TWI443116B - Wettable silicone hydrogel contact lenses and related compositions and methods - Google Patents

Description

Wettable hydrogel hydrogel contact lens and related compositions and methods

In particular, the present invention is directed to a hydroxyl hydrogel ophthalmic device and related compositions and methods. More particularly, the present invention relates to molded wettable hydrogel hydrogel contact lenses and related compositions and methods.

Hydroxyl hydrogel contact lenses have become popular because of the ability of contact lens wearers to wear these glasses for longer periods of time than their non-oxygenated hydrogel contact lenses. For example, depending on the particular lens, the oxygenated hydrogel contact lens can be worn daily, worn weekly, bi-weekly or worn on a monthly basis or worn or worn every day. Wear it in two weeks or wear it every month. The benefits to the lens wearer associated with the hydrogel contact lenses can be attributed, at least in part, to the combination of the hydrophilic component of the contact lens and the hydrophobic character of the ruthenium containing polymer.

Non-oxygenated hydrogel contact lenses, such as 2-hydroxyethyl methacrylate (HEMA based hydrogel contact lenses), are often found in non-polar resin contact lens molds (eg, contact lens molds derived from polyolefin-based resins). Produced in. In other words, the lens precursor composition for non-oxygenated hydrogel contact lenses is polymerized in a non-polar resin contact lens mold to produce a HEMA-based polymeric lens product. Due to the hydrophilic nature of the polymeric components of HEMA-based contact lenses, HEMA-based glasses are compatible on the eye and have an ophthalmically acceptable surface wettability, even though produced using a non-polar resin mold.

In contrast, existing oxygenated hydrogel contact lenses obtained from non-polar resin molds have hydrophobic eyeglass surfaces. In other words, the surfaces of the hydroxyl hydrogel contact lenses have low wettability and are therefore incompatible or unacceptable to the eye. For example, such helium-hydrogel contact lenses can be associated with increased lipid deposition, protein deposition, combination of spectacles with the surface of the eye, and general stimuli for lens wearers.

In an effort to overcome these problems, attempts have been made to surface or surface modify the hydroxyl hydrogel contact lens or lens product to increase the hydrophilicity and wettability of the lens surface. Examples of surface treatments of silicone hydrogel lenses include coating the surface of the lens, adsorbing chemicals onto the surface of the lens, and altering the chemical nature or electrostatic charge of the chemical groups on the surface of the lens. Surface treatments have been described which include coating the surface of the polymeric eyeglasses with a plasma gas or using a plasma gas on the surface of the contact lens mold to treat the mold prior to forming the polymeric eyeglasses. Unfortunately, several drawbacks are associated with this approach. The surface treatment of contact lenses requires more mechanical and time to produce contact lenses than manufacturing methods that do not use surface treatment or modification. In addition, surface treated silicone hydrogel contact lenses can exhibit reduced surface wettability when the lenses are worn and/or touched by the lens wearer. For example, increasing the touch on surface treated glasses can result in degradation or wear of the hydrophilic surface.

Another method of increasing the wettability and eye compatibility of the oxygenated hydrogel glasses is to polymerize the hydroxyl hydrogel in the presence of a second composition comprising a polymeric wetting agent such as polyvinylpyrrolidone (PVP). Contact lens precursor composition. Such types of eyeglasses are referred to herein as silicone hydrogel contact lenses having a polymeric internal wetting agent, and typically comprise an interpenetrating polymer network (IPN) comprising a high molecular weight polymer such as PVP. As is generally understood by those skilled in the art, IPN refers to a combination of two or more different polymers in a network form in which at least one polymer is synthesized and/or crosslinked in the presence of another polymer, both There are no covalent bonds between them. An IPN can consist of two chains that form two separate but adjacent or interpenetrating networks. Examples of IPNs include step-by-step IPN, synchronous IPN, half-IPN, and average IPN. While helium oxygen hydrogel contact lenses comprising a polymeric wetting agent IPN avoid problems associated with surface treatment, such lenses may not retain their eye compatibility over a prolonged period of time, including surface wettability. For example, since the internal humectant does not covalently combine to form other components of the polymeric spectacles, when worn by the spectacles wearer, it may leach from the spectacles and thereby cause surface wettability to decrease over time and The discomfort of the wearer of the glasses increases.

As an alternative to the surface treatment as described above or the use of a polymeric wetting agent IPN, it has been found that a polar resin mold can be used in place of a non-polar resin mold to produce a helium oxygen hydrogel contact lens having an ophthalmically acceptable surface wettability. For example, a helium oxygen hydrogel contact lens formed in an ethylene vinyl alcohol based or polyvinyl alcohol based mold has the desired surface wettability. An example of a polar resin suitable for use in the manufacture of contact lens molds for the production of non-polymerized wetting agent IPN without surface treatment of hydroxyl hydrogel contact lenses is a resin of ethylene-vinyl alcohol copolymer, such as by Nippon Gohsei, Ltd. ethylene sold by the trade name SOARLITE ^TM - vinyl alcohol copolymer resin. In addition to its polarity, SOARLITE ^TM described as having the following characteristics: high mechanical strength, antistatic properties, low contractility when used in molding processes when, excellent oil resistance and solvent resistance, small coefficient of thermal expansion and good resistance to Grinding.

Although SOARLITE ^TM based on the on the mold surface is not used for the polymerization treatment or wetting agent IPN produce compatible silicone hydrogel contact lenses on the eye to provide alternative advantageous, but non-polar SOARLITE ^TM die mold resin (such as polypropylene The mold) is less deformable or flexible than the non-polar resin mold and is relatively difficult to work with.

According to the above, need to be seen compatible silicone hydrogel contact lenses on the eye, and the silicon which is obtained from SOARLITE ^TM hydrogel contact lens mold more prone compared and used without surface treatment or a polymeric wetting Agent IPN (including PVP IPN) to achieve eye compatibility. In addition, it is highly desirable to provide an ophthalmically compatible hydroxyl hydrogel contact lens from a non-polar or polyolefin-based contact lens mold member (such as an invisible hydrogel having an eye-compatible surface wettability). A method of spectacles that overcomes the shortcomings of prior methods. That is, there is a need for an improved method for preparing an ophthalmic compatible hydrogel contact lens that does not require surface treatment of the resulting contact lens product or the use of a polymeric wetting agent IPN as a polymerizable hydrogel. Part of the lens precursor composition. The present invention satisfies these needs.

The contact lenses, lens products, compositions and methods of the present invention address the needs and problems associated with prior art oxygenated hydrogel contact lenses and their current methods of production. It has been surprisingly found that an eye-compatible, oxygenated hydrogel contact lens can be obtained by extracting a relatively large amount of removable material in a pre-extracted polymeric hydrogel hydrogel contact lens product. Obtained in addition to the removable materials and hydration to produce a helium oxygen hydrogel contact lens. Pre-extracted polymeric hydrogel lens products having a removable component (i.e., one or more removable materials, including extractable materials and the like) typically contain at least about 10% by weight of the removable component. . The pre-extracted polymeric hydrogel hydrogel lens product is then extracted (to thereby remove the extractable component) and hydrated to form an ophthalmic hydrogel invisible having an ophthalmically acceptable surface wettability as described herein. glasses. The oxygenated hydrogel contact lens of the present invention has a time that allows the patient to comfortably wear the lens for a prolonged period of time, such as at least one day, at least one week, at least two weeks, or about one month without removing oxygen from the eye. , surface wettability, modulus, water content, ion current and design.

In one aspect, the invention is directed to a polymerizable silicone hydrogel contact lens precursor composition. The precursor compositions are effective to form a helium oxygen hydrogel contact lens. After polymerization, the precursor formulation results in the formation of an extractable hydratable contact lens preform. The precursor composition comprises the following: (i) at least about 20% by weight of a reactive fluoroacryloyloxyl macromonomer, and (ii) at least about 45% by weight of a monomer composition free of bismuth, It comprises a hydrophilic vinyl-containing monomer, an acrylic monomer and an acrylate functionalized ethylene oxide oligomer, and (iii) a polyoxyalkylene oxide extractable component.

In one embodiment, the polymerizable silicone hydrogel contact lens precursor composition comprises at least about 25% by weight, and preferably from about 25% to about 35% by weight, of reactive fluorine-containing dimethyl propylene fluorenyl hydrazine. Oxygen macromonomer. An exemplary reactive fluorine-containing dimethyl propylene fluorenyl oxime macromonomer of the present invention is α-ω-bis(methacryloxyethyliminocarboxycarbonylpropyl)-poly (two Methyl methoxyoxane)-poly(trifluoropropylmethyloxirane)-poly(ω-methoxy-poly(ethylene glycol) propylmethyl decane) (also referred to herein as M3U) And the CAS registration number is 697234-74-5).

In another embodiment, the polymerizable silicone hydrogel contact lens precursor compositions of the present invention comprise from about 45 to about 55% by weight of a monomer composition free of barium. Particularly preferred is a hydrazine-free hydrophilic component comprising N-vinyl-N-methylacetamide, methyl methacrylate and triethylene glycol dimethacrylate.

In another embodiment, the polymerizable silicone hydrogel contact lens precursor composition comprises from about 10% to about 30% by weight of the polyoxyalkylene oxide extractable component. In an even more specific embodiment, the polyoxyalkylene oxime extractable component optionally comprises from about 0.1 to 6 parts chain transfer agent and from about 99.9 to 94 parts polyoxyalkylene oxime. Illustrative polyoxyalkylene oxime extractable components include dimethyl methoxyalkane-oxyethylene block copolymers such as dimethyl decane-ethylene oxide block copolymers containing about 75% by weight ethylene oxide. One such dimethyloxane-ethylene oxide block copolymer is DBE 712 (Gelest, Morrisville, PA).

Chain transfer agents for use in the compositions, lenses, and methods described herein include mercaptans, disulfides, organic halides, allyloxy ethers, and allyloxy alcohols. In a particularly preferred embodiment, the chain transfer reagent is allyloxyethanol.

In other embodiments of the invention, the polymerizable silicone hydrogel contact lens precursor composition may also comprise one or more of the following: a UV absorber, a colorant or an initiator. The ultraviolet absorber may, for example, be a photopolymerizable hydroxybenzophenone such as 2-hydroxy-4-propenyloxyethoxybenzophenone. The color former used in the present invention may be, for example, a phthalocyanine pigment such as phthalocyanine blue. In addition, the initiator included in the polymerizable silicone hydrogel contact lens precursor formulation can be, for example, a thermal initiator such as 2,2'-azobis(2,4-dimethylvaleronitrile) (VAZO) -52).

In a more specific embodiment, the polymerizable silicone hydrogel contact lens precursor composition of the present invention comprises alpha-omega-bis(methacryloxyethyliminocarboxycarbonylpropyl)-poly (dimethyloxane)-poly(trifluoropropylmethyloxirane)-poly(ω-methoxy-poly(ethylene glycol) propylmethyloxirane), N-vinyl- N-methylacetamide, methyl methacrylate and triethylene glycol dimethacrylate.

In a preferred embodiment, the precursor composition of the present invention comprises α-ω-bis(methacryloxyethylethyleniminocarboxyethoxypropyl)-poly(dimethyloxane). - poly(trifluoropropylmethyl decane)-poly(ω-methoxy-poly(ethylene glycol) propylmethyl decane), N-vinyl-N-methyl acetamide, The component can be extracted by methyl methacrylate, triethylene glycol dimethacrylate and dimethyloxane-ethylene oxide block copolymer.

In another embodiment, the extractable component comprises DBE 712, which optionally contains allyloxyethanol.

In a more specific embodiment of the polymerizable silicone hydrogel contact lens precursor composition, alpha-omega-bis(methacryloxyethyliminocarboxycarbonylpropyl)-poly(dimethyl) Alkyl oxyalkylene)-poly(trifluoropropylmethyl decane)-poly(ω-methoxy-poly(ethylene glycol) propylmethyl decane) and N-vinyl-N- The ratio of the combination of acetalamine, methyl methacrylate and triethylene glycol dimethacrylate is in the range of from about 0.50 to about 0.65 by weight.

In a preferred embodiment, the polymerizable hydrogel contact lens precursor composition comprises alpha-omega-bis(methacryloxyethyliminocarboxyethoxypropyl)-poly (two) Methyl methoxyoxane)-poly(trifluoropropylmethyloxirane)-poly(ω-methoxy-poly(ethylene glycol) propylmethyl decane), N-vinyl-N- Methylacetamide, methyl methacrylate, triethylene glycol dimethacrylate, 2-hydroxy-4-propenyloxyethoxybenzophenone, phthalocyanine blue, 2,2'-even Nitrogen bis(2,4-dimethylvaleronitrile) and DBE 712 (in combination with allyloxyethanol).

Particularly preferred weight percent of the above components in the exemplary polymerizable silicone hydrogel contact lens precursor composition is about 28% by weight alpha-omega-bis(methacryloxyethyl) Imino-carboxy ethoxypropyl)-poly(dimethyloxane)-poly(trifluoropropylmethyloxirane)-poly(ω-methoxy-poly(ethylene glycol) propyl Methyl methoxyoxane), about 37% by weight of N-vinyl-N-methylacetamide, about 13.5% by weight of methyl methacrylate, about 0.16% by weight of dimethyl Triethylene glycol acrylate, about 0.7% by weight of 2-hydroxy-4-propenyloxyethoxybenzophenone, about 0.1% by weight of phthalocyanine blue, about 0.4% by weight 2,2'-azobis(2,4-dimethylvaleronitrile) and about 20% DBE 712 (in combination with allyloxyethanol).

According to another aspect, the present invention provides a helium oxygen hydrogel contact lens produced from any of the above polymerizable lens precursor compositions.

In another aspect, the invention provides a hydroxamed hydrogel contact lens obtained by reacting a polymerizable lens precursor composition as described herein in the absence of an extractable component.

According to another aspect, the present invention is directed to a hydroxyl hydrogel contact lens produced by the following steps: polymerizing a polymerizable lens precursor composition as described herein to form a pre-extracted polymeric hemohydrate hydrogel Contact lenses, extractable components are extracted from pre-extracted contact lenses to form an extracted polymeric lens product, and the extracted polymeric lens product is hydrated to form a hydroxyl hydrogel contact lens. The resulting hydrated contact lens product typically extracted with an oxygen permeability within about 40 to about 48 wt.% Equilibrium water content in the range of wt% and a range of about 100-115 barrer (D _k × 10 ^-11).

In an embodiment of this aspect of the invention, a helium oxygen hydrogel contact lens is produced according to the above method, wherein the polymerizable lens precursor composition comprises a thermal initiator, and the polymerizing step further comprises polymerizing the lens precursor The body composition is heated to a temperature greater than about 50 °C.

In another embodiment, a helium oxygen hydrogel contact lens is produced by polymerizing a polymerizable lens precursor composition as described above to form a pre-extracted polymeric hemohydrogel contact lens, wherein DBE and a combination of allyloxyethanol; extracting the polyoxyalkylene oxide extractable component from a pre-extracted polymeric hydrogel contact lens to form an extracted polymeric lens product, and hydrating the extracted polymeric lens product to form a Batches of one or more of the following characteristics of low-variability helium hydrogel contact lenses: equilibrium water content, oxygen permeability, static contact angle, dynamic contact angle, hysteresis, refractive index, ion current, modulus and tensile strength . For example, depending on the particular characteristics of the lens product, the variability of any one or more of the aforementioned lens features is typically less than about 20%, and preferably less than about 10%. In one or more embodiments, the variability of any one or more of the spectacles diameter, the equilibrium water content, and/or the ion current is about 5% or less, more preferably about 3% or less than 3%. And even more preferably about 2% or less than 2%.

In another aspect, the present invention provides a helium oxygen hydrogel contact lens having an equilibrium water content of at least about 40% and an oxygen permeability (D _k x 10 ^-11 ) of from about 90 to 120 barrer.

In one of the above embodiments, there is provided a hydroxyl hydrogel contact lens further comprising one or more features selected from the group consisting of: a surface contact angle of the lens of from about 70[deg.] to about 75[deg.], drawn The modulus of extension is less than about 0.7 MPa and the ion current is about 1.5-5 (x 10 ^-3 mm ² /min).

In certain embodiments, the oxygenated hydrogel contact lenses of the present invention may also have a rounded peripheral edge, or may be one of: spherical, aspherical, monofocal, or rotationally stable toric contact lenses. .

In another embodiment, the present invention provides a heralloy hydrogel contact lens as described herein in a sealed package.

In another embodiment, the oxygenated hydrogel contact lenses of the present invention are not surface treated.

In another aspect, the invention provides a method of producing a polymerizable silicone hydrogel contact lens precursor composition. The method comprises combining the following: (i) at least about 25% by weight of a reactive fluorine-containing dimethyl propylene fluorenyloxy macromonomer, and (ii) at least about 45% by weight of a macromonomer containing no hydrazine a body composition and (iii) a polyoxyalkylene oxime oxygen extractable component to thereby produce a polymerizable hydrogel hydrogel contact lens precursor composition, wherein the bismuth-free macromer monomer composition comprises a hydrophilic content Vinyl monomer, acrylic monomer and acrylate functionalized ethylene oxide oligomer.

