silicone hydrogel contact lenses and methods for making silicone hydrogel contact lenses

专利摘要:
SILICON HYDROGEL CONTACT LENSES AND METHODS FOR THE MANUFACTURE OF SILICON HYDROGEL CONTACT LENSES. Silicone hydrogel contact lenses, when hydrated, have a plurality of depressions on one or more of the lens surfaces. The depressions have a depth of less than 1 micrometer, or less than 100 nanometers. Silicone hydrogel contact lenses were not subjected to plasma treatment. The methods of making silicone hydrogel contact lenses are also described.
公开号:BR112012007373B1
申请号:R112012007373-7
申请日:2010-09-30
公开日:2020-11-03
发明作者:Yuwen Liu；Yuan Ji；David Morsley；Charles Francis；Arthur Back
申请人:Coopervision International Holding Company, Lp；
IPC主号:

专利说明:

Cross Reference to Related Orders
This application claims the benefit of United States Provisional Application Serial No. 61 / 278,072, filed on October 1, 2009, the descriptions of which are incorporated in their entirety here by reference. Field
The present invention relates to contact lenses and methods of making contact lenses, for example, 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 with hydrophilic surfaces. For example, some silicone hydrogel contact lenses are surface treated with plasma, some silicone hydrogel contact lenses include a hydrophilic polymeric wetting agent in the polymerizable composition used to produce the silicone hydrogel contact lenses, and some silicone hydrogel contact lenses are cast in contact lens molds formed from a polar resin.
Sharma et al., United States Patent Application Publication US 2008/0143956 describe silicone hydrogel contact lenses on which a lens surface is wrinkled and includes raised edges extending upwardly from the lens surface. The wrinkled surface provided on the rear surface of the lens is said to facilitate the exchange of fluid between the lens and the cornea of the lens wearer's eye. The lens is a die-cast lens, which is formed before the wrinkled surface is supplied to the lenses. Cast-molded or formed contact lenses are initially provided with a modified surface layer, for example, a silicate surface layer, and subsequently that modified surface becomes the wrinkled surface. For example, the surface can be modified by treating with plasma or other energy. After forming the modified surface layer, the lens is swelled with a polymerizable swelling agent, for example, including ethylene build-up, such that the swelling agent is polymerizable by free radical polymerization. Depending on the amount of expansion, the modified surface layer, for example, the silicate layer, is wrinkled to a varying degree. The polymerization of the polymerizable wetting agent serves to stabilize the modified wrinkled surface layer. This multi-step process, particularly stabilization and surface modification processing after lens formation, is relatively complex and difficult to control, as well as adding to the cost of manufacturing silicone hydrogel contact lenses.
There remains a need for new contact lenses having desirable properties, such as surface wetting, and for new methods, for example, economical methods, of making contact lenses with such desirable properties. summary
New silicone hydrogel contact lenses and methods of making silicone hydrogel contact lenses have been described. The present silicone hydrogel contact lenses have contact lens bodies with surfaces having new surface characteristics. Among other things, the anterior lens surface and the posterior lens surface are hydrophilic and must be subjected to plasma treatment and / or treatment with a polymerizable wetting agent after the lens body is formed. The present methods directly manufacture the present contact lenses without subjecting the contact lenses to plasma treatment and / or treatment with a polymerizable wetting agent after the lens body is formed.
In a broad sense, an example of the present silicone hydrogel contact lenses comprises a lens body comprising an anterior surface and a posterior surface, after hydration in water or an aqueous solution, at least one of the anterior and posterior surfaces. the rear surface of the lens body when wet comprises a plurality of depressions with an average diameter between about 150 20 nanometers and less than 1500 nanometers, and the lens body has not been subjected to a form of plasma treatment, the lens body is not treated with a polymerizable wetting agent after the lens body is formed, or both.
A further example of the present silicone hydrogel contact lenses comprises 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, the density of depressions being about 100 depressions per 900 square micrometers to about 1200 depressions per 900 square micrometers.
In one embodiment, the plurality of depressions has an average diameter between 30 about 130 nanometers and less than about 630 nanometers, or the plurality of depressions has an average diameter between about 150 nanometers and less than about 550 nanometers.
The plurality of depressions can have an average depth of about 4 nanometers or about 15 nanometers to about 30 nanometers or about 60 nanometers 35 or about 100 nanometers. For example, a plurality of depressions can have an average depth of 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 about 15 nanometers to about 90 nanometers.
