CN101473263B - Wettable silicone hydrogel contact lenses and related compositions and methods - Google Patents

Abstract

Silicone hydrogel contact lenses having ophthalmically acceptable surface wettabilities are obtained from pre-extracted polymerized silicone hydrogel contact lens products having relatively large amounts of removable or extractable materials. The silicone hydrogel contact lenses can be obtained from non-polar resin based contact lens molds and without surface treatments or an interpenetrating polymeric network of a polymeric wetting agent. Related lens products, polymerizable compositions, and methods are also described.

Description

Wettable silicone hydrogel contact lenses and related compositions and methods

Related Application Cross-References

This application asserts U.S. Patent Application No. 60/804,911 filed June 15, 2006, U.S. Patent Application No. 60/887,513 filed January 31, 2007, and U.S. Patent Application No. 60/887,513 filed March 13, 2007 Application Serial No. 60/894,609 and US Patent Application Serial No. 11/761,272, filed June 11, 2007, each of which is incorporated herein by reference in its entirety.

technical field

The present invention is particularly directed to silicone hydrogel ophthalmic devices and related compositions and methods. More specifically, the present invention relates to molded wettable silicone hydrogel contact lenses and related compositions and methods.

Background technique

Silicone hydrogel contact lenses have gained popularity due to the ability of contact lens wearers to keep the lenses on their eyes for a longer period of time than non-silicone hydrogel contact lenses. For example, silicone hydrogel contact lenses may be worn or prescribed as daily, weekly, biweekly, or monthly wear, depending on the particular lens. Wear biweekly or monthly. The benefits to lens wearers associated with silicone hydrogel contact lenses can be attributed, at least in part, to the combination of the hydrophilic component and the hydrophobic nature of the silicone polymer-containing material of the contact lens.

Non-silicone hydrogel contact lenses (such as those based on 2-hydroxyethyl methacrylate (HEMA)) are often used in non-polar resin contact lens molds (such as contact lens molds produced from polyolefin-based resins) produced in. Lens precursor compositions for non-silicone hydrogel contact lenses are polymerized in non-polar resin contact lens molds to produce HEMA-based polymerized lens products. Due to the hydrophilic nature of the polymeric components of HEMA-based contact lenses, HEMA-based lenses are ocularly compatible and have ophthalmically acceptable surface wettability even though produced using non-polar resin molds.

In contrast, existing silicone hydrogel contact lenses obtained from nonpolar resin molds have hydrophobic lens surfaces. In other words, the surface of the silicone hydrogel contact lens has low wettability and thus is not ophthalmically compatible or acceptable. For example, the silicone hydrogel contact lenses can be associated with less desirable characteristics such as increased lipid deposition, protein deposition, bonding of the lens to the eye surface, and general irritation to the lens wearer.

In an effort to overcome these problems, attempts have been made to employ surface treatments or surface modifications of silicone hydrogel contact lenses or lens products to increase the hydrophilicity and wettability of the lens surface. Examples of surface treatments of silicone hydrogel lenses include coating the lens surface, adsorbing chemicals onto the lens surface, and changing the chemical properties or electrostatic charges of chemical groups on the lens surface. Surface treatments have been described that include the use of plasma gases to coat polymeric lens surfaces, or the use of plasma gases on contact lens mold surfaces to treat the molds and then form polymeric lenses. Unfortunately, several disadvantages are associated with this approach. Surface treatment of contact lenses requires more machinery and time to produce contact lenses than manufacturing methods that do not use surface treatment or modification. Furthermore, surface-treated silicone hydrogel contact lenses can exhibit reduced surface wettability when the lenses are worn and/or handled by the lens wearer. For example, increased handling of surface-treated eyeglasses can lead to degradation or abrasion of the hydrophilic surface.

Another approach to increasing the wettability and ocular compatibility of silicone hydrogel lenses is to polymerize the silicone hydrogel contact lens precursor in the presence of a second composition comprising a polymeric wetting agent such as polyvinylpyrrolidone (PVP) combination. Lenses of this type are referred to herein as silicone hydrogel contact lenses with polymeric internal wetting agents, and typically comprise an interpenetrating polymer network (IPN) comprising a high molecular weight polymer such as PVP. As understood by those of ordinary skill in the art, IPN refers to the combination of two or more different polymers in the form of a network, wherein at least one polymer is synthesized and/or crosslinked in the presence of another polymer, and the two There is no covalent bond between them. An IPN can consist of two chains forming two independent but contiguous or interpenetrating networks. Examples of IPNs include step IPNs, synchronous IPNs, half IPNs, and uniform IPNs. While silicone hydrogel contact lenses including the polymeric wetting agent IPN avoid problems associated with surface treatments, the lenses may not retain their ocular compatibility, including surface wettability, over extended periods of time. For example, since internal wetting agents are not covalently bound to form other components of the polymeric lens, they may leach from the lens when worn by the lens wearer, and thus lead to reduced surface wettability and Increased discomfort in glasses wearers.

As an alternative to surface treatment or the use of polymeric wetting agents IPN as described above, it has been found that polar resin molds can be used instead of non-polar resin molds to produce silicone hydrogel contact lenses with ophthalmically acceptable surface wettability. For example, silicone hydrogel contact lenses formed in ethylene-vinyl alcohol-based or polyvinyl alcohol-based molds have the desired surface wettability. An example of a polar resin suitable for use in the manufacture of contact lens molds for producing unsurface-treated silicone hydrogel contact lenses without the polymeric wetting agent IPN is an ethylene-vinyl alcohol copolymer resin, such as that produced by Nippon Gosei Kagaku Kogyo Co., Ltd. Ethylene-vinyl alcohol copolymer resin sold under the trade name SOARLITE ^™ by Nippon Gohsei, Ltd. In addition to its polarity, Solit ^™ is described as having the following characteristics: extremely high mechanical strength, antistatic properties, low shrinkage when used in the molding process, good oil and solvent resistance, small coefficient of thermal expansion and good wear resistance.

While Solit ^™ -based molds offer an advantageous alternative for producing ophthalmically compatible silicone hydrogel contact lenses without the use of surface treatments or the polymeric wetting agent IPN, Solit ^™ molds are comparable to non-polar resin molds. (such as polypropylene molds) are less deformable or flexible, and are relatively more difficult to handle than non-polar resin molds.

From the above, it can be seen that there is a need for ophthalmically compatible silicone hydrogel contact lenses that are easier to produce than those obtained from Solit ^™ contact lens molds and that do not require surface treatment or the use of polymeric wetting agents IPN (including PVP IPN) for eye compatibility. Furthermore, it would be highly desirable to provide a method of producing eye-compatible silicone hydrogel contact lenses, such as silicone hydrogel contact lenses with eye-compatible surface wettability, from non-polar resin or polyolefin-based contact lens mold members, The method overcomes the disadvantages of existing manufacturing methods. That is, there is a need for an improved process for preparing ophthalmically compatible silicone hydrogel contact lenses that requires neither surface treatment of the resulting contact lens product nor the use of polymeric wetting agents IPN as prepolymerizable silicone hydrogel contact lenses. part of the body composition to provide eyewear products with features that contribute to long-term comfort. The present invention meets these needs.

Contents of the invention

The contact lenses, lens products, compositions and methods of the present invention address needs and problems associated with existing silicone hydrogel contact lenses and current methods of production thereof. It has surprisingly been found that ophthalmically compatible silicone hydrogel contact lenses are obtained by combining certain components to provide, after polymerization, a pre-extracted polymerized silicone hydrogel contact lens product having one or more particularly desirable characteristics. It can be obtained by polymerizing the composition. In one or more embodiments, prior to extraction, the hydrogel contact lens product has about 10% by weight or more extractable components. In certain embodiments, the silicone hydrogel contact lens product prior to extraction has an extractables content of at least about 20% by weight. For example, the silicone hydrogel contact lens product prior to extraction can have an extractables content of from about 22% to about 30% by weight. In at least one specific embodiment, the silicone hydrogel contact lens product prior to extraction has an extractables content of about 26% by weight. In one or more embodiments of the inventive products and methods, provided herein is a silicone hydrogel contact lens product that does not employ polyalkylene silica extractable components, but that advantageously results in a Compared to compositions and glasses that have different and required characteristics.

Features of the silicone hydrogel contact lenses provided herein include ophthalmically acceptable surface wettability as described herein. In addition, the silicone hydrogel contact lenses of the present invention have oxygen permeability, surface wettability, modulus, water content, ion flux, and design that allow the lenses of the present invention to be comfortably worn by the patient's eyes for extended periods of time, such as at least One day, at least one week, at least two weeks, or about a month without removing the glasses from the eyes.

In one aspect, the invention is directed to a polymerizable silicone hydrogel contact lens precursor composition. The precursor composition is effective to form a silicone hydrogel contact lens.

In a particular aspect, provided herein is a polymerizable composition comprising, consisting essentially of, or consisting entirely of: α-ω-bis(methacryloxyethyliminocarboxyethylene Oxypropyl)-poly(dimethylsiloxane)-poly(trifluoropropylmethylsiloxane)-poly(omega-methoxy-poly(ethylene glycol)propylmethylsiloxane ), N-vinyl-N-methylacetamide, methyl methacrylate, ethylene glycol dimethacrylate, allyloxy alcohol and free radical initiators.

In one or more embodiments, the polymerizable composition further comprises a UV absorber, such as 2-hydroxy-4-acryloyloxyethoxybenzophenone.

In one or more other embodiments, the polymerizable composition further comprises a colorant, eg, a phthalocyanine pigment, such as phthalocyanine blue.

In one or more other embodiments, the free radical initiator included in the polymerizable composition is 2,2'-azobisisobutyronitrile.

The present invention further includes any one or more of the above-described polymerizable compositions comprising about 34% by weight of α-ω-bis(methacryloyloxyethyliminocarboxyethoxypropyl )-poly(dimethylsiloxane)-poly(trifluoropropylmethylsiloxane)-poly(ω-methoxy-poly(ethylene glycol)propylmethylsiloxane).

In one or more other embodiments, the polymerizable composition may comprise any one or more of: (i) about 46% by weight of N-vinyl-N-methylacetamide, (ii) about 17% by weight methyl methacrylate, (iii) about 0.5% by weight ethylene glycol dimethacrylate, and (iv) about 1% by weight allyloxy alcohol.

In one or more other embodiments, the polymerizable composition comprises about 0.9% by weight of 2-hydroxy-4-acryloyloxyethoxybenzophenone.

In one or more other embodiments, the polymerizable composition comprises about 0.1% by weight phthalocyanine blue.

In one or more other embodiments, the polymerizable composition comprises about 0.3% by weight of a free radical initiator.

In another specific embodiment, the polymerizable composition comprises 34% by weight of α-ω-bis(methacryloxyethyliminocarboxyethoxypropyl)-poly(dimethylsiloxane) - Poly(trifluoropropylmethylsiloxane)-poly(omega-methoxy-poly(ethylene glycol)propylmethylsiloxane), about 46% by weight of N-vinyl-N-methyl Acetamide, about 17% by weight of methyl methacrylate, about 0.5% by weight of ethylene glycol dimethacrylate, about 1% by weight of allyloxy alcohol, about 0.9% by weight of 2-hydroxy-4 - Acryloyloxyethoxybenzophenone, about 0.1% by weight of phthalocyanine blue and about 0.3% by weight of 2,2'-azobisisobutyronitrile.

