HK1170311B - Silicone hydrogel contact lenses and methods of making silicone hydrogel contact lenses - Google Patents

Description

Silicone hydrogel contact lenses and methods of making silicone hydrogel contact lenses

Cross reference to related applications

This application claims the benefit of U.S. provisional application No. 61/278,072 filed on 10/1/2009, the entire disclosure of which is incorporated herein by reference.

Technical Field

The present invention relates to contact lenses and methods of making contact lenses, such as silicone hydrogel contact lenses and methods of making silicone hydrogel contact lenses.

Background

Silicone hydrogel contact lenses have become an important tool in vision correction. Various techniques have been employed to produce silicone hydrogel contact lenses having hydrophilic surfaces. For example, the surface of some silicone hydrogel contact lenses is plasma treated, some silicone hydrogel contact lenses include a hydrophilic polymeric wetting agent in the polymerizable composition used to make the silicone hydrogel contact lenses, and some silicone hydrogel contact lenses are cast in contact lens molds formed from a polar resin.

U.S. patent application publication US2008/0143956 to charlmar et al discloses silicone hydrogel contact lenses in which the lens surface is wrinkled and includes ridges extending upwardly from the lens surface. The wrinkled surface provided on the rear surface of the lens is said to facilitate fluid exchange between the lens and the cornea of the lens wearer's eye. The lens is a cast molded lens that is formed prior to providing the wrinkled surface to the lens. The formed or cast molded contact lens initially has a modified surface layer, such as a silicate surface layer, and subsequently the modified surface becomes a wrinkled surface. For example, the surface may be modified by treatment with plasma or other energy sources. After forming the modified surface layer, the lens is swelled with a polymerizable swelling agent that includes, for example, ethylenically unsaturated moieties such that the swelling agent can be polymerized by free radical polymerization. Depending on the amount of swelling, the modified surface layer (e.g., silicate layer) may wrinkle to varying degrees. The polymerizable swelling agent is polymerized to stabilize the wrinkled modified surface layer. This multi-step process, particularly surface modification and stabilization treatment after lens formation, is relatively complex and difficult to control, and increases the cost of manufacturing silicone hydrogel contact lenses.

There remains a need for novel contact lenses having desirable properties, such as surface wettability, and novel methods (e.g., cost-effective methods) of making contact lenses having such desirable properties.

Disclosure of Invention

Novel silicone hydrogel contact lenses and methods of making silicone hydrogel contact lenses have been discovered. The present silicone hydrogel contact lenses have contact lens bodies (contact lens bodies) with surfaces having novel surface characteristics. Wherein the front lens surface and the back lens surface are hydrophilic and do not have to be subjected to a plasma treatment and/or a treatment with a polymerizable swelling agent after forming the lens body. The present methods directly produce the present contact lenses without the need for plasma treatment and/or treatment with a polymerizable swelling agent of the contact lenses after forming the lens bodies.

In one broad aspect, an example of the present silicone hydrogel contact lenses comprises a lens body comprising an anterior surface and a posterior surface, wherein upon hydration in water or an aqueous solution, at least one of the anterior surface and the posterior surface of the lens body comprises a plurality of depressions having an average diameter of between about 150 nanometers and less than 1500 nanometers when wetted, and wherein upon formation of the lens body, the lens body is not subjected to one form of plasma treatment, the lens body is not treated with a polymerizable swelling agent, or is not subjected to both plasma and swelling agent treatments.

An additional example of the present silicone hydrogel contact lenses includes a non-plasma treated silicone hydrogel lens body comprising an anterior surface and a posterior surface, at least one of the surfaces comprising a plurality of depressions having a density of from about 100 depressions per 900 square microns to about 1200 depressions per 900 square microns.

In one embodiment, the average diameter of the plurality of depressions is between about 130 nanometers and less than about 630 nanometers, or the average diameter of the plurality of depressions is between about 150 nanometers and less than about 550 nanometers.

The plurality of depressions may have an average depth of about 4 nanometers or about 15 nanometers to about 30 nanometers or about 60 nanometers or about 100 nanometers. For example, the average depth of the plurality of depressions can be from about 4 nanometers to about 65 nanometers, from about 4 nanometers to about 40 nanometers, from about 4 nanometers to about 20 nanometers, from about 8 nanometers to about 20 nanometers, or from about 15 nanometers to about 90 nanometers.

In one embodiment, the average surface roughness of at least one of the anterior and posterior surfaces of the lens body is from about 5 nanometers RMS or about 7 nanometers RMS or about 10 nanometers RMS to about 20 nanometers RMS or about 25 nanometers RMS or about 30 nanometers RMS. Thus, the average surface roughness of the present silicone hydrogel contact lenses can be from about 5nm RMS to about 30nm RMS, from about 7nm RMS to about 25nm RMS, or from about 10nm RMS to about 20nm RMS.

In one embodiment, the average density of depressions (meaning the average number of depressions per 900 square micron surface) on at least one of the anterior and posterior surfaces of the lens body is from about 5 or about 80 or about 100 or about 200 depressions per 900 square micron surface to about 1000 or about 1200 or about 1500 depressions per 900 square micron surface. Thus, the average density of depressions on at least one of the anterior and posterior surfaces of the lens bodies of the present contact lenses can be from about 5 depressions per 900 square micrometer surface to about 1500 depressions per 900 square micrometer surface, from about 80 depressions per 900 square micrometer surface to about 1500 depressions per 900 square micrometer surface, from about 100 depressions per 900 square micrometer surface to about 1200 depressions per 900 square micrometer surface, or from about 200 depressions per 900 square micrometer surface to about 1000 depressions per 900 square micrometer surface.

A plurality of depressions extend inwardly into the lens body, for example, from the front and/or back surface of the otherwise substantially smooth lens body. Thus, the multiple depressions of the present invention and the otherwise substantially smooth front and/or back surfaces of the present lens bodies should not, and reasonably should not, be considered ridges. In brief, the lens body of the present invention can be free of ridges. Furthermore, as noted above, the plurality of depressions on the anterior surface, the posterior surface, or both of the present lens bodies, along with other surface characteristics of the present contact lenses, can provide surface roughness. However, it has been found that the surface roughness does not substantially adversely affect the comfort of the lens wearer. In addition, it should be understood that the depression present on a surface of the lens body does not extend through the entire thickness of the lens body to the other opposing surface, and thus, the present depression is not a hole extending through the lens body.

The ability of the present contact lenses to substantially maintain an advancing contact angle and a time of water break water film break time (water break time) after hydration of, for example, at least 12 hours, indicates that the beneficial surface wetting properties of the lens bodies of the present contact lenses can be maintained for a longer period of time or be substantially durable or even substantially permanent, rather than a phenomenon that occurs only immediately following or following hydration. The wetting properties of the present contact lenses may be suitable for extended continuous wear by lens wearers wearing the lenses, for example, for at least about 1 day, or about 5 days, or about 10 days, or up to about 30 days.

In one embodiment, the lens body is water swellable, e.g., having a swelling factor of at least about 20%. The Equilibrium Water Content (EWC) of the lens body can be at least about 25% or at least about 30% or at least about 35% or at least about 40% or at least about 50% or more.

The lens body of the present silicone hydrogel contact lenses comprises units of at least one of: a silicone-containing monomer, a silicone-containing macromer, a silicone-containing prepolymer, or a combination thereof. The lens body can comprise a hydrophilic silicone-containing polymeric material.

In certain embodiments, the lens body of the present contact lenses does not include a hydrophilic polymeric internal wetting agent physically entangled within the polymeric matrix of the lens body. For example, a hydrophilic polymeric wetting agent is not included in the polymerizable composition that is cured to form the lens body.

In one embodiment, the lens body of the present contact lenses is fully or partially cured while in direct contact with a contact lens mold comprising a non-polar material. For example and without limitation, the non-polar material may comprise polypropylene, similar non-polar materials, and mixtures thereof. In certain embodiments, the present silicone hydrogel contact lenses are cast molded in contact lens mold assemblies formed from a nucleated thermoplastic polypropylene resin having

(i) A melt flow rate between about 15g/10min and about 40g/10min,

(ii) about 0.900g/cm³The density of (a) of (b),

(iii) a linear flow molding shrinkage of about 0.010in/in to about 0.020in/in,

(iv) a tensile strength of about 5600psi,

(v) a tensile elongation of about 8.0%,

(vi) a modulus of flexibility of about 200,000psi to about 290,000psi,

(vii) a Rockwell hardness of about 110, or a combination of two or more thereof.

The present contact lenses can have a lens body comprising the reaction product of a polymerizable composition comprising a reactive ingredient. The reactive components comprise: (1) at least one component selected from the group consisting of: silicone-containing monomers, silicone-containing macromers, silicone-containing prepolymers, and mixtures thereof; (2) at least one hydrophilic monomer; and (3) at least one crosslinking agent that crosslinks the reactive ingredients during polymerization to form a polymeric lens body. In one embodiment, the lens body is formed by a method comprising polymerizing the polymerizable composition in the absence of a diluent. In other words, the polymerizable composition is a diluent-free polymerizable composition.

The molecular weight of the silicone-containing monomer used in the polymerizable composition of the present invention can be less than 700 daltons (Dalton). The silicone-containing macromer used in the polymerizable composition of the present invention can have a molecular weight of from about 700 daltons to about 2000 daltons. The molecular weight of the silicone-containing prepolymer used in the polymerizable composition of the present invention can be greater than 2000 daltons. The molecular weight can be a number average molecular weight or a weight average molecular weight, as understood by one of skill in the art.

In one embodiment, the lens body of the present contact lenses is a cast molded lens body comprising an anterior surface and a posterior surface, each surface being free of plasma treated surfaces. In other words, the lens body, including the anterior and posterior surfaces, is formed by a single cast molding step, and is formed without exposing the surfaces to a form of plasma treatment. In another embodiment, the lens body of the present contact lenses includes a surface layer having a composition different from the remainder of the lens body, e.g., a surface layer formed by exposing the lens body to water or an aqueous solution.

In some embodiments, the lens bodies of the present contact lenses are not extracted with an organic solvent or an aqueous solution comprising an organic solvent component prior to hydration in water or an aqueous solution. The present contact lenses can have an effectively or sufficiently wettable surface that is not extracted with an organic solvent (such as, and not limited to, a volatile alcohol) or an aqueous solution comprising an organic solvent. The ophthalmically acceptable or biocompatible contact lenses can be obtained by rinsing or washing with water once or more. It can be appreciated that the present contact lenses comprise a lens body that has been washed with an aqueous wash solution that is free of volatile alcohols. The lens can be washed one or more times with the liquid free of volatile alcohol and can be washed in the final contact lens package or in one or more other wash containers.

