cl, Br or I.

7. The amphiphilic branched prepolymer of any one of claims 2-5, wherein the functionalized polysiloxane compound is defined by formula (1) or (2)

FG-G₁-PDMS-G₂-FG(1)

CR(-G₁-PDMS-G₂-FG)_a1(2)

Wherein

G₁And G₂Independently of one another, straight-chain or branched C₁-C₁₀An alkylene divalent group,Wherein q is an integer of 1 to 5 and alk' are independently of each other C₁-C₆Alkylene divalent group or-R'₁-X₁-E-X₂-R’₂-a divalent radical of (A), wherein R'₁And R'₂Independently of one another, straight-chain or branched C₁-C₁₀Alkylene diradicals or as defined aboveDivalent group of (2), X₁And X₂Independently of one another, are selected from the group consisting of-O-),-S-andwherein R' is H or C₁-C₈Alkyl, E is an alkyl, cycloalkyl, alkylcycloalkyl, alkylaryl or aryl diyl group having up to 40 carbon atoms, which may have ether, thio or amine linkages in the backbone;

PDMS is a polysiloxane divalent radical of formula (3)

Wherein nu is 0 or 1, omega is an integer of 0-5, U₁And U₂Independently of one another represents-R 'as defined above'₁-X₁-E-X₂-R’₂A divalent radical of (A) or (B) as defined aboveA divalent radical of (2), D₁、D₂And D₃Independently of one another, are divalent radicals selected from the group consisting of- (CH)₂CH₂O)_t-CH₂CH₂-, where t is an integer from 3 to 40, -CF₂-(OCF₂)_a-(OCF₂CF₂)_b-OCF₂-, wherein a and b are, independently of one another, integers from 0 to 10, with the proviso that a + b is a number from 10 to 30, and divalent radicals of the formula (4),

wherein R is₃、R₄、R₅、R₆、R₇、R₈、R₉And R₁₀Independently of one another are C₁-C₁₀Alkyl radical, C₁-C₁₀Aminoalkyl radical, C₁-C₁₀Hydroxyalkyl radical, C₁-C₁₀Ether, C₁-C₄Alkyl-or C₁-C₄Phenyl substituted by alkoxy, C₁-C₁₀Fluoroalkyl, C₁-C₁₀Fluoroether, C₆-C₁₈Aryl radicals fromFrom the group, -alk- (OCH)₂CH₂)_n-OR₁₁Wherein alk is C₁-C₆Alkylene divalent radical, R₁₁Is hydrogen or C₁-C₆Alkyl, and n is an integer from 1 to 10; m and p are each independently an integer from 0 to 350 and (m + p) is from 1 to 700, with the proviso that D₁、D₂And D₃At least one of (a) is represented by formula (4);

CR is a polyvalent organic group having a valence of a 1;

a1 is an integer of 3,4 or 5; and

FG is an amino group selected from the group consisting of an-NHR', a hydroxyl group, a carboxylic acid group, an acyl halide group of formula-COX, an anhydride group, an aldehyde group, an azlactone group, an isocyanate group, an epoxy group, an aziridine group, a thiol (-SH), and an amide group (-CONH)₂) Wherein R' is hydrogen or C₁-C₂₀Unsubstituted or substituted, straight-chain or branched alkyl groups, X ═ Cl, Br or I.

8. An amphiphilic branched prepolymer according to claim 7 wherein part of the ethylenically functionalized polysiloxane is obtained by reacting a first ethylenically functionalized vinyl monomer with a functionalized polysiloxane compound of formula (1) in a molar equivalent ratio of from 70% to 90%.