In one embodiment, at least one of the front and back surfaces of the lens body has an average surface roughness of about 5 nanometers RMS or about 7 nanometers RMS or about 10 nanometers RMS at about 20 nanometers of RMS or about 25 nanometers of RMS or about 30 nanometers of RMS. In this way, the present silicone hydrogel contact lenses can have an average surface roughness of about 5 nanometers of RMS to about 30 nanometers of RMS, from about 7 nanometers of RMS to about 25 nanometers of RMS or about 10 nanometers RMS to about 20 nanometers RMS.
In one embodiment, the average density of the depressions, meaning the average number of depressions per 900 square micrometers of surface, on at least one of the anterior and posterior surfaces of the lens body is about 5 or about 80 or about from 100 or about 200 depressions per 900 square micrometers of surface to about 1000 or about 1200 or about 1500 depressions per 900 square micrometers of surface. Thus, the average density of the depressions in at least one of the anterior and posterior surfaces of the lens body of the present contact lenses can be from about 5 depressions per 900 square micrometers of surface to about 1500 depressions per 900 micrometers surface squares, from about 80 depressions per 900 square micrometers of surface to about 1500 depressions per 900 square micrometers of surface, from about 100 depressions per 900 square micrometers of surface to about 1200 depressions per 900 square micrometers of surface, or from about 200 depressions per 900 square micrometers of surface to about 1000 depressions per 900 square micrometers of surface.
A plurality of depressions extend internally into the lens body, for example, from the otherwise substantially smooth anterior and / or posterior surface of the lens body. Thus, the present plurality of depressions, as well as the otherwise substantially smooth anterior and / or posterior surface of the present lens bodies are not, and cannot reasonably be considered to be raised edges. In summary, the present lens bodies can be free of raised edges. In addition, as noted above, a plurality of depressions on the anterior surface, on the posterior surface, or both of the present lens bodies, together with other surface characteristics of the present contact lenses, can provide a degree of surface roughness. However, it has been found that such surface roughness does not substantially adversely impact the wearer of the lens. In addition, it is understood that the depressions present on the surface of the lens bodies do not extend over the total thickness of the lens body to the other opposite surface, and therefore the present depressions are not pores that extend through the bodies of lens.
The ability of the present contact lenses to substantially maintain the advance of the contact angle and water dispersion times over a period of time, for example, at least 12 hours after hydration, indicates that the beneficial surface wetting properties of the lens bodies of the present contact lenses remain for a substantial period of time or are substantially permanently or even substantially permanent, rather than being a phenomenon that occurs only immediately after or following hydration. The wetting properties of the present contact lenses can be useful for lens wearers who wear such lenses on an extended basis, for example, for at least about 1 day or about 5 days or about 10 days or even about 30 days of continuous use.
In one embodiment, the lens body is swellable in water, for example, having a swelling factor of at least about 20 percent. 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 bodies of the present silicone hydrogel contact lenses comprise units of at least one monomer containing silicone, macromer containing silicone, prepolymer containing silicone, or combinations thereof. The lens bodies may comprise a polymeric material containing hydrophilic silicone.
In certain embodiments, the lens bodies of the present contact lenses include no hydrophilic polymeric internal wetting agent physically entangled in the polymeric matrix of the lens body. For example, no hydrophilic polymeric wetting agent is included in the polymerizable composition that is cured to form the lens body.
In one embodiment, the lens bodies of the present contact lenses are completely or partially cured while in direct contact with a contact lens mold that comprises 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 by casting in a contact lens mold assembly formed of a nucleated thermoplastic polypropylene resin having (i) a melt flow rate between about 15g / 10 minutes and about 40 g / 10 minutes, (ii) a density of about 0.900 g / cm3, (iii) a linear flow mold shrinkage of about 0.010 to about 0.020 inch / inch, (iv) a resistance tensile strength of approximately 386.10571 BAR (5600 psi), (v) a tensile elongation in production of approximately 8.0%, (vi) a flexural modulus of approximately 13.78949 BAR (200,000 psi) at approximately 19.99476 BAR (290,000 psi), (vii) a Rockwell hardness of about 110, or combinations of two or more of the same.