In another embodiment, there is provided any one or more of the polymerizable compositions described herein free of polyalkylene silica extractable components.

In another aspect, a silicone hydrogel contact lens produced from a polymerizable composition as provided herein is provided.

Also provided is a silicone hydrogel contact lens formed from a polymerizable composition as described herein that is substantially free of extractable components.

Also forming part of the present invention is a silicone hydrogel contact lens produced by polymerizing a polymerizable composition as provided herein to form a pre-extraction polymerized silicone hydrogel contact lens comprising an extractable component , extracting extractable components from a contact lens prior to extraction to form an extracted polymeric lens product, and hydrating the extracted polymeric lens product to form a silicone hydrogel contact lens.

In one or more embodiments, the silicone hydrogel contact lenses produced as described above have an equilibrium water content in the range of about 42% to about 50% by weight and an oxygen transmission rate in the range of about 80-110 barr. Sex (D _k × 10 ^-11 ).

In one or more other embodiments, the silicone hydrogel contact lenses produced as described above have a modulus of about 0.6 to about 1.2 MPa.

In one or more other embodiments, there is provided a silicone hydrogel contact lens produced as described above, wherein the step of polymerizing comprises heating the polymerizable composition to a temperature greater than about 65°C.

In another aspect, provided herein is an equilibrium water content in the range of about 42% by weight to about 50% by weight, an oxygen permeability (D _k x 10 ⁻¹¹ ) in the range of About 0.6 to about 1.2 MPa, an ion current of about 1-5 (×10 ⁻³ mm ² /min), an advancing contact angle of about 52° to about 62°, a receding contact angle of about 40° to 60° and a hysteresis of Silicone hydrogel contact lenses of about 5° to about 15°.

In one or more embodiments, a silicone hydrogel contact lens as described herein is additionally characterized as a lens body having a rounded peripheral edge.

In one or more other embodiments, the silicone hydrogel contact lenses of the present invention may be: (i) spherical lenses, (ii) aspheric lenses, (iii) single-focal lenses, (iv) multi-focal lenses, or ( v) Rotationally stabilized toric contact lenses.

In one or more other embodiments, the silicone hydrogel contact lenses of the present invention are in sealed packages.

In one or more other embodiments, the silicone hydrogel contact lenses as provided herein are not surface treated.

In another aspect, provided herein is a method of producing a polymerizable silicone hydrogel contact lens precursor composition. In one or more embodiments, the method comprises combining α-ω-bis(methacryloxyethyliminocarboxyethoxypropyl)-poly(dimethylsiloxane)-poly( Trifluoropropylmethylsiloxane)-poly(omega-methoxy-poly(ethylene glycol)propylmethylsiloxane), N-vinyl-N-methylacetamide, methyl methacrylate ester, ethylene glycol dimethacrylate, allyloxy alcohol, and a free radical initiator to thereby produce a polymerizable silicone hydrogel contact lens precursor composition.

In one or more embodiments of the method, the step of combining additionally includes a UV absorber.

In one or more specific embodiments, the step of combining additionally includes 2-hydroxy-4-acryloyloxyethoxybenzophenone.

In one or more other embodiments of the method, the step of combining additionally includes a colorant, for example a phthalocyanine pigment, such as phthalocyanine blue.

In one or more specific embodiments of the method, the free radical initiator is 2,2'-azobisisobutyronitrile.

In one or more specific embodiments, the method comprises combining the following:

(i) about 30% to 40% by weight of α-ω-bis(methacryloxyethyliminocarboxyethoxypropyl)-poly(dimethylsiloxane)-poly(trifluoro Propylmethylsiloxane)-poly(omega-methoxy-poly(ethylene glycol)propylmethylsiloxane),

(ii) about 40% to 50% by weight of N-vinyl-N-methylacetamide,

(iii) from about 10% to 25% by weight of methyl methacrylate, and

(iv) less than about 5% by weight of ethylene glycol dimethacrylate, allyloxy alcohol, 2-hydroxy-4-acryloyloxyethoxybenzophenone, phthalocyanine blue and 2,2' - Combinations of azobisisobutyronitrile.

In one or more other embodiments of the method, the step of combining comprises combining about 34% by weight of α-ω-bis(methacryloyloxyethyliminocarboxyethoxypropyl)-poly(di Methylsiloxane)-poly(trifluoropropylmethylsiloxane)-poly(omega-methoxy-poly(ethylene glycol)propylmethylsiloxane), about 46% by weight of N- Vinyl-N-methylacetamide, about 17% by weight of methyl methacrylate, about 0.5% by weight of ethylene glycol dimethacrylate, about 1% by weight of allyloxy alcohol, about 0.9% by weight 2-hydroxy-4-acryloyloxyethoxybenzophenone, about 0.1% by weight of phthalocyanine blue and about 0.3% by weight of 2,2'-azobisisobutyronitrile, so as to provide polymerizable Silicone hydrogel contact lens precursor compositions.

In one or more other embodiments, the method further comprises polymerizing the polymerizable lens precursor composition to form a polymerized silicone hydrogel contact lens prior to extraction.

In one or more specific embodiments of the method, the step of polymerizing comprises heating the polymerizable lens precursor composition.

In one or more other embodiments, the method further comprises placing the polymerizable lens precursor composition in a non-polar resin contact lens mold prior to the step of polymerizing.

In one or more other embodiments, the method further comprises extracting the polymerized contact lens prior to extraction to form an extracted polymerized lens product substantially free of extractable components, and hydrating the extracted polymerized lens product to form silicone hydrogel contact lenses.

In another aspect, provided herein is a silicone hydrogel contact lens comprising the reaction product of a polymerizable composition as described herein that is substantially free of extractable components.

Other embodiments of the eyeglasses, eyewear products, compositions and methods of the present invention will be apparent from the following description, figures, examples and claims. As can be appreciated from the above and following descriptions, each and every feature described herein and each and every combination of two or more of said features is encompassed within the scope of the present invention, provided that The features included in the combination are consistent with each other. Furthermore, any feature or combination of features may be specifically excluded from any embodiment of the invention. Other aspects and advantages of the invention are set forth in the following description and claims, especially when considered in conjunction with the accompanying examples and figures.

Description of drawings

Figure 1 is a block diagram illustrating an exemplary method of producing a silicone hydrogel contact lens.

Figure 2 is a block diagram illustrating the compositions, lens products and contact lenses of the present invention.

Detailed ways

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

definition

It should be noted that, as used in this specification, the singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to a "contact lens" includes a single lens as well as two or more lenses, the same or different, and reference to a "precursor composition" refers to a single composition as well as two or more lenses that are the same or different. different compositions and more.

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

The term "hydrogel" as used herein refers to a polymeric substance, usually a network or matrix of polymer chains, capable of swelling in or through water. The network or matrix may or may not be crosslinked. Hydrogel refers to a water-swellable or water-swellable polymeric substance, including contact lenses. Thus, the hydrogel can be (i) unhydrated and water-swellable, or (ii) partially hydrated and water-swellable, or (iii) fully hydrated and water-swellable.

The term "substituted" as in, for example, "substituted alkyl" refers to a moiety (eg, alkyl) substituted with one or more non-interfering substituents such as, but not limited to, _C3 -C _Cycloalkyl (such as cyclopropyl, cyclobutyl, etc.), halo (such as fluoro, chloro, bromo and iodo), cyano, alkoxy, lower phenyl, substituted Phenyl, etc. For substitution on the phenyl ring, the substituents may be in any orientation (that is, in the ortho, meta or para position).

The term "silicon hydrogel" or "silicon hydrogel substance" refers to a specific hydrogel that includes a silicon (Si) component or a siloxane component. For example, silicon hydrogels are typically prepared by combining silicon-containing materials with conventional hydrophilic hydrogel precursors. Silicone hydrogel contact lenses are contact lenses comprising a silicone hydrogel substance, including vision correcting contact lenses. Silicone hydrogel contact lenses have properties different from conventional hydrogel-based lenses.

A "silicone-containing component" is a component containing at least one [-Si-O-Si] linkage in a monomer, macromer or prepolymer, where each silicon atom optionally has one or more Organic group substituents (R ₁ , R ₂ ) or substituted organic group substituents, which may be the same or different, eg -SiR ₁ R ₂ O-.

"Optional" or "as the case may be" means that the subsequently described event may or may not occur such that the description includes instances where the event occurs and instances where it does not.

"Molecular mass" in the context of the polymers of the present invention refers to the nominal average molecular mass of the polymer, usually determined by size exclusion chromatography, light scattering techniques or intrinsic velocity in 1,2,4-trichlorobenzene measurement method to measure. Molecular weight in the case of polymers may be expressed as number average molecular weight or weight average molecular weight, and in the case of a manufacturer supplied material will depend on the supplier. The basis for any such molecular weight determination can readily be provided by the supplier if not provided in packaged material. Generally references herein to the molecular weight of a macromer or polymer refer herein to the weight average molecular weight. Molecular weight determinations of both number average molecular weight and weight average molecular weight can be measured using gel permeation chromatography techniques or other liquid chromatography techniques. Other methods of measuring molecular weight values may also be used, such as number average molecular weight using end group analysis or measuring colligative properties such as freezing point depression, boiling point elevation, or osmotic pressure, or using light scattering techniques, ultracentrifugation, or viscometry method to determine the weight average molecular weight.

A "network" or "matrix" of a hydrophilic polymer generally means crosslinks between polymer chains formed by covalent or physical bonds (eg hydrogen bonds).

A "hydrophilic" substance is a water-loving substance. The compounds have an affinity for water and are often charged or have polar side chain groups that attract water.

A "hydrophilic polymer" in the present invention is defined as a polymer capable of swelling in water but not necessarily soluble in water.

A "hydrophilic component" is a hydrophilic substance which may or may not be a polymer. Hydrophilic components include those that, when combined with the remaining reactive components, are capable of providing a water content of at least about 20%, such as at least about 25%, to the resulting hydrated lens.

An "ophthalmically compatible silicone hydrogel contact lens" as used herein refers to a silicone hydrogel contact lens that can be worn on the eye of a human without the human experiencing or reporting significant discomfort, including eye irritation and the like. Ophthalmically compatible silicone hydrogel contact lenses with ophthalmically acceptable surface wettability and typically not causing or concomitant with significant corneal swelling, corneal dehydration (“dry eye disease”), superior corneal epithelial arcuate (“SEAL”) or other obvious discomfort.

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

"Substantially absent" or "substantially free" of a feature or entity means that the feature or entity is almost completely or completely absent, eg containing 5% or less of some given entity. For example, a composition substantially free of a certain entity may contain less than about 5%, or less than about 4%, less than about 3%, less than about 2%, or even less than about 1% of a given entity.