9. The amphiphilic branched prepolymer of claim 6, wherein the polymerizable composition comprises a bulky hydrophobic vinyl monomer selected from the group consisting of N- [ tris (trimethylsiloxy) silylpropyl ] (meth) acrylamide; n- [ tris (dimethylpropylsiloxy) silylpropyl ] (meth) acrylamide; n- [ tris (dimethylphenylsiloxy) silylpropyl ] (meth) acrylamide; n- [ tris (dimethylethylsiloxy) silylpropyl ] (meth) acrylamide; n- (2-hydroxy-3- (3- (bis (trimethylsiloxy) methylsilyl) propoxy) propyl) -2-methacrylamide; n- (2-hydroxy-3- (3- (bis (trimethylsiloxy) methylsilyl) propoxy) propyl) acrylamide; n, N-bis [ 2-hydroxy-3- (3- (bis (trimethylsiloxy) methylsilyl) propoxy) propyl ] -2-methacrylamide; n, N-bis [ 2-hydroxy-3- (3- (bis (trimethylsiloxy) methylsilyl) propoxy) propyl ] acrylamide; n- (2-hydroxy-3- (3- (tris (trimethylsiloxy) silyl) propoxy) propyl) -2-methacrylamide; n- (2-hydroxy-3- (3- (tris (trimethylsiloxy) silyl) propoxy) propyl) acrylamide; n, N-bis [ 2-hydroxy-3- (3- (tris (trimethylsiloxy) silyl) propoxy) propyl ] -2-methacrylamide; n, N-bis [ 2-hydroxy-3- (3- (tris (trimethylsiloxy) silyl) propoxy) propyl ] acrylamide; n- [ 2-hydroxy-3- (3- (tert-butyldimethylsilyl) propoxy) propyl ] -2-methacrylamide; n- [ 2-hydroxy-3- (3- (tert-butyldimethylsilyl) propoxy) propyl ] acrylamide; n, N-bis [ 2-hydroxy-3- (3- (tert-butyldimethylsilyl) propoxy) propyl ] -2-methacrylamide; n, N-bis [ 2-hydroxy-3- (3- (tert-butyldimethylsilyl) propoxy) propyl ] acrylamide; 3-methacryloxypropyl pentamethyldisiloxane; TRIS (trimethylsiloxy) silylpropyl methacrylate (TRIS); (3-methacryloxy-2-hydroxypropoxy) propylbis (trimethylsiloxy) methylsilane); (3-methacryloxy-2-hydroxypropoxy) propyltris (trimethylsiloxy) silane; 3-methacryloxy-2- (2-hydroxyethoxy) -propoxy) propylbis (trimethylsiloxy) methylsilane; carbamic acid N-2-methacryloyloxyethyl-O- (methyl-bis-trimethylsiloxy-3-propyl) silyl ester; 3- (trimethylsilyl) propyl vinyl carbonate; 3- (vinyloxycarbonylthio) propyl-tris (trimethyl-siloxy) silane; 3- [ tris (trimethylsiloxy) silyl ] propyl vinyl carbamate; 3- [ tris (trimethylsiloxy) silyl ] propylallyl carbamate; 3- [ tris (trimethylsiloxy) silyl ] propyl vinyl carbonate; tert-butyldimethyl-siloxyethyl vinyl carbonate; trimethylsilylethyl vinyl carbonate; trimethylsilylmethyl vinyl carbonate; t-butyl (meth) acrylate, cyclohexyl acrylate, isobornyl methacrylate, polysiloxane containing vinyl monomers having 3-8 silicon atoms, and combinations thereof.

10. An amphiphilic branched prepolymer according to any one of claims 1-6, wherein the first reactive functional group, the second reactive functional group of the functionalized polysiloxane compound, the third reactive functional group of the chain transfer agent and the fourth reactive functional group are independent of each other and are selected from the group consisting of amino groups of formula-NHR', hydroxyl groups, carboxylic acid groups, acyl halide groups of formula-COX, anhydride groups, aldehyde groups, azlactone groups, isocyanate groups, epoxy groups, aziridine groups, amide groups (-CONH)₂) And combinations thereof, wherein R' is hydrogen or C₁-C₂₀An unsubstituted or substituted, straight chain or branched alkyl group, X ═ Cl, Br or I, provided that a first or fourth reactive functional group can react with a second or third functional group in the presence or absence of a coupling agent to form a covalent linkage.