The present contact lenses may have a lens body that comprises a reaction product of a polymerizable composition that comprises reactive ingredients. Reactive ingredients include: (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 cross-linking agent that cross-links reactive ingredients during polymerization to form a polymeric lens body. In one embodiment, the lens body is formed by a process that comprises the polymerization of a polymerizable composition in the absence of a diluent. In other words, the polymerizable composition is a diluent-free polymerizable composition.
Silicone-containing monomers useful in the present polymerizable compositions may have a molecular weight of less than 700 Daltons. Silicone-containing macromers useful in the present polymerizable compositions can have a molecular weight of about 700 Daltons to about 2000 Daltons. Silicone-containing prepolymers useful in the present polymerizable compositions can have a molecular weight greater than 2000 Daltons. The molecular weight can be a numerical average molecular weight or a weighted average molecular weight, as understood by persons of ordinary skill in the art.
In one embodiment, the lens bodies of the present contact lenses are molded by casting the lens bodies which include an anterior surface and a posterior surface, each surface being free of a plasma treated surface. In other words, the lens bodies, including the anterior and posterior surfaces, are formed from a single casting molding step, and are formed without exposing the surfaces to a plasma treatment form. In another embodiment, the lens bodies of the present contact lenses include a surface layer having a different composition relative to the rest of the lens body, for example, a surface layer formed by exposing the lens body to water or a aqueous solution.
In some embodiments, the lens bodies of the present contact lenses are not subjected to extraction with an organic solvent or an aqueous solution including an organic solvent component prior to hydration in the water or aqueous solution. The present contact lenses can have surfaces effectively and sufficiently wetted without extraction with an organic solvent, for example, and without limitation, a volatile alcohol, or an aqueous solution including an organic solvent. Such bio-compatible or ophthalmically acceptable contact lenses can be obtained by washing or spraying water, or a plurality of washing or spraying water. It can be understood that the present contact lenses comprise lens bodies that have been washed with washing liquids or a volatile alcohol-free washing liquid containing water. The lenses can be washed with such volatile alcohol-free liquids one or more times, and the washing can take place in the final contact lens package or in one or more other washing containers.
The lens bodies of the present contact lenses can be contacted with liquid water or an aqueous medium before being placed in a packaging liquid. The aqueous medium 10 can include a surfactant component. In one embodiment, such water or aqueous medium does not include an organic solvent or a volatile alcohol.
In another broad aspect of the present invention, methods of making contact lenses are provided. The present methods comprise forming a body of contact lenses having an anterior surface and a posterior surface, and after hydration in water or an aqueous solution, at least one between the anterior surface and the posterior surface of the lens body when wet it comprises a plurality of depressions with an average diameter between about 50 nanometers and less than 1500 nanometers, and that: (A) the lens body has not been subjected to a form of plasma treatment, (B) lens body is not treated with a 2-0 polymerizable wetting agent after the lens body is formed or both (A) and (B).
The forming step can comprise the polymerization of a polymerizable composition comprising reactive ingredients. Reactive ingredients include (1) at least one component selected from the group consisting of silicone-containing monomers, silicone-containing macromers, silicone-containing prepolymers and mixtures thereof; (2) 25 at least one hydrophilic monomer and (3) at least one crosslinking agent effective to crosslink the reactive ingredients during the polymerization step.
Contact lenses and lens bodies made in accordance with the present methods can be the contact lenses and contact lens bodies described anywhere here. The present methods can be performed using a contact lens mold that comprises a non-polar material, for example, as described anywhere here.
Various embodiments of the present invention are described in detail in the additional disclosure and detailed description below. Any feature or combination of features described here is included in the scope of the present invention as long as the features included in any such combination are not mutually inconsistent as will be evident from the context, this specification, and the knowledge of someone of ordinary experience. in the technique. In addition, any feature or combination of features can be specifically excluded from any embodiment of the present invention. Additional embodiments of the present invention are evident in the following detailed description, examples and claims, the contents of which are an integral part of the present application. Brief Description of the Figures
Figure 1 shows the mean depression diameter (nm) determined by Atomic Force Microscopy (AFM) testing of a series of 16 test contact lenses and a series of commercially available silicone hydrogel contact lenses.
Figure 2 shows the average depth of depression (nm) determined by AFM testing of a series of 16 test contact lenses and a series of commercially available silicone hydrogel contact lenses.
Figure 3 shows the density of the surface depression determined by AFM testing of a series of 16 test contact lenses and a series of commercially available silicone hydrogel contact lenses.