The lens bodies of the present contact lenses can be contacted with liquid water or an aqueous medium prior to placement in a packaging liquid. The aqueous medium may include a surfactant component. In one embodiment, the water or aqueous medium does not include an organic solvent or a volatile alcohol.

In another broad aspect of the invention, a method of manufacturing a contact lens is provided. The present methods comprise forming a contact lens body having an anterior surface and a posterior surface, wherein upon hydration in water or an aqueous solution, at least one of the anterior surface and the posterior surface of the lens body comprises a plurality of depressions having an average diameter of between about 50 nanometers and less than 1500 nanometers when wetted, and wherein: after forming the lens body, (a) the lens body has not been subjected to a form of plasma treatment, (B) the lens body has not been treated with a polymerizable swelling agent, or both (a) and (B).

The forming step can comprise polymerizing a polymerizable composition comprising the reactive ingredients. The reactive component comprises (1) at least one component selected from the group consisting of: silicone-containing monomers, silicone-containing macromers, silicone-containing prepolymers, and mixtures thereof; (2) at least one hydrophilic monomer and (3) at least one crosslinking agent effective to crosslink the reactive ingredients during the polymerization step.

The contact lenses and lens bodies made according to the present methods can be contact lenses and contact lens bodies described elsewhere herein.

The present methods can be implemented using contact lens molds comprising, for example, a non-polar material as set forth elsewhere herein.

Various embodiments of the invention are described in detail in the following detailed description and additional disclosure. Any feature or combination of features described herein is included within the scope of the present invention provided that the features included in any such combination are not clearly contradicted by context, this description, and the knowledge of one of ordinary skill in the art. In addition, any feature or combination of features may be specifically excluded from any embodiment of the present invention. Additional embodiments of the invention will be apparent in the following description, examples and claims, the contents of which are an integral part of the present application.

Drawings

Fig. 1 shows the average diameter (nm) of the pits for a series of 16 test contact lenses and a series of commercially available silicone hydrogel contact lenses as determined by Atomic Force Microscope (AFM) testing.

Fig. 2 shows the average depth (nm) of depression for a series of 16 test contact lenses and a series of commercially available silicone hydrogel contact lenses as determined by AFM testing.

Fig. 3 shows the surface depression density of a series of 16 test contact lenses and a series of commercially available silicone hydrogel contact lenses as determined by AFM testing.

Fig. 4 shows the average RMS surface roughness (nm) of a series of 16 test contact lenses and a series of commercially available silicone hydrogel contact lenses as determined by AFM testing.

Fig. 5-10 show a series of photographs showing the lens surface morphology after hydration of 16 test contact lenses as determined by AFM.

Fig. 11-14 show a series of photographs showing the lens surface morphology after hydration for various commercially available lenses as determined by AFM.

Fig. 15-18 show a series of photographs of several test contact lenses and commercial contact lenses in both the wet or hydrated state and the dry state.

Detailed Description

In the context of this specification, additional disclosure, claims, and accessories, the following terms will be used according to the definitions set forth below.

The term "hydrogel" as used herein refers to a polymeric material, typically a network or matrix of polymer chains, that is capable of swelling in or with water. A hydrogel is also understood to be a material that keeps water in an equilibrium state. The network or matrix may or may not be crosslinked. By hydrogel is meant a water-swellable or water-swollen polymeric material, including contact lenses. Thus, the hydrogel may be (i) unhydrated and water swellable, or (ii) partially hydrated and water swollen, or (iii) fully hydrated and water swollen. The hydrogel may be a silicone hydrogel, a silicone-free hydrogel, or a substantially silicone-free hydrogel.

The term "silicone hydrogel" or "silicone hydrogel material" refers to a particular hydrogel that includes a silicon (Si) -containing component or a Silicone (SiO) -containing component. For example, silicone hydrogels are typically prepared by combining silicon-containing materials with conventional hydrophilic hydrogel precursors. Silicone hydrogel contact lenses are contact lenses, including vision correction contact lenses, comprising a silicone hydrogel material.

The "silicone-containing" component is a monomer, macromer or prepolymer containing at least one [ -Si-O-Si-]A linking component in which each silicon atom may optionally in some way bear one or more organic group substituents (R) which may be the same or different₁，R₂) Or a substituted organyl group substituent, e.g. to which each silicon atom may optionally be chemically (e.g. covalently) bonded, e.g. — SiR₁R₂O-。

In the context of the polymers described herein, "molecular weight" refers to the nominal average molecular weight of the polymer, which is typically determined by size exclusion chromatography, light scattering techniques, or intrinsic velocity determination of 1, 2, 4-trichlorobenzene. In the context of polymers, molecular weight may be expressed as a number average molecular weight or a weight average molecular weight, and in the case of materials supplied by vendors, will depend on the supplier. Typically, if the basis for any such molecular weight determination is not provided in the packaging material, it can be readily provided by the supplier. Generally, reference herein to the molecular weight of a monomer, macromer, prepolymer, or polymer is referred to herein as a weight average molecular weight. Molecular weight determinations (both number average and weight average) can be measured using gel permeation chromatography or other liquid chromatography techniques. Other methods of measuring molecular weight values may also be used, such as determining number average molecular weight using end group analysis or measuring colligative properties (e.g., freezing point depression, boiling point elevation, or osmotic pressure) or determining weight average molecular weight using light scattering techniques, ultracentrifugation, or viscometry.

The "network" or "matrix" of hydrophilic polymers generally means crosslinks formed between polymer chains by covalent bonding or by physical bonding (e.g., hydrogen bonding). The network may comprise two or more polymeric components and may comprise an Interpenetrating Polymer Network (IPN) in which one polymer is physically entangled with a second polymer such that there are, if any, covalent bonds between them, but the polymers cannot be separated from each other without disrupting the network.

"hydrophilic" substances are substances that are water-loving or that have an affinity for water. Hydrophilic compounds have an affinity for water and generally carry an electrical charge or have polar moieties or groups that attract water.

As used herein, a "hydrophilic polymer" is defined as a polymer that has an affinity for water and is capable of absorbing water. The hydrophilic polymer need not be soluble in water. The hydrophilic polymer is soluble or insoluble (e.g., substantially insoluble) in water.

A "hydrophilic component" is a hydrophilic material that may or may not be a polymer. Hydrophilic components include those components that, when combined with the remaining reactive components, are capable of providing a water content of at least about 20% (w/w) (e.g., at least about 25% (w/w)) to the resulting hydrated lens. The hydrophilic component may include a hydrophilic monomer, a hydrophilic macromer, a hydrophilic prepolymer, a hydrophilic polymer, or a combination thereof. Hydrophilic macromers, hydrophilic prepolymers and hydrophilic polymers are also understood to have hydrophilic and hydrophobic portions. Typically, the hydrophilic and hydrophobic portions are present in relative amounts such that the macromer, prepolymer, or polymer is hydrophilic.

"monomer" refers to a relatively low molecular weight polymerizable compound, such as a compound having an average molecular weight of less than 700 daltons. In one example, a monomer may comprise a single unit of a molecule containing one or more functional groups capable of undergoing polymerization to form a polymer in combination with other molecules, either of the same structure or of a different structure than the monomer.

"macromer" refers to medium and high molecular weight compounds or polymers, which may contain one or more functional groups capable of polymerization or further polymerization. For example, the macromer may be a compound or polymer having an average molecular weight of about 700 daltons to about 2,000 daltons.

"prepolymer" refers to a polymerizable or crosslinkable higher molecular weight compound. The prepolymers used herein may contain one or more functional groups. In one example, the prepolymer may be a series of monomers or macromers that are bonded together such that the overall molecule is still polymerizable or crosslinkable. For example, the prepolymer can be a compound having an average molecular weight greater than about 2,000 daltons.

"Polymer" refers to a material formed by polymerizing one or more monomers, macromers, prepolymers, or mixtures thereof. It is to be understood that a polymer, as used herein, refers to a molecule that is not polymerizable but capable of crosslinking to other polymers, for example, other polymers present in the polymerizable composition or other polymers formed in the polymerizable composition during reaction of the monomers, macromers, and/or prepolymers.

"interpenetrating polymer network" or "IPN" refers to a combination of two or more different polymers in the form of a network, at least one of which is synthesized and/or crosslinked in the presence of the other and without or substantially without any covalent bonding between the two. IPNs may be composed of two chains forming two separate but side-by-side or interpenetrating networks. Examples of IPNs include sequential IPNs, synchronous IPNs, semi-IPNs, and homogeneous IPNs.

"pseudo IPN" refers to a polymeric reaction product in which at least one of the different polymers is crosslinked, while at least one other polymer is non-crosslinked (e.g., linear or branched), wherein on a molecular scale, the non-crosslinked polymer is distributed in and held by the crosslinked polymer such that the non-crosslinked polymer is substantially inseparable from the network.

By "polymeric mixture" is meant a polymeric reaction product in which the different polymers are all linear or branched and substantially free of cross-linking, wherein the resulting polymeric blend obtained is a mixture of polymers on a molecular scale.

"graft polymer" refers to a branched polymer having side chains comprising a homopolymer or copolymer different from the backbone.

Unless otherwise specified, "attached" may refer to any of the following: charge attachment, grafting, complexing, bonding (chemical bonding or hydrogen bonding), or attachment.

As used herein, "ophthalmically acceptable lens-forming component" refers to a lens-forming component that can be incorporated into a hydrogel contact lens and which does not experience or report significant discomfort to the lens wearer, including ocular irritation and the like. Ophthalmically acceptable hydrogel contact lenses have ophthalmically acceptable surface wettability and typically do not cause or are associated with significant corneal swelling, corneal dehydration ("dry eye"), epithelial arcuate lesions ("SEAL"), or other significant discomfort.

The term "organic solvent" refers to an organic substance capable of solvating or dissolving at least one material (such as, and without limitation, unreacted materials, diluents, and the like) present in a contact lens body that has not previously been subjected to an extraction process. In one example, the material is insoluble or water-in-aqueous material. In another example, the material is one that is not or not substantially soluble in water or aqueous solutions, i.e., the solvation of the material in an organic solvent is increased as compared to water or aqueous solutions. Thus, the organic solvent in contact with the unextracted contact lens body is effective to solvate or dissolve, or increase the solvation or more greatly dissolve, the at least one material present in the lens body, thereby reducing the concentration of the at least one material present in the lens body, or reducing the concentration of the at least one material present in the lens body as compared to a lens body treated with water or an aqueous solution. The organic solvent may be used undiluted (i.e., 100% organic solvent), or may be used in the form of a composition comprising less than 100% organic solvent (e.g., and without limitation, an aqueous solution comprising organic solvent). Typically, the organic solvent acts (e.g., directly acts) on the at least one material to solvate or dissolve the at least one material. Examples of organic solvents include, but are not limited to, alcohols (e.g., alkanols, such as ethanol, isopropanol, and the like), chloroform, butyl acetate, tripropylene glycol methyl ether, dipropylene glycol methyl ether acetate, and the like, and mixtures thereof.