11. The amphiphilic branched prepolymer of claim 7, wherein the first reactive functional group, the second reactive functional group of the functionalized polysiloxane compound, the third reactive functional group of the chain transfer agent, and the fourth reactive functional group are independent of each other and are selected from the group consisting of an amino group of the formula-NHR', a hydroxyl group, a carboxylic acid group, an acid halide group of the formula-COX, an acid anhydride group, an aldehyde group, an azlactone group, an isocyanate group, an epoxy group, an aziridine group, an amide group (-CONH)₂) And combinations thereof, wherein R' is hydrogen or C₁-C₂₀An unsubstituted or substituted, straight chain or branched alkyl group, X ═ Cl, Br or I, provided that a first or fourth reactive functional group can react with a second or third functional group in the presence or absence of a coupling agent to form a covalent linkage.

12. The amphiphilic branched prepolymer according to any one of claims 1-6, wherein the first and second diene-based functionalized vinyl monomers are independent of each otherSelected from (meth) acrylic acid C₁-C₆Hydroxyalkyl ester, C₁-C₆Hydroxyalkyl (meth) acrylamides, (meth) acrylic acid C₁-C₆Aminoalkyl esters, allyl alcohols, allylamines, C₁-C₆Aminoalkyl (meth) acrylamides, aziridinyl (meth) acrylates C₁-C₁₂Alkyl esters, glycidyl (meth) acrylate, C₁-C₆Alkyl (meth) acrylic acid, (meth) acryloyl chloride, (meth) acryloyl bromide, (meth) acryloyl iodide, (meth) acrylic acid C₁-C₆Isocyanatoalkyl esters, 2-vinyl-4, 4-dimethyl-1, 3-oxazoline-5-one, 2-isopropenyl-4, 4-dimethyl-1, 3-oxazoline-5-one, 2-vinyl-4-methyl-4-ethyl-1, 3-oxazoline-5-one, 2-isopropenyl-4-methyl-4-butyl-1, 3-oxazoline-5-one, 2-vinyl-4, 4-dibutyl-1, 3-oxazoline-5-one, 2-isopropenyl-4-methyl-4-dodecyl-1, 3-oxazoline-5-one, 2-vinyl-4-methyl-1, 3-oxazoline-5-one, 2-isopropenyl-4, 4-diphenyl-1, 3-oxazoline-5-one, 2-isopropenyl-4, 4-pentamethylene-1, 3-oxazoline-5-one, 2-isopropenyl-4, 4-tetramethylene-1, 3-oxazoline-5-one, 2-vinyl-4, 4-diethyl-1, 3-oxazoline-5-one, 2-vinyl-4-methyl-4-nonyl-1, 3-oxazoline-5-one, 2-isopropenyl-4-methyl-4-phenyl-1, 3-oxazoline-5-one, and mixtures thereof, 2-isopropenyl-4-methyl-4-benzyl-1, 3-oxazoline-5-one, 2-vinyl-4, 4-pentamethylene-1, 3-oxazoline-5-one, and 2-vinyl-4, 4-dimethyl-1, 3-oxazoline-6-one, 2-vinyl-4, 4-dimethyl-1, 3-oxazoline-5-one (VDMO), 2-isopropenyl-4, 4-dimethyl-1, 3-oxazoline-5-one (IPDMO), and combinations thereof.