Figure 4 shows the average RMS (nm) surface roughness determined by AFM testing a series of 16 test contact lenses and a series of commercially available silicone hydrogel contact lenses.
Figure 5-10 show a series of photographs showing the surface morphology of the lens as determined by AFM's 16 test contact lenses after hydration.
Figures 11-14 show a series of photographs showing the lens surface morphology as determined by AFM from various commercially available lenses after hydration.
Figures 15-18 shows a series of photographs of various test contact lenses and a commercially available contact lens in either a wet or hydrated state or in a dry state. Detailed Description
Definitions. In the context of this description, Annex and additional claims of the description, the following terminology will be used according to the definitions described below.
As used herein, the term "hydrogel" refers to a polymeric material, typically a network or matrix of polymer chains, capable of swelling in water or becoming swollen with water. A hydrogel can also be understood to be a material that retains water in an equilibrium state. The network or matrix may or may not be cross-linked. Hydrogels refer to polymeric materials, including contact lenses that are swellable in water or swell in water. Thus, a hydrogel can either be (i) dehydrated and swellable in water, or (ii) partially hydrated and swelled with water, or (iii) completely hydrated and swelled with water. The hydrogel can be a silicone hydrogel, a silicone-free hydrogel, or an essentially silicone-free hydrogel. The term "silicone hydrogel" or "silicone hydrogel material" refers to a particular hydrogel that includes a component containing silicon (Si) or a component containing silicone (SiO). For example, a silicone hydrogel is typically prepared by combining a material containing silicon with conventional hydrophilic hydrogel precursors is used .. A silicone hydrogel contact lens is a contact lens, including a vision correction contact lens, which comprises a silicone hydrogel material.
A "silicone-containing" component is a component that contains at least one [-Si-O-Si-] bond, in a monomer, macromer or prepolymer, with each silicon atom optionally having some way, for example, it can optionally be chemically, such as covalently, attached to, one or more substituents of organic radical (R1, R2) or substituents of substituted organic radical that can be the same or different, for example, -SiR ^ O-. "Molecular mass" in the context of a polymer described here refers to the nominal average molecular mass of a polymer, typically determined by size exclusion chromatography, light scattering techniques, or intrinsic rate determination in 1,2,4-trichlorobenzene . Molecular weight in the context of a polymer can be expressed as either a numerical average molecular weight or a weighted average molecular weight, and in the case of materials provided by the seller, it will depend on the supplier. Typically, the basis for any such molecular weight determination can easily be provided by the supplier if not provided in the packaging material. Typically, references here to the molecular weights of monomers, macromers, prepolymers or polymers here refer to the weighted average molecular weight. Both molecular weight, numerical mean and weighted mean determinations can be measured using gel permeation chromatographic techniques or other liquid chromatographic techniques. Other methods for measuring molecular weight values can also be used, such as using final group analysis or measuring colligative properties (for example, freezing point depression, boiling point elevation, or osmotic pressure ) to determine the numerical average molecular weight or the use of light scattering, ultracentrifugation or viscometry techniques to determine the weighted average molecular weight.
A "network" or "matrix" of a hydrophilic polymer typically means that the crosslinks are formed between the polymer chains by covalent bonds or by physical bonds, for example, hydrogen bonds. A network may include two or more polymeric components, and may include an interpenetrating polymer (IPN) network in which a polymer is physically entangled with a second polymer such that there is some, if any, covalent bond between them, but the polymers they cannot be separated from each other without destroying the network.
A "hydrophilic" substance is one that is sensitive to water or has an affinity for water. Hydrophilic compounds have an affinity for water and are generally charged or have polar fractions or groups that attract water.
A "hydrophilic polymer" as used herein is defined as a polymer having an affinity for water and capable of absorbing water. A hydrophilic polymer is not necessarily soluble in water. A hydrophilic polymer can be soluble in water or insoluble, for example, substantially insoluble in water.
A "hydrophilic component" is a hydrophilic substance that may or may not be a polymer. Hydrophilic components include those that are capable of providing at least about 20% (weight / weight), for example, at least about 25% (weight / weight) of water content to the resulting hydrated lenses when combined with the remaining reactive components. A hydrophilic component can include hydrophilic monomers, hydrophilic macromers, hydrophilic prepolymers, hydrophilic polymers, or combinations thereof. Hydrophilic macromers, hydrophilic prepolymers, and hydrophilic polymers can also be understood to have hydrophilic moieties and hydrophobic moieties. Typically, the hydrophilic portion and the hydrophobic portion are present in relative amounts such that the macromers, prepolymers, or polymers are hydrophilic.