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

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

"Lower alkyl" refers to an alkyl group containing 1 to 6 carbon atoms, which may be straight or branched, such as methyl, ethyl, n-butyl, isobutyl, tert-butyl.

Other definitions can also be found in the following sections.

review

As previously discussed, the invention provided herein is based at least in part on the discovery/formulation that avoiding the problems associated with polar resin molds, avoiding the need for complex and expensive post-polymerization procedures, and addressing the problems associated with polymerizing wetting agents can be used. IPN-Related Problems Methods to Prepare Ophthalmically Compatible Silicone Hydrogel Contact Lenses. Furthermore, the formulations provided herein do not require more than about 30% of removable or extractable components that are not substantially incorporated into the polymerized silicone hydrogel contact lens product and are extracted along with other unreacted components removal from the resulting molded contact lens product. For example, an ophthalmically compatible silicone hydrogel contact lens can be obtained from a pre-extraction compound having at least 10% and less than about 30% of the extractable content of a dehydration-extracted silicone hydrogel contact lens as discussed herein. A polymerized silicone hydrogel contact lens product is obtained. In certain embodiments, lens formulations are free of polyalkylene silica components.

In particular, methods of producing ophthalmically compatible silicone hydrogel contact lenses include incorporating specific combinations of components into polymerizable silicone contact lens precursor compositions. The materials impart desirable characteristics to the resulting final contact lens, thereby providing an extracted contact lens product, which is then hydrated to produce a final silicon hydrogel having ophthalmically acceptable surface wettability and other beneficial characteristics as described herein. Adhesive Contact Lenses

These and other important aspects of the invention are described in detail and exemplified in the following sections.

Components of polymerizable silicone hydrogel contact lens precursor compositions

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

The precursor composition of the present invention generally comprises at least the following components: α-ω-bis(methacryloxyethyliminocarboxyethoxypropyl)-poly(dimethylsiloxane)-poly( Trifluoropropylmethylsiloxane)-poly(omega-methoxy-poly(ethylene glycol)propylmethylsiloxane), N-vinyl-N-methylacetamide, methyl methacrylate Esters, Ethylene Glycol Dimethacrylate, Allyloxy Alcohol and Free Radical Initiators. In certain embodiments, the compositions consist essentially of the foregoing components. In other embodiments, the composition consists entirely of the foregoing components.

α-ω-bis(methacryloxyethyliminocarboxyethoxypropyl)-poly(dimethylsiloxane)-poly(trifluoropropylmethylsiloxane)-poly(ω -Methoxy-poly(ethylene glycol)propylmethylsiloxane)

The first component α-ω-bis(methacryloxyethyliminocarboxyethoxypropyl)-poly(dimethylsiloxane)-poly(trifluoropropylmethylsiloxane) - Poly(ω-methoxy-poly(ethylene glycol)propylmethylsiloxane) is a reactive fluorinated acryloyl silicone macromonomer commonly known as "M3U" (CAS Registry No. 697234-74 -5). As shown in the general structure below, the macromer is a triblock copolymer, that is to say comprising three different siloxane polymer blocks. The center block has trifluoromethyl substituents, while acryloyl moieties are present at each end.

The variables n, m, and h correspond to the number of repeat units of each block, and each independently ranges from about 3 to about 200, while p (the number of ethylene oxide repeat units) ranges from about 2 to about 12 . An especially preferred macromer corresponding to the above structure is one in which n is in the range of 50-200, m is in the range of 2-50 and h is in the range of 1-15. 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. M3U can be readily synthesized according to the procedure set forth in Example 1 of International Patent Publication No. WO 2006/026474.

Depending on the values of the variables n, m, h, and p, the molecular weight of the silicone macromer component (i.e., M3U) typically ranges from about 8,000 daltons to about 25,000 daltons, and Preferably in the range of about 10,000 Daltons to about 20,000 Daltons. A particularly preferred silicone macromer for use in the present invention has a molecular weight of about 16,000 Daltons. For example, the macromer can have a weight average molecular weight (Mw) of about 16,200 Daltons and a number average molecular weight (Mn) of about 12,800 Daltons.

The polymerizable silicone hydrogel precursor compositions provided herein generally contain at least about 25% by weight of α-ω-bis(methacryloyloxyethyliminocarboxyethoxypropyl)-poly(dimethyl methylsiloxane)-poly(trifluoropropylmethylsiloxane)-poly(omega-methoxy-poly(ethylene glycol)propylmethylsiloxane), and preferably contains at least about 30 wt. % of α-ω-bis(methacryloxyethyliminocarboxyethoxypropyl)-poly(dimethylsiloxane)-poly(trifluoropropylmethylsiloxane)-poly (omega-methoxy-poly(ethylene glycol)propylmethylsiloxane). Even more preferably, the polymerizable composition of the present invention contains from about 25% to about 40% by weight of α-ω-bis(methacryloyloxyethyliminocarboxyethoxypropyl)-poly(di methylsiloxane)-poly(trifluoropropylmethylsiloxane)-poly(omega-methoxy-poly(ethylene glycol)propylmethylsiloxane), or optimally contains about 30 wt. % to about 40% by weight of α-ω-bis(methacryloxyethyliminocarboxyethoxypropyl)-poly(dimethylsiloxane)-poly(trifluoropropylmethylsilane oxane)-poly(omega-methoxy-poly(ethylene glycol)propylmethylsiloxane). An especially preferred polymerizable composition comprises about 34% by weight of α-ω-bis(methacryloxyethyliminocarboxyethoxypropyl)-poly(dimethylsiloxane)- Poly(trifluoropropylmethylsiloxane)-poly(omega-methoxy-poly(ethylene glycol)propylmethylsiloxane).

N-vinyl-N-methylacetamide

The polymerizable composition as provided herein additionally comprises N-vinyl-N-methylacetamide (VMA), a hydrophilic vinyl-containing ( _CH2 =CH-) monomer. The structure of VMA corresponds to _CH3C (O)N( _CH3 )-CH= _CH2 .

Other hydrophilic vinyl-containing monomers that may be incorporated into the lens materials of the present invention include the following: N-vinyllactams (e.g., N-vinylpyrrolidone (NVP)), N-vinyl-N-ethyl Acetamide, N-vinyl-N-ethylformamide, N-vinylformamide, N-2-hydroxyethylvinyl carbamate, N-carboxy-β-alanine N-vinyl ester.

N-vinyl-N-methylacetamide is preferably present in the polymerizable composition in an amount ranging from about 35% to about 55% by weight of the precursor composition used to make silicone lens products, and even More preferably present in an amount ranging from about 40% to about 50% by weight of the precursor composition. Representative weights of N-vinyl-N-methylacetamide include each of the following: about 40 wt%, 41 wt%, 42 wt%, 43 wt%, 44 wt%, 45 wt%, 46 wt%, 47 wt% % by weight, 48% by weight, 49% by weight or 50% by weight of the precursor composition. In a preferred embodiment, the polymerizable composition as provided herein comprises about 46% by weight of N-vinyl-N-methylacetamide.

Methyl methacrylate (MMA)

The polymerizable precursor composition used to prepare the silicone hydrogel contact lens products of the present invention additionally includes an acrylic monomer, such as methyl methacrylate.

Methyl methacrylate is preferably present in an amount ranging from about 10 wt. % to about 25 wt. % of the precursor composition used to make the silicone hydrogel lens product, and even more preferably from about 10 wt. The weight % is present in an amount ranging from the precursor composition. Representative weight percents of methyl methacrylate, based on the total precursor formulation, include each of the following: about 10 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt%, 15 wt%, 16 % by weight, 17% by weight, 18% by weight, 19% by weight, 20% by weight, 21% by weight, 22% by weight, 23% by weight, 24% by weight and 25% by weight.

Ethylene glycol dimethacrylate (EGDMA)

The precursor composition additionally comprises an acrylate-functionalized ethylene oxide oligomer, that is, having _from about 1 to about 8 consecutive ethylene oxide ( _CH2CH2O- ) monomer subunits terminated with reactive groups ( Such as acrylate groups) functionalized ethylene oxide oligomers. Acrylate-functionalized ethylene oxide oligomers are preferably ethylene oxide monomers or 1-mers and are homodifunctional, that is, terminated at each end with a methacrylate group . The general structure is provided below, where the variable s corresponds to the number of ethylene oxide monomers.

In the above structure, s is generally between 1 and about 8, preferably 1 to about 4. That is, preferred values of s include 1, 2, 3, 4, 5, 6, 7 and 8. The acrylate functionalized ethylene oxide oligomer is preferably ethylene oxide dimethacrylate, where s has a value of one.

The acrylate functionalized ethylene oxide oligomer (that is to say EGDMA) is usually 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 EGDMA component include the following amounts: about 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.8 wt%, 0.9 wt%, 1 wt%, 2 wt%, 3 wt% %, 4% by weight or 5% by weight of the precursor composition. In a preferred embodiment, the precursor composition of the present invention comprises about 0.5% by weight of EGDMA.

Allyloxy alcohol

In addition to the above, the polymerizable composition of the present invention comprises a chain transfer agent. Chain transfer reagents are reagents that promote the reaction between free radical species and non-radical species. Preferred chain transfer agents for use in the present invention are allyloxy compounds, that is to say compounds containing one or more allyloxy moieties. Exemplary chain transfer agents falling into this category include allyloxy alcohols. The chain transfer agents can be used individually or as a mixture.

Compounds containing at least one allyloxy moiety have the following general structure:

where the boxed moiety corresponds to the allyloxy moiety, and Q represents the residue or residue of the parent molecule, such as an alcohol or any small organic molecule, which, when linked together with the allyloxy moiety, is capable of acting as a chain transfer agent. Q is preferably derived from alcohols, such as ethanol, propanol, butanol, etc. or substituted forms thereof. Q is preferably the residue of ethanol and has _the structure ( _-CH2CH2OH ) such that the chain transfer reagent corresponds to 2-allyloxyethanol.

The present inventors have discovered that the inclusion of a chain transfer agent, such as an allyloxy compound, is effective in providing extracted hydrated silicone contact lens bodies with reduced variability in size and physical properties. Thus, the addition of chain transfer agents to "normalize" or "fine-tune" the precursor lens composition such that the resulting extracted hydrated contact lens population typically exhibits any one or more of the following characteristics can be reduced from batch to batch. Denaturation: Equilibrium water content, oxygen permeability, static contact angle, dynamic contact angle (advancing contact angle or receding contact angle), hysteresis, refractive index, ion flow, modulus, tensile strength, etc.

A lot or population as used herein refers to a plurality of contact lenses. It will 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 certain instances, a batch of contact lenses refers to at least 10 contact lenses, at least 100 contact lenses, at least 1000 contact lenses, or more.