In an embodiment of this aspect of the invention, the above method further comprises combining a macromonomer, a ruthenium-free monomer composition and an extractable component, an ultraviolet absorber, and a color former. Exemplary colorants include phthalocyanine pigments such as phthalocyanine blue. Preferred UV absorbers are photopolymerizable hydroxybenzophenones such as 2-hydroxy-4-propenyloxyethoxybenzophenone.

In a particular embodiment of the method, the amount of the reactive fluorine-containing dimethyl propylene fluorenyl oxy macromonomer is in the range of from about 25% by weight to about 35% by weight.

In another embodiment of the method, the amount of the bismuth-free monomer composition is in the range of from about 45 to about 55% by weight.

In another embodiment of the method, the polyoxyalkylene oxime oxygen extractable component is present in an amount ranging from about 10% by weight to about 30% by weight.

In a preferred embodiment of the method, the reactive fluorine-containing dimethyl propylene fluorenyl oxime macromonomer is α-ω-bis(methacryl oxiranylethylimino carboxy ethoxy propyl acrylate Base)-poly(dimethyloxane)-poly(trifluoropropylmethyloxirane)-poly(ω-methoxy-poly(ethylene glycol)propylmethyl decane) (M3U ).

In another embodiment of the method, the ruthenium-free monomer component comprises N-vinyl-N-methylacetamide, methyl methacrylate, and triethylene glycol dimethacrylate.

In another embodiment of the method, the polyoxyalkylene oxime extractable component further comprises a chain transfer agent such as a thiol, disulfide, organic halide or allyloxy alcohol. In a particularly preferred embodiment, the chain transfer reagent is allyloxyethanol.

In a preferred embodiment of the method, the polyoxyalkylene oxime oxygen extractable component comprises from about 0.05% to about 7% by weight of allyloxyethanol. An illustrative polyoxyalkylene oxime extractable component is a dimethyl siloxane-ethylene oxide block copolymer, such as a dimethyl siloxane-ethylene oxide block copolymer containing 75% by weight of ethylene oxide. Particularly preferred as the polyoxyalkylene oxime oxygen extractable component is DBE 712.

In another embodiment of the method, the combining step further comprises combining the initiator with the other components. A thermal initiator such as 2,2'-azobis(2,4-dimethylvaleronitrile) (VAZO-52) is preferred.

In another aspect, provided herein is a method of producing a polymerizable silicone hydrogel contact lens precursor composition. The method comprises α-ω-bis(methacryloxyethyl iminocarboxyethoxypropyl)-poly(dimethyloxane)-poly(trifluoropropylmethyloxane) )-Poly(ω-methoxy-poly(ethylene glycol) propylmethyl decane), N-vinyl-N-methylacetamide, methyl methacrylate and triethyl methacrylate The glycol esters are combined to thereby produce a polymerizable hydrogel hydrogel contact lens precursor composition.

In one embodiment of the above method, the combining step further comprises combining the dimethyloxane-ethylene oxide block copolymer extractable component (e.g., DBE 712) with the other components.

In one embodiment of the above process, the relative amount of allyloxyethanol and DBE 712 is in the range of from about 0.1 parts to about 5 parts of allyloxyethanol and from about 99.9 parts to about 95 parts of DBE 712.

In another embodiment of the foregoing method, the combining step further comprises combining the phthalocyanine blue with the other components.

In another embodiment, the combining step further comprises combining 2-hydroxy-4-propenyloxyethoxybenzophenone with the other components.

In another embodiment of the method, the combining step comprises adding 2,2'-azobis(2,4-dimethylvaleronitrile) to the combination.

In a preferred embodiment of the foregoing process, α-ω-bis(methacryloxyethyl iminocarboxyethoxypropyl)-poly(dimethyloxane)-poly(trifluoro Propylmethyl decane)-poly(ω-methoxy-poly(ethylene glycol) propylmethyl decane) with N-vinyl-N-methylacetamide, methyl methacrylate The ratio of the combination of triethylene glycol dimethacrylate is in the range of from about 0.50 to about 0.65 by weight.

In another aspect, provided herein is a method of producing a polymerizable silicone hydrogel contact lens precursor composition, wherein the method comprises alpha-omega-bis(methacryloxyethyliminocarboxyl) Ethoxypropyl)-poly(dimethyloxane)-poly(trifluoropropylmethyloxirane)-poly(ω-methoxy-poly(ethylene glycol)propylmethyloxime Alkyl), N-vinyl-N-methylacetamide, methyl methacrylate, triethylene glycol dimethacrylate, 2-hydroxy-4-propenyloxyethoxybenzophenone, Phthalocyanine blue, 2,2'-azobis(2,4-dimethylvaleronitrile) combined with DBE 712 (optionally containing allyloxyethanol) to thereby produce a polymerizable hydrogel hydrogel invisible A lens precursor composition.

In one embodiment, the above method comprises the following relative amounts of components: about 28% by weight of alpha-omega-bis(methacryloxyethyliminocarbomethoxypropyl)-poly( Dimethyl methoxyoxane)-poly(trifluoropropylmethyl decane)-poly(ω-methoxy-poly(ethylene glycol) propylmethyl decane), about 37% by weight N-vinyl-N-methylacetamide, about 13.5% by weight of methyl methacrylate, about 0.16% by weight of triethylene glycol dimethacrylate, about 0.7% by weight 2-hydroxy-4-propenyloxyethoxybenzophenone, about 0.1% by weight of phthalocyanine blue, about 0.4% by weight of 2,2'-azobis (2,4-) Dimethylvaleronitrile) and about 20% DBE 712 (including allyloxyethanol as appropriate).

In another embodiment of the foregoing method, the combining step results in the formation of a combination of components, and the method further comprises combining the components to form a mixture.

In another embodiment, the method further comprises filtering the mixture.

In another embodiment, the method comprises polymerizing a polymerizable lens precursor composition to form a pre-extracted polymeric hemohydrogel contact lens.

In another embodiment, the method further comprises placing the polymerizable lens precursor composition in a non-polar resin contact lens mold prior to the polymerizing step.

In another embodiment, the foregoing method comprises extracting a pre-extracted polymeric contact lens to form an extracted polymeric lens product in the absence of an extractable component, and hydrating the extracted polymeric lens product to form a helium oxygen hydrogel contact lens .

In another aspect, the present invention provides a method of improving the efficacy of a dimethyloxane-ethylene oxide block copolymer for use in the preparation of a hydrogel contact lens. The method comprises the step of adding from about 0.1% to about 10% by weight of allyloxyethanol to the dimethyloxane-ethylene oxide block copolymer to provide a product for preparing a hydroxyl hydrogel contact lens. Allyloxyethanol-dimethyloxane oxide ethylene block copolymer.

The amount of allyloxyethanol used in the addition step is preferably effective to produce an extracted hydrated hydrogel hydrogel contact lens product having a coefficient of expansion in the range of from about 0.90 to about 1.10, such as from about 0.95 to about 1.05. In at least one embodiment, the coefficient of expansion is from about 0.98 to about 1.02.

Other embodiments of the spectacles, spectacles products, compositions, and methods of the present invention are apparent from the following description, illustration, examples, and claims. As will be understood from the above and the following description, each and every feature and each of the features described herein, and each or both of the features are included in the scope of the invention, the The features included in the combination are consistent with each other. In addition, any feature or combination of features may be specifically excluded from any embodiment of the invention. Other aspects and advantages of the present invention are set forth in the following embodiments and claims.

The invention will now be described more fully below. However, the present invention may be embodied in many different forms and should not be construed as being limited to the embodiments set forth herein; rather, the embodiments are provided so that this disclosure will be thorough and complete, and The scope of the invention.

definition

It must be noted that, as used in the specification, the singular " Thus, for example, reference to "a contact lens" includes a single lens and two or more identical or different glasses, and reference to "precursor composition" refers to a single composition and two or more of the same or Different compositions, and the like.

In describing and claiming the present invention, the following terms will be used in accordance with the definitions set forth below.

The term "hydrogel" as used herein refers to a polymeric material that is typically a polymer chain network or matrix that is capable of swelling or swelling with water. The network or matrix may or may not be crosslinked. Hydrogel refers to a polymeric material that swells or swells when exposed to water, including contact lenses. Thus, the hydrogel can be (i) unhydrated and swellable with water, or (ii) partially hydrated and swelled with water, or (iii) fully hydrated and swelled with water.

Such as (e.g.) "of the substituted alkyl group" in the term "substituted" means substituted with one or more non-interfering substituents of moiety (e.g. an alkyl group), a substituted group such as (but not limited to) C ₃ -C ₈ cycloalkyl (e.g. cyclopropyl, cyclobutyl and the like), halo (e.g. fluoro, chloro, bromo and iodo), cyano, alkoxy, lower phenyl, Substituted phenyl and its analogs. For substitutions on the phenyl ring, the substituents can be in any orientation (i.e., ortho, in between, or in pairs).

The term "hydrogenated hydrogel" or "hydroxyl hydrogel material" refers to a specific hydrogel comprising a cerium (Si) component or a cerium component. For example, hydroxyl hydrogels are typically prepared by combining a hydrazine-containing material with a conventional hydrophilic hydrogel precursor. Hydroxyl hydrogel contact lenses are contact lenses comprising a hydroxyl hydrogel material, including contact lenses that correct vision. The characteristics of the helium-hydrogel contact lenses are different from those of the conventional hydrogel-based glasses.

The "oxygen-containing component" is a component containing at least one [-Si-O-Si] linkage in a monomer, a macromonomer or a prepolymer, wherein each of the ruthenium atoms may have one or more as the case may be. The same or different organic group substituents (R ₁ , R ₂ ) or substituted organic group substituents such as —SiR ₁ R ₂ O—.

The term "bonding agent" as used herein refers to a collection of atoms or atoms used to bond interconnecting moieties, such as polymer ends and repeating unit blocks. The linker moiety can be hydrolytically stable or can include a linkage that is physiologically hydrolyzable or enzymatically degradable. Preferably, the linking agent is hydrolytically stable.

"Optional" or "as appropriate" means that the events described below may or may not occur, such that the description includes instances in which the event occurred and instances in which the event did not occur.

For example, when referring to a collection of atoms having a specific atomic length (eg, ranging from 2 to 50 atoms in length) in a linking agent, the term "length" is based on the number of atoms in the longest chain of the set of atoms, and the substituents. Nothing. For example, since a hydrogen atom is a substituent on carbon and is not considered in the approximate overall length of the chain, it is considered that -CH ₂ CH ₂ - has a length of two carbon atoms, even if each methylene group itself contains a total of three atom. Similarly, the linking agent -O-C(O)-CH ₂ CH ₂ C(O)NH- is considered to have a chain length of 6 atoms indicated by underlining.

"Molecular mass" in the context of a polymer of the invention means the nominal average molecular mass of the polymer, usually by size exclusion chromatography, light scattering techniques or in 1,2,4-trichlorobenzene. The internal velocity measurement method was used for measurement. The molecular weight in the case of a polymer can be expressed as a number average molecular weight or a weight average molecular weight, and in the case of a material supplied by a manufacturer, it will depend on the supplier. The basis for any such molecular weight determination can be readily provided by the supplier if not provided in the form of an encapsulating material. Generally, the molecular weight of a macromonomer or polymer referred to herein is referred to herein as a weight average molecular weight. The molecular weight determination of the number average molecular weight and the weight average molecular weight can be measured using gel permeation chromatography or other liquid chromatography techniques. Other methods of measuring molecular weight values may also be used, such as using end group analysis or measuring dependencies (eg, freezing point drop, boiling point increase, or osmotic pressure) to determine the number average molecular weight, or using light scattering techniques, ultracentrifugation, or Viscosity measurement to determine the weight average molecular weight.

The "network" or "matrix" of a hydrophilic polymer generally means a crosslink formed between covalent bonds or physical bonds (e.g., hydrogen bonds) between polymer chains.

"Non-interfering substituents" are those groups which, when present in a molecule, generally do not react with other functional groups contained in the same molecule.

"Hydrophilic" substances are hi-water substances. The compounds have an affinity for water and are often charged or have polar side chain groups that attract water.

The "hydrophilic polymer" of the present invention is defined as a polymer which is capable of swelling in water but does not need to be soluble in water.

The "hydrophilic component" is a hydrophilic substance which may or may not be a polymer. The hydrophilic component comprises those hydrophilic components capable of providing at least about 20% (e.g., at least about 25%) water content to the resulting hydrated spectacles when combined with the remaining reactive components.

As used herein, "a compatible oxygenated hydrogel contact lens" refers to a hydroxyl hydrogel that can be worn on the human eye without human experience or substantial discomfort (including eye irritation and similar discomfort). Contact lenses. Eye-compatible, oxygenated hydrogel contact lenses have an ophthalmically acceptable surface wettability and generally do not cause significant corneal swelling, corneal dehydration ("dry eye"), or superior corneal epithelial arch lesion ("SEAL") Or other significant discomfort or unrelated to these conditions.

"Substantially" or "substantially" or "about" means almost all or completely, such as 95% or more of a given amount.

"Alkyl" means a hydrocarbon chain generally having a length in the range of from about 1 to 20 atoms. The hydrocarbon chains are preferably, but not necessarily, saturated, and although generally straight chain is preferred, they may be branched or straight chain. Exemplary alkyl groups include methyl, ethyl, propyl, butyl, pentyl, 1-methylbutyl, 1-ethylpropyl, 3-methylpentyl, and the like. When referring to three or more carbon atoms, "alkyl" as used herein includes cycloalkyl.

An "oligomer" is a molecule composed of a limited number of monomeric subunits and typically consists of from about 2 to about 8 monomeric subunits.

"Lower alkyl" means an alkyl group having from 1 to 6 carbon atoms and may be straight or branched, such as methyl, ethyl, n-butyl, isobutyl, tert-butyl.

It is believed that the "potency" of a particular batch of polyoxyalkylene oxime (e.g., eucalyptus) as used herein provides a range of from 0.98 to 1.02 times the diameter of the contact lens mold used at a given concentration (and all other factors being the same). The ability of the final diameter to extract the hydrated lens product. The greater the reduction in the diameter of the final lens product, the greater the "efficiency" of the polyoxyalkylene.

The term "expansion coefficient" as used herein refers to the ratio of the outer diameter of a hydrated hydrogel hydrogel contact lens to the outer diameter of a portion of a contact lens mold insert used to form the lens forming surface of a contact lens mold. Thus, when the contact lens mold insert has an outer diameter of 14.2 mm and the hydrated hydrogenated hydrogel contact lens has an outer diameter of 14.2 mm, the coefficient of expansion of the contact lens is 1.00.

Other definitions can also be found in the following sections.

Summary of the invention

As previously discussed, the invention provided herein is based, at least in part, on the use of avoiding problems associated with polar resin molds, avoiding the need for complex and expensive post-polymerization procedures, and addressing issues associated with polymeric wetting agent IPNs. The method to prepare a compatible oxygenated hydrogel contact lens on the eye. Surprisingly, it has been found that by incorporating a particular component into a formulation for making a silicone hydrogel contact lens and then removing the same component from the resulting molded contact lens product (unreacted with the other components) The components are combined together to produce a compatible contact lens product on the eye.

In particular, the inventors have discovered an eye-compatible oxygenated hydrogel contact lens by incorporating a relatively large amount of one or more removable materials into a polymerizable silicone contact lens precursor composition. Methods. While such materials impart the desired characteristics to the resulting final contact lens product, they are in fact removed, for example, by extraction to provide an extracted contact lens product, which is then hydrated to produce an ophthalmically acceptable The final hemohydrogel contact lens product of surface wettability and other beneficial characteristics as described herein.

In a related aspect, there is provided a method of improving the efficacy of a dimethyloxane-ethylene oxide block copolymer for use in the preparation of a hydrogel contact lens, wherein the method comprises about 0.1% by weight to About 10% by weight of allyloxyethanol is added to the dimethyloxane-ethylene oxide block copolymer to provide allyloxyethanol-dimethylhydrazine for the preparation of the hydroxyl hydrogel contact lens product. Oxyalkylene oxide block copolymer. It has been advantageously found that the addition of allyloxyethanol to the dimethyloxane-ethylene oxide block copolymer is effective, for example, prior to mixing with the other components of the polymerizable contact lens precursor composition. Or any of the potential adverse effects of the article number or similar dimethyloxane-ethylene oxide block copolymer or analog thereof to "normalize" to thereby provide for one or more eyeglass sizes or variations in various physical properties. Accept the tolerated final lens product.

These and other important aspects of the invention are described and illustrated in detail in the following section.

Component of a polymerizable silicone hydrogel contact lens precursor composition

The hydroxyl hydrogel contact lenses of the present invention are typically produced from materials referred to herein as "polymerizable silicone hydrogel contact lens precursor compositions" or "precursor compositions." The precursor composition is a mixture of various reagents used to prepare the hydroxyl hydrogel contact lenses, i.e., the reaction mixture prior to the reaction (in the case of the present invention, polymerization).

The precursor compositions of the present invention typically comprise at least the following components: (i) at least about 25% by weight of a reactive fluorine-containing dimethyl propylene fluorenyloxy macromonomer, and preferably from about 25% to about 35. % by weight of the reactive fluorine-containing dimethyl propylene fluorenyl siloxane macromonomer, (ii) at least about 45% by weight of a ruthenium-free monomer composition, and (iii) a polyoxyalkylene oxime extractable Component. The ruthenium-free monomer composition includes a hydrophilic vinyl-containing monomer, an acrylic monomer, and an acrylate-functionalized ethylene oxide oligomer.