13. The amphiphilic branched prepolymer according to claim 7, wherein the first and second diene-functional vinyl monomers are independently selected from the group consisting of (meth) acrylic acid C₁-C₆Hydroxyalkyl ester, C₁-C₆Hydroxyalkyl (meth) acrylamides, (meth) acrylic acid C₁-C₆Aminoalkyl esters, allyl alcohols, allylamines, C₁-C₆Aminoalkyl (meth) acrylamides, aziridinyl (meth) acrylates C₁-C₁₂Alkyl estersGlycidyl (meth) acrylate, C₁-C₆Alkyl (meth) acrylic acid, (meth) acryloyl chloride, (meth) acryloyl bromide, (meth) acryloyl iodide, (meth) acrylic acid C₁-C₆Isocyanatoalkyl esters, 2-vinyl-4, 4-dimethyl-1, 3-oxazoline-5-one, 2-isopropenyl-4, 4-dimethyl-1, 3-oxazoline-5-one, 2-vinyl-4-methyl-4-ethyl-1, 3-oxazoline-5-one, 2-isopropenyl-4-methyl-4-butyl-1, 3-oxazoline-5-one, 2-vinyl-4, 4-dibutyl-1, 3-oxazoline-5-one, 2-isopropenyl-4-methyl-4-dodecyl-1, 3-oxazoline-5-one, 2-vinyl-4-methyl-1, 3-oxazoline-5-one, 2-isopropenyl-4, 4-diphenyl-1, 3-oxazoline-5-one, 2-isopropenyl-4, 4-pentamethylene-1, 3-oxazoline-5-one, 2-isopropenyl-4, 4-tetramethylene-1, 3-oxazoline-5-one, 2-vinyl-4, 4-diethyl-1, 3-oxazoline-5-one, 2-vinyl-4-methyl-4-nonyl-1, 3-oxazoline-5-one, 2-isopropenyl-4-methyl-4-phenyl-1, 3-oxazoline-5-one, and mixtures thereof, 2-isopropenyl-4-methyl-4-benzyl-1, 3-oxazoline-5-one, 2-vinyl-4, 4-pentamethylene-1, 3-oxazoline-5-one, and 2-vinyl-4, 4-dimethyl-1, 3-oxazoline-6-one, 2-vinyl-4, 4-dimethyl-1, 3-oxazoline-5-one (VDMO), 2-isopropenyl-4, 4-dimethyl-1, 3-oxazoline-5-one (IPDMO), and combinations thereof.

14. A method of making a silicone hydrogel contact lens, the method comprising the steps of:

(i) obtaining an amphiphilic branched polysiloxane prepolymer according to any one of claims 1 to 13;

(ii) preparing a lens-forming composition using an amphiphilic branched polysiloxane prepolymer, said composition comprising

(a) 60-99% by weight of an amphiphilic branched polysiloxane prepolymer,

(b) From 0.1% to 5% by weight of a free radical initiator and

(c) 0 to 20% by weight of at least one polymerizable component selected from the group consisting of hydrophilic vinyl monomers, silicone-containing vinyl macromers having only one ethylenically unsaturated group, hydrophobic vinyl monomers, linear polysiloxane crosslinkers terminated with two ethylenically unsaturated groups, crosslinkers having a molecular weight of less than 700 daltons, polymerizable UV-absorbers and mixtures thereof,

wherein the weight percent of components (a) - (c) are relative to the total amount of all polymerizable components in the lens-forming composition, including those not listed above;

(iii) adding a lens-forming composition to a mold having a first mold half having a first molding surface defining an anterior surface of a contact lens and a second mold half having a second molding surface defining a posterior surface of a contact lens, wherein said first and second mold halves are configured to be received in one another so as to form a cavity between said first and second molding surfaces for receiving a lens-forming material; and

(iv) the lens-forming material is polymerized within the cavity to form a silicone hydrogel contact lens.

15. The method of claim 14, wherein the mold is a reusable mold wherein the lens-forming material in the cavity is actinically cured under a spatial limitation of actinic radiation to form a silicone hydrogel contact lens.

16. A silicone hydrogel contact lens comprising a polymeric material that is the polymerization product of a lens-forming composition comprising the amphiphilic branched polysiloxane prepolymer of any one of claims 1-13.