Generally, the polymerizable compositions as provided herein contain from about 0.1% to about 5% by weight of allyloxy alcohol. The polymerizable compositions of the present invention preferably contain from about 0.5% to about 3% by weight of allyloxy alcohol. That is, the polymerizable composition may preferably contain any of the following exemplary weight percents of allyloxy alcohol, such as allyloxyethanol: 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7 , 0.8,0.9,1,1.1,1.2,1.3,1.4,1.5,1.6,1.7,1.8,1.9,2,2.1,2.2,2.3,2.4,2.5,2.6,2.7,2.8,2.9 or 3% by weight.

free radical initiator

其对应于2，2′-偶氮二异丁腈(AIBN)，可购自杜邦(DuPont)(美国特拉华州威尔明顿(Wilmington，DE))。本文所述的所有

热引发剂均购自杜邦(DuPont)(美国特拉华州威尔明顿(Wilmington，DE))，且适用于本文所提供的组合物中。

热引发剂为经取代的偶氮腈化合物，其经热分解，每分子产生两个自由基。

溶液在64℃下的半衰期为10小时。各

引发剂的级数(例如前述实例中的“64”)对应于溶液半衰期为10小时所处的摄氏温度。In addition to the above, the precursor composition of the present invention typically comprises one or more initiator compounds, that is to say compounds capable of initiating polymerization of the precursor composition. Preferred are thermal initiators, that is to say initiators having a "polymerization onset" temperature. By selecting a thermal initiator with a higher onset decomposition temperature and using a relatively small amount of initiator, it is possible to reduce the ion flux of the lenses of the present invention, which can affect the amount of removable species removed or extracted during the extraction step. For example, an exemplary thermal initiator that can be used is

It corresponds to 2,2'-azobisisobutyronitrile (AIBN), commercially available from DuPont (Wilmington, DE, USA). All of the

Thermal initiators were all purchased from DuPont (Wilmington, DE, USA) and were suitable for use in the compositions provided herein.

Thermal initiators are substituted azonitrile compounds that upon thermal decomposition generate two free radicals per molecule.

The solution has a half-life of 10 hours at 64°C. each

The order number of the initiator (eg "64" in the previous example) corresponds to the temperature in degrees Celsius at which the solution has a half-life of 10 hours.

引发剂包括2，2′-偶氮双(2，4-二甲基戊腈)(

)、2，2′-偶氮双(2-甲基丙腈)(

)和偶氮二异丁腈(

)。具有约50℃的开始分解温度，而

具有约90℃的开始分解温度。适用于可聚合组合物中的其它热引发剂包括腈类，诸如1，1′-偶氮双(环己腈)和2，2′-偶氮双(2-甲基丙腈)以及其它类型的引发剂，诸如购自西格玛奥德里奇(SigmaAldrich)的引发剂。Other suitable for use in the compositions provided herein

Initiators include 2,2'-azobis(2,4-dimethylvaleronitrile) (

), 2,2'-azobis(2-methylpropionitrile)(

) and azobisisobutyronitrile (

). has an onset decomposition temperature of about 50°C, while

Has an onset decomposition temperature of about 90°C. Other thermal initiators suitable for use in polymerizable compositions include nitriles such as 1,1'-azobis(cyclohexanenitrile) and 2,2'-azobis(2-methylpropionitrile) and other types Initiators such as those available from Sigma Aldrich.

引发剂的一者)的前体组合物获得。具体来说，如本文所述的前体组合物较佳含有约0.07、0.08、0.09、0.1、0.2、0.3、0.4、0.5、0.6或0.7重量％的自由基引发剂。Ophthalmically compatible silicone hydrogel contact lenses can range from about 0.05% to about 1.0% by weight or preferably from about 0.07% to about 0.7% by weight of free radical initiators such as those described above

A precursor composition of one of the initiators is obtained. In particular, precursor compositions as described herein preferably contain about 0.07, 0.08, 0.09, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, or 0.7% by weight of the free radical initiator.

Other Components of Silicone Hydrogel Contact Lens Precursor Compositions

The lens precursor compositions of the present invention may also include other components such as ultraviolet (UV) absorbers or UV radiation or energy absorbers and/or colorants.

 UV416购自氰特工业公司(Cytec Industries))、2-羟基-4-(2羟基-3-甲基丙烯酰氧基)丙氧基二苯甲酮和光可聚合的苯并三唑(以诺波克(NORBLOC)

7966购自诺拉姆科(Noramco))。适用于本发明的其它光可聚合UV吸收剂包括可聚合的烯系不饱和三嗪、水杨酸酯、经芳基取代的丙烯酸酯和其混合物。一般来说，UV吸收剂如果存在，那么以对应于约0.5重量％的前体组合物至约1.5重量％的组合物的量提供。尤其较佳者为包括约0.6重量％至约1.0重量％UV吸收剂的组合物。说明性组合物可含有(例如)约0.5重量％、0.6重量％、0.7重量％、0.8重量％、0.9重量％、1.0重量％、1.1重量％、1.2重量％、1.3重量％、1.4重量％或约1.5重量％的UV吸收剂。The UV absorber can be, for example, a strong UV absorber that exhibits relatively high absorption values 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-acryloyloxyethoxybenzophenone (known as

UV416 was purchased from Cytec Industries), 2-hydroxy-4-(2-hydroxy-3-methacryloyloxy)propoxybenzophenone and photopolymerizable benzotriazole (Enox Polk (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. Generally, the UV absorber, if present, is provided in an amount corresponding to about 0.5% by weight of the precursor composition to about 1.5% by weight of the composition. Especially preferred are compositions comprising from about 0.6% to about 1.0% by weight UV absorber. Illustrative compositions can contain, for example, about 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, or About 1.5% by weight of UV absorber.

The precursor compositions of the present invention may also include colorants, although tinted and clear lens products are contemplated. The colorant is preferably a reactive dye or pigment effective to provide color to the resulting lens product.

Reactive dyes are those that bond to the silicone 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-(sulfoxy)ethane) base) sulfonyl) phenyl) azo-3-methyl-5-oxo-1H-pyrazol-1-yl); [2-naphthalenesulfonic acid, 7-(acetamido)-4-hydroxy -3-((4-((sulfoxyethyl)sulfonyl)phenyl)azo)-]; [5-((4,6-dichloro-1,3,5-triazine-2- base) 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-sulfoxy)ethyl)sulfonyl)phenyl)amino)sulfonyl derivatives] and [ 2,7-Naphthalenesulfonic acid, 4-amino-5-hydroxy-3,6-bis((4-((2-(sulfoxy)ethyl)sulfonyl)phenyl)azo)-tetrasodium salt ].

Especially preferred colorants for use in the present invention are phthalocyanine pigments such as phthalocyanine blue and phthalocyanine green, chromia-alumina-cobaltous oxide, chromium oxide and various iron oxides of red, yellow, brown and black . Generally, if employed, colorants will comprise from about 0.05% to about 0.5% by weight of the composition, or preferably from about 0.07% to about 0.3% by weight of the composition. Illustrative weight percentages of colorants such as phthalocyanine pigments include the following weight %: 0.05 weight %, 0.06 weight %, 0.07 weight %, 0.08 weight %, 0.09 weight %, 0.1 weight %, 0.2 weight %, 0.3 weight %, 0.4% by weight, 0.5% by weight, etc. Opacifiers such as titanium dioxide may also be incorporated. For some applications, a mixture of colors may be used to better simulate the appearance of a natural iris.

A representative precursor composition comprises about 30% to 40% by weight of α-ω-bis(methacryloxyethyliminocarboxyethoxypropyl)-poly(dimethylsiloxane)- Poly(trifluoropropylmethylsiloxane)-poly(omega-methoxy-poly(ethylene glycol)propylmethylsiloxane), about 40% to 50% by weight of N-vinyl- N-methylacetamide, about 10% to 25% by weight of methyl methacrylate and less than about 5% by weight of ethylene glycol dimethacrylate, allyloxy alcohol, 2-hydroxy-4- The combination of acryloyloxyethoxybenzophenone, phthalocyanine blue and 2,2'-azobisisobutyronitrile, that is to say produced by combining the above components.

Exemplary precursor compositions are provided in Example 1. In a particularly preferred embodiment, the polymerizable composition may comprise, consist essentially of, or consist entirely of the following components in the following amounts (in % by weight): about 34% by weight of α-ω- Bis(methacryloxyethyliminocarboxyethoxypropyl)-poly(dimethylsiloxane)-poly(trifluoropropylmethylsiloxane)-poly(ω-methoxy - poly(ethylene glycol) propylmethylsiloxane), about 46% by weight of N-vinyl-N-methylacetamide, about 17% by weight of methyl methacrylate, about 0.5% by weight of di Ethylene glycol methacrylate, about 1% by weight of allyloxy alcohol, about 0.9% by weight of 2-hydroxy-4-acryloyloxyethoxybenzophenone, about 0.1% by weight of phthalocyanine blue and about 0.3% by weight of 2,2'-azobisisobutyronitrile.

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 the compositions in storage containers, such as bottles, etc., or in dispensing devices, such as manual or automatic pipetting devices.

Method of forming silicone hydrogel contact lenses

Generally, in producing a silicone hydrogel contact lens, the components of the silicone hydrogel contact lens precursor composition are individually weighed and then combined. The resulting precursor composition is then typically mixed, eg, using magnetic or mechanical mixing, and optionally filtered to remove particulates.

Glasses of the present invention may be produced, for example, as illustrated in FIG. 1 .

Figure 1 is a block diagram illustrating a method of producing a silicone hydrogel contact lens. Specifically, Figure 1 illustrates a method of injection molding a silicone hydrogel contact lens. Injection molded contact lenses can themselves be produced in a form suitable for placement directly on the human eye without further processing to alter the lens to fit the lens on the eye. Silicone hydrogel contact lenses of the present invention produced using an injection molding procedure such as the procedure illustrated in FIG. 1 are referred to herein as "injection molded silicone hydrogel contact lenses." The lenses of the present invention are understood to be "fully molded silicone hydrogel contact lenses" if no machining is used to alter the lens design after the lens product is delensed from the mold member.

Illustrative methods for producing contact lenses, such as silicone hydrogel contact lenses, are described in at least the following patents: U.S. Pat. , No. 5,039,459, No. 5,080,839, No. 5,094,609, No. 5,260,000, No. 5,607,518, No. 5,760,100, No. 5,850,107, No. 5,935,492, No. 6,099,852, No. 6,367,929, No. 6,86 6,869,549, 6,939,487, and US Patent Publication Nos. 20030125498, 20050154080, and 20050191335.

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

The lens precursor composition of the present invention may be provided in a container, dispensing device, or contact lens mold prior to the curing or polymerization procedure.

Returning to step 102 of FIG. 1 , the lens precursor composition is placed on the lens-forming surface of a concave contact lens mold member. A female contact lens mold member is generally referred to as a first contact lens mold member or an anterior contact lens mold member. For example, a concave contact lens mold member has a lens forming surface that defines the front surface of the contact lens produced by the 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-like cavity. Accordingly, the method illustrated in FIG. 1 includes a step 104 of closing a contact lens mold by placing two contact lens mold members in contact with each other to form a contact lens-like cavity. The polymerizable silicone hydrogel lens precursor composition 202 is located in a contact lens-like cavity. The second contact lens mold member is referred to as a convex contact lens mold member or a posterior contact lens mold member. For example, the second contact lens mold member includes a lens forming surface that defines the rear surface of the contact lens produced in the contact lens mold.