The term "surfactant" or "surfactant component" refers to a substance that is capable of reducing the surface tension of water (e.g., water or an aqueous solution containing the substance). The surfactant or surfactant component helps to bring water containing the surfactant or surfactant component into closer contact with the lens body when contacted with a contact lens body that has not previously been subjected to an extraction treatment with an organic solvent and/or more effectively wash or remove at least one material present in the lens body from the lens body relative to water without the surfactant or surfactant component by reducing the surface tension of the water. Generally, the surfactant or surfactant component does not act directly on the at least one material to solvate or dissolve the at least one material. Examples of surfactants or surfactant components include, but are not limited to, zwitterionic surfactants (including betaine forms), nonionic surfactants (including polysorbate (e.g., polysorbate 80) forms, poloxamer (poloxamer) or poloxamine (poloxamine) forms), fluorinated surfactants and the like, and mixtures thereof.

Other definitions may also be found in sections below.

Hydrogels represent one class of materials for use in the present contact lenses. Hydrogels comprise an aqueous hydrated cross-linked polymeric system in an equilibrium state. Thus, a hydrogel is a copolymer made from one or more reactive ingredients. The reactive ingredients may be crosslinked using a crosslinking agent.

The hydrophilic monomer can be, for example, a silicone-containing monomer having a hydrophilic moiety, a silicone-free hydrophilic monomer, or a combination thereof. Hydrophilic monomers may be used in combination with hydrophobic monomers. The hydrophilic monomer may be a monomer having both a hydrophilic portion (mode or mobility) and a hydrophobic portion. The type and amount of hydrophilic monomer used in the polymerizable lens composition can vary depending on the type of other lens-forming monomers used. Non-limiting illustrations of hydrophilic monomers for use in silicone hydrogels are provided herein.

Crosslinking agents for the monomers, macromers, or prepolymers used to make the hydrogels can include those known in the art, and examples of crosslinking agents are also provided herein. Suitable crosslinkers include, for example, diacrylate- (or divinyl ether-) functionalized ethylene oxide oligomers or monomers such as tri (ethylene glycol) dimethacrylate (TEGDMA), tri (ethylene glycol) divinyl ether (TEGDVE), Ethylene Glycol Dimethacrylate (EGDMA), and propylene glycol dimethacrylate (TMGDMA). Typically, the crosslinking agent is present in the polymerizable silicone hydrogel composition in a relatively small total amount of the polymerizable composition, for example, in an amount in the range of about 0.1% (w/w) to about 10% (w/w), or about 0.5% (w/w) to about 5% (w/w), or about 0.75% (w/w) to about 1.5% (w/w), by weight of the polymerizable composition.

The silicone hydrogel lens formulation comprises at least one silicone-containing component, at least one compatible hydrophilic monomer, and at least one compatible cross-linking agent. For purposes of the polymerizable lens formulations discussed herein, "compatible" component refers to a component that, when present in the polymerizable composition prior to polymerization, forms a single phase that is stable for a period of time sufficient to produce a polymerized lens body from the composition. For some components, it was found that multiple concentrations can have compatibility. Additionally, a "compatible" component is a component that when polymerized to form a polymeric lens body results in a lens having sufficient physical properties (e.g., sufficient clarity, modulus, tensile strength, etc.) for use as a contact lens.

The Si and attached O moieties (Si-O moieties) of the silicone-containing component can be present in the silicone-containing component in an amount greater than 20% (w/w), e.g., greater than 30% (w/w), of the total molecular weight of the silicone-containing component. Useful silicone-containing components contain polymerizable functional groups such as vinyl, acrylate, methacrylate, acrylamide, methacrylamide, N-vinyl lactam, N-vinyl amide, and styryl functional groups. The silicone-containing component of the contact lenses of the invention may be obtained, for example, by polymerization, and comprises one or more silicone-containing monomers, one or more silicone-containing macromers, one or more silicone-containing prepolymers, or mixtures thereof. Silicone hydrogel contact lenses manufactured as described herein may be based on a silicone-containing monomer and/or a silicone-based macromer and/or a silicone-based prepolymer, and a hydrophilic monomer or co-monomer and a crosslinking agent. Examples of other silicone-containing components that can be used in the lenses of the invention, in addition to the other silicone-containing compounds described herein, can be found in U.S. Pat. Nos. 3,808,178, 4,120,570, 4,136,250, 4,139,513, 4,153,641, 4,740,533, 5,034,461, 5,496,871, 5,959,117, 5,998,498 and 5,981,675, and U.S. patent application publications 2007/0066706A1, 2007/0296914A1 and 2008/0048350A1, all of which are incorporated herein by reference in their entirety. The silicone-containing component can be a silicone-containing monomer or a silicone-containing macromer or a silicone-containing prepolymer.

The silicone-containing monomer, macromer or prepolymer can have, for example, the following general structure (I):

wherein R is⁵Is H or CH₃X is O or NR⁵⁵Wherein R is⁵⁵Is H or a monovalent alkyl group having 1 to 4 carbon atoms, a is 0 or 1, L is a divalent linking group containing 1 to 20 carbon atoms or 2 to 10 carbon atoms, which may optionally also contain ether and/or hydroxyl groups, e.g., a polyethylene glycol chain, p may be 1 to 10 or 2 to 5, R₁、R₂And R₃May be the same or different and are independently selected from the group consisting of: a hydrocarbon group having 1 to about 12 carbon atoms (e.g., methyl), a hydrocarbon group substituted with one or more fluorine atoms, a siloxane group, and a siloxane-containing chain moiety, wherein R is₁、R₂And R₃At least one of which comprises at least one siloxane unit (-OSi). For example, R₁、R₂And R₃At least one of which may comprise-OSi (CH)₃)₃and/or-OSi (R)⁵²R⁵³R⁵⁴) Wherein R is⁵²、R⁵³、R⁵⁴Independently an ethyl group, a methyl group, a benzyl group, a phenyl group, or a monovalent siloxane chain comprising from 1 to about 100, or from about 1 to about 50, or from about 1 to about 20 Si-O repeat units.

R₁、R₂And R₃One, two or all three of them may also comprise other siloxane groups or silicon groupsAn alkylene oxide chain moiety. If a combined linkage of-X-L-is present in the silicone-containing monomer, macromer or prepolymer of structure (I), it may contain one or more heteroatoms that are O or N. The combinatorial linkage may be linear or branched, wherein the carbon chain segments thereof may be linear. The combined linkage of-X-L-may optionally contain one or more functional groups selected from, for example, carboxyl, amide, carbamate, and carbonate. Examples of such combinatorial linkages are provided, for example, in U.S. patent No. 5,998,498 and U.S. patent application publication nos. 2007/0066706a1, 2007/0296914a1 and 2008/0048350, the entire disclosures of which are incorporated herein by reference. The silicone-containing monomer, macromer or prepolymer used in the present invention may comprise a single acryloyl group, such as that shown in structure (I), or it optionally may have two acryloyl groups, e.g., one at each end of the monomer, monomer or prepolymer. Combinations of two types of silicone-containing monomers, macromers or prepolymers can optionally be used in the polymerizable compositions used in the present invention.

Examples of silicone-containing components useful in the present invention include, for example and without limitation, polysiloxanylalkyl (meth) acrylic monomers, macromers, or prepolymers, including, without limitation, methacryloxypropyltris (trimethylsiloxy) silane, pentamethyldisiloxymethyl methacrylate, and methyldi (trimethylsiloxy) methacryloxymethylsilane.

A specific example of a useful silicone-containing monomer, macromer or prepolymer can be, for example, 3- [ tris (trimethylsilyloxy) silyl ] methacrylate]Propyl ester ("Tris", available from Gransted (Gelest), Morisville, Pa., USA) and monomethacryloxy-terminated polydimethylsiloxane ("MCS-M11", available from Gransted, Morisville, Pa., USA). Examples of some silicone-containing monomers are disclosed in U.S. patent application publication No. 2008/0269429. These silicone-containing monomers can have an alkylene group as a divalent linking group (e.g., - (CH)₂)_p-) and "a" can be 0 for structure (I) and have at least two siloxane groups. These silicone-containing components are designated herein as silicone-containing monomers of structure (A). Exemplary, non-limiting structures of these silicone-containing monomers are shown below:

other specific examples of silicone-containing components useful in the present invention may be, for example, 3-methacryloxy-2-hydroxypropoxy) propyl bis (trimethylsiloxy) methylsilane ("SiGMA", available from Grasitter, Morisville, Pa., U.S.A.) and methyl bis (trimethylsiloxy) silylpropylglyceryl ethyl methacrylate ("SiGEMA"). These silicone-containing components include at least one hydroxyl group and at least one ether group and at least two siloxane groups in the divalent linking group L shown in structure (I). These silicone-containing components are designated herein as silicone-containing components of the structure (B) class. Additional details regarding such silicone-containing components are provided, for example, in U.S. patent No. 4,139,513, which is incorporated herein by reference in its entirety. For example, SiGMA may be represented by the following exemplary, non-limiting structure:

the silicone-containing components of structures (A) and (B) may be used alone or in any combination thereof in the polymerizable compositions used in the present invention. The silicone-containing component of structures (a) and/or (B) may be further used in combination with at least one silicone-free hydrophilic monomer, such as those described herein. If used in combination, for example, the amount of the silicone-containing component of structure (A) can be, for example, from about 10% (w/w) to about 40% (w/w), or from about 15% (w/w) to about 35% (w/w), or from about 18% (w/w) to about 30% (w/w). The amount of the silicone-containing component of structure (B) can be, for example, from about 10% (w/w) to about 45% (w/w), or from about 15% (w/w) to about 40% (w/w), or from about 20% (w/w) to about 35% (w/w).

Currently useful polymerizable compositions can include one or more non-silicone-containing hydrophobic monomers. Examples of the hydrophobic monomer include, but are not limited to, acrylic acid and methacrylic acid and derivatives thereof. An example of a non-silicone-containing hydrophobic monomer includes, but is not limited to, methyl methacrylate, and combinations of two or more hydrophobic monomers may be employed.