Reactive fluoropropenyl fluorenyloxy macromonomer

As described above, the oxime contact lenses of the present invention are prepared from a precursor composition comprising a reactive fluoropropenyl fluorenyloxy macromonomer. Although not required, macromonomers are generally referred to as a oxoxane block copolymer or a triblock polymer, ie consisting of two or three different helium oxide polymer "blocks" or segments and A macromonomer having at least one reactive acrylonitrile group at one end of the linear macromonomer and preferably having a reactive acryl oxime group at both ends.

The fluorine-containing fluorenyloxy macromonomer used in the present invention usually has at least one fluorine substituent. The fluorine substituent is preferably present on one of the repeating units of the block polymer such that the overall macromonomer has more than one fluorine atom. Preferred fluorine-containing macromonomers are those macromonomers having from about 1% to about 10% by weight fluorine and preferably from about 1% to about 5% by weight fluorine.

In general, at least one of the blocks of the copolymer or triblock polymer has a repeating unit -[Si(CH ₃ ) ₂ O]-, and at least one other block comprises a halogen atom having a fluorine-containing substituent Preferably, the fluoroalkyl substituent is preferred, and wherein the alkyl group is a lower alkyl group. In the case where the macromonomer is a triblock polymer, preferably one block has a repeating unit -[Si(CH ₃ ) ₂ O]-, and the second block is wherein the germanium atom has a fluoroalkyl substituent. a block, preferably wherein the alkyl group is a lower alkyl group, and the third block has an alkyl group substituted with a hydrophilic component (eg, a short polyethylene glycol (PEG) chain (CH ₂ CH ₂ O) _p ) After the atom. The third block mentioned above preferably comprises a ruthenium atom substituted with an alkylene linkage agent covalently bonded to polyethylene glycol, wherein the PEG is optionally blocked (such as a lower alkyl group or a benzene group) The base and the alkyl linker moiety are closest to the ruthenium atom. The polyethylene glycol segment typically has from about 1 to about 25 subunits, and more preferably from about 2 to about 12 subunits. The PEG segment preferably has from about 4 to about 10 subunits. The three oxoxane blocks mentioned above may be in any order.

The above-described exemplary oxime macromonomers are described in U.S. Patent No. 6,867, 245, the disclosure of which is incorporated herein by reference. Any one or more of the macromonomers described therein are suitable for use in the compositions and contact lenses of the present invention, and especially those having a (-SiO-) block, wherein the germanium atoms have A substituent which is an alkyl or other hydrocarbon chain substituted with one or more fluorine atoms.

For example, a representative alkoxy macromonomer comprises repeating units of the following triblocks: Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are each independently selected from -H, lower alkyl, fluoroalkyl and (-CH ₂ ) _o (OCH ₂ CH ₂ ) _p O- Y, wherein o is in the range of 1 to 10, p (the number of ethylene oxide repeating units) is in the range of from about 1 to about 25, and Y is H, lower alkyl or benzyl. The variables n, m and h correspond to the number of repeating units of each block and are each independently in the range of from about 3 to about 200. At least one R group preferably Si-O which is covalently bonded to each of the blocks n, m and h is a lower alkyl group, and even more preferably a methyl group. That is, preferably, in block n, at least one of R ₁ or R ₂ is a methyl group; in block m, at least one of R ₃ or R ₄ is a methyl group; In the segment h, at least one of R ₅ or R ₆ is a methyl group. Preferably, at least one of the blocks n, m and h has a repeating unit -Si(CH ₃ ) ₂ O-, wherein the two R groups covalently bonded to the oxime are methyl. For example, preferred macromonomers comprise the following polymer triblocks: Wherein R ₁ , R ₃ and R ₅ are each independently selected from -H, lower alkyl, fluoroalkyl (including difluoroalkyl and trifluoroalkyl) and (-CH ₂ )o (OCH ₂ CH ₂ ) _p O-Y, wherein o is in the range of 1 to 10, p (the number of ethylene oxide repeating units) is in the range of from about 2 to about 12, and Y is H, lower alkyl or benzyl, which is limited The condition is that at least one of (i) R ₁ , R ₃ and R ₅ is -H or lower alkyl, and (ii) at least one of R ₁ , R ₃ and R ₅ is a fluoroalkyl group, and Iii) At least one of R ₁ , R ₃ and R ₅ is (-CH ₂ ) _o (OCH ₂ CH ₂ ) _p O-Y, wherein the value of the specific variable is as described above. A particularly preferred macromonomer for use in the present invention is a macromonomer comprising the above triblock polymer structure wherein R ₁ is methyl, R ₃ is fluoroalkyl, and R ₅ is (-CH _{2 o} (OCH ₂ CH ₂ ) _p O-Y, and n is in the range of 50 to 200, m is in the range of 2 to 50, and h is in the range of 1 to 15.

When referring to a fluoropropenyl fluorenyloxy macromonomer, the Si-O-Si portion of the macromonomer typically comprises greater than about 20% by weight of the total molecular weight of the oxime macromonomer component, for example greater than 30. weight%. The oxime macromonomer of the present invention comprises an acrylonitrile group, and preferably has two propylene fluorenyl groups, that is, one at each end, wherein one or more olefin carbons of the propylene sulfhydryl moiety are optionally organic groups (such as Alkyl) substitution.

The acryl thiol moiety is a moiety derived from acrylic acid, for example Wherein in the acrylic acid, each of R ₇ , R ₈ and R ₉ is H. However, according to the present invention, the fluorenyl moiety is wherein R ₉ is H or an alkyl group, preferably a lower alkyl group, and R ₇ and R ₈ are each independently H, an alkyl group or a carboxyl group, However, it is limited that only one of R ₇ or R ₈ may be a carboxyl group. W is oxygen or nitrogen. In the case where W is nitrogen, the corresponding propylene sulfhydryl moiety is referred to as acrylamide. In a preferred embodiment, R ₇ and R ₈ are each hydrogen and R ₉ is a lower alkyl group such as methyl, ethyl or propyl. R _{9 is} preferably a methyl group, and the above-mentioned acryl-based moiety is present on both ends of the linear macromonomer. In the respective acrylonitrile groups contained in the macromonomer, the values of R ₇ , R ₈ and R ₉ are independent. That is, for a macromonomer having one or more acrylonitrile groups, the values of R ₇ , R ₈ and R ₉ of each propylene fluorenyl moiety are independently selected. However, in a preferred embodiment, the values of each of R ₇ , R ₈ and R ₉ in each propylene fluorenyl group are the same, and thus the macromonomer is considered to be a homobifunctional group - meaning a terminal reactive group the same. Where the reactive groups at the ends are different, the macromonomers are considered to be heterobifunctional. Illustrative acryl-based polymerizable functional groups that may be present at the end of the oxime macromonomer include methacrylate groups, acrylamide groups, and methacrylamide groups.

Other examples of suitable oxo-containing monomers are polydecyloxyalkyl (meth) acrylate monomers including, but not limited to, fluoro-substituted methacryloxypropyl propyl (trimethyl)矽 alkoxy) decane, pentamethyldimethoxymethyl methacrylate and methyl bis(trimethyldecyloxy)methacryloxymethyl decane.

One type of suitable helium-containing component is a poly(organosiloxane) prepolymer, such as a fluorine-substituted alpha, - bis methacryloxy-propyl polydimethyl decane. Another example is a fluorine-substituted mPDMS (mono-n-butyl-terminated polydimethyloxane terminated with monomethacryloxypropyl).

The hafnoxy polymer portion of the macromonomer (i.e., one or more of the decane polymer blocks) is typically bonded to the end of the acrylonitrile group by the insertion of a linking agent. Each of the linking agents typically has a length of from about 4 atoms to about 20 atoms, wherein the illustrative linking agent can include one or more of the following: -O-C(O)-, -C(O)-O- , -C(O)-NH-, -O-C(O)-NH-, -C(O)-O-(CH ₂ ) _a , -C(O)-O-(CH ₂ ) _a NH- C(O)(O)-(CH ₂ ) _b -O-(CH ₂ ) _c -, -O-C(O)-O-(CH ₂ ) _a -, -O-C(O)-O- (CH ₂ ) _a NH-C(O)(O)-(CH ₂ ) _b and analogs thereof, wherein a, b and c are each independently in the range of from 1 to about 10. That is, a, b, and c are each independently selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, and 10. The linking agent is preferably a straight chain rather than a branched chain, and optionally contains one or more heteroatoms O or N. Thus, in addition to comprising one or more alkylene chain segments, the linking agent may optionally contain one or more functionalities selected from, for example, a carboxyl group, a guanylamino group, a urethane group, and a carbonate group. base.

The molecular weight of the oxime macromonomer component is typically in the range of from about 8,000 daltons to about 25,000 daltons, and preferably in the range of from about 10,000 daltons to about 20,000 daltons. A particularly preferred oxoxane macromer for use in the present invention has a molecular weight of about 16,000 Daltons.

A particularly preferred class of oxoxane macromonomers are triblock polymers having the general formula: Wherein the values of n, m, h and p are as described above. The above macromonomer is called α-ω-bis(methacryloxyethylethylimidocarboxyethoxypropyl)-poly(dimethyloxane)-poly(trifluoropropylmethyl) Alkane/poly(ω-methoxy-poly(ethylene glycol) propylmethyl oxane) or M3U. In a particularly preferred embodiment, n is about 121, m is about 7.6, h is about 4.4, and p is about 7.4. The M3U can be easily synthesized according to the procedure set forth in Example 1 of International Patent Publication No. WO 2006/026474.

The polymerizable hydroxyl hydrogel precursor compositions provided herein typically comprise at least about 20% by weight of a fluoropropenyl fluorene macromonomer, and preferably at least about 25% by weight of a fluoropropenyl group. Oxygen macromonomer. The compositions of the present invention preferably comprise from about 25% to about 40% by weight of the fluoropropenylhydrazine macromonomer, and more preferably from about 25% to about 35% by weight of the macromonomer.

Non-oxygenated monomer composition

In addition to the oxime macromonomer, the spectacles, lens products and compositions of the present invention further comprise a ruthenium free monomer component or composition comprised of a plurality of additives. The monomer composition containing no antimony usually contains more than one hydrophilic compound. The hydrophilic component comprises those components capable of providing at least about 20% (or even at least about 25%) water content to the resulting hydrated eyeglass when combined with other precursor formulation components. The fluorene-free monomer composition (meaning each compound constituting the monomer composition) generally constitutes at least about 45% by weight of the lens precursor composition, based on the molecular weight of each precursor composition component. The inert monomer composition preferably comprises from about 45% to about 55% by weight of the precursor composition. The flawless monomer composition of the present invention excludes a hydrophilic compound containing one or more deuterium atoms. Thus, the monomer composition of the present invention is referred to herein as "the composition containing no antimony".

The monomers which may be included in the inert monomer composition typically have at least one polymerizable double bond and at least one hydrophilic functional group. Examples of the polymerizable double bond include acrylic acid, methacrylic acid, vinyl group, O-vinylacetamyl group and N-vinyl decylamine, N-vinylguanidinyl double bond, and the like. These hydrophilic monomers may be, but are not necessarily, crosslinkers. It is considered that as a subset of the acrylonitrile moiety as described above, the "acrylic" or "acrylic" or acrylate containing monomer is a monomer containing an acrylic group (CR'H=CRCOW), wherein R is H or CH ₃ , R' is H, an alkyl group or a carbonyl group, and W is O or N.

The hydrophilic component of the present invention generally comprises the following components which are free of bismuth, wherein one or more of the components are hydrophilic: a monomer containing a hydrophilic vinyl group (CH ₂ =CH-), an acrylic monomer and An acrylate functionalized ethylene oxide (-(OCH ₂ CH ₂ ) _n ) oligomer.

Illustrative acrylic monomers include N,N-dimethyl decylamine (DMA), 2-hydroxyethyl acrylate, glyceryl methacrylate, 2-hydroxyethyl methacrylamide, methacrylic acid, acrylic acid Methyl methacrylate (MMA) and mixtures thereof.

As noted above, the monomer composition comprising all of the individual hydrophilic and non-hydrophilic components comprises at least about 45% by weight of the precursor composition. Therefore, the weight percentage of each component constituting the monomer composition will vary within this range. The monomer composition preferably comprises from about 45% to about 55% by weight of the precursor composition, and thus, the weight percent of each component is from about 0.05% to about 40% by weight or about 0.05% of the precursor composition. The change is between % by weight and about 50% by weight to achieve the desired total weight percentage of the precursor composition. The acrylic monomer component is preferably present in an amount of from about 7% by weight to about 20% by weight of the precursor composition of the precursor composition for the preparation of the hydrogen spectacles product, and even more preferably in an amount of about 10% by weight of the precursor composition. It is present in an amount of about 18% by weight. Illustrative weight percentages of acrylic monomers include the following: about 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, or 18%, based on the total precursor formulation.

As stated above, the monomer composition also comprises a hydrophilic vinyl-containing monomer. Hydrophilic vinyl-containing monomers which may be incorporated into the spectacles of the present invention include the following: N-vinyl decylamine (e.g., N-vinylpyrrolidone (NVP)), N-vinyl-N- Methylacetamide (VMA), N-vinyl-N-ethylacetamide, N-vinyl-N-ethylformamide, N-vinylformamide, N-2-carbamate Hydroxyethyl vinyl ester, N-carboxy-β-alanine N-vinyl ester. A particularly preferred vinyl containing monomer is N-vinyl-N-methylacetamide (VMA). The structure of VMA corresponds to CH ₃ C(O)N(CH ₃ )-CH=CH ₂ .

The vinyl-containing monomer component of the monomer composition is preferably present in an amount ranging from about 20% by weight to about 50% by weight of the precursor composition prior to the preparation of the hydrogen-oxygen glasses product, and even more preferably in the precursor form. The composition is present in an amount ranging from about 25% to about 42% by weight. Representative weights of vinyl-containing monomers include the following weights: about 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32% by weight of the precursor composition %, 33% by weight, 34% by weight, 35% by weight, 36% by weight, 37% by weight, 38% by weight, 39% by weight, 40% by weight, 41% by weight or 42% by weight.

The monomer composition additionally comprises an acrylate functionalized ethylene oxide oligomer, i.e., having from about 2 to about 8 continuous ethylene oxide (CH ₂ CH ₂ O-) monomeric subunits and terminally reactive groups (such as An acrylate-based functionalized ethylene oxide oligomer. One or both ends of the oligomer may be functionalized with an acrylate group. Examples include reagents with one or more molar equivalents capable of introducing one or more reactive acrylate groups into one or both ends of an oligomer (eg, isocyanate ethyl methacrylate ("IEM"), methyl Acrylic acid anhydride, methacrylonitrile chloride or the like) is reacted to produce an ethylene oxide oligomer having an oxyethylene group having an acrylic group at one or both ends. Representative oligomers are described by the following general formula: Wherein s is in the range of from 2 to about 8, preferably from 2 to about 4, and R ₉ is H or alkyl, preferably lower alkyl, and R ₇ and R ₈ are each independently H, alkane A group or a carboxyl group, which is limited to a case where only one of R ₇ or R ₈ may be a carboxyl group. R _{9 is} preferably a lower alkyl group such as a methyl group, and each of R ₇ and R ₈ is H. The variable F is selected from the group consisting of -OH, a capping group such as an alkoxy group or an acrylate group as shown below. The following structure shows a homobifunctional oxyethylene oligomer having the same acrylate group at each end. However, in theory, the acrylate moieties at each end may be the same or different.

Preferred acrylate functionalized ethylene oxide oligomers for use in the present invention include oligo-ethylene oxide monomethacrylate and oligo-ethylene oxide dimethacrylate. Preferred acrylate functionalized ethylene oxide oligomers for use in the present invention are propylene glycol dimethacrylate.

The acrylate functionalized ethylene oxide oligomers are typically present in the precursor composition in relatively small amounts. For example, the oligomer is present in the precursor composition in an amount ranging from about 0.05% to about 10% by weight, preferably from about 0.075% to about 5% by weight. Representative amounts of the oligomer component include the following amounts: about 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.8%, 0.9%, and 1% by weight of the precursor composition. 2% by weight, 3% by weight, 4% by weight or 5% by weight.

Polyoxyalkylene oxime extractable component

As previously stated, the precursor compositions of the present invention specifically include polyoxyalkylene oxide (PAOS) removable or extractable components. (The terms "removable" and "extractable" are used interchangeably herein and refer to a component that is removed after polymerization of the lens precursor composition). The PAOS extractable component of the present invention is represented by polyoxyalkylene oxime, wherein the polyoxyalkylene may be polyethylene glycol, polypropylene glycol, a copolymer of ethylene glycol and propylene glycol, and a terpolymer of polyethylene glycol and polypropylene glycol. Including block copolymers and triblock polymers. Such polyoxyalkylene oxides are sometimes referred to herein as eucalyptus oil; as used herein, the term "anthracene oil" is intended to encompass any such polyoxyalkylene oxime.