"Non-polar resin contact lens mold" or "hydrophobic resin contact lens mold" as used herein refers to a contact lens mold formed or produced from a non-polar or hydrophobic resin. Accordingly, non-polar resin-based contact lens molds may comprise non-polar or hydrophobic resins. For example, the contact lens mold can comprise one or more polyolefins, or can be formed from a polyolefin resinous substance. Examples of nonpolar 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 hydrophobic surfaces. For example, a non-polar resin mold or a hydrophobic resin mold can have a static contact angle of about 90° or greater as determined using the trapping bubble method. Conventional silicone hydrogel contact lenses produced in the mold had clinically unacceptable surface wettability at the contact angle.

The method further includes curing 106 the polymerizable silicone hydrogel lens precursor composition to form a pre-extracted polymerized silicone hydrogel contact lens product 204 (as shown in FIG. 2 ). During curing, the lens-forming components of the polymerizable silicone hydrogel lens precursor composition polymerize to form a polymerized lens product. Curing can therefore also be understood as a polymerization step. Curing 106 may include exposing the polymerizable lens precursor composition to radiation, such as thermal radiation or any other means effective to polymerize the components of the lens precursor composition. For example, curing 106 can include exposing the polymerizable lens precursor composition to a polymerizing amount of heat or ultraviolet (UV) light. Curing can optionally be carried out in an oxygen-free environment. For example, curing can be performed under an inert atmosphere, such as under nitrogen, argon, or other inert gas. In a particular embodiment, curing comprises heating a polymerizable composition as provided herein to a temperature greater than about 55°C.

Pre-extracted polymerized silicone hydrogel contact lens product 204 refers to the polymerized product prior to being subjected to an extraction procedure that removes substantially all removable/extractable components from the polymerized product. The pre-extracted polymerized silicone hydrogel contact lens product may be provided on or within a contact lens mold, extraction tray, or other device prior to contacting with the extraction composition. For example, the pre-extracted polymerized silicone hydrogel contact lens product can be provided in a lens-shaped cavity of a contact lens mold after a curing procedure; can be provided in a contact lens mold member after demolding the contact lens mold On or within; or after the delensing procedure and before the extraction procedure, may be provided on or within the extraction tray or other device. The polymeric silicone hydrogel contact lens product prior to extraction includes a lens-forming component, such as a lens-shaped silicon-containing polymeric network or matrix, and a removable component that is removable from the lens-forming component. Removable components include unreacted monomers, oligomers, partially reacted monomers, or other reagents that are not covalently linked or immobilized relative to the lens forming component. The removable component may also include one or more additives, including organic additives, including diluents, which may be extracted from the polymerized lens product during the extraction procedure as previously discussed. Thus, materials that may contain removable components include linear uncross-linked, cross-linked and/or branched polymers of extractable species that are not cross-linked or immobilized relative to the polymer backbone, network or matrix of the lens body. .

In addition, the removable component may include other materials, such as volatile materials, that may be passively or actively removed from the pre-extracted polymerized silicone hydrogel contact lens product prior to extraction. For example, a portion of the removable components can evaporate between the demolding step and the extraction step.

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

The pre-extracted polymerized silicone hydrogel contact lens product 204 is then separated from the contact lens mold member in which it was positioned during a delensing step 110 (shown in FIG. 1 ). The polymerized contact lens product prior to extraction can delens with either the male mold member or the female mold member, depending on which mold member the polymerized contact lens product remains adhered to during demolding of the contact lens mold.

After delensing the pre-extracted silicone hydrogel contact lens product, the method includes extracting 112 extractable species from the pre-extracted silicone hydrogel contact lens product. The extracted silicone hydrogel contact lens product 206 (shown in FIG. 2 ) can be obtained through the extraction step 112 . Extraction step 112 refers to the procedure of contacting the pre-extracted polymerized silicone hydrogel contact lens product with one or more extraction compositions, and may include a single extraction step or several consecutive extractions. For example, a polymerized silicone hydrogel contact lens product or a batch of polymerized silicone hydrogel contact lens product is contacted with one or more volumes of a liquid extraction medium. Extraction media typically include one or more solvents. Extraction media include, for example, ethanol, methanol, propanol, and other alcohols. The extraction medium may also comprise a mixture of alcohols 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 reagents that facilitate the removal of hydrophobic unreacted components from the polymerized silicone hydrogel lens product. For example, the extraction medium may comprise, consist essentially of, or consist entirely of water, buffer solutions, and the like. Extraction 112 can be performed at various temperatures, including room temperature. For example, extraction can occur at room temperature (eg, about 20°C), or it can occur at elevated temperature (eg, from about 25°C to about 100°C). Additionally, in certain embodiments, extraction step 112 may include contacting the lens product with a mixture of alcohol and water, which in some cases may comprise the final step of a multi-step extraction procedure.

After performing extraction on the pre-extracted polymeric silicone hydrogel contact lens product to provide an extracted polymeric silicone hydrogel contact lens product, the method includes hydrating 114 the extracted polymeric silicone hydrogel contact lens product. The hydration step 114 can include, for example, contacting the extracted polymeric silicone hydrogel contact lens product or batches or batches of the product with water or an aqueous solution to form a hydrated silicone hydrogel contact lens 208 (as shown in FIG. 2 ) . For example, the extracted polymeric silicone hydrogel contact lens product can be hydrated by placing in two or more separate volumes of water, including deionized water. In certain embodiments, the hydration step 114 is combined with the extraction step 112 so that both steps can be performed at a single station in a contact lens production line. The hydration step 114 can be performed in a vessel at room temperature or elevated temperature and, if necessary, under elevated 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, the pre-extracted polymeric silicone hydrogel contact lens product and the extracted polymeric silicone hydrogel contact lens product are considered to be water-swellable products or elements, and the hydrated silicone hydrogel contact lens is considered to be invisible. Eyeglasses are water-swelled products or elements. A silicone hydrogel contact lens as used herein refers to a silicone hydrogel element that has undergone a hydration step. Thus, the silicone hydrogel contact lens can be a fully hydrated silicone hydrogel contact lens, a partially hydrated silicone hydrogel contact lens, or a dehydrated silicone hydrogel contact lens. A dehydrated silicone hydrogel contact lens refers to a contact lens that has undergone a hydration procedure and then dehydrated to remove water from the lens.

After hydrating the extracted silicone hydrogel contact lens product to produce the silicone hydrogel contact lens, the method includes a step 116 of packaging the silicone hydrogel contact lens 208 . For example, the silicone hydrogel contact lens 208 may be placed in a blister pack or other suitable container that includes a volume of liquid, such as saline solution, including buffered saline solution. 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, packaged silicone hydrogel contact lenses can be exposed to germicidal amounts of radiation, including thermal radiation, such as by autoclaving, gamma radiation, electron beam radiation, or ultraviolet radiation.

Properties of Silicone Hydrogel Glasses

As discussed above, the compositions and methods provided herein provide ophthalmically compatible silicone hydrogel contact lenses. The polymerized silicone hydrogel lens product prior to extraction is extracted and hydrated to form a silicone hydrogel contact lens having ophthalmically acceptable surface wettability. The glasses of the present invention have oxygen permeability, surface wettability, modulus, water content, ion flux, design, and combinations thereof that make the glasses of the present invention fit the patient's eyes comfortably for extended periods of time, such as at least one day, at least one week , for at least two weeks or about a month without removing the glasses from the eyes.

An "ophthalmically compatible silicone hydrogel contact lens" as used herein refers to a silicone hydrogel contact lens that can be worn on the eye of a human without the human experiencing or reporting substantial discomfort, including eye irritation and the like. Ophthalmically compatible silicone hydrogel contact lenses have ophthalmically acceptable surface wettability and generally do not cause significant corneal swelling, corneal dehydration (“dry eye disease”), superior corneal epithelial arcuate (“SEAL”), or other Obvious discomfort or not related to the described condition. Silicone hydrogel contact lenses having ophthalmically acceptable surface wettability are those that do not adversely affect the tear film of the eyeglass wearer's eye to the extent that lens wearers experience or report problems with placing or wearing a silicone hydrogel contact lens on the eye. Silicone hydrogel contact lenses for the degree of glasses-related discomfort. Ophthalmically compatible silicone hydrogel contact lenses meet clinically acceptable requirements for daily wear or extended wear contact lenses.

The silicone hydrogel contact lenses of the present invention comprise a lens body having surfaces having ophthalmically acceptable surface wettability (OASW), such as an anterior surface and a posterior surface. Wettability refers to the hydrophilicity of one or more surfaces of a contact lens. In one measure, a lens surface is considered wettable, or ophthalmically acceptable, wettable if the lens receives a score of 3 or more in the wettability assay performed as follows. Contact lenses are immersed in distilled water, removed from the water, and the length of time it takes for a water film to recede from the lens surface (eg, water break-up time (water BUT or WBUT)) is measured. The analysis provides a rating for the glasses on a linear scale of 1-10, where a score of 10 refers to glasses in which water droplets take 20 seconds or more to recede from the glasses. Although in vitro assessment of WBUT is only one measure or indication for OASW, it can be considered that a silicone hydrogel contact lens having a water BUT of more than 5 seconds, such as at least 10 seconds or more desirably at least about 15 seconds, has ocular with acceptable surface wettability. Alternatively, OASW can be assessed in vivo. Eyewear is considered to have OASW if the eyewear can be worn on the patient's eye for at least 6 hours without the patient reporting discomfort or irritation.

Wettability can also be determined by measuring the contact angle on one or both lens surfaces. The contact angle can be a dynamic or static contact angle. Lower contact angles generally refer to increased wettability of the contact lens surface. For example, the wettable surface of a silicone hydrogel contact lens as provided herein can have a contact angle of less than about 90°. However, in certain embodiments of the inventive lenses, the lenses have a contact angle of no greater than 80°, and in other embodiments, the inventive silicone hydrogel contact lenses have a contact angle of less than about 75° and even more preferably less than about 70° advancing contact angle. In one embodiment, the eyewear has an advancing contact angle in the range of about 52° to about 62°.

The silicone hydrogel contact lenses of the present invention comprise lens bodies having ophthalmically acceptable surface wettability. For example, the lens bodies of the silicone hydrogel contact lenses of the present invention generally have anterior and posterior surfaces, each having ophthalmically acceptable surface wettability.

In one embodiment, the lens body of the silicone hydrogel contact lens comprises a silicone hydrogel substance. The lens body has a dry weight no greater than 90% of the dry weight of the lens body before extraction. For example, the lens body of the polymerized silicone hydrogel contact lens product prior to extraction can have a dry weight X. Following the extraction procedure, the lens body of the extracted polymerized silicone 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 polymerized silicone hydrogel contact lens product can be contacted with a wide variety of organic solvents, followed by a hydration step to produce a silicone hydrogel contact lens. Next, the hydrated silicone hydrogel contact lens was dehydrated and weighed to determine the lens body dry weight of the silicone hydrogel contact lens.