Other specific examples of useful silicone-containing components for use in the present invention may be a chemical represented by the following formula or a chemical described in japanese patent application publication No. 2008-202060A, the entire contents of which are incorporated herein by reference, for example,

X-22-1625

mw 9,000 or 18,000

FMM，Mw＝1,500

X-22-1622，Mw＝582

DMS-R18，Mw＝4500～5500

MCR-M07，Mw＝1132

Still further specific examples of useful silicone-containing components for use in the present invention may be chemicals represented by the formula or described in U.S. application publication No. 2009/0234089, which is incorporated herein by reference in its entirety. In one example, the silicone-containing component can comprise one or more hydrophilic polysiloxane components represented by the general formula (II),

wherein R is₁Selected from hydrogen or methyl; r₂Selected from hydrogen or C_1-4A hydrocarbyl group; m represents an integer of 0 to 10; n represents an integer of 4 to 100; a and b represent 1 or an integer of 1 or more; a + b equals 20 to 500; b/(a + b) equals 0.01 to 0.22; and the configuration of the siloxane units comprises a random configuration. Examples of such silicone-containing components are described in the examples section of U.S. patent application publication No. 2009/0234089, including example 2, page 7.

Other silicone-containing components may also be used. For example, other suitable types may include, for example, poly (organosiloxane) monomers, macromers, or prepolymers, such as α, ω -bis-methacryloxy-propylpolydimethylsiloxane. Another example is mPDMS (monomethacryloxy terminated mono n-butyl terminated polydimethylsiloxane). Other useful silicone-containing components include silicone-containing vinyl carbonate or vinyl carbamate monomers, macromonomers or prepolymers, including, but not limited to, 1, 3-bis [4- (ethyleneoxycarbonyloxy) but-1-yl ] tetramethylsiloxane 3- (ethyleneoxycarbonylthio) propyl- [ tris (trimethylsiloxysilane ], 3- [ tris (trimethylsiloxy) silyl ] propyl allyl carbamate, 3- [ tris (trimethylsiloxy) silyl ] propyl vinyl carbamate, trimethylsilylethyl vinyl carbonate and trimethylsilylmethyl vinyl carbonate, examples of one or more of these silicone-containing components may be provided, for example, in U.S. Pat. No. 5,998,498 and U.S. patent application publication No. 2007/0066706A1, U.S. Pat. No. 3,8978, U.S. Pat. No. 4,, 2007/0296914A1 and 2008/0048350, the entire disclosure of which is incorporated herein by reference.

Some silicone-containing monomers, macromers or prepolymers that can be used in accordance with the present invention can be used as a single discrete monomer, macromer or prepolymer or can be used as a mixture of two or more discrete monomers, macromers or prepolymers. For example, MCR-M07 is typically provided as a mixture of silicone-containing compounds having a broad molecular weight distribution. Alternatively, some of the silicone-containing monomers, macromers or prepolymers that can be used in accordance with the present invention can be provided as two or more monomers, macromers or prepolymers having discrete molecular weights. For example, X-22-1625 may be available in a lower molecular weight form having a molecular weight of about 9000 daltons and in a higher molecular weight form having a molecular weight of about 18,000 daltons.

The silicone-free hydrophilic monomers are included in the polymerizable compositions used to make the contact lenses of the invention. The silicone-free monomers do not include hydrophilic compounds containing one or more silicon atoms. In the polymerizable composition, the silicone-free hydrophilic monomer can be used in combination with a silicone-containing monomer, macromer or prepolymer to form a silicone hydrogel. In the polymerizable composition, the silicone-free hydrophilic monomer can be used in combination with other silicone-free monomers (including silicone-free hydrophilic monomers and silicone-free hydrophobic monomers) to form a silicone-free hydrogel. In silicone hydrogels, silicone-free hydrophilic monomer components include those capable of providing at least about 10% (w/w) or even at least about 25% (w/w) water content to the resulting hydrated lens when combined with other polymerizable composition components. In the case of silicone hydrogels, the total silicone-free monomers may comprise from about 25% (w/w) to about 75% (w/w), or from about 35% (w/w) to about 65% (w/w), or from about 40% (w/w) to about 60% (w/w) of the polymerizable composition.

Monomers that can be included as silicone-free monomers typically have at least one polymerizable double bond, at least one hydrophilic functional group, or both. Examples of polymerizable double bonds include, for example, vinyl double bonds, acrylic double bonds, methacrylic double bonds, acrylamide double bonds, methacrylamido double bonds, fumaric double bonds, maleic double bonds, styryl double bonds, isopropenylphenyl double bonds, O-vinyl ester double bonds of carbonic acid, O-vinyl ester double bonds of carbamic acid, allyl double bonds, O-vinylacetyl double bonds and N-vinyllactam double bonds and N-vinylamido double bonds. In one example, the hydrophilic monomer is a vinyl-containing monomer (e.g., an acrylic-containing monomer or a non-acrylic-containing vinyl monomer). The hydrophilic monomer itself may serve as a crosslinking agent.

The silicone-free hydrophilic monomer can be, but need not be, a cross-linking agent. Considered a subgroup of the above acryloyl moieties, "acrylic" monomers or "acrylic-containing" monomers or acrylate-containing monomers are monomers containing an acrylic group (CR' H ═ CRCOX), where R is H or CH₃R' is H, alkyl or carbonyl and X is O or N, which monomers are also known to polymerize readily.

In the case of silicone hydrogels, the silicone-free hydrophilic component can comprise a non-silicon containing monomeric component comprising an acrylic monomer (e.g., a monomer having a vinyl group at the α -carbon and a carboxylic acid terminus, a monomer having a vinyl group at the α -carbon and an amide terminus, etc.) and a vinyl group (CH)₂A hydrophilic monomer (i.e., a monomer containing a vinyl group that is not part of an acrylic group) of CH —.

Illustrative acrylic monomers include N, N-Dimethylacrylamide (DMA), 2-hydroxyethyl acrylate, glycerol methacrylate, 2-hydroxyethyl methacrylate (HEMA), methacrylic acid, acrylic acid, Methyl Methacrylate (MMA), ethylene glycol methyl ether methacrylate (EGMA), and any mixture thereof. In one example, the total acrylic monomer content is present in an amount in the range of about 5% (w/w) to about 50% (w/w) of the polymerizable composition from which the silicone hydrogel lens product is prepared, and may be present in an amount in the range of about 10% (w/w) to about 40% (w/w) or about 15% (w/w) to about 30% (w/w) of the polymerizable composition.

As described above, the silicone-free monomer may further comprise a vinyl-containing hydrophilic monomer. Hydrophilic vinyl-containing monomers that can be incorporated into the lens materials of the present invention include, but are not limited to, the following: n-vinyl lactams (e.g., N-vinyl pyrrolidone (NVP)), N-vinyl-N-methyl acetamide (VMA), N-vinyl-N-ethyl acetamide, N-vinyl-N-ethyl formamide, N-vinyl formamide, N-2-hydroxyethyl vinyl carbamate, N-carboxy-beta-alanine N-vinyl ester, and the like and mixtures thereof. An example of a vinyl-containing monomer is N-vinyl-N-methylacetamide (VMA). The structure of VMA corresponds to CH₃C(O)N(CH₃)-CH＝CH₂. In one example, the total vinyl-containing monomer content of the polymerizable composition is present in an amount in the range of about 0% to about 50% (w/w) (e.g., up to about 50% (w/v)) of the polymerizable composition from which the silicone hydrogel lens product is prepared, and can be present in an amount in the range of about 20% (w/w) to about 45% (w/w) or about 28% (w/w) to about 40% (w/w) of the polymerizable composition. Other silicone-free lens-forming hydrophilic monomers known in the art may also be suitable.

Crosslinking agents useful in the manufacture of the present contact lenses (e.g., the present silicone hydrogel contact lenses) include, but are not limited to, the crosslinking agents described above. Examples of acrylate-functionalized ethylene oxide oligomers used in the crosslinking agent may include oligo-ethylene oxide dimethacrylate. The crosslinker can be TEGDMA, TEGDVE, EGDMA, TMGDMA, or any combination thereof. Typically, the crosslinking agent is present in the polymerizable silicone hydrogel composition in a relatively small total amount of the polymerizable composition, for example, in an amount in the range of about 0.1% (w/w) to about 10% (w/w), or about 0.5% (w/w) to about 5% (w/w), or about 0.75% (w/w) to about 1.5% (w/w), by weight of the polymerizable composition.

The silicone hydrogel lens polymerizable compositions described herein may also include additional components, such as, for example, one or more initiators (e.g., one or more thermal initiators, one or more Ultraviolet (UV) initiators, visible light initiators, combinations thereof, and the like), one or more UV absorbers or compounds, or UV radiation or energy absorbers, colorants, pigments, mold release agents, antimicrobial compounds, and/or other additives. In the context of the present application, the term "additive" refers to a compound or any chemical agent provided in the present hydrogel contact lens polymerizable compositions or polymerized hydrogel contact lens products, but which is not necessary for the manufacture of hydrogel contact lenses.

The polymerizable composition may comprise one or more initiator compounds, i.e., compounds capable of initiating polymerization of the polymerizable composition. A thermal initiator, i.e., an initiator having an "initiation (kick-off)" temperature, may be used. For example, one exemplary thermal initiator for use in the polymerizable compositions of the present invention is 2, 2' -azobis (isobutyronitrile) (Ibz @)-64)。-64 has an initiation temperature of about 62 ℃, which is the temperature at which polymerization of the reactive components of the polymerizable composition will begin. Another thermal initiator is 2, 2' -azobis (2, 4-dimethylvaleronitrile) ((R))-52) having an initiation temperature of about 50 ℃. A further thermal initiator for use in the compositions of the present invention is azo-bis-isobutyronitrile (A)-88) having an initiation temperature of about 90 ℃. All VAZO thermal initiators described herein are available from DuPont (Wilmington, del, USA). Additional thermal initiators include nitrites such as 1, 1 '-azobis (cyclohexanecarbonitrile) and 2, 2' -azobis (2-methylpropanenitrile), as well as other types of initiators such as those available from Sigma Aldrich. Ophthalmically compatible silicone hydrogel contact lenses can be obtained from polymerizable compositions comprising from about 0.05% (w/w) to about 0.8% (w/w), or from about 0.1% (w/w) to about 0.6% (w/w)-64 or other thermal initiator.

The UV absorber can be, for example, a strong UV absorber that exhibits a relatively high absorption value in the UV-a range of about 320 nm to 380nm, but is relatively transparent above about 380 nm. Examples include photopolymerizable hydroxybenzophenones and photopolymerizable benzotriazoles, such as 2-hydroxy-4-acryloxyethoxybenzophenone (available as CYASORB UV416 from Cytec Industries, Parcel (West Paterson, NJ, USA), 2-hydroxy-4- (2-hydroxy-3-methacryloyloxy) propoxybenzophenone, and photopolymerizable benzotriazoles (available as CYASORB UV416 from Cytec Industries, Inc.)7966 obtained from Nolam family (Noramco) (Athens, GA, USA, Athens, Georgia, USA)). 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 from about 0.5% by weight of the polymerizable composition to about 1.5% by weight of the composition. For example, the composition may include from about 0.6% (w/w) to about 1.0% (w/w) of one or more UV absorbers.