In general, polyoxyalkylene oxime is characterized by having a polydimethyl methoxy alkane (PDMS) backbone wherein a certain percentage of methyl groups are replaced by a polyalkenyloxy group as described above. In a preferred embodiment, the polyalkenyloxy group is covalently attached to the oxane backbone via a spacer. The spacers are typically from about 2 to about 12 atoms in length and are typically used to facilitate attachment of the polyoxyalkylene chain to the siloxane backbone. Exemplary spacers include an alkyl chain, a substituted alkyl chain, an amino acid, and the like. Preferred spacers are lower alkyl such as ethyl, propyl, butyl, pentyl, hexyl and the like. Alternatively, the polyoxyalkylene oxide used herein may be a dimethyloxane oxyethylene block copolymer such as those available from Gelest (Morrisville, PA). In general, the polyoxyalkylene oxides of the present invention will contain at least about 25% by weight polyoxyalkylene, and more typically will comprise from about 30% to about 90% by weight polyoxyalkylene. Preferably, the polyoxyalkylene oxide contains about 50% by weight or more of the polyoxyalkylene. Illustrative polyoxyalkylene oxime contains about 25% by weight polyoxyalkylene, 40% by weight, 50% by weight, 60% by weight, 70% by weight, 75% by weight, 80% by weight or 85% by weight of polyoxyalkylene. . In general, materials having about 55% by weight or more by weight of ethylene oxide are water soluble. Particularly preferred for use in the present invention are polyoxyalkylene oxides in which the polyoxyalkylene is a polyethylene glycol or a propylene oxide-oxyethylene block copolymer.

Exemplary polyoxyalkylene oxides are available from Gelest (PA, USA). Representative polyoxyalkylene oxides include dimethyloxane (75% ethylene oxide) block copolymer (PDMS-co-PEG); dimethyloxane [65-70% (60% propylene oxide/40) % ethylene oxide) block copolymer (PDMS-co-PPO-PEG); dimethyloxane (25-30% ethylene oxide) block copolymer (PDMS-co-PEG); dimethyloxoxime Alkane [50-55% (60% propylene oxide / 40% ethylene oxide)] block copolymer (PDMS-co-PPO-PEG); dimethyl methoxy alkane (50-55% ethylene oxide) block copolymer (PDMS-co-PEG); dimethyloxane (80-85% ethylene oxide) block copolymer (PDMS-co-PPO-PEG) and dimethyloxane (80% ethylene oxide) block Copolymer (PDMS-co-PEG). The above polyoxyalkylene oxime corresponds to the following abbreviations (Gelest): DBE-712, DBP-732, DBE-224, DBP-534, DBE-621, DBE-821, and DBE-814. A preferred polyoxyalkylene oxime is dimethyl methoxy alkane (75% ethylene oxide) block copolymer (DBE-712).

While the PAOS extractable component can be present in the precursor composition in any amount, it is preferred that the extractable component be present in an amount ranging from about 2% to about 30% by weight, preferably from about 10% to about 30% by weight. presence. The extractable component is preferably present in an amount ranging from about 10% by weight to about 28% by weight. Exemplary amounts of extractable components in the precursor composition include the following weight %: about 10% by weight, about 12% by weight, about 15% by weight, about 20% by weight, about 25% by weight, about 29% by weight or about 30% by weight.

In some cases, the PAOS removable component also contains a chain transfer reagent in addition to the polyoxyalkylene oxide. The chain transfer reagent is an agent that promotes a reaction between a radical substance and a non-radical substance. Exemplary chain transfer reagents for use in the present invention include thiols, disulfides, organic halides, and allyloxy compounds. Some illustrative examples of chain transfer agents include mercaptans such as butanol, lauryl mercaptan, octyl thioglycolate, ethylene glycol bis(thioglycolate), 1,4-butanediol bis (sulfur) Propionate), trimethylolpropane ginseng (thioglycolate), trimethylolpropane ginseng (β-thiopropionate), isoprene tetraol (β-thiopropionate) And analogs thereof; disulfides such as diphenyl disulfide; halides such as carbon tetrachloride, carbon tetrabromide, chloroform, dichlorobenzene and the like; and allyloxy compounds such as alkenes Propoxyl alcohol and its analogs. These chain transfer agents can be used individually or in the form of a mixture of any of the foregoing. Preferred for use in the present invention are allyloxy compounds, i.e., compounds containing one or more allyloxy moieties.

A compound comprising at least one allyloxy moiety has the following general structure: Wherein the box portion corresponds to the allyloxy moiety, and Q represents a residue or residue of the parent molecule, such as an alcohol or any small organic molecule which, when attached to the allyloxy moiety, acts as a chain transfer agent. . Q is preferably derived from an alcohol such as ethanol, propanol, butanol, and the like or a substituted form thereof. Q is preferably a residue of ethanol and has a structure (-CH ₂ CH ₂ OH) such that the chain transfer reagent corresponds to 2-allyloxyethanol.

The inventors have discovered that the addition of a chain transfer reagent to an extractable component, such as the extractable components described herein, as appropriate, effectively provides an extracted hydrated xenon contact lens body having reduced size and physical property variability. . Thus, a chain transfer agent is added to "normalize" or "fine tune" the precursor lens composition such that the resulting extracted hydrated contact lens population typically has a variability of less than one or more of the following characteristics: equilibrium water content Oxygen permeability, static contact angle, dynamic contact angle (advancing contact angle or receding contact angle), hysteresis, refractive index, ion current, modulus, tensile strength and the like. For example, depending on the particular characteristics of the lens product, the variability of any one or more of the aforementioned lens features is typically less than about 20%, and preferably less than about 10%. In one or more embodiments, the variability of any one or more of the spectacles diameter, the equilibrium water content, and/or the ion current is about 5% or less, more preferably about 3% or less than 3%. And even more preferably about 2% or less than 2%. The diameter of the lens in the lens population preferably has a variability of less than about 1.5%.

A batch or group system as used herein refers to a plurality of contact lenses. It can be appreciated that improved statistical values are achieved when the number of contact lenses in a contact lens lot or population is sufficient to provide a meaningful standard error. In some cases, a batch of contact lenses refers to at least 10 contact lenses, at least 100 contact lenses, at least 1000 contact lenses or more.

Accordingly, in one aspect, the present invention provides a method for improving the oxygenation efficiency of a polyoxyalkylene by adding thereto from about 0.1% by weight to about 10% by weight of a chain transfer agent, preferably an allylic oxygen. The base compound, and more preferably the allyloxy alcohol, provides a chain transfer reagent polyoxyalkylene oxide for the preparation of a hydroxyl hydrogel contact lens product. The chain transfer agent is preferably added in an amount ranging from about 0.1% by weight to about 6% by weight. The "potency" of a particular batch of polyoxyalkylene oxide (eg, eucalyptus) as used herein is believed to provide a lens forming surface or contact lens insert with a contact lens mold at a given concentration (and all other factors being the same) The mold forms the ability of the final extracted hydrated lens product having an outer diameter in the range of from about 0.90 to about 1.10 times the outer diameter of the mold, such as from about 0.95 to about 1.05 times. In at least one embodiment, the outer diameter of the hydrated lens product is from about 0.98 to 1.02 times the outer diameter of the contact lens mold used or the mold insert used to form the contact lens mold. The greater the reduction in the diameter of the final lens product, the greater the "efficiency" of the polyoxyalkylene. While the final spectacles diameter is a measure of the ability of the chain transfer agent to provide a oxiranium contact lens product having the desired characteristics within the clinically acceptable range as described above, prior to mixing with the other components of the precursor composition The addition of a chain transfer agent to the polyoxyalkylene oxime additionally provides a greater consistency (i.e., reduced denaturation) of the large amount of measurable characteristics of the final contact lens product.

The resulting mixture of chain transfer agent and polyoxyalkylene oxime will preferably contain from about 0.1 to about 5 parts chain transfer agent and from about 99.9 to 95 parts polyoxyalkylene oxime. That is, the chain transfer agent-polyoxyalkylene oxide mixture may contain any of the following exemplary amounts of chain transfer agents: 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.5, 2. 2.5, 3, 3.5, 4, 4.5 or 5 parts, and corresponding parts of polyoxyalkylene oxime, for example, 99.9, 99.8, 99.7, 99.6, 99.5, 99.4, 99.3, 99.2, 99.1, 99, 98.5, 98, 97.5, 97, 96.5, 96, 95.5 or 95.

Additional components of the oxygenated hydrogel contact lens precursor composition

The lens precursor compositions of the present invention may also include additional components such as ultraviolet (UV) absorbers or UV radiation or energy absorbers and/or colorants. The UV absorber can be a relatively strong UV absorber that exhibits relatively high absorbance values, for example, in the UV-A range of about 320-380 nm, but is relatively transparent above about 380 nm. Examples include photopolymerizable hydroxybenzophenones and photopolymerizable benzotriazoles such as 2-hydroxy-4-propenyloxyethoxybenzophenone (with CYASORB) UV416 from Cytec Industries), 2-hydroxy-4-(2-hydroxy-3-methylpropenyloxy)propoxybenzophenone and photopolymerizable benzotriazole (with NORBLOC) 7966 was purchased from Noramco). Other photopolymerizable UV absorbers suitable for use in the present invention include polymerizable ethylenically unsaturated triazines, salicylates, aryl substituted acrylates, and mixtures thereof. In general, the UV absorber, if present, is provided in an amount corresponding to from about 0.5% by weight of the precursor composition to about 1.5% by weight of the composition. Particularly preferred are compositions comprising from about 0.6% to about 1.0% by weight of the UV absorber.

The precursor compositions of the present invention may also include colorants, although encompassing colored eyewear products and clear lens products. The colorant is preferably a reactive dye or pigment that effectively provides color to the resulting lens product. The reactive dyes are dyes that bind to the oxygenated hydrogel lens material and do not bleed. Exemplary colorants include the following: benzenesulfonic acid, 4-(4,5-dihydro-4-((2-methoxy-5-methyl-4-((2-(sulfooxy))) (sulfonyl) phenyl) azo-3-methyl-5-sideoxy-1H-pyrazol-1-yl); [2-naphthalenesulfonic acid, 7-(ethinyl)-4 -hydroxy-3-((4-((sulfoethyl)sulfonyl)phenyl)azo)-];[5-((4,6-dichloro-1,3,5-triazine) -2-yl)amino-4-hydroxy-3-((1-sulfo-2-naphthyl)azo-2,7-naphthalene-disulfonic acid, trisodium salt]; [copper, 29H, 31H - phthalocyanine (2-)-N ₂₉ , N ₃₀ , N ₃₁ , N ₃₂ )-, sulfo ((4((2-sulfooxy)ethyl)sulfonyl)phenyl)amino)sulfonate Mercapto derivatives] and [2,7-naphthalenesulfonic acid, 4-amino-5-hydroxy-3,6-bis((4-((2-(sulfooxy)ethyl)sulfonyl)benzene) Base) azo)-tetrasodium salt].

Particularly preferred colorants for use in the present invention are phthalocyanine pigments such as phthalocyanine blue and phthalocyanine green, chromium oxide-alumina-cobalt oxide, chromium oxide, and various iron oxides of red, yellow, brown, and black. An opacifier such as titanium dioxide can also be incorporated. For some applications, a mixture of colors can be used to better simulate the appearance of a natural iris.

Furthermore, the precursor compositions of the present invention may comprise one or more initiator compounds, i.e., compounds capable of initiating polymerization of the precursor composition. A thermal initiator, that is, an initiator having a "polymerization onset" temperature is preferred. By selecting a thermal initiator having a higher onset decomposition temperature and using a relatively low amount of initiator, it is possible to reduce the ion current of the glasses of the present invention, thereby affecting the amount of removable material removed or extracted in the extraction step. For example, one exemplary thermal initiator used in the precursor compositions of the present invention is 2,2'-azobis(2,4-dimethylvaleronitrile) (VAZO) -52). VAZO -52 has an onset decomposition temperature of about 50 ° C which is the temperature at which the reactive component in the precursor composition begins to polymerize. Another thermal initiator suitable for use in the compositions of the present invention is azobisisobutyronitrile (VAZO). -88) which has an initial decomposition temperature of about 90 °C. Also suitable initiator is VAZO -64,2,2'-azobisisobutyronitrile. All of the VASO thermal initiators described herein are available from DuPont (Wilmington, DE). Additional thermal initiators include nitriles such as 1,1'-azobis(cyclohexanecarbonitrile) and 2,2'-azobis(2-methylpropionitrile), as well as other types of initiators such as commercially available Their initiators from Sigma Aldrich. The ophthalmically compatible oxygenated hydrogel contact lens can comprise from about 0.2 to about 0.7 parts of VAZO-52 (or from about 0.1 to about 0.8% by weight) or from about 0.1 parts to about 0.6 parts of VAZO-88 (from about 0.05 to about 0.5). % by weight) obtained from the precursor composition.

The precursor compositions of the present invention may also comprise a release aid, i.e., effective to render the cured contact lens more susceptible to removal of one or more compounds from its mold. Exemplary release aids include hydrophilic oxime, polyoxyalkylenes, and combinations thereof.

The precursor composition may additionally comprise a diluent selected from the group consisting of hexanol, ethoxyethanol, isopropanol (IPA), propanol, decyl alcohol, and combinations thereof. If a diluent is used, it is usually present in an amount ranging from about 10% to about 30% by weight. Compositions having relatively high concentrations of diluent tend to, but are not required to have, lower ion current values, reduced modulus and increased elongation, and water BUTs greater than 20 seconds.

Other materials suitable for use in the preparation of hydroxyl hydrogel contact lenses are described in U.S. Patent No. 6,867,245.

The term "additive" in the context of the present application means that the polymerizable silicone hydrogel contact lens precursor composition or the pre-extracted polymeric hydrogel contact lens product of the present invention is provided but not produced. A compound or any chemical necessary for a gel contact lens. While this may not be necessary for the preparation of a silicone hydrogel contact lens, this in no way indicates that one or more advantages are imparted to the precursor composition or the resulting lens product due to the inclusion of one or more additives in the compositions of the present invention. For example, including a removable additive can, for example, facilitate processing of the contact lens during manufacture, as compared to a hydrogel contact lens obtained from the same precursor composition without additives. One or more characteristics of the enhanced hydrogel contact lens, or a combination thereof. The additive as used herein is an additive that can be removed from the pre-extracted polymeric hydrogel hydrogel contact lens product. For example, the additive may be substantially non-reactive or may not react with other components of the polymerizable silicone hydrogel lens precursor composition such that the additive does not substantially constitute a covalent combination of the resulting polymeric lens product. section. Depending on its molecular weight and shape, most, if not all, of the additives may be extracted from the polymerized hydrogel contact lens product. Thus, the additives in the compositions of the present invention can be extracted from the polymerized hydrogel hydrogel contact lens product during the extraction procedure. Accordingly, it is also believed that the polyoxyalkylene oxide as previously described as a removable or extractable component is an "additive" as used herein.

In addition to the PAOS extractable component, examples of the additive include, but are not limited to, ethylene glycol stearate, diethylene glycol monolaurate, C ₂ -C ₂₄ alcohol, and/or C ₂ -C ₂₄ amine. The additive may also contain one or more polar or hydrophilic end groups such as, but not limited to, a hydroxyl group, an amine group, a sulfhydryl group, a phosphate group, and a carboxylic acid group to facilitate mixing of the additive with other materials present in the composition. Dissolved.

The additive may be in liquid or solid form and includes a hydrophobic or amphiphilic compound or agent.

In certain embodiments, the additive may be referred to as a diluent, substantially a non-reactive agent or an extractable agent. In addition to the PAOS extractable components previously described, the precursor compositions of the present invention may also contain an alcohol or a non-alcohol diluent. If such other diluents are used, they are typically present in an amount of less than about 10% by weight. The additives provided in the compositions of the present invention may provide any one or more of the following functions, for example, they may (i) contribute to the formation of polymerizable hydrazines, such as by promoting the formation of a homogeneous composition or a composition that is not phase separated. An oxygen hydrogel contact lens precursor composition; (ii) enhancing the pre-extracted polymerization, such as by promoting release of a contact lens mold containing a contact lens product, and/or promoting release of the contact lens product from a contact lens mold. Processability of oxygen hydrogel contact lens products; (iii) improved control of physical parameters of contact lenses, such as by reducing the variability of contact lens physical parameters in a contact lens population (eg, in different batches of contact lenses) (iv) enhancing the wettability of the contact lens, such as by enhancing the wettability of the contact lens surface; (v) actively affecting the modulus of the contact lens, such as by reducing the modulus or increasing the modulus as needed; Vi) The ion current of the contact lens can be positively affected, such as by reducing the ion current of the contact lens, as compared to a contact lens obtained from a lens product that does not include an additive. Accordingly, the additive provided in the composition of the present invention can serve as a compatibilizer, a mold release aid, a mirror release aid, a physical parameter control agent, a wettability enhancer, a modulus influencer, an ion flow reducer, or the foregoing. A combination of one or more.

The compatibilizing agent can improve or enhance the miscibility of the components of the precursor composition of the present invention. For example, a compatibilizer can reduce phase separation associated with cerium-containing polymers and other spectacles forming components as compared to non-compatibilizing formulations.

The additive is preferably evenly distributed throughout the polymeric composition and is substantially (if not completely) removed from the polymerization product during the extraction procedure. Thus, the contact lenses of the present invention are preferably produced by small physical or dimensional variability between batches, thereby improving the yield of clinically acceptable ocular oxygen-compatible hydrogel contact lenses.