A "monomer" refers to a relatively low molecular weight compound, for example, a compound with an average molecular weight less than 700 Daltons, which is polymerizable. In one example, a monomer may comprise a single unit of a molecule containing one or more functional groups capable of polymerization to combine with other molecules to form a polymer, the other molecules being of the same or different structures as the monomer.
A "macromer" refers to medium or high molecular weight compounds or polymers, which may contain one or more functional groups capable of further polymerization or polymerization. For example, a macromer can be a compound or polymer with an average molecular weight of about 700 Daltons to about 2,000 Daltons.
A "prepolymer" refers to a higher molecular weight polymerizable or crosslinkable compound. A prepolymer, as used here, may contain one or more functional groups. In one example, a prepolymer can be a series of monomers or macromers joined such that the total molecule remains polymerizable or crosslinkable. For example, a prepolymer can be a compound with an average molecular weight greater than about 2,000 Daltons.
A "polymer" refers to a material formed by the polymerization of one or more monomers, macromers, prepolymers or mixtures thereof. As used here, a polymer is understood to refer to a molecule that is not capable of being polymerized, but that is capable of being cross-linked to other polymers, for example, to other polymers present in a polymerizable composition or during the reaction of monomers, macromers and / or prepolymers to form other polymers in a polymerizable composition.
An "interpenetrating polymer network" or "IPN" refers to a combination of two or more different polymers, in the form of a network, of which at least one is synthesized and / or cross-linked in the presence of the other without or substantially without any hollow connection. - lens between them. An IPN can be composed of two types of chains forming two separate networks, but in juxtaposition or interpenetration. Examples of IPNs include sequential IPNs, simultaneous IPNs, semi-IPNs and homo-IPNs.
A "pseudo IPN" refers to a polymeric reaction product where at least one of the different polymers is cross-linked while at least one other polymer is non-cross-linked (for example, linear or branched), the polymer being non-cross-linked it is distributed in and maintained by the cross-linked polymer on a molecular scale such that the non-cross-linked polymer is substantially non-extractable from the network.
A "polymeric mixture" refers to a polymeric reaction product where different polymers are both linear or branched, substantially without crosslinking, the resulting polymeric mixture being obtained is a polymer mixture on a molecular scale.
A "graft polymer" refers to a branched polymer having side chains that comprise a homopolymer or copolymer other than that of the main chain. "Bond" can refer to any bond, graft, complex, bond (chemical bond or hydrogen bond), or bond, unless otherwise specified.
As used here, an "ophthalmically acceptable lens forming component" refers to a lens forming component that can be incorporated into a hydrogel contact lens without the lens wearer experiencing or reporting substantial discomfort, including eye irritation and similar. Ophthalmically acceptable hydrogel contact lenses have ophthalmically acceptable surface wettability, and typically do not cause or are not associated with significant horny swelling, corneal dehydration ("dry eye"), arched lesions of the upper epithelium ("SEALs"), or other discomfort significant. The term "organic solvent" refers to an organic substance that has the ability to solvate or dissolve at least one material, for example, and without limitation, unreacted materials, thinners and the like, present in a contact lens body that are not was previously subjected to extraction processing. In one example, the material is a material that is not soluble or does not dissolve in water or an aqueous solution. In another example, the material is a material that is not as soluble or does not dissolve as much as in water or an aqueous solution, that is, the material has increased solvation in the organic solvent when compared to water or an aqueous solution, so the organic solvent in contact with such an undrawn contact lens body is effective for solvating or dissolving at least one material present in the lens body, or increase solvation or dissolve to a greater degree the at least one material present in the lens body to reduce the concentration of at least one material in the lens body, or to reduce the concentration of at least one material in the lens body when compared to a lens body treated with water or an aqueous solution. The organic solvent can be used without dilution, i.e., 100% organic solvent, or it can be used in a composition including less than 100% organic solvent, for example, and without limitation, an aqueous solution including an organic solvent. In general, an organic solvent acts, for example, directly on the at least one material to solvate or dissolve the at least one material. Examples of organic solvents include, without limitation, alcohols, for example, 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 which has the ability to reduce the surface tension of water, for example, water or an aqueous solution in which the substance is present. the surfactant or surfactant component facilitates the water containing the surfactant or surfactant component, when in contact with a contact lens body which has not previously been subjected to extraction processing with an organic solvent, to more intimately contact the lens body and / or more effectively wash or remove at least one material present in the lens body from the lens body relative to the water without the surfactant or surfactant component. Generally, a surfactant or surfactant component does not act directly on the at least one material to solvate or dissolves the at least one material. Examples of surfactants or surfactant component include, without limitation, zwitterionic surfactants inc including forms of betaine, non-ionic surfactants including forms of polysorbate such as polysorbate 80, forms of poloxamers or poloxamines, fluorinated surfactants, and the like and mixtures thereof.