The polymerizable compositions used in the present invention may also include colorants, but both tinted and clear lens products are contemplated. In one example, the colorant is a reactive dye or pigment effective to provide color to the resulting lens product. Colorants can include, for example, VAT blue 6(7, 16-dichloro-6, 15-dihydroanthracene azine-5, 9, 14, 18-tetrone), 1-amino-4- [3- (. beta. -sulfatoethylsulfonyl) anilino ] -2-anthraquinone sulfonic acid (c.i. reactive blue 19, RB-19), copolymers of reactive blue 19 with hydroxyethyl methacrylate (RB-19HEMA), 1, 4-bis [4- [ (2-methacryloyl-oxyethyl) phenylamino ] anthraquinone (reactive blue 246, RB-246, available from arnan Chemical Company, alvareron (Athlone, Ireland)), 1, 4-bis [ (2-hydroxyethyl) amino ] -9, 10-anthracenedione bis (2-propenoate) (RB-247), Reactive blue 4(RB-4) or a copolymer of reactive blue 4 with hydroxyethyl methacrylate (RB-4HEMA or "blue HEMA"). Other exemplary colorants are disclosed, for example, in U.S. patent application publication No. 2008/0048350, the entire disclosure of which is incorporated herein by reference. Other suitable colorants for use in the present invention are phthalocyanine pigments (e.g., phthalocyanine blue and phthalocyanine green), chromium-aluminum-cobalt oxide, chromium oxide, and various iron oxides of the red, yellow, brown, and black colors. Opacifiers such as titanium dioxide may also be included. For some applications, mixtures of colors may be used. If employed, the colorant may be present in an amount ranging from about 0.1% (w/w) to about 15% (w/w), or from about 1% (w/w) to about 10% (w/w), or from about 4% (w/w) to about 8% (w/w).

The polymerizable composition may also comprise a release aid, i.e., one or more ingredients effective to more easily remove the cured contact lens from the cured contact lens mold. Exemplary release aids include hydrophilic silicones, polyalkylene oxides, and combinations thereof. The polymerizable composition may further comprise a diluent selected from the group consisting of: hexanol, ethoxyethanol, Isopropanol (IPA), propanol, decanol, and combinations thereof. The diluent (if employed) is typically present in an amount in the range of about 10% (w/w) to about 30% (w/w). Compositions having relatively higher diluent concentrations tend to, but do not necessarily, have lower ionic flux (ionoflox) values, reduced modulus and increased elongation, and water film break up times (WBUT) of greater than 20 seconds. Additional materials suitable for use in the manufacture of hydrogel contact lenses are described in U.S. patent No. 6,867,245, the entire disclosure of which is incorporated herein by reference. However, in certain embodiments, the polymerizable composition is free of diluent.

Various methods of curing polymerizable compositions in the manufacture of contact lenses are known, including spin casting and static casting. Spin casting methods involve filling a polymerizable composition into a mold and rotating the mold in a controlled manner while exposing the polymerizable composition to UV light. The static casting method involves providing a polymerizable composition between two mold sections, wherein one mold section is shaped to form the anterior lens surface and the other mold section is shaped to form the posterior lens surface, and curing the polymerizable composition by exposure to UV light, heat, visible light, or other radiation. Additional details and methods of forming contact lenses can be found, for example, in U.S. patent application publication nos. 2007/0296914 and 2008/0048350, the entire disclosures of each of which are incorporated herein by reference.

After the reaction mixture is allowed to cure, the resulting polymer is separated from the mold. In some cases, such as in static cast molding, the two mold members are first separated, followed by separation of the polymer from the mold.

The resulting polymer may also be treated with a washing solution including, but not limited to, water, aqueous solutions, organic solvents, and aqueous solutions including organic solvents. A washing treatment may be used to remove diluent (if used), unreacted components, by-products, and the like, and to hydrate the polymer to form a water-swellable hydrogel. Lenses made using currently useful polymerizable formulations or compositions do not require extraction with organic solvents or aqueous solutions containing organic solvents prior to hydration and packaging. Lenses that have not been subjected to organic solvent extraction can be washed with water or an aqueous solution (e.g., physiological saline or an aqueous solution of a surfactant or surfactant component). Depending on the solubility characteristics of the diluent (if any) and residual unpolymerized monomers, the solvent initially used may be an organic liquid, such as ethanol, methanol, isopropanol, mixtures thereof or the like, or a mixture of one or more organic liquids and water, followed by extraction with pure water (or physiological saline or surfactant solution) to produce a silicone hydrogel comprising the polymer swollen with water. In one embodiment, no diluent is present in or with the polymerizable composition. In any case, the lens is hydrated in water or an aqueous solution (e.g., a packaging solution) during or after washing. It will be appreciated that when a lens is washed with an aqueous solution as described herein, it will become at least partially hydrated. The washing/extraction process, the hydration process, or both the washing/extraction and hydration processes may be performed using heated, pressurized, or vacuum liquids. The hydrated silicone hydrogel may comprise from 20% (w/w) to 80% (w/w) water, for example from 30% (w/w) to 70% (w/w) water or from 40% (w/w) to 60% (w/w) water, based on the total weight of the hydrogel.

The monomers of the polymerizable compositions that are currently useful can be polymerized alone or copolymerized with other monomers to obtain contact lens materials.

TABLE I

TABLE II

TABLE III

TABLE IV

The copolymer can be prepared by: one or more silicone-containing monomers, macromers or prepolymers, such as the first and second silicone-containing monomers, macromers or prepolymers, are combined with one or more silicone-free monomers, such as those set forth in table II, and crosslinkers, such as those set forth in table III, for example, the monomers, macromers or prepolymers of structures (a) and (B) are combined with the silicone-free monomers and crosslinkers. Polymerization initiators such as those set forth in Table IV are added to the mixture.

Copolymers in the form of contact lenses can be prepared using suitable lens molds made of, for example, a non-polar material such as polypropylene (e.g., a nucleated thermoplastic polypropylene resin), or by first combining the components listed in table I, in the form of a film between Teflon (Teflon) lined glass slides. The monomer mixture is dispensed into a mold or slide recess and then the initiator is "initiated" by, for example, heating to a suitable initiation temperature. After molding is complete, the mold is opened and the polymer is separated from the mold. The lens is then contacted with water or an aqueous solution (as described elsewhere herein) to wash the lens. The lens may be hydrated in water or an aqueous solution, as described elsewhere herein. The lenses can then be packaged in blisters or blister packs, such as blisters with PBS solution. After forming the lens body, the present contact lens bodies are not subjected to a form of plasma treatment and/or are not treated with a polymerizable swelling agent.

The present contact lenses can have acceptable wettability, as shown, for example, by their various properties (e.g., advancing contact angle, water film break off time (WBUT), uptake of wetting solution), and other techniques.

The contact lens can have at least one of an anterior surface and a posterior surface of the lens body that, when wet, comprises a plurality of depressions having an average diameter between about 150 nanometers and less than 1500 nanometers, or a plurality of depressions having an average diameter between about 130 nanometers and less than about 630 nanometers, or a plurality of depressions having an average diameter between about 150 nanometers and less than about 550 nanometers.

The plurality of depressions may have an average depth of about 4 nanometers to about 100 nanometers, or the plurality of depressions may have an average depth of about 4 nanometers to about 4 nanometers, about 4 nanometers to about 40 nanometers, or the plurality of depressions may have an average depth of about 4 nanometers to about 20 nanometers. In one embodiment, the average depth of the plurality of depressions can be from about 8 nanometers to about 20 nanometers, or the average depth of the plurality of depressions can be from about 15 nanometers to about 90 nanometers.

The average surface roughness of the contact lenses of the invention may be from about 5 nanometers Root Mean Square (RMS) to about 30 nanometers RMS, or the average surface roughness may be from about 7 nanometers RMS to about 25 nanometers RMS, or the average surface roughness may be from about 10 nanometers RMS to about 20 nanometers RMS.

The density or average density of the plurality of depressions (meaning the number of depressions per 900 square micron surface or the average number of depressions per 900 square micron surface) can be from about 5 depressions per 900 square micron surface to about 1500 depressions per 900 square micron surface, or the average density of the plurality of depressions can be from about 80 depressions per 900 square micron surface to about 1500 depressions per 900 square micron surface, or the average density of the plurality of depressions can be from about 200 depressions per 900 square micron surface to about 1000 depressions per 900 square micron surface. In one embodiment, the average density of the plurality of depressions can be from about 100 depressions per 900 square microns surface to about 1200 depressions per 900 square microns surface.

Following hydration in water or an aqueous solution, the advancing contact angle of at least one of the anterior and posterior surfaces of the lens body of the present contact lenses can be less than 100 ° and the water film break time (WBUT) can be greater than five (5) seconds. After hydration in water or an aqueous solution for at least 12 hours, the advancing contact angle of at least one of the anterior and posterior surfaces of the lens body of the present contact lenses can be less than 100 ° and the water film break time can be greater than five (5) seconds. In one embodiment, immediately after hydration in water and an aqueous solution, the advancing contact angle of at least one of the anterior and posterior surfaces of the lens body is less than 100 ° and the water film break time is greater than 5 seconds and after hydration in water or an aqueous solution for at least 12 hours, the advancing contact angle of at least one of the anterior and posterior surfaces of the lens body is less than 100 ° and the water film break time is greater than 5 seconds.

Immediately following hydration in water or an aqueous solution, a first advancing contact angle of at least one of the anterior and posterior surfaces of the lens body of the contact lens of the present invention differs from a second advancing contact angle of the anterior or posterior surface of the lens body after at least 12 hours of hydration in water or an aqueous solution by no more than 30 °, or the first advancing contact angle differs from a second advancing contact angle of the anterior or posterior surface of the lens body after at least 12 hours of hydration in water or an aqueous solution by no more than 20 °, or the first advancing contact angle differs from a second advancing contact angle of the anterior or posterior surface of the lens body after at least 12 hours of hydration in water or an aqueous solution by no more than 10 °.

Following hydration in water or an aqueous solution, the first water film breaking time of the anterior or posterior surface of the lens body of the contact lens of the present invention differs from the second water film breaking time of the anterior or posterior surface of the lens body after at least 12 hours of hydration in water or an aqueous solution by no more than 15 seconds, or the first water film breaking time differs from the second water film breaking time of the anterior or posterior surface of the lens body after at least 12 hours of hydration in water or an aqueous solution by no more than 10 seconds, or the first water film breaking time differs from the second water film breaking time of the anterior or posterior surface of the lens body after at least 12 hours of hydration in water or an aqueous solution by no more than 5 seconds.