For example, in certain methods, a pre-extracted polymeric silicone hydrogel contact lens product is delensed from a contact lens mold member and weighed to provide a dry weight of the pre-extracted polymeric silicone hydrogel contact lens product. The pre-extracted lens product is then contacted with alcohol for about 6 hours, and then hydrated with water. The hydrated lenses were 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 lenses were weighed to determine the lens body dry weight of the silicone hydrogel contact lenses. The dry weights are then compared to determine the amount of extractable material present in the polymerized silicone hydrogel contact lens product prior to extraction. A pre-extracted polymerized lens product having an extractable component content of about 40% yields a silicone hydrogel contact lens body having a dry weight of about 60% of the pre-extracted lens product. A pre-extracted polymerized lens product having an extractable component content of about 70% yields a lens body of a silicone hydrogel contact lens having a dry weight of about 30% of the pre-extracted lens product, and the like.

The amount of extractables or extractable component content present in the polymerized silicone hydrogel contact lens product prior to extraction can be determined using the following equation:

E=((dry weight of lens product before extraction−dry weight of extracted and hydrated contact lens)/dry weight of lens product before extraction)×100.

E is the percentage of extractables present in the lens product before extraction.

For example, the polymerized silicone hydrogel contact lens product prior to extraction can have a dry weight of about 20 mg. If the silicone hydrogel contact lens obtained from that product has a dry weight of about 17 mg, then that silicone hydrogel contact lens comprises a lens body with a dry weight of 85% of the dry weight of the lens product before extraction. It is understood that the pre-extracted lens product has an extractable component content of about 15% by weight. As another example, a polymeric silicone hydrogel contact lens product prior to extraction may have a dry weight of about 18 mg, and if a dehydrated silicone hydrogel contact lens obtained from the lens product has a dry weight of about 13 mg, The silicone hydrogel contact lens then comprises a lens body having a dry weight of about 72% of the lens product prior to extraction. The pre-extracted polymerized silicone hydrogel contact lens product had an extractable component content of about 28% by weight.

In certain embodiments, the dry weight of the lens body of the silicone hydrogel contact lens (ie, the silicone hydrogel contact lens that has been subjected to an extraction and hydration procedure) is greater than 70% of the dry weight of the lens body prior to extraction. For example, the dry weight of the lens body after extraction can be about 70% to about 90% of the dry weight of the lens body before extraction. Certain embodiments of the present lenses comprise lens bodies having a dry weight of about 70% to about 78% of the dry weight of the lens body prior to extraction. In at least one embodiment, the silicone hydrogel contact lens has a dry weight of about 74% of the dry weight of the lens body before extraction.

Although the pre-extracted polymerized silicone hydrogel contact lens products of the present invention contain extractable species, the extracted forms of the silicone hydrogel contact lenses of the present invention have minimal, if not significant, amounts of extractables in the resulting lens body. substance. In certain embodiments, the amount of extractable matter 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 species can be determined by contacting the extracted contact lens with an additional volume of a strong solvent such as chloroform.

Furthermore, the lens products and contact lenses of the present invention can be distinguished from Surface-treated silicone hydrogel contact lenses. The lens products and contact lenses of the present invention are distinguishable from silicone hydrogel contact lenses with the polymeric wetting agent IPN because extractable components can be extracted from the lens product and are substantially absent in the hydrated contact lens.

The silicone hydrogel contact lenses of the present invention can comprise lens bodies obtained from non-polar resin contact lens molds that have substantially the same surface morphology when examined in the hydrated and dehydrated states. In addition, the hydrated lens body may have a surface roughness slightly less than that of the dehydrated lens body. For example, a lens body of the present invention may have a surface that includes nanometer-sized peaks that are evident when analyzing root mean square (RMS) roughness data of the lens surface. The mirror bodies may comprise regions between the peaks that are differentially raised between the peaks to provide a substantially similar surface morphology with reduced roughness. For example, peak shape remains substantially the same, although peak height may decrease upon spiking body hydration.

Alternatively or additionally, embodiments of the non-polar resin molded silicone hydrogel contact lenses of the present invention may comprise optical components that are visually visible when viewed with an electron microscope, such as a scanning electron microscope, a transmission electron microscope, or a scanning transmission electron microscope. Discriminated mirror bodies of silicon-rich and silicon-poor regions. Based on chemical analysis, it is known that the silicon-poor regions are regions within the lens that are substantially or completely free of silicon. The silicon-depleted regions may be larger than said regions in surface-treated silicone hydrogel contact lenses or silicone hydrogel contact lenses comprising the polymeric wetting agent IPN. The size of silicon-rich regions, silicon-poor regions, or both can be determined using conventional image analysis software and equipment, such as the image analysis system available from Bioquant (Tennessee, USA). The image analysis software system can be used to outline the boundaries of silicon-rich and silicon-poor regions and determine the cross-sectional area, diameter, volume, etc. of the regions. In certain embodiments, the silicon-poor region 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 silicon-poor region of other silicon hydrogel contact lenses.

The unsurface-treated lens bodies of the present invention generally provide ophthalmically acceptable surface wettability. In other words, in one embodiment, the lens body of the silicone hydrogel contact lens of the present invention is a lens body without surface treatment. In other words, the lens body is produced without surface treatment of the lens body to provide ophthalmically acceptable surface wettability. For example, the illustrative lens bodies do not include plasma treatments or additional coatings to make the surface of the lens body more acceptable to the eye. While the lenses of the present invention have ophthalmically acceptable surface wettability, certain embodiments may include surface treatments if desired.

Certain embodiments of the lenses of the present invention comprise injection molded element lenses obtained from non-polar resin contact lens molds. A polymerized silicone hydrogel contact lens product refers to a product that is polymerized or cured in a non-polar resin contact lens mold. Alternatively, stated another way, the polymerized silicone hydrogel contact lens product is produced in a non-polar resin contact lens mold. As discussed herein, the contact lens molds are molds produced using or based on non-polar or hydrophobic resinous substances. Such substances generally have relatively large contact angles on their lens-forming surfaces.

The lenses of the present invention may comprise a hydrated lens body having an advancing contact angle on the front surface, the back surface, or both the front and back surfaces of less than 90°. The lens body typically has an advancing mirror surface contact angle of less than 75°, for example the lens body has an advancing mirror surface contact angle (in °) of about one of: 74, 73, 72, 71, 70, 69, 68, 67, 66, 65, 64, 63, 62, 61, 60, 59, 58, 57, 56, 55, 54, 53, 52, 51, or 50. The mirror body can also have a receding contact angle of the mirror surface of less than about 75°. For example, the mirror body can have a mirror surface receding contact angle (in °) of about one of: 60, 59, 58, 57, 56, 55, 54, 53, 52, 51, 50, 49, 48, 47, 46, 45, 44, 43, 42, 41 or 40. In one or more embodiments, the lens body has a receding contact angle of about 40° to about 60°.

The hysteresis, which is the difference between the advancing and receding contact angles, is typically from about 5° to about 25°. In preferred embodiments, however, the hysteresis is in the range of about 5° to about 15°, although in some cases the glasses may have a lag greater than about 25°, which is still clinically acceptable.

Advancing contact angles can be determined using conventional methods known to those of ordinary skill in the art. For example, the advancing and receding contact angles of contact lenses can be measured using conventional drop shape methods such as the stopped drop method or the trapping bubble method. Advancing and receding water contact angles for silicone hydrogel contact lenses can be obtained using a Kruss DSA100 apparatus (Kruss GmbH, Hamburg, Germany) and as described by D.A. Brandreth:" Dynamic contact angles and contact angle hysteresis", Journal of Colloid and Interface Science, Vol. 62, 1977, pp. 205-212 and R. Napkwas R. Knapikowski, M. Kudra: Kontaktwinkelmessungen nach dem Wilhelmy-Prinzip-Ein statistischer Ansatz zur Fehierbeurteilung", Chemical Technology (Chem.Technik), Vol. 45, 1993, pp. 179-185 and As described in US Patent No. 6,436,481.

For example, the advancing contact angle and receding contact angle can be measured using the trapping method using phosphate-buffered saline (PBS; pH=7.2). Lenses were spread flat on a quartz surface and rehydrated with PBS for 10 minutes prior to testing. Bubbles are placed on the lens surface using an automated injection system. The bubble size can be increased and decreased to obtain a receding angle (a plateau is obtained when increasing the bubble size) and an advancing angle (a plateau is obtained when decreasing the bubble size).

Alternatively or additionally, the glasses of the present invention may comprise lens bodies exhibiting a water break-up time (BUT) of greater than 5 seconds. For example, an embodiment of the present eyeglasses comprising a lens body with 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 generally comprise lens bodies having a modulus of less than 1.6 MPa. Eyeglasses are generally characterized by a modulus between about 0.5 and about 1.5 mPa, preferably between about 0.6 and about 1.2 mPa. In one or more embodiments, the glasses have a modulus between about 0.8 to about 1.0 MPa. For example, the lens body can have a modulus of about 1.2 MPa, 1.1 MPa, 1.0 MPa, 0.9 MPa, 0.8 MPa, about 0.7 MPa, about 0.6 MPa, or about 0.5 MPa. The lens body modulus is selected to provide a comfortable fit of the glasses when placed on the eye and to allow the eyewear wearer to adapt the operation of the glasses.

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

The ion current of the spectacle body of the present invention is generally less than about 5×10 ⁻³ mm ² /min. While certain lens bodies of the present invention may have ion currents as high as about 7 x 10 ^-3 mm ² /min, it is believed that when the ion current is less than about 5 x 10 ^-3 mm ² /min, and when the contact lens does not include an MPC , can reduce corneal dehydration staining. In certain embodiments, the ion flux of the mirror body is in the range of about 2×10 ⁻³ mm ² /min to about 5×10 ⁻³ mm ² /min. For example, the ion current may be about 2×10 ⁻³ mm ² /min, 2.5× ^{10 −3} mm 2 /min, 3.0× ^{10 −3} mm ² /min, 3.5× ^{10 −3} mm ^{2 /} min, 4.0 ×10 ⁻³ mm ² /min, 4.5× ^{10 −3} mm ² /min or about 5×10 ⁻³ mm ² /min. However, as described herein, the ion flux can be greater than 7 x 10 ^-3 mm ² /min and still not cause corneal dehydration staining or other clinical problems.

The ion current of the spectacle body of the present invention can be determined using conventional methods known to those of ordinary skill in the art. For example, the ionoflux of a contact lens or lens body can be measured using a technique substantially similar to the "Ionoflux Technique" described in US Patent No. 5,849,811. For example, eyeglasses to be measured may be placed between male and female portions in the eyeglass holder. The male and female portions include a flexible sealing ring between the eyeglass and each male or female portion. After the eyeglasses are positioned in the eyeglass holder, the eyeglass holder is placed in the threaded cap. A cap is screwed onto the glass tube to define the feed chamber. The feed chamber can be filled with 16 ml of 0.1 molar NaCl solution. The receiving chamber can be filled with 80ml of deionized water. The leads of the conductivity meter were immersed in deionized water in the receiving chamber, and a stir bar was added to the receiving chamber. The receiving chamber was placed in an incubator and the temperature was maintained at about 35°C. Finally, the feeding chamber is submerged into the receiving chamber. Conductivity measurements can be taken every two minutes for about 20 minutes starting 10 minutes after the feed chamber is immersed in the receiving chamber. Conductivity versus time data should be substantially linear.