Additional definitions can also be found in the sections that follow.
Lens formulations. Hydrogels represent a class of materials used for present contact lenses. Hydrogels comprise a cross-linked, hydrated polymeric system containing water in a steady state. Consequently, hydrogels are copolymers prepared from one or more reactive ingredients. The reactive ingredients are crosslinkable with a crosslinking agent.
Hydrophilic monomer. The hydrophilic monomer can be, for example, a silicone-containing monomer having a hydrophilic part, a hydrophilic silicone-free monomer, or a combination thereof. The hydrophilic monomer can be used in combination with a hydrophobic monomer. The hydrophilic monomer can be a monomer having both hydrophilic and hydrophobic fractions or parts. The type and amount of the hydrophilic monomer used in the composition of polymerizable lenses may vary depending on the types of other lens forming monomers that are used. Non-limiting illustrations are provided here with respect to hydrophilic monomers for use in silicone hydrogels.
Crosslinking agent. Crosslinking agents for monomers, macromers, or prepolymers used in the preparation of hydrogels can include those that are known in the art, and examples of crosslinking agents are also provided here. Suitable crosslinking agents include, for example, a diacrylate (or divinyl ether) functionalized ethylene oxide monomer or oligomer, such as, for example, tri (ethylene glycol) dimethacrylate (TEGDMA) tri (ethylene glycol) divinyl ether (TEGDVE), ethylene glycol dimethacrylate (EGDMA), and trimethylene glycol dimethacrylate (TMGDMA). Typically, the 15 crosslinking agents are present in the polymerizable silicone hydrogel composition in relatively small total amounts in the polymerizable composition, such as in an amount ranging from about 0.1% (weight / weight) to about 10% (weight / weight), or from about 0.5% (weight / weight) to about 5% (weight / weight), or from about 0.75% (weight / weight) to about 1.5% (weight / weight), by weight of the polymerizable composition.
Silicone Hydrogel Lens Formulations. A silicone hydrogel lens formulation comprises at least one component containing silicone, at least one compatible hydrophilic monomer, and at least one compatible cross-linking agent. With respect to polymerizable lens formulations as described here, "compatible" components refer to components that, when present in a polymerizable composition prior to polymerization, form a single phase that is stable for an appropriate period of time to allow for manufacture of a polymerized lens body of the composition. For some components, a range of concentrations can be found to be compatible. In addition, “compatible” components are components that, when polymerized to form a polymerized lens body, produce a lens 30 that has adequate physical characteristics to be used as a contact lens (eg, adequate transparency, modulus, tensile strength , etc.)
Component containing silicone. The Si and O portion attached (O portion attached to Si) of the silicone-containing component may be present in the silicone-containing component in an amount greater than 20% (weight / weight), for example, greater than 30% (pe- 35 weight) of the total molecular weight of the silicone-containing component. Useful silicone-containing components comprise polymerizable functional groups such as vinyl, acrylate, methacrylate, acrylamide, methacrylamide, N-vinyl lactam, N-vinylamide, and functional styryl groups. The silicone-containing components from which the present contact lenses can be obtained, for example, by polymerization, include one or more monomers containing silicone, one or more macromers containing silicone, one ounce plus prepolymers containing silicon, or mixtures thereof. Silicone hydrogel contact lenses produced as described here can be based on a silicone-containing monomer and / or a silicone-based macronomer and / or a silicone-based prepolymer, and a hydrophilic monomer or co-monomer , and a crosslinking agent. In addition to other silicone-containing compounds described herein, examples of yet other silicone-containing components that may be useful in the present lenses can be found in United States Patent 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 Order Publication United States Patent Nos. 2007/0066706 A1, 2007/0296914 A1, and 2008/0048350 A1, all of which are incorporated in their entirety here by reference. The silicone-containing component can be a silicone-containing monomer or a silicone-containing macromer or a silicone-containing prepolymer.