Contact lens packages are provided that include a contact lens body (such as those described above) and a packaging solution. The packaging solution may contain a wetting agent or an agent (e.g., a surfactant or hydrophilic polymer) that helps prevent or eliminate adherence of the lens to the blister package. The surfactant may be a non-ionic surfactant, such as polysorbate 80, a poloxamer, poloxamine, or sugar. The hydrophilic polymer may be in the form of: polyvinyl pyrrolidone, polyethylene glycol, polyvinyl alcohol, or combinations thereof.

In the case of contact lens packages, the package may additionally include a base member having a cavity configured to contain a contact lens body and a packaging solution; and a seal attached to the base member configured to maintain the contact lens and packaging solution under sterile conditions for a period of time equivalent to the shelf life of the contact lens.

Examples of the invention

The following non-limiting examples illustrate certain aspects of the present invention.

The following abbreviations and corresponding compounds and structures are used in the examples.

MCR-M07 ═ monomethacryloxy-terminated polydimethylsiloxane, as previously explained (graves, morrisville, pa).

MCS-M11 is monomethacryloxy terminated polydimethylsiloxane (Gransted, Morisville, Pa., USA). The structure is as follows:

FMM ═ silicone-containing component, as previously explained (Shin-Etsu Silicones, Akron, OH, USA) by Akron, ohio).

M5A ═ silicone-containing component, which is the same as or structurally similar to the hydrophilic polysiloxane macromer a described in example 2 of U.S. patent application publication No. 2009/0234089 (asahi kasei Aime co., ltd., Kanagawa, Japan).

X22-1622 ═ silicone-containing components as previously explained (sinews silicone, usa, akron, ohio).

X22-1625 ═ silicone-containing components as previously explained (sinews silicone, usa, akron, ohio).

SiGMA ═ 3-methacryloxy-2-hydroxypropoxy) propylbis (trimethylsiloxy) methylsilane. The structure is as follows:

tris ═ 3- [ Tris (trimethylsilyloxy) silyl ] propyl methacrylate. The structure is as follows:

DMS-R18 ═ methacryloxy terminated polydimethylsiloxane, as previously explained (graves, morrisville, pa).

DMA ═ N, N-dimethylacrylamide.

VMA ═ N-vinyl-N-methylacetamide.

MMA ═ methyl methacrylate.

HEMA ═ hydroxyethyl methacrylate.

EGMA ═ ethylene glycol methyl ether methacrylate.

EGDMA ═ ethylene glycol dimethacrylate.

TEGDMA ═ tri (ethylene glycol) dimethacrylate.

TEGDVE ═ tris (ethylene glycol) divinyl ether.

2, 2' -azobis (isobutyronitrile).

PBS ═ phosphate buffered saline (20mM, pH ═ 7.3)

MPC ═ 2-methacryloyloxyethyl phosphorylcholine (HEMA-PC,NOF corporation, Tokyo, Japan (Tokyo, Japan)).

VB6 ═ VAT blue 6(7, 16-dichloro-6, 15-dihydroanthracene azine-5, 9, 14, 18-tetraone).

EHMA 2-ethylhexyl methacrylate

IBM ═ isoborneol methacrylate

AE ═ allyloxyethanol

Preparation of contact lenses

The polymerizable lens compositions were prepared by mixing various combinations of ingredients and components as shown in Table AB below. The lens formulations are formed into lenses in the following general manner.

Contact lens molds are injection molded from non-polar polypropylene resin using conventional injection molding techniques and equipment. Each contact lens mold includes a female mold member having a concave optical quality surface to form the anterior surface of the contact lens and a male mold member having a convex optical quality surface to form the posterior surface of the contact lens. The female mold member can be understood as a front surface mold, and the male mold member can be understood as a back surface mold.

An amount (about 60 μ l) of the polymerizable lens composition was placed on the concave surface of the female mold member. The male and female mold members are placed in contact to position the polymerizable lens composition in a contact lens forming cavity formed between the female mold member concave surface and the male mold member convex surface. The male member is held in place by an interference fit between the female member and the surrounding area of the male member.

The contact lens molds containing the polymerizable lens composition are then placed in an oven where the polymerizable lens composition is cured at a temperature of about 100 ℃ for about 30 minutes. After curing, the contact lens mold contains the polymerized contact lens product within the contact lens forming cavity.

The contact lens molds were removed from the oven and allowed to cool to room temperature (about 20 ℃). Mechanically demolding the contact lens mold to separate the male and female mold members from each other. The polymerized contact lens product remains attached to the male mold member.

The polymerized contact lens product is then mechanically delensed from the male mold member to separate the contact lens product from the male mold member.

The isolated contact lens products were then washed in water, hydrated in PBS and subjected to various test procedures to characterize the hydrated contact lens products. In some cases, the contact lens product is tested as dry, i.e., in the case of a contact lens product in a dry state, it is dry, e.g., before washing, extraction or hydration, or after drying to remove retained water or solvent.

Methods of characterizing lens products

Contact lens products, particularly the front and back surface topography of contact lens bodies of the products, are analyzed using Atomic Force Microscopy (AFM). The Instrument used was a Vickers (Veeco) CP II atomic force microscope sold by Vickers instruments Inc., san Barbara, Calif., USA. The instrument was used in a tapping mode of operation with a scan rate of 0.5Hz and scan dimensions of 10x10 microns, 20x20 microns, 30x30 microns, and 40x40 microns. The data was analyzed using the following software: 2.1 layout Image analysis (Image analysis), supplied by Utility instruments.

The following procedure was followed:

dry and wet lens images were taken using a wikipedia CP II atomic force microscope operating in tapping mode. The wet lenses tested were in PBS solution. For a specific lens type, 3 lenses were tested to take Atomic Force Microscope (AFM) images. AFM data was acquired by scanning at least 3 different areas of a lens sample. The wet lens specimens were removed from the vials or blister packs and mounted on top of a polypropylene mold immersed in the PBS solution. Surface topography images were then taken in a liquid environment at different scan sizes (10 μmx10 μm, 20 μmx20 μm, 30 μmx30 μm, 40 μmx40 μm) and at a scan rate of 0.5 Hz. Dry lens specimens were mounted on clean stainless steel wafers using double-sided carbon tape and tested under dry conditions at different scan sizes (10. mu. mx 10. mu.m, 20. mu. mx 20. mu.m, 30. mu. mx 30. mu.m, 40. mu. mx 40. mu.m) and scan rates of 0.5 Hz. Surface depressions were further analyzed using 2.1 layout image analysis (wikipedia instruments). The surface dishing distribution or the number of cycles was counted from the AFM image in the 30 μmx30 μm area. The 50 surface depressions were further analyzed to obtain the average diameter and average depth of the depressions in the AFM images. In addition, the same software is used to calculate the Root Mean Square (RMS) roughness for different lens types.

Water film break time (WBUT). Prior to testing, lenses were soaked in 3ml fresh PBS for at least 24 hours. Immediately prior to testing, the lens was subjected to shaking to remove excess PBS, and the length of time (seconds) it took for the water film to recede from the lens surface was determined (e.g., water film break time (water BUT or WBUT)).

Advancing the contact angle. Advancing contact angles can be determined using conventional methods known in the art. For example, the advancing contact angle of a contact lens provided by the present invention can be measured using a bubble trap method. Advancing contact angles of silicone hydrogel contact lenses can be determined using a gruus DSA100 instrument (gruus, burgh, germany) and as described in the following documents: d.a. blandreth (d.a. brandreth): "Dynamic contact angle 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 to 212 and r. kapupikoski, m. kudre (m.kudra): "measurement of contact angles according to the Williams principle, a statistical failure assessment method (Kontaktwilkkelmesung nach dem Wilhelmy-Prinzip-Ein statischer Ansatz zur Feiherbeuriteung)", chemical technology (chem. Technik), Vol.45, 1993, pp.179 to 185; and U.S. patent No. 6,436,481, all of which are incorporated herein by reference in their entirety.

As an example, advancing contact angles can be determined using a captive bubble method and using phosphate buffered saline (PBS; pH 7.2). Prior to testing, the lenses were soaked in ph7.2pbs solution for at least 30 minutes or overnight. The lenses were tiled on a quartz surface and rehydrated with PBS for 10 minutes prior to testing. An automatic injection system is used to place the bubbles on the lens surface. The bubble size can be increased and decreased to obtain a receding angle (plateau obtained when increasing the bubble size) and an advancing angle (plateau obtained when decreasing the bubble size).

Static contact angle. The static contact angle can be determined using conventional methods known to those skilled in the art. For example, static contact angles can be determined using the captive bubble method or using a DSA100 droplet analysis system (gruus, burgh, germany). Prior to testing, the lenses were soaked in ph7.2pbs solution for at least 30 minutes or overnight.

Modulus. The modulus of the lens body can be determined using conventional methods known to those skilled in the art. For example, a contact lens about 4mm wide can be cut from the central portion of the lens, and the modulus (in MPa) can be determined from the initial slope of the stress-strain curve obtained by performing a tensile test in air at a rate of 10mm/min at 25 ℃ and at a humidity of at least 75% using Instron 3342 (Instron, Inc., NoFock, MA, USA).

The ion flux. The ion flux of the lens body of the lenses of the invention can be determined using conventional methods known to those skilled in the art. For example, the ion flux of a contact lens or lens body can be measured using a Technique substantially similar to the "ion flux Technique" (Ionoflux Technique) described in U.S. patent No. 5,849,811. For example, a lens to be measured can be placed in the lens holder between the convex portion and the concave portion. The male and female portions include flexible sealing rings between the lens and the respective male or female portion. After placing the lens in the lens holder, the lens holder is placed in the threaded cap. The cap is screwed onto the glass tube to define the supply chamber. The supply chamber can be filled with 16ml of 0.1 molar NaCl solution. The receiving chamber may 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 a thermostat and the temperature was maintained at about 35 ℃. Finally, the supply chamber is immersed in the receiving chamber. Conductivity measurements are taken starting 10 minutes after the supply chamber is immersed in the receiving chamber, and may be taken every 2 minutes for about 20 minutes. The conductivity versus time data should be substantially linear.

Tensile strength. The tensile strength of the lens body can be determined using conventional methods known to those skilled in the art. For example, a contact lens about 4mm wide can be cut from the central portion of the lens, and the tensile strength (in MPa) can be determined from tests conducted using Instron 3342 (Instron, Nofock, Mass., USA).

And (3) elongation. The elongation of the lens body can be determined using conventional methods known to those skilled in the art. For example, the elongation (%) can be measured using Instron 3342 (Instron corporation, Nofock, Mass., USA).