Exemplary precursor compositions of the present invention are provided in Examples 1, 3 and 4.

Certain embodiments of the precursor compositions of the present invention include polymerizable silicone hydrogel contact lens precursor compositions provided in non-polar resin contact lens molds. Other embodiments include such compositions in storage containers such as bottles and the like, or in dispensing devices such as manual or automatic pipetting devices.

Method of forming a helium oxygen hydrogel contact lens

In general, in the production of a helium oxygen hydrogel contact lens, the components of the helium oxygen hydrogel contact lens precursor composition are each weighed and then combined. The resulting precursor composition is then typically mixed, for example, using magnetic or mechanical mixing, and optionally filtered to remove particulates.

The spectacles of the present invention can be produced, for example, as illustrated in FIG. 1 is a block diagram illustrating a method of producing a helium oxygen hydrogel contact lens. In particular, Figure 1 illustrates a method of casting a hydroxyl hydrogel contact lens. The cast contact lens can itself be produced in a form suitable for direct placement on the human eye without further processing to modify the lens to make the lens suitable for use on the eye. The oxygenated hydrogel contact lenses of the present invention produced using a casting process such as the procedure illustrated in Figure 1 are herein considered to be "cast-formed hydroxyl hydrogel contact lenses." The glasses of the present invention are understood to be "fully formed hydroxyl hydrogel contact lenses" if processing is not used to alter the design of the lens that causes the lens product to be removed from the mold member.

Illustrative methods for producing contact lenses, such as neohydrogenated hydrogel contact lenses, are described in U.S. Patent Nos. 4,121,896, 4,495,313, 4,565,348, 4,640,489, 4,889,664, 4,985,186. , 5,039,459, 5,080,839, 5,094,609, 5,260,000, 5,607,518, 5,760,100, 5,850,107, 5,935,492, 6,099,852, 6,367,929, 6,822,016, 6,867,245, No. 6,869,549, No. 6,939,487, and U.S. Patent Publication Nos. 20030125498, No. 20050154080, and No. 20050191335.

Returning to Figure 1, the method outlined in the block diagram will now be briefly described. The illustrated method includes a step 102 of placing a polymerizable silicone hydrogel lens precursor composition ( 202 , as shown in Figure 2) on or in a contact lens mold member. The polymerizable silicone hydrogel lens precursor composition refers to a prepolymerized or precured composition suitable for polymerization. The polymerizable compositions of the invention as used herein may also be referred to as "monomer mixtures" or "reaction mixtures." The polymerizable composition or lens precursor composition is preferably not polymerized to any significant extent prior to curing or polymerization of the composition. However, in some cases, the polymerizable composition or lens precursor composition can be partially polymerized prior to being subjected to curing.

Prior to the curing or polymerization procedure, the lens precursor compositions of the present invention can be provided in a container, dispensing device or contact lens mold.

Returning to step 102 of Figure 1, the lens precursor composition is placed on the lens forming surface of the concave contact lens mold member. A concave contact lens mold member generally refers to a first contact lens mold member or a front contact lens mold member. For example, a concave contact lens mold member has a lens forming surface that defines a front surface of a contact lens produced from a contact lens mold.

The first contact lens mold member is placed in contact with the second contact lens mold member to form a contact lens mold having a contact lens shaped cavity. Thus, the method illustrated in Figure 1 includes the step 104 of closing the contact lens mold by placing the two contact lens mold members in contact with one another to form a contact lens shaped cavity. The polymerizable silicone hydrogel lens precursor composition 202 is located in a contact lens shaped cavity. The second contact lens mold member refers to a convex contact lens mold member or a rear contact lens mold member. For example, the second contact lens mold member includes a lens forming surface that defines a rear surface of the contact lens produced in the contact lens mold.

As used herein, "non-polar resin contact lens mold" or "hydrophobic resin contact lens mold" refers to a contact lens mold formed or produced from a non-polar or hydrophobic resin. Thus, the non-polar resin based contact lens mold can comprise a non-polar or hydrophobic resin. For example, the contact lens molds can comprise one or more polyolefins or can be formed from a polyolefin resin material. Examples of non-polar resin contact lens molds used in the context of the present application include polyethylene contact lens molds, polypropylene contact lens molds, and polystyrene contact lens molds. Non-polar resin based contact lens molds typically have a hydrophobic surface. For example, the non-polar resin mold or the hydrophobic resin mold may have a static contact angle of about 90 or more as determined using the trapping bubble method. At these contact angles, conventional oxygenated hydrogel contact lenses produced in such molds have clinically unacceptable surface wettability.

The method further includes curing 106 a polymerizable silicone hydrogel lens precursor composition to form a pre-extracted polymeric hemohydrogel contact lens product 204 (as shown in Figure 2). During curing, the lens forming components of the polymerizable silicone hydrogel lens precursor composition are polymerized to form a polymeric lens product. Therefore, curing can also be understood as a polymerization step. Curing 106 can include the manner in which the polymerizable lens precursor composition is exposed to radiation, such as heat radiation or any other component of an effective polymeric lens precursor composition. For example, curing 106 can include exposing the polymerizable lens precursor composition to a polymeric amount of heat or ultraviolet (UV) light. Curing can be carried out in an oxygen-free environment as appropriate. For example, curing can be carried out under an inert atmosphere, such as under nitrogen, argon or other inert gases.

The pre-extracted polymeric hydrogel contact lens product 204 refers to a polymeric product prior to undergoing an extraction procedure that removes substantially all of the removable/extractable components from the polymerization product. The pre-extracted polymeric hemohydrogel contact lens product can be provided on or in a contact lens mold, extraction tray or other device prior to contact with the extraction composition. For example, after the curing process, the pre-extracted polymeric hemohydrogel contact lens product can be provided in the lens-like cavity of the contact lens mold; after the contact lens mold is released, it can be provided in a contact lens mold member. Top or inside; or after the stripping procedure and prior to the extraction procedure, may be provided on or in the extraction tray or other device. The pre-extracted polymeric oxygenated hydrogel contact lens product comprises a lens forming component such as a enamel-containing polymeric network or matrix in the form of a spectacles and a removable component removable from the spectacles forming component. The removable component also includes, in addition to the PAOS extractable component, unreacted monomers, oligomers, partially reacted monomers, or other agents that are not covalently attached or immobilized relative to the lens forming component. The removable component can also include one or more additives, including organic additives, including diluents, which can be extracted from the polymeric lens product during the extraction procedure as previously discussed. Thus, the material which may comprise a removable component includes not only the polyoxyalkylene oxime extractable component, but also an extractable or unremovable extractable relative to the polymer backbone, network or matrix of the lens body. Linear uncrosslinked, crosslinked, and/or branched polymers of the material.

Additionally, the removable component can include other materials, such as volatile materials, that can be passively or actively removed from the pre-extracted polymeric hydrogel contact lens product prior to extraction. For example, a portion of the removable component can be evaporated between the demolding step and the extraction step.

After curing the polymerizable lens precursor composition, demolding of the contact lens mold 108 is performed . Demolding refers to the method of separating two mold members, such as male and female mold members, of a mold or polymerization device containing a pre-extracted polymeric contact lens product. The pre-extracted polymeric hemohydrogel contact lens product is located on one of the demolded mold members. For example, the polymeric hemohydrogel contact lens product can be located on a male mold member or a female mold member.

The pre-extracted polymeric hemo-hydrogel contact lens product 204 is then separated from the contact lens mold member to which it is positioned during the mirror removal step 110 (shown in Figure 1). The pre-extracted polymeric contact lens product can be removed from the convex mold member or the concave mold member depending on the mold member in which the polymeric contact lens product remains adhered during release of the contact lens mold.

After the pre-extracted silicone hydrogel contact lens product is delensed, the method comprising the pre-extraction from silicon hydrogel contact lens product 112 was extracted extractable material. Extraction step 112 results in an extracted hydroxyl hydrogel contact lens product 206 (shown in Figure 2). Extraction step 112 refers to the process of contacting the pre-extracted polymeric hydrogel gel contact lens product with one or more extraction compositions, and may include a single extraction step or several sequential extractions. For example, a polymeric oxygenated hydrogel contact lens product or a batch of polymeric hydroxyl hydrogel contact lens product is contacted with one or more volumes of liquid extraction media. The extraction medium typically includes one or more solvents. For example, the extraction medium includes ethanol, methanol, propanol, and other alcohols. The extraction medium may also comprise a mixture of an alcohol and water, such as a mixture of 50% ethanol and 50% deionized water, or a mixture of 70% ethanol and 30% deionized water, or a mixture of 90% ethanol and 10% deionized water. . Alternatively, the extraction medium can be substantially or completely alcohol free and can include one or more agents that facilitate removal of the hydrophobic unreacted component from the polymerized hydrogel hydrogel lens product. For example, the extraction medium can comprise, consist essentially of, or consist entirely of water, a buffer solution, and the like. Extraction 112 can be carried out at various temperatures, including room temperature. For example, the extraction can occur at room temperature (eg, about 20 °C), or it can occur at elevated temperatures (eg, from about 25 °C to about 100 °C). Moreover, in certain embodiments, the extracting step 112 can include contacting the lens product with a mixture of alcohol and water, which in some cases can include the final step of the multi-step extraction procedure.

After the polymerization silicone hydrogel contact lens product to provide a pre-extraction of the extracted polymerized silicone hydrogel contact lens product was extracted, the method comprising the extracted polymerized hydrated 114 of silicon hydrogel contact lens product. The hydrating step 114 can, for example, comprise contacting the extracted polymeric hydrogel hydrogel contact lens product or one or more batches of the product with water or an aqueous solution to form a hydrated hydrogel hydrogel contact lens 208 (shown in Figure 2). ). For example, the extracted polymeric oxygenated hydrogel contact lens product can be hydrated by being placed in two separate volumes or two separate volumes of water, including deionized water. In certain embodiments, the hydrating step 114 is combined with the extraction step 112 such that the two steps are performed at a single location in the contact lens production line. The hydration step 114 can be carried out in a vessel at room temperature or elevated temperature and, if necessary, under high pressure. For example, hydration can occur in water at a temperature of about 120 ° C (eg, 121 ° C) and a pressure of 103 kPa (15 psi).

Thus, as apparent from the above, it is believed that the pre-extracted polymeric hydrogel contact lens product and the extracted polymeric hydrogel hydrogel contact lens product are products or components of water swellability and are considered to be hydrated hydrophobic water. Gel contact lenses are water swellable products or components. As used herein, a hydroxyl hydrogel contact lens refers to a hydroxyl hydrogel element that has undergone a hydration step. Thus, the helium oxygen hydrogel contact lens can be a fully hydrated neohydrogen hydrogel contact lens, a partially hydrated neohydrogen hydrogel contact lens or a dehydrated hydrogenated hydrogel contact lens. A dehydrated hydrogel contact lens refers to a contact lens that has undergone a hydration procedure and is subsequently dehydrated to remove water from the lens.

After hydrating the extracted oxygenated hydrogel contact lens product to produce a helium oxygen hydrogel contact lens, the method includes the step 116 of encapsulating the helium oxygen hydrogel contact lens 208 . For example, silicone hydrogel contact lens 208 may be placed include a volume of liquid (such as physiological saline solution, including buffered saline solution of physiological and) the blister pack or other suitable container. Examples of liquids suitable for the lenses of the present invention include phosphate buffered saline and borate buffered saline. As shown in step 118 , the blister pack or container is then sealed and subsequently sterilized. For example, encapsulated neohydrogenated hydrogel contact lenses can be exposed to sterilizing amounts of radiation, including thermal radiation, such as by autoclave treatment, gamma radiation, electron beam radiation, or ultraviolet radiation.

Characteristics of oxygenated hydrogel glasses

As discussed above, the compositions and methods provided herein provide an ophthalmically compatible silicone hydrogel contact lens. A pre-extracted polymeric hydrogel lens product having a removable component as described herein is extracted and hydrated to form a hydroxyl hydrogel contact lens having an ophthalmically acceptable surface wettability. The spectacles of the present invention have oxygen permeability, surface wettability, modulus, water content, ion flow, design, and combinations thereof, which make the spectacles of the present invention suitable for comfortable stretching of the patient's eyes, such as at least one day, at least One week, at least two weeks, or about one month, without removing the glasses from your eyes.

As used herein, "a compatible oxygenated hydrogel contact lens" refers to a hydroxyl hydrogel that can be worn on the human eye without human experience or substantial discomfort (including eye irritation and similar discomfort). Contact lenses. Eye-compatible, oxygenated hydrogel contact lenses have an ophthalmically acceptable surface wettability and generally do not cause significant corneal swelling, corneal dehydration ("dry eye"), or superior corneal epithelial arch lesion ("SEAL") Or other significant discomfort or unrelated to these conditions. An oxygenated hydrogel contact lens having an ophthalmically acceptable surface wettability means a tear film that does not adversely affect the eye of the wearer of the lens to cause the wearer of the lens to experience or report placement or wear on the eye. Hydroxyl hydrogel contact lenses for the degree of discomfort associated with oxygen hydrogel contact lenses. Eye-compatible, oxygenated hydrogel contact lenses meet the clinically acceptable requirements for daily or long-term wear of contact lenses.

The hydroxyl hydrogel contact lenses of the present invention comprise a lens body having an ophthalmically acceptable surface wettability (OASW) surface, such as a front surface and a back surface. Wetability refers to the hydrophilicity of one or more surfaces of a contact lens. In a measurement method, if the glasses obtain a score of 3 or more in the wettability test performed as follows, the surface of the lens may be considered to be wettable, or may be considered to have an ophthalmically acceptable wettability. . The contact lens is immersed in distilled water, removed from the water, and the length of time it takes for the water film to recede from the surface of the lens (eg, water dispersal time (water BUT or WBUT)) is measured. The assay provides a level of eyeglasses in the linear range of 1-10, with 10 points being the glasses in which the water droplets need to recede from the glasses for 20 seconds or more. While the in vitro evaluation of WBUT is only one measurement method or indication for OASW, it can be considered that a helium oxygen hydrogel contact lens having a water BUT of 5 seconds or more (such as at least 10 seconds or more preferably at least about 15 seconds) has An acceptable surface wettability for the eye. Alternatively, OASW can be evaluated in vivo. If the spectacles can be worn on the patient's eyes for at least 6 hours and the patient does not report discomfort or irritation, the spectacles are considered to have OASW.

Wettability can also be determined by measuring the contact angle on the surface of one or both of the glasses. The contact angle can be a dynamic or static contact angle. A lower contact angle generally refers to an increase in the wettability of the surface of the contact lens. For example, the wettable surface of the helium oxygen hydrogel contact lens can have a contact angle of less than about 120°. However, in certain embodiments of the spectacles of the present invention, the spectacles have a contact angle of no greater than 90°, and in other embodiments, the oxyahydrogel contact lenses of the present invention have a less than about 80° and even more preferably less than Enter the contact angle before about 75°.

The hydroxyl hydrogel contact lenses of the present invention comprise a lens body having an ophthalmically acceptable surface wettability. For example, the mirror body of the oxygenated hydrogel contact lenses of the present invention typically has a front surface and a back surface, each surface having an ophthalmically acceptable surface wettability.

In one embodiment, the mirror body of the helium oxygen hydrogel contact lens comprises a helium oxygen hydrogel material. The mirror body has a dry weight of no more than 90% of the dry weight of the mirror body before extraction. For example, the mirror body of the pre-extracted polymeric hemohydrogel contact lens product can have a dry weight X. After the extraction procedure, the mirror of the extracted polymeric hydrogel contact lens product has a dry weight of less than or equal to 0.9X. As discussed above, during the extraction step, the pre-extracted polymeric hydrogel gel contact lens product can be contacted with a wide variety of organic solvents, followed by a hydration step to produce a hydroxyl hydrogel contact lens. Next, the hydrated hydrogel hydrogel contact lens was dehydrated and weighed to determine the dry weight of the lens body of the hydroxyl hydrogel contact lens.

For example, in some methods, the pre-extracted polymeric hemohydrogel contact lens product is removed from the contact lens mold member and weighed to provide a pre-extracted polymeric hydrogel contact lens product. weight. The pre-extracted lens product is then contacted with the alcohol for about 6 hours and then hydrated with water. The hydrated spectacles are then dried at about 80 ° C for about 1 hour and then dried under vacuum at about 80 ° C for about 2 hours. The dried glasses were weighed to determine the dry weight of the lens body of the hydrogenated hydrogel contact lens. The dry weights are then compared to determine the amount of extractable material present in the pre-extracted polymeric hydrogel hydrogel contact lens product. The pre-extracted polymeric lens product having a level of extractable component of about 40% produces a lens body having a dry weight of about 60% of the hydrogel contact lens of the pre-extracted lens product. The pre-extracted polymeric lens product having an extractable component content of about 70% produces a lens body having a dry weight of about 30% of the oxygenated hydrogel contact lens of the pre-extracted lens product, and the like.

The amount of extractables or extractable component present in the pre-extracted polymeric hydrogel contact lens product can be determined using the following equation: E = ((dry weight of pre-extracted lens product - extracted and The dry weight of the hydrated contact lens) / the dry weight of the pre-extracted lens product) × 100.