A monomer, macromer, or prepolymer containing silicone may have, for example, the following general structure (I):
where R5 is H or CH3, X is O or NR55 where R55 is H or a monovalent alkyl group with 1 to 4 carbon atoms, a is 0 or 1, L is a divalent bonding group comprising from 1 to 20 carbon atoms carbon, or from 2 to 10 carbon atoms, which can also optionally comprise ether and / or hydroxyl groups, for example, a polyethylene glycol chain, p can be from 1 to 10, or from 2 to 5, Ri, R2, and R3 can be the same or different and are groups independently selected from hydrocarbon groups having 1 to about 12 carbon atoms (e.g., methyl groups), hydrocarbon groups substituted with one or more fluorine atoms, a siloxanyl group, and fractions containing siloxane chain, with at least one of Ri, R2, and R3 comprising at least one siloxane unit (-OSi). For example, at least one of R1; R2, and R3 can comprise - OSi (CH3) 3 and / or -OSi (R52R53R54) where R52, R53, R54 are independently ethyl, methyl, benzyl, phenyl 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-0 repeating units.
One, two or all three of R2 R2, and R3 can also comprise other siloxanil groups or fractions containing siloxane chain. The combined bond of -XL-, where present in a monomer containing silicone, macromer or prepolymer of structure (I), can contain one or more hetero atoms that are either O or N. The combined bond can be straight or branched, where the carbon chain segments of the same can be linear chain. The combined bond of -X-L- can optionally contain one or more functional groups selected from, for example, carboxyl, amide, carbamate, and carbonate. Examples of such combined links are provided, for example, in United States Patent No. 5,998,498 and United States Patent Application Publications Nos. 2007/0066706 A1, 2007/0296914 A1, and 2008/0048350, all descriptions of which are incorporated herein by reference. The silicone-containing monomer, macromer or prepolymer used in accordance with the present invention may comprise a single acryloyl group, as shown in structure (I), or optionally may have two acryloyl groups, such as one at each end of the monomer , macromer or prepolymer. Combinations of both types of monomers, macromers or prepolymers containing silicone optionally can be used in the polymerizable compositions useful in accordance with the present invention.
Useful examples of silicone-containing components according to the present invention include, for example, and without limitation, polysiloxanylalkyl (meth) acrylic monomers, macromers or acrylic prepolymers including, without limitation, methacryloxypropyl tris (trimethylsiloxy) silane, pentamethyldisyl methyl methacrylate, pentamethyldisyl and methyldi (trimethylsiloxy) methacryloxymethyl silane.
Specific useful examples of silicone-containing monomers, macromers or prepolymers can be, for example, 3- [tris (trimethylsilyloxy) silyl] propyl methacrylate ("Tris" provided by Gelest, Morrisville, PA, USA), and monomethacryloxypropyl-terminated polydimethylsiloxane ("MCS-MII" provided by Gelest, Morrisville, PA, USA). Examples of some silicone-containing monomers are described in United States Patent Application Publication No. 2008/0269429. Such silicone-containing monomers can have an alkylene group as a covalent bonding group (e.g., - (CH2) P-) and "a" can be 0 with reference to structure (I), and at least two siloxanyl groups. These silicone-containing components are referred to here as the structure-class (A) silicone-containing monomers. The exemplary non-limiting structures of these silicone-containing monomers are shown as follows:


Other specific examples of silicone-containing components useful in the present invention may be, for example, 3-methacryloxy-2-hydroxypropyloxy) propylbis (trimethylsiloxy) methylsilane ("SiGMA", available from Gelest, Morrisville, PA, USA) and methacrylate tildi (trimethylsiloxy) silylpropylglycerol ("SiGEMA"). Such silicone-containing components include at least one hydroxyl group and at least one ether group in the divalent bonding group L shown in structure (I) and at least two siloxanyl groups. These silicone-containing components are referred to here as structure-containing silicone (B) class components. Additional details on this class of silicone-containing components are provided, for example, in United States Patent No. 4,139,513, which is incorporated in its entirety here by reference. SiGMA, for example, can be represented by the following exemplary non-limiting structure:

The silicone-containing components of Structures (A) and (B) can be used individually or in any combination thereof in useful polymerizable compositions according to the present invention. The silicone-containing components of structures (A) and / or (B) can also be used in combination with at least one hydrophilic silicone-free monomer as described herein. If used in combination, for example, the amount of silicone-containing components of Structure (A) can be, for example, from about 10% (weight / weight) to about 40% (weight / weight), or about 15% (weight / weight) to about 35% (weight / weight), or about 18% (weight / weight) to about 30% (weight / weight). The amount of silicone-containing components of Structure (B) can be, for example, from about 10% (weight / weight) to about 45% (weight / weight), or from about 15% (weight / weight) to about 40% (weight / weight), or about 20% (weight / weight) to about 35% (weight / weight).