Oxygen permeability (Dk). The Dk of the lenses of the invention can be determined using conventional methods known to those skilled in the art. For example, Dk values can be determined using modified polarographic analysis methods such as single-lens polarographic measurement of oxygen permeability (Dk) of hyper-transport soft contact lenses (A single-lens polar measurement of oxygen permeability (Dk) for permeable contact lenses), M. cut Blaker (M.Chhabra), et al, Biomaterials (Biomaterials)28(2007) 4331-.

Equilibrium Water Content (EWC). The water content of the lenses of the invention can be determined using conventional methods known to those skilled in the art. For example, hydrated silicone hydrogel contact lenses 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 ℃ and under vacuum, and the dried lenses can then be weighed. The weight difference was determined by subtracting the dry lens weight from the hydrated lens weight. The water content (%) is (weight difference/hydrated weight) x 100.

Central Thickness (CT) of the lens. CT can be determined using conventional methods known to those skilled in the art. For example, CT may be measured using a Reader (Rehder) ET gauge (Rehder Development Company, Castro Valley, Calif., USA).

A series of 16 contact lenses were formed and tested as described above. The 16 lenses were formed in polypropylene (nucleated) molds from the polymerizable compositions listed in table AB.

Watch AB

A series of commercially available silicone hydrogel contact lenses were also tested using AFM to analyze surface topography. These include commercially available lenses (which areNot subjected to a form of plasma treatment as part of its process), includingAn ophthalmic lens andlenses (cooper vision, pleisanton, CA), CLARITI^TMLenses (safflon, Twickenham, UK) andOASYS^TMa lens,An ophthalmic lens andTRUEYE^TMglasses lens (Johnson Vision Care Corp (Johnson)&Johnson Vision Care, Inc.), Jackson Will, Florida, USA. Lenses also include commercially available lenses (which have been subjected to a form of plasma treatment as part of their process), includingLens (Bausch)&Lomb), Rochester, new york, USA (Rochester, NY, USA)), PREMIO^TMLenses (Menicone, Japan), and NIGHT&A lens,Lens and AIRLenses (Vision kang (Ciba Vision), douus, georgia, USA).

Some results of these AFM tests are shown in fig. 1-4 and table AC. In addition, fig. 5-18 show photographs of the lens surface.

The size, depth and density of the depressions, and RMS roughness of each test lens front/back surface, whether the AFM analysis was performed immediately after hydration, or after 12 hours of hydration, or after 24 hours of hydration, were still substantially the same, e.g., ± between 10% and 15%.

As shown in table AC below and in fig. 1, the average diameter of the surface depressions in the contact lenses manufactured from formulations 1-14 and 16 ranged between 175.7nm to 615.8 nm. The average diameter of the surface depressions for some of the inventive formulations is, for example, in the following range: between about 150nm and about 1500nm, between about 130nm and about 630nm, between about 150nm and about 1500nm, between about 170nm and about 570nm, between about 180nm and about 380nm, or between about 250nm and about 390 nm. The average dimple diameter of the contact lens of formulation 15 was 1174.6 nm. Of the commercial lenses tested, lenses that were not subjected to one form of plasma treatment (i.e.,a lens,Lens, Clariti^TMAn ophthalmic lens andlenses) had no detectable surface depressions or had surface depressions of lenses with an average diameter greater than formulations 1-14 and 16. Lenses that have been subjected to one form of plasma treatment (i.e.,lens, PREMIO^TMLens, NIGHT&A lens,Lens and AIRA lens) has no surface depressions or surface depressions with a slightly larger average diameter of between, for example, about 400nm and about 800 nm.

Watch AC

As shown in table AC and fig. 2, the average depth of surface depressions in contact lenses manufactured from formulations 1-14 and 16 was in the range between 5.1nm and 48.1 nm. The average surface depression depth of the contact lens of formulation 15 was 61.6 nm. The average depth of the surface depression of some of the inventive formulations is, for example, in the following range: between about 4nm and about 60nm, between about 4nm and about 20nm, between about 8nm and about 40nm, between about 8nm and about 20nm, between about 15nm and about 90nm, or between about 15nm and about 30 nm.

As shown in Table AC and FIG. 3, the contact lenses produced from formulations 1 through 14 and 16 had a distribution or density of surface depressions between 135 depressions/900 μm²And 1062 recesses/900 μm²Within the range of (a). The density of the contact lens of formulation 15 was 5 pits/900 μm². The density of some of the inventive formulations was in the following range: between about 5 depressions/900 μm²And about 1500 depressions/900 μm²Between about 80 depressions/900 μm²And about 1500 depressions/900 μm²Between about 200 depressions/900 μm²And about 1000 depressions/900 μm²Middle and intermediateAt about 100 depressions/900 μm²And about 1200 depressions/900 μm²Between 2 depressions/900 μm²And 700 depressions/900 nm²Between or between about 100 depressions/900 μm²And about 600 depressions/900 μm²In the meantime. The tested commercial lenses that were not subjected to one form of plasma treatment either had no surface sag or had a surface sag density substantially lower than the lenses of formulations 1-14 and 16.

As shown in table AC and fig. 4, the average RMS surface roughness of contact lenses manufactured from formulations 1-16 was in the range between 6.9 and 19.7. The average RMS surface roughness of some of the inventive formulations was in the following range: between about 5nm and about 30nm, between about 5nm and about 20nm, between about 5nm and about 15nm, between about 7nm and about 25nm, between about 10nm and about 30nm, between about 15nm and 30nm, or between 15nm and 20 nm. The average RMS surface roughness of tested commercial lenses that were not subjected to one form of plasma treatment tended to be somewhat lower, for example in the range between about 5nm and about 10 nm.

In addition, table AD below includes the results of the property characterization test of lenses made using the formulations of the present invention.

Watch AD

Fig. 5-18 include a set of photographs showing lens surface morphology as determined by Atomic Force Microscopy (AFM) using tap mode. Fig. 5-10 show lenses manufactured from formulations 1-16 after hydration in PBS. FIGS. 11-14 show photographs of morphologies of various commercially available lenses, includingCLARITI^TM、PREMIO^TM、OASYS^TM、TRUEYE^TM、NIGHT &And AIRLenses, as determined using tap mode AFM after hydrating the lenses in PBS.

In fig. 16-18, the contact lenses and commercial offers of formulations 1, 5, 15 are presentedTap mode AFM results for lenses tested in both wet or hydrated state (hydrated in PBS) and dry state. The results show that there are surface depressions in both wet and dry lenses. Thus, the surface depression is not due to (e.g., not solely due to) hydration of the lens.

A number of publications, patents and patent applications have been cited above. The entire contents of each of the cited publications, patents, and patent publications are incorporated herein by reference.

While the invention has been described in terms of various specific examples and embodiments, it is to be understood that the invention is not so limited and can be practiced in various ways within the scope of the following claims.

Claims (85)

1. A silicone hydrogel contact lens, comprising:

a silicone hydrogel lens body comprising an anterior surface and a posterior surface, wherein upon hydration in water or an aqueous solution, at least one of the anterior surface and the posterior surface of the lens body is substantially smooth when wet and comprises a plurality of depressions extending inwardly into the lens body from the substantially smooth surface, the plurality of depressions having an average diameter between about 150 nanometers and less than 1500 nanometers, and wherein after formation of the lens body, the lens body has not been subjected to one form of plasma treatment, the lens body has not been treated with a polymerizable swelling agent, or both.

2. The contact lens of claim 1, wherein the plurality of depressions have an average diameter between about 150 nanometers and less than about 630 nanometers.

3. The contact lens of claim 1, wherein the plurality of depressions have an average diameter between about 150 nanometers and less than about 550 nanometers.

4. The contact lens of claim 1, wherein the plurality of depressions have an average depth of about 4 nanometers to about 100 nanometers.

5. The contact lens of claim 1, wherein the plurality of depressions have an average depth of about 4 nanometers to about 65 nanometers.

6. The contact lens of claim 1, wherein the plurality of depressions have an average depth of about 15 nanometers to about 40 nanometers.

7. The contact lens of any one of claims 1-6, wherein the plurality of depressions has about 5 depressions/900 μm²To about 1500 depressions/900 μm²The average density of (a).

8. The contact lens of any one of claims 1-6, wherein the plurality of depressions has about 80 depressions/900 μm²To about 1500 depressions/900 μm²The average density of (a).

9. The contact lens of claim 1, which isWherein the plurality of recesses has about 200 recesses/900 μm²To about 1000 depressions/900 μm²The average density of (a).

10. The contact lens of claim 1, wherein at least one of the anterior surface and the posterior surface of the lens body has an average surface roughness of about 5 nanometers RMS to about 30 nanometers RMS.

11. The contact lens of claim 1, wherein at least one of the anterior surface and the posterior surface of the lens body has an average surface roughness of about 7 nanometers RMS to about 25 nanometers RMS.

12. The contact lens of claim 1, wherein at least one of the anterior surface and the posterior surface of the lens body has an average surface roughness of about 10 nanometers RMS to about 20 nanometers RMS.

13. The contact lens of claim 1, wherein at least one of the anterior surface and the posterior surface of the lens body has an advancing contact angle of less than 100 ° and a water break up time (water break up time) of greater than 5 seconds at least 12 hours after hydration in the water or the aqueous solution.

14. The contact lens of claim 1, wherein the lens body has a swelling factor of at least 20%.

15. The contact lens of claim 1, wherein the lens body comprises a hydrophilic silicone-containing polymeric material.

16. The contact lens of claim 1, wherein the lens body does not comprise a hydrophilic polymeric internal wetting agent.

17. The contact lens of claim 1, wherein the lens body is fully or partially cured while in direct contact with a contact lens mold comprising a non-polar material.

18. The contact lens of claim 17, wherein the non-polar material comprises polypropylene.

19. The contact lens of claim 17, wherein the non-polar material is a nucleated thermoplastic polypropylene resin.

20. The contact lens of claim 1, wherein the lens body comprises a reaction product of a polymerizable composition comprising:

a reactive component comprising at least one silicone-containing monomer, at least one silicone-containing macromer, at least one silicone-containing prepolymer, or mixtures thereof,

at least one hydrophilic monomer, and

at least one crosslinking agent that crosslinks the reactive ingredients during polymerization to form a polymer.

21. The contact lens of claim 20, wherein the reactive component comprises a silicone-containing monomer having a molecular weight of less than 700 daltons (Dalton).

22. The contact lens of any one of claims 20 and 21, wherein the reactive ingredients comprise a silicone-containing macromer having a molecular weight between about 700 daltons and about 2,000 daltons.

23. The contact lens of any one of claims 20 and 21, wherein the reactive ingredients comprise a silicone-containing prepolymer having a molecular weight greater than 2,000 daltons.

24. The contact lens of claim 1, wherein the lens body is formed by a method comprising polymerizing a polymerizable composition in the absence of a diluent.