The spectacle bodies of the present invention generally have a high oxygen permeability. For example, the lens body has an oxygen permeability with a Dk of not less than 60 Barrer. Embodiments of the eyeglasses of the present invention comprise lens bodies having a Dk of about 80 barr, about 90 barr, about 100 barr, about 110 barr, about 120 barr, about 130 barr, about 140 barr, or greater . The eyeglasses preferably have a Dk of about 70 to about 110 barrer and more preferably about 80 to 100 barrer.

The Dk of the lenses of the present invention can be determined using conventional methods known to those of ordinary skill in the art. For example, Dk values can be determined using the Mocon method as described in US Patent No. 5,817,924. The Dk value can be determined using a commercially available apparatus with the model designation Mocon Ox-Tran System.

The lenses of the present invention also comprise a lens body having an ophthalmically acceptable water content. For example, embodiments of the lenses of the present invention comprise lens bodies having an equilibrium water content of not less than about 30%. In certain embodiments, the lens body has an equilibrium water content in the range of about 40% to about 60% by weight. For example, the lenses provided herein can have an equilibrium water content of about 35%, about 40%, about 45%, about 50%, about 55%, about 60%, or even about 65%. In one or more embodiments, the lens body has an equilibrium water content of about 42% to about 50% by weight.

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

In addition to the specific values identified above, the eyeglasses of the present invention may have values that range between any combination of the specific values identified above.

For example, the contact lenses of the present invention can have a water content of about 42% to about 50%, an ion current value of about 3 to about 5 (×10 ⁻³ mm ² /min), an ion current value of about 52° to about 62° Advancing contact angle, receding contact angle from about 40° to about 60°, hysteresis from about 5° to about 15°, Young's modulus (Young's moduli) from about 0.6 MPa to about 1.2 MPa, at least about 100% Elongation and its combination. In certain embodiments, the elongation is from about 100% to about 300%.

As discussed herein, the eyeglasses of the present invention have features and properties that allow the eyewear to be worn for extended periods of time. For example, the glasses of the present invention may be worn as daily wear glasses, weekly wear glasses, bi-weekly wear glasses, or monthly wear glasses. The lenses of the present invention comprise a hydrated lens body having surface wettability, modulus, ion flux, oxygen permeability, and water content that contribute to lens comfort and usability.

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

The spectacles of the invention also comprise a lens body comprising a peripheral edge region. The peripheral edge region may comprise a rounded portion. For example, the peripheral edge region may comprise a rounded rear edge surface, a rounded front 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 lens body of the eyeglasses of the present invention may comprise a rounded peripheral edge.

The lenses of the present invention may comprise lens bodies with a thickness profile that addresses the problems associated with existing silicone hydrogel contact lenses while still being comfortable for the lens wearer. By changing the thickness of the lens body and the modulus of the lens body, the hardness of the lens body can be controlled. For example, the hardness of a contact lens region can be defined as the product of the Young's modulus of the lens and the square of the lens thickness in the given region. Accordingly, certain embodiments of the present eyeglasses may comprise lens bodies having a center hardness (eg, the hardness of the center of the eyeglass or the center of the viewing zone) of less than about 0.007 MPa- ^mm2 , eyeglass interface hardness of less than about 0.03 MPa- ^mm2 , or combinations thereof . A lenticular junction can be defined as the junction of the lenticular zone with the bevel or, for unbeveled spectacles, a point approximately 1.2 mm from the edge of the lens (see US Patent No. 6,849,671). In other embodiments, the spectacles of the present invention may comprise a lens body with a center hardness greater than 0.007 MPa-mm ² , a lens interface hardness greater than about 0.03 MPa-mm ² , or a combination thereof.

The silicone hydrogel contact lenses of the present invention can be provided in sealed packages. For example, the silicone hydrogel contact lenses of the present invention may be provided in sealed blister packs or other similar containers suitable for delivery to lens wearers. The lenses may be stored in an aqueous solution, such as saline solution, within the package. Some suitable solutions include phosphate buffered saline and borate buffered solutions. The solution may include an antiseptic or may be free of antiseptics or preservatives, as desired. Solutions may also include surfactants, such as poloxamers and the like, if desired.

Glasses are preferably sterile in airtight packages. For example, the eyeglasses can be sterilized prior to sealing the package or can be sterilized within the sealed package. Sterilized eyeglasses may be eyeglasses that have been exposed to a germicidal amount of radiation. For example, the glasses can be autoclaved glasses, gamma irradiated glasses, ultraviolet radiation exposed glasses, and the like.

example

The following examples illustrate certain aspects and advantages of the invention, however, the invention is in no way to be considered limited to the specific examples described below.

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

Methods of making contact lenses, such as silicone hydrogel contact lenses, are further described in the following patents: 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 , No. 5,080,839, No. 5,094,609, No. 5,260,000, No. 5,607,518, No. 5,760,100, No. 5,850,107, No. 5,935,492, No. 6,099,852, No. 6,367,929, No. 6,822,016, No. 48, 6 6,939,487 and US Patent Publication Nos. 20030125498, 20050154080, and 20050191335.

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

The following well-known chemical species are referred to in the examples, and in some cases, by their abbreviations set forth below.

Substances and methods

abbreviation

AE: Allyloxyethanol

DI: Deionization

MMA: methyl methacrylate

M3U: M3-U; α-ω-bis(methacryloxyethyliminocarboxyethoxypropyl)-poly(dimethylsiloxane)-poly(trifluoropropylmethylsiloxane) alk)-poly(omega-methoxy-poly(ethylene glycol)propylmethylsiloxane; dimethacryloylsiloxane-containing macromonomer

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 colorant: 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 (freshly distilled under vacuum)

PDMS: Polydimethylsiloxane

PDMS-co-PEG: block copolymer of polydimethylsiloxane and PEG containing 75% PEG and MW 600 (DBE712 from Gelest)

PEG: polyethylene glycol

PP: Propylene Propylene

EGDMA: Ethylene glycol dimethacrylate

TEGDVE: Triethylene glycol divinyl ether

TPTMA: Trimethylolpropane Trimethacrylate

UV416: 2-(4-benzoyl-3-hydroxyphenoxy)ethyl acrylate

Vazo-64: Azobisisobutyronitrile (V-64; thermal initiator)

VMA: N-vinyl-N-methylacetamide (freshly distilled under vacuum)

VM: vinyl methacrylate

Method for characterizing eyeglass products

Advancing Contact Angle/Receding Contact Angle Advancing contact angle can be determined using conventional methods known to those of ordinary skill in the art. For example, the advancing and receding contact angles of the contact lenses provided herein can be measured using conventional drop shape methods such as the stopped drop method or the trapping bubble method. Advancing and receding water contact angles for silicone hydrogel contact lenses can be obtained using a Kruss DSA100 apparatus (Kruss GmbH, Hamburg, Germany) and as described by DA Brandreth:" Dynamic contact angles and contact angle hysteresis (Dynamic contact angles and contact angle hysteresis)", Journal of Colloid and Interface Science (Journal of Colloid and Interface Science), volume 62, 1977, pages 205-212 and R. Napkowski ( R. Knapikowski), M. Kudra: "Kontaktwinkelmessungen nach dem Wilhelmy-Prinzip-Ein statistischer Ansatzzur Fehierbeurteilung", Chemical Technology (Chem. Technik), Vol. 45, 1993, pp. 179-185 and US Patent as described in No. 6,436,481.

For example, the advancing contact angle and receding contact angle can be measured using the trapping method using phosphate-buffered saline (PBS; pH=7.2). Lenses were spread flat on a quartz surface and rehydrated with PBS for 10 minutes prior to testing. Bubbles are placed on the lens surface using an automated injection system. The bubble size can be increased and decreased to obtain a receding angle (a plateau is obtained when increasing the bubble size) and an advancing angle (a plateau is obtained when decreasing the bubble size).

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

Ion Current The ion current of the spectacle body of the present invention can be determined using conventional methods known to those of ordinary skill in the art. For example, ionoflux of a contact lens or lens body can be measured using a technique substantially similar to the "Ionoflux Technique" described in US Pat. No. 5,849,811. For example, eyeglasses to be measured may be placed between male and female portions in the eyeglass holder. The male and female portions include a flexible sealing ring between the eyeglass and each male or female portion. After the eyeglasses are positioned in the eyeglass holder, the eyeglass holder is placed in the threaded cap. A cap is screwed onto the glass tube to define the feed chamber. The feed chamber can be filled with 16 ml of 0.1 molar NaCl solution. The receiving chamber can be filled with 80ml of deionized water. The leads of the conductivity meter were immersed in deionized water in the receiving chamber, and a stir bar was added to the receiving chamber. The receiving chamber was placed in an incubator and the temperature was maintained at about 35°C. Finally, the feeding chamber is submerged into the receiving chamber. Conductivity measurements can be taken every two minutes for about 20 minutes starting 10 minutes after the feed chamber is immersed in the receiving chamber. Conductivity versus time data should be substantially linear.

Oxygen Permeability The Dk of the lenses of the present invention can be determined using conventional methods known to those of ordinary skill in the art. For example, Dk values can be determined using the Mocon method as described in US Patent No. 5,817,924. The Dk value can be determined using a commercially available apparatus with the model designation Mocon Ox-Tran System.

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

Example 1

Preparation of Polymerizable Silicone Hydrogel Contact Lens Precursor Compositions

The reagents and relative amounts specified below were used to prepare polymerizable silicone hydrogel contact lens precursor compositions. This formulation is referred to herein as "HM formulation".

Table 1

compound (abbreviation) Unit quantity (part) Weight % (weight ratio)

M3U 35 34.3 VMA 47 46.1 MMA 17 16.7 EGDMA 0.5 0.49 AE 1.1 1.1

UV416 0.9 0.88 Colorants (PB15; Phthalocyanine Blue, m3u Blue) 0.1 0.10 VAZO-64 0.3 0.29

A total of 101.9 copies

The components in Table 1 were weighed and mixed to form a mixture. The mixture was filtered through a 0.2-20.0 micron syringe filter into a bottle 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 compound is provided in unit amount except for the respective weight percentage (expressed in weight/weight; weight ratio). Since the relative parts of the components add up to a total close to 100, in this case the weight percentages of the components are substantially the same as the relative parts. The ratio of MMA to VMA in the polymerizable composition was 0.36:1.