E is the percentage of extractables present in the pre-extracted lens product.

For example, the pre-extracted polymeric hemohydrogel contact lens product can have a dry weight of about 20 mg. If the oxygenated hydrogel contact lens obtained from the product has a dry weight of about 17 mg, the hydrogenated hydrogel contact lens comprises a lens body having a dry weight of 85% of the dry weight of the pre-extracted lens product. It will be appreciated that the pre-extracted lens product has an extractable component content of about 15% by weight. As another example, the pre-extracted polymeric hydrogel contact lens product can have a dry weight of about 18 mg, and if the dehydrated hydrogel contact lens obtained from the lens product has about 13 mg On dry weight, the helium oxygen hydrogel contact lens comprises a mirror body having a dry weight of about 72% of the pre-extracted lens product. The pre-extracted polymeric hydrogel contact lens product has an extractable component content of about 28% by weight.

In certain embodiments, the mirror body of the helium-oxygen hydrogel contact lens (i.e., the oxygenated hydrogel contact lens that has been subjected to the extraction and hydration procedure) is substantially more than 40% of the dry weight of the lens body prior to extraction. For example, the dry weight of the lens body after extraction can be from about 40% to about 90% of the dry weight of the pre-extracted lens body. Certain embodiments of the lenses of the present invention comprise a lens body having a dry weight of from about 50% to about 80% of the dry weight of the pre-extracted lens body.

As discussed herein, the amount of extractable component in the pre-extracted lens product (eg, unreacted reagent, such as linearity of extractable material that is not crosslinked or immobilized relative to the polymer backbone, network, or matrix of the lens body) An optical fiber precursor composition having no polyoxyalkylene oxime extractable component when the uncrosslinked, crosslinked or branched polymer is greater than 10%, such as at least 15%, at least 20%, at least 25% or more The ophthalmic hydrogel contact lenses obtained from the pre-extracted oxygenated hydrogel contact lens products (e.g., the lens products obtained from "mass formulations") may have ophthalmically acceptable surface wettability. Applicants have discovered that one or more removable/extractable additives are included in the precursor composition or the polymerized pre-extracted lens product to increase the content of the extractable component and produce an eye with a larger amount of the formulated lens product. Ophthalmic hydrogel contact lenses with acceptable surface wettability.

While the pre-extracted polymeric hydrogel contact lens product of the present invention has a relatively large amount of extractable material, the extracted form of the hydroxyl hydrogel contact lens of the present invention has very little extractable material in the resulting lens body. In certain embodiments, the amount of extractable material remaining in the extracted lens is from about 0.1% to about 4%, such as from about 0.4% to about 2% by weight. The additional extractable material can be determined by contacting the extracted contact lens with an additional volume of a strong solvent such as chloroform.

In addition, since the extractable component is present and distributed throughout the polymerizable silicone hydrogel lens precursor composition and the pre-extracted polymeric oxygenated hydrogel contact lens product, the lens product and contact lens of the present invention can be Different from surface treated helium hydrogel contact lenses. Since the extractable component can be extracted from the lens product and is substantially absent from the hydrated contact lens, the lens products and contact lenses of the present invention can be distinguished from the oxygenated hydrogel contact lens having the polymeric wetting agent IPN.

The hydroxyl hydrogel contact lenses of the present invention may comprise a lens body obtained from a non-polar resin contact lens mold having substantially the same surface morphology when examined in a hydrated and dehydrated state. Further, the hydrated mirror bodies may have a surface roughness slightly smaller than the surface roughness of the dehydrated mirror body. For example, the lens body of the glasses of the present invention may have a surface comprising a nanometer size peak, which is apparent when analyzing the root mean square (RMS) roughness data of the surface of the lens. The mirror body can include regions between the peaks of the differential ridges between the peaks to provide reduced roughness while substantially similar surface morphology. For example, although the peak height can be reduced when the mirror body is hydrated, the peak shape remains substantially the same.

Alternatively or additionally, embodiments of the non-polar resin molded oxygenated hydrogel contact lenses of the present invention may comprise visually visible when viewed with an electron microscope such as a scanning electron microscope, a transmission electron microscope, or a scanning transmission electron microscope. Identify the mirrors of the rich and poor areas. Based on chemical analysis, it can be understood that the barren area is a substantially or completely flawless intraocular region. The barren zone may be larger than the surface treated hemohydrogel contact lens or the oxygenated hydrogel contact lens comprising the polymeric wetting agent IPN. The size of the rich zone, the barren zone, or both can be determined using conventional image analysis software and devices, such as image analysis systems available from Bioquant (Tennessee). The image analysis software system can be used to outline the boundary contours of the rich and barren regions and to determine the cross-sectional area, diameter, volume and the like of the regions. In certain embodiments, the barren zone has a cross-sectional area that is at least 50%, at least 60%, at least 70%, at least 80%, or at least 90% greater than the barren zone of other hemihydrate hydrogel contact lenses.

The untreated surface of the present invention generally provides ophthalmically acceptable surface wettability. In other words, in one embodiment, the mirror body of the helium oxygen hydrogel contact lens of the present invention is a mirror body that has not been surface treated. In other words, the lens body is produced without surface treatment of the lens body to provide an ophthalmically acceptable surface wettability. For example, the illustrative scope does not include a plasma treatment or additional coating to make the surface of the mirror body more acceptable on the eye. However, certain embodiments are necessary if the lenses of the present invention have ophthalmically acceptable surface wettability due to the amount of removable material present in the pre-extracted polymeric hydrogel hydrogel contact lens product. Surface treatment can be included.

Certain embodiments of the lenses of the present invention comprise cast molded component mirrors obtained from non-polar resin contact lens molds. The polymeric hemohydrogel contact lens product refers to a product that is polymerized or cured in a non-polar resin contact lens mold. Alternatively, in another manner, the polymeric hemohydrogel contact lens product is produced in a non-polar resin contact lens mold. As discussed herein, the contact lens molds are molds that are produced using non-polar or hydrophobic resinous materials or based on non-polar or hydrophobic resinous materials. These materials typically have a relatively large contact angle on their lens forming surface.

The silicone hydrogel contact lenses of the present invention may also include one or more comfort enhancers that enhance the invisibility experienced by the wearer or wearer of the eyeglasses relative to the silicone hydrogel contact lens without the comfort enhancer. The comfort of the glasses. Examples of comfort enhancers include dehydration reducing agents, tear film stabilizers, or agents that both reduce dehydration and stabilize the tear film of the eye in which the contact lens is placed. Such comfort enhancers include polymeric materials that have an affinity for water. In certain embodiments, the polymeric material comprises one or more amphiphilic groups. Examples of materials suitable for use as comfort enhancers include polymerizable phospholipids, such as those comprising the choline phosphate component. In certain embodiments, the precursor composition comprises a methacrylate phosphorylcholine monomer such that in this case the amphiphilic material phosphorylcholine is included in the resulting cross-linked network.

As discussed herein, the comfort of the oxygenated hydrogel lenses of the present invention can also be enhanced by including one or more removable comfort enhancements in the lens precursor composition and the pre-extracted silicone hydrogel contact lens product. Agent to enhance. For example, some of the removable materials described herein include agents that reduce the ion current of the lenses of the present invention as compared to glasses obtained from the same composition of the non-removable material. Reducing the ion flux of the lens can help reduce corneal dehydration of the lens wearer and reduce corneal staining caused by wearing the lens.

As discussed herein, the spectacles of the present invention have features and characteristics that allow the spectacles to be worn for an extended period of time. For example, the spectacles of the present invention can be worn as wearing glasses every day, wearing glasses every week, wearing bi-weekly glasses, or wearing glasses every month. The spectacles of the present invention comprise a hydrated mirror body having surface wettability, modulus, ion flow, oxygen permeability, and water content that contribute to the comfort and usability of the lens. In certain embodiments, the spectacles of the present invention comprise a hydrated lens body having features selected from the group consisting of: a contact angle of less than about 95°, a tensile modulus of less than about 1.6 MPa, less than about 7 An ion current of ×10 ^-3 mm ² /min, an oxygen permeability (Dk) of at least about 70 barrer, a water content of at least about 30% by weight, and combinations thereof. However, in other embodiments, the ion current may be greater than 7 x 10 ^-3 mm ² /min, but still does not cause corneal dehydration staining or other clinical problems.

The spectacles of the present invention may comprise a hydrated mirror body having a front contact angle of less than 120° on the front surface, the back surface or the front and back surfaces. In certain embodiments, the mirror body has a mirror surface advancing contact angle of less than 90°, such as the mirror body having about 85°, about 80°, about 75°, about 70°, about 65°, about 60°, about 55. ° or about 50° of the mirror surface advancing contact angle. The mirror body may also have a mirror surface receding contact angle of less than 80°, for example, the mirror body may have a mirror surface of about 75°, about 70°, about 65°, about 60°, about 55°, about 50°, or about 45°. Retreat contact angle. The hysteresis as the difference between the advancing contact angle and the receding contact angle may be from about 5° to about 35°. However, in certain embodiments, the hysteresis can be greater than 25°, but is still clinically acceptable.

The advancing contact angle can be determined using conventional methods known to those skilled in the art. For example, a conventional drop shape method, such as a sessile drop method or a trapped bubble method, can be used to measure the contact angle and the receding contact angle of the contact lens. Kruss DSA 100 appliances (Kruss GmbH, Hamburg) and DABrandreth: "Dynamic contact angles and contact angle hysteresis", Journal of Colloid and Interface Science, No. 62, for the forward and backward water contact angles of the hydrogel contact lenses. Vol., 1977, pp. 205-212 and R. Knapikowski, M. Kudra: Kontaktwinkelmessungen nach dem Wilhelmy-Prinzip-Ein statistischer Ansatz zur Fehierbeurteilung", Chem. Technik, Vol. 45, 1993, pages 179-185 and US patents Measured as described in No. 6,436,481.

For example, the advancing contact angle and the receding contact angle can be determined using a trapped bubble method using phosphate buffered physiological saline (PBS; pH = 7.2). The glasses were tiled on the quartz surface and rehydrated with PBS for 10 minutes prior to testing. Air bubbles are placed on the surface of the glasses using an automatic injection system. The bubble size can be increased and decreased to obtain a receding angle (a platform is obtained when the bubble size is increased) and an advancing angle (a platform is obtained when the bubble size is reduced).

Alternatively or additionally, the spectacles of the present invention may comprise a lens body exhibiting a water dispel time (BUT) of greater than 5 seconds. For example, embodiments of the lenses of the present invention comprising a mirror body having a water BUT of at least 15 seconds (such as 20 seconds or more) may have an ophthalmically acceptable surface wettability.

The spectacles of the present invention may comprise a lens body having a modulus of less than 1.6 MPa. In some embodiments, the mirror has a modulus of less than 1.0 MPa. For example, the mirror body can have a modulus of about 0.9 MPa, about 0.8 MPa, about 0.7 MPa, about 0.6 MPa, about 0.5 MPa, about 0.4 MPa, or about 0.3 MPa. The modulus of the mirror body of the present invention is preferably from about 0.4 to about 0.8 MPa, and even more preferably between about 0.4 and about 0.6 MPa. In an embodiment, the mirror body has a modulus between about 0.4 and 0.5 MPa. The mirror body modulus is selected to provide a comfortable eyeglass when placed on the eye and to allow the eyewear wearer to adapt to the operation of the eyewear.

The modulus of the mirror body can be determined using conventional methods known to those skilled in the art. For example, a contact lens having a width of about 4 mm can be cut from the center portion of the lens, and the tensile modulus (unit: MPa) can be at least 75% humidity at 25 ° C by using Instron 3342 (Instron Corporation). The initial slope of the stress-strain curve obtained by tensile testing at a rate of 10 mm/min in air was measured.

The ion current of the lens body of the glasses of the present invention is typically less than about 5 x 10 ^-3 mm ² /min. While some of the scopes of the lenses of the present invention may have an ion current of up to about 7 x 10 ^-3 mm ² /min, the ion current is less than about 5 x 10 ^-3 mm ² /min, and when the contact lens is not Corneal dehydration staining can be reduced when MPC is included. In some embodiments, the ion current of the mirror body is about 4.5 x 10 ^-3 mm ² /min, about 4 x 10 ^-3 mm ² /min, about 3.5 x 10 ^-3 mm ² /min, about 3 x 10 ^-3 mm ² /min or less. However, as described herein, the ion current can be greater than 7 x 10 ^-3 mm ² /min, but still does not cause corneal dehydration staining or other clinical problems.

The ion current of the lens body of the glasses of the present invention can be determined using conventional methods known to those skilled in the art. For example, the ion current of the contact lens or lens body can be measured using a technique substantially similar to the "Ionoflux Technique" described in U.S. Patent No. 5,849,811. For example, the spectacles to be measured can be placed between the convex and concave portions of the device that retains the spectacles. The male and female portions include a flexible sealing ring between the eyeglasses and each of the male or female portions. After positioning the glasses in the device that holds the glasses, the device that retains the glasses is placed in a threaded cover. Screw the cover onto the glass tube to define the material chamber. The raw material chamber can be filled with 16 ml of a 0.1 molar concentration of NaCl solution. The receiving chamber can be filled with 80 ml of deionized water. The wire of the conductivity meter is immersed in deionized water in the receiving chamber and a stir bar is added to the receiving chamber. The receiving chamber was placed in an incubator and the temperature was maintained at approximately 35 °C. Finally, the material substance chamber is immersed in the receiving chamber. The conductivity measurement can be performed every two minutes starting from 10 minutes after the raw material chamber is immersed in the receiving chamber for about 20 minutes. The relationship between conductivity and time should be substantially linear.

The lens body of the glasses of the present invention generally has high oxygen permeability. For example, the mirror body has an oxygen permeability of Dk of not less than 60 barrer. Embodiments of the spectacles of the present invention comprise a lens body having a Dk of about 80 barrer, about 90 barrer, about 100 barrer, about 110 barrer, about 120 barrer, about 130 barrer, about 140 barrer or greater.

The Dk of the glasses of the present invention can be determined using conventional methods generally known to those skilled in the art. For example, the Dk value can be determined using the Mocon method as described in U.S. Patent No. 5,817,924. The Dk value can be determined using a commercially available instrument of the Mocon Ox-Tran System model name.

The spectacles of the present invention also comprise a lens body having an ophthalmically acceptable water content. For example, embodiments of the glasses of the present invention comprise a lens body having a water content of not less than 30%. In certain embodiments, the mirror body has a water content of about 35%, about 40%, about 45%, about 50%, about 55%, about 60%, or about 65%.

The water content of the lenses of the present invention can be determined using conventional methods generally known to those skilled in the art. For example, a hydrated hydrogel hydrogel contact lens can be removed from an aqueous liquid, wiped to remove excess surface water, and weighed. The weighed glasses can then be dried in an oven at 80 ° C in vacuum and the dried glasses can then be weighed. The weight difference was determined by subtracting the weight of the dry glasses from the weight of the hydrated glasses. The water content (%) is (weight difference / hydration weight) × 100.

The spectacles of the present invention may have values in the range between any combination of the specific values determined above, in addition to the specific values determined above. For example, the contact lenses of the present invention can have a water content of from about 45% to about 55%, an ion current value of from about 3 to about 4, a static contact angle of from about 35 to about 45, from about 55 to about 80. °Advance contact angle, about 47° to about 55° receding contact angle, lag of about 11° to about 25°, Young's moduli of about 0.47 MPa to about 0.51 MPa, about 140% to about 245% elongation and combinations thereof.

In certain particular embodiments of the helium oxygen hydrogel contact lenses of the present invention, the lens body has a modulus of less than 0.5 MPa, an ion current of less than 4, and a water content of about 42-46%.

The oxygenated hydrogel contact lens of the present invention is a contact lens for correcting vision or enhancing vision. The glasses can be spherical or aspherical. The glasses can be single focus glasses or multifocal glasses, including bifocal glasses. In certain embodiments, the spectacles of the present invention are rotationally stable spectacles, such as rotationally stable toric contact lenses. The rotationally stable contact lens can be a contact lens comprising a mirror body comprising a ballast. For example, the mirror body can have a ballast, a surrounding ballast, and/or one or more thinned upper and lower regions.

The spectacles of the present invention also include a scope comprising a peripheral edge region. The peripheral edge region may include a circular portion. For example, the peripheral edge region can comprise a rounded trailing edge surface, a rounded leading edge surface, or a combination thereof. In some embodiments, the peripheral edge is completely rounded from the front surface to the back surface. Thus, it will be appreciated that the scope of the eyeglasses of the present invention can comprise a rounded peripheral edge.

The spectacles of the present invention may comprise a lens body whose thickness profile solves the problems associated with prior oxyhydrogel contact lenses but is still comfortable for the lens wearer. The hardness of the mirror body can be controlled by changing the thickness of the mirror body and the modulus of the mirror body. For example, the hardness of a region of a contact lens can be defined as the product of the Young's modulus of the eyeglass and the square of the eyeglass thickness of the designated area. Thus, certain embodiments of the glasses of the present invention may comprise a mirror having a central hardness (e.g., a center of the eyeglass or a center of the viewing zone) of less than about 0.007 MPa-mm ² , a lens joint hardness of less than about 0.03 MPa-mm ^{2 ,} or a combination thereof. body. The spectacles junction can be defined as the junction of the spectacles and bevels or (for slanted glasses) at a point of about 1.2 mm from the edge of the spectacles (see U.S. Patent No. 6,849,671). In other embodiments, the spectacles of the present invention may comprise a lens body having a center hardness greater than 0.007 MPa-mm ² and a lens joint hardness greater than about 0.03 MPa-mm ² or a combination thereof.