25. The contact lens of any one of claims 20 and 21, wherein the polymerizable composition is free of hydrophilic polymeric internal wetting agents.

26. The contact lens of claim 1, wherein the surface of the lens body does not include a silicate layer.

27. The contact lens of claim 1, wherein the lens body is not surface treated to enhance surface wettability compared to an unpressed lens body.

28. The contact lens of claim 1, wherein the lens body is not extracted with an organic solvent or an aqueous solution comprising an organic solvent component prior to hydration in the water or the aqueous solution.

29. The contact lens of claim 1, wherein the lens body is free of a surface coating having a different composition than the lens body.

30. A silicone hydrogel contact lens, comprising:

a non-plasma treated silicone hydrogel lens body comprising an anterior surface and a posterior surface, at least one of the anterior surface and the posterior surface comprising a plurality of depressions extending inwardly into the lens body from the substantially smooth surface, the plurality of depressions having an average density of about 100 depressions per 900 μ ι η²To about 1200 depressions/900 μm²。

31. The contact lens of claim 30, wherein the plurality of depressions have an average diameter between about 150 nanometers and less than about 630 nanometers.

32. The contact lens of claim 30, wherein the plurality of depressions have an average diameter between about 150 nanometers and less than about 550 nanometers.

33. The contact lens of claim 30, wherein the plurality of depressions have an average depth of about 4 nanometers to about 100 nanometers.

34. The contact lens of claim 30, wherein the plurality of depressions have an average depth of about 4 nanometers to about 65 nanometers.

35. The contact lens of claim 30, wherein the plurality of depressions have an average depth of about 15 nanometers to about 40 nanometers.

36. The contact lens of claim 30, wherein the plurality of depressions has about 200 depressions/900 μ ι η²To about 1000 depressions/900 μm²The average density of (a).

37. The contact lens of claim 30, wherein at least one of the anterior surface and the posterior surface of the lens body has an average surface roughness of about 5 nanometers RMS to about 30 nanometers RMS.

38. The contact lens of claim 30, wherein at least one of the anterior surface and the posterior surface of the lens body has an average surface roughness of about 7 nanometers RMS to about 25 nanometers RMS.

39. The contact lens of claim 30, wherein at least one of the anterior surface and the posterior surface of the lens body has an average surface roughness of about 10 nanometers RMS to about 20 nanometers RMS.

40. The contact lens of claim 30, wherein the lens body has a swelling factor of at least 20%.

41. The contact lens of claim 30, wherein the lens body comprises a hydrophilic silicone-containing polymeric material.

42. The contact lens of claim 30, wherein the lens body does not comprise a hydrophilic polymeric internal wetting agent.

43. The contact lens of claim 30, wherein the lens body is fully or partially cured while in direct contact with a contact lens mold comprising a non-polar material.

44. The contact lens of claim 43, wherein the non-polar material comprises polypropylene.

45. The contact lens of claim 43, wherein the non-polar material is a nucleated thermoplastic polypropylene resin.

46. The contact lens of claim 30, wherein the lens body comprises a reaction product of a polymerizable composition comprising:

a reactive component comprising at least one silicone-containing monomer, at least one silicone-containing macromer, at least one silicone-containing prepolymer, or mixtures thereof,

at least one hydrophilic monomer, and

at least one crosslinking agent that crosslinks the reactive ingredients during polymerization to form a polymer.

47. The contact lens of claim 46, wherein the reactive component comprises a silicone-containing monomer having a molecular weight of less than 700 daltons (Dalton).

48. The contact lens of any one of claims 46 and 47, wherein the reactive ingredients comprise a silicone-containing macromer having a molecular weight between about 700 daltons and about 2,000 daltons.

49. The contact lens of any one of claims 46 and 47, wherein the reactive ingredients comprise a silicone-containing prepolymer having a molecular weight greater than 2,000 daltons.

50. The contact lens of claim 30, wherein the lens body is formed by a method comprising polymerizing a polymerizable composition in the absence of a diluent.

51. The contact lens of any one of claims 46 and 47, wherein the polymerizable composition is free of hydrophilic polymeric internal wetting agents.

52. The contact lens of claim 30, wherein the surface of the lens body does not include a silicate layer.

53. The contact lens of claim 30, wherein the lens body is not surface treated to enhance surface wettability compared to an unpressed lens body.

54. The contact lens of claim 30, wherein the lens body is free of a surface coating having a different composition than the lens body.

55. A method of manufacturing a silicone hydrogel contact lens, comprising

Forming a silicone hydrogel contact lens body having an anterior surface and a posterior surface, wherein upon hydration in water or an aqueous solution, at least one of the anterior surface and the posterior surface of the lens body is substantially smooth when wet and comprises a plurality of depressions extending inwardly into the lens body from the substantially smooth surface, the plurality of depressions having an average diameter between about 150 nanometers and less than 1500 nanometers and about 100 depressions per 900 μm²To about 1200 depressions/900 μm²And wherein after forming the lens body, the lens body is not subjected to a form of plasma treatment, the lens body is not treated with a polymerizable swelling agent, or both.

56. The method of claim 55, wherein the forming step comprises polymerizing a polymerizable composition comprising: a reactive component comprising at least one silicone-containing monomer, at least one silicone-containing macromer, at least one silicone-containing prepolymer, or a mixture thereof; at least one hydrophilic monomer and at least one cross-linking agent effective to cross-link the reactive ingredients.

57. The method of any one of claims 55 and 56, wherein the lens body does not comprise an internal polymeric wetting agent.

58. The method of any one of claims 55 and 56, wherein the lens body does not comprise a silicate layer.

59. The method of claim 56, wherein the polymerizing step occurs at least in part in a contact lens mold comprising a non-polar material.

60. The method of claim 59, wherein the non-polar material comprises polypropylene.

61. The method of claim 59, wherein said non-polar material is a nucleated thermoplastic polypropylene resin.

62. The method of claim 56, wherein the reactive component comprises a silicone-containing monomer having a molecular weight of less than 700 daltons.

63. The method of claim 56, wherein the reactive ingredients comprise a silicone-containing macromer having a molecular weight between about 700 daltons and about 2,000 daltons.

64. The method of claim 56, wherein the reactive ingredients comprise a silicone-containing prepolymer having a molecular weight greater than 2,000 daltons.

65. The method of claim 55, wherein the contact lens body is as in any one of claims 1-54.

66. A silicone hydrogel contact lens, comprising:

a silicone hydrogel lens body comprising an anterior surface and a posterior surface, wherein upon hydration in water or an aqueous solution, at least one of the anterior surface and the posterior surface of the lens body is substantially smooth when wet and comprises a plurality of depressions extending inwardly into the lens body from the substantially smooth surface, the plurality of depressions having an average diameter between about 150 nanometers and less than 1500 nanometers and about 100 depressions per 900 μ ι η²To about 1200 depressions/900 μm²And wherein after forming the lens body, the lens body is not subjected to a form of plasma treatment, the lens body is not treated with a polymerizable swelling agent, or both.

67. The contact lens of claim 66, wherein the plurality of depressions has about 100 depressions/900 μm²To about 1200 depressions/900 μm²And the lens body has not been subjected to a form of plasma treatment.

68. The contact lens of claim 66 or 67, wherein the plurality of depressions have an average diameter of between about 150 nanometers and less than 1500 nanometers.

69. The contact lens of claim 66 or 67, wherein the plurality of depressions have an average diameter between about 150 nanometers and less than 630 nanometers.

70. The contact lens of claim 66 or 67, wherein the plurality of depressions have an average diameter of between about 170 nanometers and less than 570 nanometers.

71. The contact lens of claim 66, wherein the plurality of depressions has about 5 depressions/900 μm²To about 1500 depressions/900 μm²The average density of (a).

72. The contact lens of claim 66 or 67, wherein the plurality of depressions has about 200 depressions/900 μm²To about 1000 depressions/900 μm²The average density of (a).

73. The contact lens of claim 66 or 67, wherein at least one of the anterior surface and the posterior surface of the lens body has an average surface roughness of about 5 nanometers RMS to about 30 nanometers RMS.

74. The contact lens of claim 66 or 67, wherein at least one of the anterior surface and the posterior surface of the lens body has an advancing contact angle of less than 100 ° and a water film break time of greater than 5 seconds at least 12 hours after hydration in the water or the aqueous solution.

75. The contact lens of claim 66 or 67, wherein the lens body has a swelling factor of at least 20%.

76. The contact lens of claim 66 or 67, wherein the lens body does not comprise a hydrophilic polymeric internal wetting agent.

77. The contact lens of claim 66 or 67, wherein the lens body is fully or partially cured while in direct contact with a contact lens mold comprising a non-polar material.

78. The contact lens of claim 66 or 67, wherein the lens body comprises a reaction product of a polymerizable composition comprising:

a reactive component comprising at least one silicone-containing monomer, at least one silicone-containing macromer, at least one silicone-containing prepolymer, or mixtures thereof,

at least one hydrophilic monomer, and

at least one crosslinking agent that crosslinks the reactive ingredients during polymerization to form a polymer.

79. The contact lens of claim 66 or 67, wherein the lens body is formed by a method comprising polymerizing a polymerizable composition in the absence of a diluent.

80. The contact lens of claim 66 or 67, wherein the surface of the lens body does not include a silicate layer.

81. The contact lens of claim 66 or 67, wherein the lens body is not extracted with an organic solvent or an aqueous solution comprising an organic solvent component prior to hydration in the water or the aqueous solution.

82. A method of manufacturing a silicone hydrogel contact lens, comprising

Forming a silicone hydrogel contact lens body having an anterior surface and a posterior surface, wherein upon hydration in water or an aqueous solution, at least one of the anterior surface and the posterior surface of the lens body is substantially smooth when wet and comprises a plurality of depressions extending inwardly into the lens body from the substantially smooth surface, the plurality of depressions having an average diameter between about 150 nanometers and less than 1500 nanometers and about 100 depressions per 900 μm²To about 1200 depressions/900 μm²And wherein after forming the lens body, the lens body has not been subjected to a form of plasma treatment, the lens body has not been treated with a polymerizable swelling agent, or both.

83. The method of claim 82, wherein the forming step comprises polymerizing a polymerizable composition comprising: a reactive component comprising at least one silicone-containing monomer, at least one silicone-containing macromer, at least one silicone-containing prepolymer, or a mixture thereof; at least one hydrophilic monomer and at least one cross-linking agent effective to cross-link the reactive ingredients.

84. The method of claim 83, wherein the polymerizing step occurs at least in part in a contact lens mold comprising a non-polar material.

85. The method of any one of claims 82 to 84, wherein the contact lens body is as in any one of claims 66 to 81.