Example 2

Fabrication of Silicone Hydrogel Contact Lenses

The bulk precursor composition from Example 1 was degassed using repeated vacuum/nitrogen flush procedures. The degassed precursor composition is then placed into a female non-polar resin mold member. The filled female mold member is then closed by placing it in contact with the non-polar resin male mold member under pressure required to achieve a tight fit. Curing was then performed in a nitrogen batch oven with the following cycle: 30 min _N2 purge at room temperature, 60 min at 65 °C and 30 min at 100 °C. Demolding is performed by tapping the female mold member of the contact lens mold to release the male mold member therefrom, with the polymerized silicone hydrogel contact lens product adhered to the male mold member. Do mirroring by flotation or using a mechanical tripping device. The float-off method involves soaking a male mold member containing dried lenses in a bucket of water. The glasses typically leave the mold in about 10 minutes. Performed by compressing and rotating a male mold member to which the polymerized silicone hydrogel contact lens product is adhered, directing a gas between the contact lens product and the rotating male mold member, and applying a vacuum to the exposed surface of the contact lens product Mechanical off-camera. The separated lenses are then loaded onto plastic trays for extraction and hydration.

The lens dish containing the polymerized silicone hydrogel contact lens product was immersed in a solvent liquid such as industrial methylated spirits (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 method was repeated with IMS (3x), 1:1 alcohol/water (1x) and DI water (3x).

Store hydrated lenses in glass vials or blister packs containing DI water or in phosphate-buffered saline with a pH of 7.1-7.5. The sealed container was autoclaved at 121 °C for 30 min. After 24 h of autoclaving, spectacle measurements were performed. The resulting hydrated silicone hydrogel contact lenses were weighed and then dehydrated in an oven and weighed again to determine the dry weight of the dehydrated silicone hydrogel contact lenses.

Lens properties, such as contact angle (including dynamic contact angle and static contact angle), oxygen permeability, ion flux, modulus, elongation, tensile strength, water content, etc., were determined as described herein. The wettability of hydrated silicone hydrogel contact lenses was also tested by measuring the water dissipation time of the lenses.

Ocular compatibility is further tested during allocation studies in which contact lenses are placed on the human eye for 1 hour, 3 hours, or 6 hours or more, and then clinically evaluated.

Silicone hydrogel contact lenses produced from the formulations of the present invention have ophthalmically acceptable surface wettability. The silicone hydrogel contact lenses had an equilibrium water concentration (EWC) of 44-47% and were determined to have an extractables content of about 26% by weight.

The resulting hydrated contact lenses have the following properties:

Table 2

characteristic value Equilibrium Water Content (EWC) 45-47% Oxygen permeability (D _k ) 91 Bale Static contact angle (bubble wetting angle) 36-38° Dynamic contact angle (advancing contact angle) 58° Dynamic contact angle (receding contact angle) 50° Lag (forward-backward) 8° Refractive index 1.40 ion flow 3-4 Modulus 0.8-1.0MPa Tensile Strength 0.6-0.7MPa

Various modifications and other embodiments of the invention will be apparent to those skilled in the art to which this invention pertains having benefit of the teachings presented in the foregoing descriptions. Therefore, it is to be understood that this invention is not to be limited to the particular embodiments disclosed herein, which are presented by way of example. While exemplary embodiments are discussed, it should be understood that the foregoing embodiments are intended to cover all modifications, substitutions, and equivalents of the embodiments, as may fall within the spirit and scope of the invention as defined by other disclosures. Although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.

Numerous publications and patents have been cited above. Each of the cited publications and patents is incorporated herein by reference in its entirety.

Claims (26)

1. polymerisable compound, it comprises α-ω-two (methacryloxyethyl imino-carboxyl group ethoxycarbonyl propyls)-poly-(dimethyl siloxane)-poly-(trifluoro propyl methylsiloxane)-poly-(ω-methoxyl-poly-(ethylene glycol) propyl group methylsiloxane), N-vinyl-N-methylacetamide, methyl methacrylate, Ethylene glycol dimethacrylate, the pure and mild radical initiator of allyloxy.

2. polymerisable compound as claimed in claim 1, it further comprises ultraviolet light absorber, colorant or its combination.

3. polymerisable compound as claimed in claim 2, wherein said ultraviolet light absorber are 2-hydroxyl-4-acryloxy oxethyl-diphenyl-ketone.

4. polymerisable compound as claimed in claim 2, wherein said colorant are phthalocyanine color.

5. as the described polymerisable compound of arbitrary claim in the claim 1 to 4, wherein said radical initiator is 2,2 '-azoisobutyronitrile.

6. as the described polymerisable compound of arbitrary claim in the claim 1 to 5, it comprises one or more following each things: (i) α-ω of about 34 weight %-two (methacryloxyethyl imino-carboxyl group ethoxycarbonyl propyls)-poly-(dimethyl siloxane)-poly-(trifluoro propyl methylsiloxane)-poly-(ω-methoxyl-poly-(ethylene glycol) propyl group methylsiloxane), N-vinyl-N-methylacetamide of (ii) about 46 weight %, the methyl methacrylate of (iii) about 17 weight %, the Ethylene glycol dimethacrylate of (iv) about 0.5 weight %, (the allyloxy alcohol of v) about 1 weight %.

7. as the described polymerisable compound of arbitrary claim in the claim 1 to 6, it further comprises one or more following each things: (the 2-hydroxyl of vi) about 0.9 weight %-4-acryloxy oxethyl-diphenyl-ketone, (phthalocyanine blue of vii) about 0.1 weight % and the (radical initiator of viii) about 0.3 weight %.

8. polymerisable compound as claimed in claim 1, it comprises α-ω-two (methacryloxyethyl imino-carboxyl group ethoxycarbonyl propyls)-poly-(dimethyl siloxane)-poly-(trifluoro propyl methylsiloxane)-poly-(ω-methoxyl-poly-(ethylene glycol) propyl group methylsiloxane) of about 34 weight %, N-vinyl-N-methylacetamide of about 46 weight %, the methyl methacrylate of about 17 weight %, the Ethylene glycol dimethacrylate of about 0.5 weight %, the allyloxy alcohol of about 1 weight %, the 2-hydroxyl of about 0.9 weight %-4-acryloxy oxethyl-diphenyl-ketone, 2,2 of the phthalocyanine blue of about 0.1 weight % and about 0.3 weight % '-azoisobutyronitrile.

9. as the described polymerisable compound of arbitrary claim in the claim 1 to 8, wherein do not exist polyalkylene oxidation silicon can extract component.

10. silicone hydrogel contact lens, it is by making as the described polymerisable compound of arbitrary claim in the claim 1 to 9.

11. a silicone hydrogel contact lens, it is by forming as the described composition of arbitrary claim in the claim 1 to 9, and it does not have in fact can extract component.

12. a silicone hydrogel contact lens, it comprises the reaction product as the described composition of arbitrary claim in the claim 1 to 9.

13. silicone hydrogel contact lens, it makes by following steps: the described polymerisable compound of arbitrary claim comprises the extraction pre-polymerization silicone hydrogel contact lens that can extract component in polymerization such as the claim 1 to 9 with formation, contact lenses before described extraction extract the described component that extracts with the polymerization glasses product of formation through extraction, and the described polymerization glasses product through extracting of hydration is to form silicone hydrogel contact lens.

14. silicone hydrogel contact lens as claimed in claim 13, it has equilibrium water content and the oxygen permeability (D in about 80-100 Barre (barrer) scope to about 50 weight % scopes at about 42 weight % _k* 10 ^-11).

15. as claim 13 or 14 described silicone hydrogel contact lens, it has about modulus of 0.6 to about 1.2MPa.

16. silicone hydrogel contact lens as claimed in claim 13, wherein said polymerization comprise described polymerisable compound is heated to greater than about 55 ℃ temperature.

17. silicone hydrogel contact lens as claimed in claim 13, it has at the equilibrium water content of about 42 weight % to about 50 weight % scopes, the oxygen permeability (D in about 80-100 Barre scope _k* 10 ^-11), about modulus of 0.6 to about 1.2MPa, about 2-5 (* 10 ^-3Mm ²/ min) ion flow, about 52 ° to about 62 ° advancing contact angles, about 40 ° to 60 ° receding contact angle and about 5 ° to about 15 ° hysteresis.

18. one kind is not surface treated as the described silicone hydrogel contact lens of arbitrary claim in the claim 10 to 17.

19. method that produces polymerizable silicone hydrogel contact lens precursor composition, described method comprises: combination α-ω-two (methacryloxyethyl imino-carboxyl group ethoxycarbonyl propyls)-poly-(dimethyl siloxane)-poly-(trifluoro propyl methylsiloxane)-poly-(ω-methoxyl-poly-(ethylene glycol) propyl group methylsiloxane), N-vinyl-N-methylacetamide, methyl methacrylate, Ethylene glycol dimethacrylate, the pure and mild radical initiator of allyloxy, and to produce polymerizable silicone hydrogel contact lens precursor composition thus.

20. method as claimed in claim 19 further comprises ultraviolet light absorber in described combination step, colorant, or its combination.

21. method as claimed in claim 20, wherein said ultraviolet light absorber are that 2-hydroxyl-4-acryloxy oxethyl-diphenyl-ketone and described colorant are phthalocyanine color.

22. as the described method of arbitrary claim in the claim 19 to 21, wherein said combination step comprises combination:

(i) α-ω of about 30-40 weight %-two (methacryloxyethyl imino-carboxyl group ethoxycarbonyl propyls)-poly-(dimethyl siloxane)-poly-(trifluoro propyl methylsiloxane)-poly-(ω-methoxyl-poly-(ethylene glycol) propyl group methylsiloxane),

N-vinyl-N-methylacetamide of (ii) about 40-50 weight %,

The methyl methacrylate of (iii) about 10-25 weight % and

(iv) less than the Ethylene glycol dimethacrylate of about 5 weight %, allyloxy alcohol, 2-hydroxyl-4-acryloxy oxethyl-diphenyl-ketone, phthalocyanine blue and 2,2 '-combination of azoisobutyronitrile.

23. method as claimed in claim 22, wherein said combination step comprises α-ω-two (methacryloxyethyl imino-carboxyl group ethoxycarbonyl propyls)-poly-(dimethyl siloxane)-poly-(trifluoro propyl methylsiloxane)-poly-(ω-methoxyl-poly-(ethylene glycol) propyl group methylsiloxane) that makes up about 34 weight %, N-vinyl-N-methylacetamide of about 46 weight %, the methyl methacrylate of about 17 weight %, the Ethylene glycol dimethacrylate of about 0.5 weight %, the allyloxy alcohol of about 1 weight %, the 2-hydroxyl of about 0.9 weight %-4-acryloxy oxethyl-diphenyl-ketone, 2,2 of the phthalocyanine blue of about 0.1 weight % and about 0.3 weight % '-azoisobutyronitrile.

24. as the described method of arbitrary claim in the claim 19 to 23, it further comprises the described polymerizable glasses of polymerization precursor composition to form the preceding polymerization silicone hydrogel contact lens of extraction.

25. method as claimed in claim 24, it is positioned over described polymerizable glasses precursor composition in the non-polar resin contact lens molds before further being included in described polymerization.

26. method as claimed in claim 25, there is not the polymerization glasses product through extraction that can extract component in fact in its polymerization contact lenses that further comprise before the described extraction of extraction to form, and

The described polymerization glasses product through extracting of hydration is to form silicone hydrogel contact lens.

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