Desirably, the physical parameters of the oxygenated hydrogel contact lenses of the present invention, such as physical dimensions and the like, have little variability in spectacles or bulk glasses. For example, in certain embodiments, an additive such as a chain transfer agent is added to the polymerizable silicone hydrogel contact lens precursor composition to reduce the variability in the physical properties of the lens. The variability between any two batches of glasses is preferably less than 2% using such additives that control physical parameters. For example, one or more batches of the lenses of the present invention may have a variability of from about 0.5% to about 1.9%. For example, the diameter and base curve of the glasses of the present invention can be controlled to within 1.6% of the predetermined value. More specifically, if the target contact lens diameter is 14.0 mm, and if the actual diameter of the contact lens in a batch of contact lenses varies from about 13.6 mm to about 14.4 mm, one or more additives may be used during contact lens production. To reduce variability and to produce contact lenses having a diameter ranging from about 13.8 mm to about 14.2 mm. Similar controls can be provided to reduce variations in spectacles thickness, radial depth, base curvature, and the like.

The oxygenated hydrogel contact lenses of the present invention can be provided in a sealed package. For example, the oxygenated hydrogel contact lenses of the present invention can be provided in a sealed blister pack or other similar container suitable for delivery to a spectacles wearer. The spectacles can be stored in an aqueous solution within the package, such as a physiological saline solution. Some suitable solutions include phosphate buffered physiological saline solutions and borate buffer solutions. The solution may or may not include a disinfectant or a preservative if necessary. If necessary, the solution may also include a surfactant such as poloxamer and the like.

The lenses in the sealed package are preferably sterile. For example, the spectacles can be sterilized prior to sealing the package or can be sterilized within the sealed package. The sterilized spectacles may be spectacles that have been exposed to sterilizing radiation. For example, the glasses can be autoclaved glasses, gamma irradiated glasses, ultraviolet radiation exposed glasses, and the like.

Instance

The following examples illustrate some aspects and advantages of the invention, but the invention is not to be considered as limited to the specific embodiments described below.

The practice of the present invention will employ, unless otherwise indicated, conventional techniques of polymer synthesis, hydrogel formation, and the like within the skill of the art. These techniques are fully described in the literature. Reagents and materials are commercially available unless specifically stated to the contrary.

Methods of making contact lenses, such as neohydrogenated hydrogel contact lenses, are described in U.S. Patent Nos. 4,121,896, 4,495,313, 4,565,348, 4,640,489, 4,889,664, 4,985,186, 5,039,459. , Nos. 5,080,839, 5,094,609, 5,260,000, 5,607,518, 5,760,100, 5,850,107, 5,935,492, 6,099,852, 6,367,929, 6,822,016, 6,867,245, 6,869,549, No. 6,939,487 and U.S. Patent Publication Nos. 20030125498, No. 20050154080, and No. 20050191335.

In the following examples, while efforts have been made to ensure accuracy with respect to the numbers used (eg, amount, temperature, etc.), certain experimental errors and deviations should still be addressed. Unless otherwise indicated, the temperature is in °C and the pressure is at or near atmospheric pressure at sea level.

The following well-known chemical substances are mentioned in the examples, and in some cases, are mentioned by the abbreviations proposed below.

Substance and method

Abbreviation AE: allyloxyethanol DI: deionized HEMA: 2-hydroxyethyl methacrylate IPA: isopropanol MMA: methyl methacrylate M3U: M3-U; α-ω-bis (methacryl醯Ethoxyethyliminocarboxycarbonylpropyl)-poly(dimethyloxane)-poly(trifluoropropylmethyloxirane)-poly(ω-methoxy-poly(B) Glycol) propylmethyl decane; dimethyl methacrylate oxime macromonomer

The M3U used in the following examples is represented by the following formula, wherein n is 121, m is 7.6, h is 4.4, p is 7.4, and Mn = 12,800, and Mw = 16,200 (Asahikasei Aime Co., Ltd., Japan).

M3U coloring: dispersion of β copper phthalocyanine in M3U (% by weight). Copper phthalocyanine is available from BASF as Heliogen Blue K7090. N,N-DMF:DMF; N,N-dimethylformamide NVP: 1-vinyl-2-pyrrolidone (fresh distillation under vacuum) PDMS: polydimethyloxane PDMS-total PEG: block copolymer of polydimethylsiloxane and PEG, which contains 75% PEG and MW 600 (DBE712 from Gelest) PEG: polyethylene glycol PP: propyl propylene Pr: propanol TEGDMA: two Triethylene glycol methacrylate TEGDVE: triethylene glycol divinyl ether TPO: biphenyl (2,4,6-trimethyl benzhydryl) phosphine oxide TPTMA: trimethylolpropane trimethacrylic acid Ester UV416: 2-(4-Benzylmercapto-3-hydroxyphenoxy)ethyl acrylate Vazo-52: 2,2'-azobis(2,4-dimethylvaleronitrile) (V-52 ; thermal initiator) Vazo-64: azobisisobutyronitrile (V-64; thermal initiator) VMA: N-vinyl-N-methylacetamide (fresh distillation under vacuum) VM: methacrylic acid Vinyl ester

Method of characterizing eyeglass products

Advancing contact angle/reverse contact angle The advancing contact angle can be determined using conventional methods known to those skilled in the art. For example, a conventional drop shape method, such as a sessile drop method or a trapped bubble method, can be used to measure the anterior contact angle and receding contact angle of the contact lenses provided herein. The Kruss DSA 100 appliance (Kruss GmbH, Hamburg) can be used for the front and back water contact angles of the deoxygenated hydrogel contact lenses and as DABrandreth: "Dynamic contact angles and contact angle hysteresis", Journal of Colloid and Interface Science, Vol. 62 , 1977, pp. 205-212 and R. Knapikowski, M. Kudra: Kontaktwinkelmessungen nach dem Wilhelmy-Prinzip-Ein statistischer Ansatz zur Fehierbeurteilung", Chem. Technik, Vol. 45, 1993, pp. 179-185 and US Patent Measured as described in 6,436,481.

For example, the advancing contact angle and the receding contact angle can be determined using a trapped bubble method using phosphate buffered physiological saline (PBS; pH = 7.2). The glasses were tiled on the quartz surface and rehydrated with PBS for 10 minutes prior to testing. Air bubbles are placed on the surface of the glasses using an automatic injection system. The bubble size can be increased and decreased to obtain a receding angle (a platform is obtained when the bubble size is increased) and an advancing angle (a platform is obtained when the bubble size is reduced).

Modulus The modulus of the mirror body can be determined using conventional methods known to those skilled in the art. For example, a contact lens having a width of about 4 mm can be cut from the center portion of the lens, and the tensile modulus (unit: MPa) can be at least 75% humidity at 25 ° C by using Instron 3342 (Instron Corporation). The initial slope of the stress-strain curve obtained by tensile testing at a rate of 10 mm/min in air was measured.

Ion Current The ion current of the lens body of the glasses of the present invention can be determined using conventional methods known to those skilled in the art. For example, the ion current of the contact lens or lens body can be measured using a technique substantially similar to the "Ionoflux Technique" described in U.S. Patent No. 5,849,811. For example, the spectacles to be measured can be placed between the convex and concave portions of the device that retains the spectacles. The male and female portions include a flexible sealing ring between the eyeglasses and each of the male or female portions. After positioning the glasses in the device that holds the glasses, the device that retains the glasses is placed in a threaded cover. Screw the cover onto the glass tube to define the material chamber. The raw material chamber can be filled with 16 ml of a 0.1 molar concentration of NaCl solution. The receiving chamber can be filled with 80 ml of deionized water. The wire of the conductivity meter is immersed in deionized water in the receiving chamber and a stir bar is added to the receiving chamber. The receiving chamber was placed in an incubator and the temperature was maintained at approximately 35 °C. Finally, the material substance chamber is immersed in the receiving chamber. The conductivity measurement can be performed every two minutes starting from 10 minutes after the raw material chamber is immersed in the receiving chamber for about 20 minutes. The relationship between conductivity and time should be substantially linear.

Oxygen Permeability The Dk of the lenses of the present invention can be determined using conventional methods generally known to those skilled in the art. For example, the Dk value can be determined using the Mocon method as described in U.S. Patent No. 5,817,924. The Dk value can be determined using a commercially available instrument of the Mocon Ox-Tran System model name.

Equilibrium Water Content The water content of the lenses of the present invention can be determined using conventional methods generally known to those skilled in the art. For example, a hydrated hydrogel hydrogel contact lens can be removed from an aqueous liquid, wiped to remove excess surface water, and weighed. The weighed glasses can then be dried in an oven at 80 ° C in vacuum and the dried glasses can then be weighed. The weight difference was determined by subtracting the weight of the dry glasses from the weight of the hydrated glasses. The water content (%) is (weight difference / hydration weight) × 100.

Example 1 Preparation of low modulus polymerizable silicone hydrogel contact lens precursor composition

The polymerizable silicone hydrogel contact lens precursor composition was prepared using the reagents and relative amounts specified below. Due to the low modulus of the resulting hydrated contact lens product, this formulation is referred to herein as a "low modulus formulation" or "LMF."

The components in Table 1 were weighed and mixed to form a mixture. The mixture was filtered into vials via a 0.2-20.0 micron syringe filter and stored for up to about 2 weeks. (This mixture is referred to herein as a polymerizable silicone hydrogel contact lens precursor composition). In Table 1, each unit amount of each compound is provided in addition to the respective weight percentages (expressed by weight/weight; weight ratio).

In the final oxime hydrogel contact lens, the percentage of each chemical component is more closely related to the unit amount present in the composition than the corresponding weight percentage.

Example 2 Manufacture of hydrogenated hydrogel contact lenses

A large number of precursor compositions from Example 1 were degassed using a repeated vacuum/nitrogen rinse procedure. The degassed precursor composition is then placed into a concave non-polar resin mold member. The filled female mold member is then closed by contact with a non-polar resin male mold member under the pressure required to achieve a tight fit. The curing was then carried out in a nitrogen batch oven in the following cycle: 30 min N ₂ purification at room temperature, 30 min at 55 ° C and 60 min at 80 ° C. Demolding is performed by tapping a concave mold member of the contact lens mold such that the male mold member is released therefrom, wherein the polymeric oxygenated hydrogel contact lens product adheres to the male mold member. The mirror is removed by a floatation method or using a mechanical lens removal device. The floatation method involves soaking a convex mold member containing dry glasses in a bucket of water. The glasses typically leave the mold in about 10 minutes. The compressed gas is interposed between the contact lens product and the rotating male mold member by compressing and rotating the polymeric oxygenated hydrogel contact lens product to which the convex mold member is adhered, and applying a vacuum to the exposed surface of the contact lens product Perform mechanical removal. The separated spectacles are then loaded onto a plastic tray for extraction and hydration.

The spectacles containing the polymerized hydrogel contact lens product were immersed in a solvent liquid (such as industrial methylated spirit (IMS) containing 95% ethanol and 5% methanol) for 45 min at room temperature. The solvent was then drained and replaced with fresh IMS and the procedure was repeated with IMS (3 times), 1:1 alcohol/water (3 times) and DI water (3 times).

The hydrated spectacles are stored in a glass vial or blister pack containing DI water or stored in phosphate buffered physiological saline at a pH of 7.1-7.5. The sealed vessel autoclave was treated at 121 ° C for 30 min. After 24 hours of autoclaving, glasses were measured.

The resulting hydrated hydrogel hydrogel contact lenses were weighed and then dehydrated in an oven and weighed again to determine the dry weight of the dehydrated hydrogel hydrogel contact lens.

Spectacle characteristics such as contact angle (including dynamic contact angle and static contact angle), oxygen permeability, ion current, modulus, elongation, tensile strength, water content, and the like are determined as described herein. The wettability of the hydrated hydrogel hydrogel contact lens is also detected by measuring the water dispersing time of the glasses.

Eye compatibility was further tested during the dispensing study, where the contact lenses were placed on the human eye for 1 hour, 3 hours, or 6 hours or longer, and then clinical evaluation was performed.

The oxygenated hydrogel contact lenses produced from the formulations of the present invention have an ophthalmically acceptable surface wettability. The hydroxyl hydrogel contact lenses have an equilibrium water concentration (EWC) of 44 +/- 2% and have been determined to have an extractables content of 48.9 +/- 0.7%.

The resulting hydrated contact lens has the following characteristics:

In the final glasses, after the extraction procedure, most, if not all, of the eucalyptus oil is extracted with the unreacted monomer or linear polymer component. In this example, no eucalyptus oil was detected after extraction.

A series of lenses were prepared for clinical evaluation. Spectacles were prepared from the precursor composition as described in Example 1. The batch of glasses was characterized and had the following characteristics.

In each of the above tables, the GPC value is the relative reading of the residual removable content after extraction and hydration. Chloroform was used as the final extraction solvent to contact the previously extracted contact lenses, and the total residual/extractable content after extraction and hydration was in the range of about 0.4% to 2%. For each set of glasses, 3 to 5 replicate samples were measured.

Example 3 Preparation of fine-tuning low modulus polymerizable silicone hydrogel contact lens precursor composition

The polymerizable silicone hydrogel contact lens precursor composition was prepared using the reagents and amounts specified below. This formulation is referred to herein as a "fine-tuned low modulus formulation" or "MLMF" due to the low modulus and low batch-to-batch variation in the resulting hydrated hydrogel hydrogel contact lens product.

The components in Table 4 above were weighed and mixed to form a mixture. The mixture was filtered into a vial via a 0.2-5.0 micron syringe filter and stored for up to about 2 weeks.

The precursor composition differs from the precursor composition described in Example 1 in that AE is included in the oyster oil component. The AE is added to the eucalyptus oil, after which the eucalyptus oil is mixed with other chemical agents contained in the precursor formulation, and is advantageously used to reduce the variability in the size and physical properties of the resulting hydrated contact lens product.

The dispensing of the contact lenses was carried out essentially as described in Example 2 above. The resulting hydrated contact lens has physical properties similar to those described in Example 2, with the following advantageous exceptions - the variability of either or both of the spectacles diameter, EWC, and ion current is generally lower than in the absence of AE Their variability in the formulations prepared.

Example 4 Preparation of a finely tuned low modulus polymerizable hydrogel contact lens precursor composition containing varying amounts of allyloxyethanol and characterization of the resulting hydroxyl hydrogel contact lens product

The following experiment was conducted to further investigate the effect of adding varying amounts of allyloxyethanol to the eucalyptus oil to thereby reduce batch variations in size and physical properties in the final extracted hydrated contact lens product.

A monomer mixture (polymerizable hydroxyl hydrogel precursor composition) was prepared as described in Examples 1 and 3. The formulation components were the same as those described in Example 1 above, with the exception that the extractable emu oil component contained various amounts of allyloxyethanol in the emu oil as appropriate: 0, 2, 4 and 6%. Details of the formulations are provided in Tables 4 and 5 below. Various amounts of allyloxy alcohol were added to each of the three different grades of Gelest.

The monomer mixture is filtered and degassed, dispersed on the lens forming surface of the concave polypropylene contact lens mold member, and the male mold member is engaged with the female mold member to form a monomer mixture in the contact lens-like chamber Contact lens mold. The tool has an EF (expansion coefficient) of about 1.1% or an outer diameter of the steel contact lens mold insert of about 14.3 mm. Curing was carried out under N ₂ in a batch oven. The filled mold is typically placed in a N ₂ batch oven and purged with N _{2 for} 30 min to reduce the oxygen content to less than 1000 ppm, followed by the first heating to 55 ° C for 30 min, followed by heating to 80 ° C. It lasted 60 minutes.

After curing, demolding and mirror removal were performed on a benchtop stripper. All formulations of the glasses showed good release/off mirror characteristics.

The dry glasses were loaded in a polypropylene pan, and successively washed with ethanol, ethanol-water and water for about 30 minutes to extract and hydrate, and contacted with hot water. The extracted and hydrated lenses were then placed in vials containing pH 7.2 PBS buffer (containing surfactant) and autoclaved.

The glasses were measured and inspected one day after the autoclave treatment. Only the dimensions and physical properties of undeformed glasses are measured, including diameter, base curve, equilibrium water content, static and dynamic contact angles, tensile properties (modulus, tensile strength and elongation), and ion current.

result

Studying the addition of various amounts of allyloxyethanol to eucalyptus oil as one (i) reducing the difference between batches in the resulting extracted/hydrated hydrogel hydrogel contact lens product, and (ii) providing the desired size And the way physical contact lenses are used.

The diameter and physical properties of the autoclave after extraction of the hydrated contact lenses are provided in Table 7. The relationship between diameter, equilibrium water content, and ion current and allyloxyethanol content are shown in Figures 4, 5 and 6, respectively.

As shown in Figure 3, 25 parts of the eucalyptus/AE mixture were used in all three formulations (Series A1, B1 and C1); the diameter of the spectacles decreased as the AE content in the mixture increased. Each series corresponds to a contact lens prepared from a given article of eucalyptus oil, wherein the eucalyptus oils used in each series A1, B1 and C1 are different.

Glasses produced in Series A are larger than those produced in Series B or C. Early clinical trials using 25A glasses without the addition of AE's Series A enamel resulted in glasses with relatively high rates of dehydration staining, while glasses made from Series C oysters had a more satisfactory (lower) dehydration dyeing rate. . Therefore, it is desirable to determine that the efficacy of Series A No. 矽 oil should be increased to achieve even more desirable spectacles clinical characteristics. (It is believed that the potency of a particular batch of polyoxyalkylene oxime (e.g., eucalyptus) is its ability to produce a final extracted hydrated spectacles product having a reduced diameter from the contact lens mold used at a given concentration. Final spectacles product The greater the reduction in the diameter of the lens, the greater the effectiveness of the polyoxyalkylene oxime. Especially preferred is the enamel which produces the final spectacles product having a diameter in the range of 0.98 to 1.02 times the diameter of the contact lens mold used. For example, referring to Figure 3, the addition of 4% AE to the Series A oil number produces a lens diameter substantially the same as the diameter of the glasses produced by the Series C oil number prior to the addition of allyloxyethanol.

As shown in Table 6, and illustrated in Figures 4 and 5, respectively, similar trends such as EWC% and ion flow characteristics were observed.

Thus, the addition of a chain transfer agent, such as the exemplary allyloxyethanol used in this example, to the polyoxyalkylene oxime extractable component effectively fine-tunes or "fine-tunes" the precursor composition to provide similar beneficial physical properties. The ability to ultimately oxidize contact lens products. Particularly preferred are extracted hydrated contact lenses having an equilibrium water content in the range of from about 40% to about 50%, an ion current in the range of from about 2 to about 5, and a modulus of less than about 1.2 MPa.

As indicated earlier, the SO of the 5 L batch can be adjusted by adding 4% AE. As for SO batches 10627 and 11038, it already has high performance, and therefore only 0.1% of AE is added for fine tuning. To further confirm this fine tuning concept, 4% AE was added to the SO 5L batch and 0.1% AE was added to the SO 10627 batch. Two batches of M3U were used to make 25C glasses with 20, 23, 26 and 29 parts of fine-tuned SO (or SO/AE mixture) as listed in Table 5. The characteristics of the glasses are listed in Table 8.

The relationship between the diameter of the glasses and the SO content is shown in Figures 6 and 7. The diameter of the glasses decreases as the SO load increases, which is mainly due to the dilution effect of SO. The higher the diluent loading, the greater the amount of material removed after extraction and, therefore, the smaller the diameter of the final lens. Based on the diameter data of 20% and 29% of the eucalyptus oil load, it can be seen that the performance of the two fine-tuning oyster sauces is almost the same. These results demonstrate that the addition of 4% AE to the emu oil extractable component effectively "fine tune" or fine tune the exemplary extractable component SO 5L to match the efficacy of SO 10627 containing only 0.1% AE.

Turning now to the exemplary fluorine-containing dimethyl methacryloyloxyl macromonomer M3U, the data indicates that for different batches of M3U, the diameter of the spectacles varies within about 0.2 mm. As can be seen in Figures 6 and 7, the slope of D versus %SO is about -0.06 mm/% SO. With the extrapolation of this data, in order to provide glasses with similar diameters, an SO (preconditioning) content of about 25% ± 4% is selected.

The general relationship between the diameter and ion current and equilibrium water content of all 25C formulations listed in Table 6 is shown in Figure 8. Referring to Figure 8, there is a strong correlation between diameter and water content, and there is also a strong correlation between ion current and water content. Therefore, based on this figure, it is apparent that the ion current can generally be predicted based on the equilibrium water content.

It will be appreciated by those skilled in the art <RTIgt;a</RTI> that the various modifications and other embodiments of the present invention have the benefit of the teachings presented in the foregoing description. Therefore, it is understood that the invention is not limited to the specific embodiments disclosed herein, such as the embodiments presented by the examples. The exemplified embodiments are to be considered as illustrative of the embodiments of the invention. Although specific terms are employed herein, they are used in a generic and descriptive sense only and not limiting.

A large number of publications and patents have been cited above. The cited publications and patents are each incorporated herein by reference in their entirety.

102. . . Place

104. . . Closed

106. . . Curing

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112. . . extraction

114. . . Hydration

116. . . Package

118. . . Sealing and sterilization

202. . . Polymerizable silicone hydrogel lens precursor composition

204. . . Pre-extracted polymeric helium hydrogel contact lens product

206. . . Extracted Hydrogen Hydrogel Contact Lens Products

208. . . Hydrated helium hydrogel contact lens

1 is a block diagram illustrating an exemplary method of producing a helium oxygen hydrogel contact lens.

2 is a block diagram illustrating the composition, lens product, and contact lens of the present invention.

Figure 3 is a graph showing the effect of increasing the allyloxyethanol content in the polyoxyalkylene oxide used as the extractable component for forming a helium oxygen hydrogel contact lens and the resulting extracted hydration autoclave as described in Example 4. A graph of the relationship of the diameter of the contact lens product after treatment.

Figure 4 is a graph showing the effect of increasing the allyloxyethanol content in the polyoxyalkylene oxide used as the extractable component for forming a helium oxygen hydrogel contact lens and the obtained extracted hydration autoclave as described in Example 4. A graph of the equilibrium water content of the contact lens product after treatment.

Figure 5 is a graph showing the effect of increasing the allyloxyethanol content in the polyoxyalkylene oxide used as the extractable component for forming a helium oxygen hydrogel contact lens and the resulting extracted hydration autoclave as described in Example 4. A graph of the ion flux of the contact lens product after treatment.

Figure 6 is a graph showing the diameter (mm) of the extracted hydrated contact lens and the polymerizable precursor composition using a specific fluorine-containing dimethyl propylene fluorenyloxyl macromonomer (storage period 3 MU) as described in Example 4. A graph of the relationship between the exemplary polyoxyalkylene oxime/allyloxyethanol extractable components.

Figure 7 shows the exemplification of the diameter (mm) of the extracted hydrated contact lens and the polymerizable precursor composition using a specific fluorine-containing dimethyl propylene fluorenyloxyl macromonomer (yellow M3U) as described in Example 4. The relationship between the percentage of extractable components of polyoxyalkylene oxime/allyloxyethanol.

Figure 8 is a graph showing the diameter and ion current of the final extracted hydrated contact lens product produced by various polymerizable precursor compositions having an equilibrium water content and a percentage change from the polyoxyalkylene oxime/allyloxyethanol extractable component, respectively. General relationship curve.

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118. . . Sealing and sterilization

Claims (38)

A polymerizable silicone hydrogel contact lens precursor composition comprising (i) from about 25% to about 35% by weight of a reactive fluorine-containing dimethyl propylene sulfonium oxy macromonomer And (ii) at least 45% by weight of a monomer composition free of barium, and (iii) a polyoxyalkylene oxide extractable component, wherein the monomer composition containing no antimony comprises one or more monomers, The monomer has at least one polymerizable double bond and at least one hydrophilic functional group. The polymerizable silicone hydrogel contact lens precursor composition of claim 1, wherein the polymer lens precursor composition further comprises an ultraviolet absorber and a color former. The polymerizable silicone hydrogel contact lens precursor composition of claim 1 which comprises from about 10% to about 30% by weight of the polyoxyalkylene oxide extractable component. The polymerizable hydroxyl hydrogel contact lens precursor composition of claim 1, wherein the reactive fluorine-containing dimethyl propylene fluorenyl oxime macromonomer is α-ω-bis(methacryloxyloxy) Ethylimidocarboxyethoxypropyl)-poly(dimethyloxane)-poly(trifluoropropylmethyloxirane)-poly(ω-methoxy-poly(ethylene glycol) Propylmethyl decane) (M3U). The polymerizable silicone hydrogel contact lens precursor composition of claim 1, wherein the antimony-free monomer composition comprises N-vinyl-N-methylacetamide, methyl methacrylate, and Triethylene glycol methacrylate. The polymerizable hydrogel contact lens precursor composition of claim 1, wherein the polyoxyalkylene oxime extractable component further comprises a chain transfer Agent. The polymerizable silicone hydrogel contact lens precursor composition of claim 6, wherein the chain transfer agent is allyloxyethanol. The polymerizable silicone hydrogel contact lens precursor composition of claim 7, wherein the polyoxyalkylene oxide extractable component comprises from about 0.1 to 6 parts of allyloxyethanol and from about 99.9 to 94 parts of polyoxyalkylene. Oxygen. The polymerizable silicone hydrogel contact lens precursor composition of claim 1, wherein the polyoxyalkylene oxide extractable component comprises a dimethyloxane-ethylene oxide block copolymer. The polymerizable silicone hydrogel contact lens precursor composition of claim 9, wherein the polyoxyalkylene oxide extractable component comprises a dimethyloxane (75% ethylene oxide) block copolymer. The polymerizable silicone hydrogel contact lens precursor composition of claim 1 further comprising an initiator. A polymerizable silicone hydrogel contact lens precursor composition comprising α-ω-bis(methacryloxyethyliminocarboxycarbonylpropyl)-poly(dimethyloxane) )-poly(trifluoropropylmethyloxirane)-poly(ω-methoxy-poly(ethylene glycol)propylmethyl decane), N-vinyl-N-methylacetamide The component may be extracted by methyl methacrylate and triethylene glycol dimethacrylate and dimethyl decane-ethylene oxide block copolymer. The polymerizable silicone hydrogel contact lens precursor composition of claim 12, wherein the extractable component comprises a dimethyloxysiloxane (75% ethylene oxide) block optionally combined with allyloxyethanol. Copolymer. Polymerizable silicone hydrogel contact lens precursor composition as claimed in claim 12 , wherein α-ω-bis-(methacryloxyethylethyleniminocarboxyethoxypropyl)-poly(dimethyloxane)-poly(trifluoropropylmethyloxirane) )-Poly(ω-methoxy-poly(ethylene glycol) propylmethyl decane) with N-vinyl-N-methylacetamide, methyl methacrylate and triethyl methacrylate The ratio of the combination of glycol esters is in the range of from about 0.55 to about 0.65 by weight. A polymerizable silicone hydrogel contact lens precursor composition according to claim 14 which comprises α-ω-bis(methacryloxyethyliminocarboxycarbonylpropyl)-poly(dimethyl Alkyloxane)-poly(trifluoropropylmethyloxirane)-poly(ω-methoxy-poly(ethylene glycol)propylmethyl decane), N-vinyl-N-A Ethyl amide, methyl methacrylate, triethylene glycol dimethacrylate, 2-hydroxy-4-propenyloxy ethoxybenzophenone, phthalocyanine blue, thermal initiator and dimethyl A decane (75% ethylene oxide) block copolymer, optionally combined with allyloxyethanol. A method of producing a polymerizable silicone hydrogel contact lens precursor composition, the method comprising: (i) combining at least 25% by weight of a reactive fluoropropenyl fluorene macromonomer, (ii) at least 45 And iii) a polyoxyalkylene oxime oxygen extractable component, wherein the hydrazine-free hydrophilic component comprises one or more monomers, the monomer having at least one The polymeric double bond and at least one hydrophilic functional group are thereby utilized to produce a polymerizable hydrogel contact lens precursor composition. The method of claim 16, wherein in the combining step, the reactivity comprises The amount of the fluoropropylene fluorenyl oxime macromonomer ranges from about 25% by weight to about 35% by weight, or the amount of the hydrazine-free hydrophilic component ranges from about 45% by weight to about 55% by weight. Or the amount of the polyoxyalkylene oxime extractable component is in the range of from about 10% by weight to 30% by weight, and a combination of the above conditions. The method of claim 16, wherein the reactive fluoropropenyl fluorenyloxy macromonomer is α-ω-bis(methacryl oxiranylethylimidocarboxyethoxypropyl)-poly (two) Methyl methoxyoxane)-poly(trifluoropropylmethyloxirane)-poly(ω-methoxy-poly(ethylene glycol) propylmethyl decane) (M3U). The method of claim 16, wherein the hydrazine-free hydrophilic component comprises N-vinyl-N-methylacetamide, methyl methacrylate, and triethylene glycol dimethacrylate. The method of claim 16, wherein the polyoxyalkylene oxime extractable component further comprises a chain transfer agent. The method of claim 16, wherein the combining step further comprises an initiator. A method of producing a polymerizable silicone hydrogel contact lens precursor composition, the method comprising: combining alpha-omega-bis(methacryloxyethyliminocarboxycarbonylpropyl)-poly( Dimethyl oxane)-poly(trifluoropropylmethyl decane)-poly(ω-methoxy-poly(ethylene glycol) propylmethyl decane), N-vinyl-N -methylacetamide, methyl methacrylate and triethylene glycol dimethacrylate and dimethyloxane-ethylene oxide block copolymer extractable components to thereby produce polymerizable oxygen Hydrogel contact lens precursor combination Things. The method of claim 22, wherein the extractable component comprises a dimethyloxysiloxane (75% ethylene oxide) block copolymer optionally combined with allyloxyethanol. The method of claim 23, wherein the relative amount of allyloxyethanol and dimethyloxane (75% ethylene oxide) is from about 0.1 part to about 5 parts of allyloxyethanol and from about 99.9 parts to about 95 parts. Within the range of methyl oxane (75% ethylene oxide). The method of claim 22, wherein the combining step further comprises a thermal initiator. The method of claim 22, wherein α-ω-bis-(methacryloxyethyl iminocarboxyethoxypropyl)-poly(dimethyloxane)-poly(trifluoropropyl) Methyl decane)-poly(ω-methoxy-poly(ethylene glycol) propylmethyl decane) with N-vinyl-N-methylacetamide, methyl methacrylate and The ratio of the combination of triethylene glycol methacrylate is in the range of from about 0.55 to about 0.65 by weight. A method of producing a polymerizable silicone hydrogel contact lens precursor composition, the method comprising: combining alpha-omega-bis(methacryloxyethyliminocarboxycarbonylpropyl)-poly( Dimethyl oxane)-poly(trifluoropropylmethyl decane)-poly(ω-methoxy-poly(ethylene glycol) propylmethyl decane), N-vinyl-N -methylacetamide, methyl methacrylate, triethylene glycol dimethacrylate, 2-hydroxy-4-propenyloxyethoxybenzophenone, phthalocyanine blue, thermal initiator and a methyl oxane (75% ethylene oxide) block copolymer, optionally containing allyloxyethanol, Thereby a polymerizable oxygenated hydrogel contact lens precursor composition is produced. The method of claim 27, further comprising polymerizing the polymerizable lens precursor composition to form a pre-extracted polymeric hemohydrogel contact lens. The method of claim 28, further comprising placing the polymerizable lens precursor composition in a non-polar resin contact lens mold prior to the step of polymerizing. The method of claim 28, further comprising extracting the pre-extracted polymeric contact lens to form an extracted polymeric lens product free of extractable components, and hydrating the extracted polymeric lens product to form a helium oxygen hydrogel contact lens . A method of improving the efficacy of a dimethyloxane-ethylene oxide block copolymer for use in the preparation of a hydrogel gel contact lens, the method comprising: from about 0.1% to about 10% by weight of an allyloxy group Ethanol is added to the dimethyloxane-ethylene oxide block copolymer to provide an allyloxyethanol-dimethyloxane oxyethylene block copolymer for use in the preparation of a hydroxyl hydrogel contact lens product. A helium oxygen hydrogel contact lens comprising a polymeric hemohydrogel contact lens polymerized from a polymerizable lens precursor composition, the precursor composition comprising a helium oxygen macromonomer, free of bismuth a monomer composition, an allyloxyethanol as a chain transfer agent at the time of polymerization, a polymerization initiator, and a UV absorber and/or a colorant, wherein the oxime macromonomer and the ruthenium-free monomer combination At least one of the materials comprises at least two polymerizable groups. The oxygenated hydrogel contact lens of claim 32, wherein the precursor composition comprises an amount of allyloxyethanol effective to produce an expansion coefficient in the range of from about 0.90 to about 1.10, in the extraction of the extractable component. Hydrated hydrogel hydrogel contact lens product. The oxime hydrogel contact lens of claim 32, wherein the oxime macromonomer comprises a reactive fluorodimethacryl oxime oxime macromonomer. The oxime hydrogel contact lens of claim 32, wherein the bismuth-free monomer composition comprises one or more monomers having at least one polymerizable double bond and at least one hydrophilic functional group. The oxygenated hydrogel contact lens of claim 32, wherein the contact lens has an equilibrium water content of at least about 40% and an oxygen permeability of about 90-120 barrer (D _k × 10 ^-11 ), further comprising a Or a plurality of features selected from the group consisting of: the surface contact angle of the lens is from about 70° to about 75°, the tensile modulus is less than about 0.7 MPa, and the ion current is about 1.5-5 (×10 ^-3). Mm ² /min). The oxygenated hydrogel contact lens of claim 32, wherein the contact lens is unsurface treated. The oxygenated hydrogel contact lens of claim 32, wherein the contact lens is unsurfaced, the contact lens being an interpenetrating polymer network having no humectant, the contact lens being invisible from a non-polar resin base The lens mold is molded, and a combination of the above conditions.