Currently useful polymerizable compositions include one or more hydrophobic monomers containing no silicone. Examples of such hydrophobic monomers include, without limitation, acrylic and methacrylic acids and derivatives thereof. An example of a hydrophobic monomer containing no silicone includes, without limitation, methyl methacrylate, combinations of two or more hydrophobic monomers may be employed.
Other specific examples of useful silicone-containing components useful in accordance with the present invention may be chemicals represented by the following formulas, or chemicals described in Japanese Patent Application Publication Number 2008-202060A, which is hereby incorporated by reference in its totality, for example,

Still other specific examples of useful silicone-containing components useful in accordance with the present invention may be chemical substances represented by the following formulas, or chemicals described in United States Patent Application Publication Number 2009/0234089, which is hereby incorporated by reference. in its entirety. In one example, the silicone-containing component may comprise 10 µm or more of hydrophilic polysiloxane component represented by the general formula (II),
being selected from hydrogen or a methyl group; R2 is selected from hydrogen or a hydrocarbon group; m represents an integer from 0 to 10; n represents an integer from 4 to 100; a and b represents integers of 1 or more; a + b is equal to 20-500; b / (a + b) is equal to 0.01-0.22; and the configuration of siloxane units includes a random configuration. Examples of such silicone-containing components are described in the Examples section of United States Patent Application Publication Number 2009/0234089, including Example 2 on page 7.
Other components containing silicone can also be used. For example, other suitable types may include, for example, poly (organosiloxane) monomers, macromers or prepolymers such as one, ω-bismethacryloxy-propyl polydimethylsiloxane. Another example is mPDMS (mono-n-butyl-terminated polydimethylsiloxane terminated in monomethacryloxypropyl). Other useful silicone-containing components include monomers, macromers or prepolymers of vinyl carbamate or vinyl carbonate containing silicone including, without limitation, 1,3-bis [4- (vinyloxycarb-onyloxy) but-1-yl] tetramethylisiloxane 3- (vinyloxycarbonylthio) ) propyl- [tris (trimethylsiloxysilane], 3- [tris (trimethylsiloxy) silyl] propyl allyl carbamate, 3- [tris (trimethylsiloxy) silyl] propyl vinyl carbamate; trimethylsilylethyl vinyl carbonate, and trimethylsilylmethyl vinyl carbonate. or more of these silicone-containing components may be provided, for example, in United States Patent No. 5,998,498 and United States Patent Application Publication Nos. 2007/0066706 A1, 2007/0296914 A1, and 2008/0048350, all descriptions of which are incorporated herein by reference.
Some of the silicone-containing monomers, macromers or prepolymers that can be used in accordance with the present invention can be used as a single monomer, macromer or discrete prepolymer, or can be used as a mixture of two or more monomers, macromers or discrete prepolymers. For example, MCR-M07 is generally supplied as a mixture of compounds containing silicone with a wide molecular weight distribution. Alternatively, some of the silicone-containing monomers, macromers or prepolymers that can be used according to the present invention can be provided as two or more monomers, macromers or prepolymers with discrete molecular weights. For example, X-22-1625 is available in a lower molecular weight version with a molecular weight of about 9000 Daltons, and as a higher molecular weight version with a molecular weight of about 18,000 Dal- 5 tons.
Free Silicone Monomers. Hydrophilic silicone-free monomers are included in the polymerizable compositions used to make the present contact lenses. Silicone-free monomers exclude hydrophilic compounds that contain one or more silicon atoms. Hydrophilic silicone-free monomers can be used in combination with silicone-containing monomers, macromers or prepolymers in polymerizable compositions to form silicone hydrogels. Hydrophilic silicone-free monomers can be used in combination with other silicone-free monomers, including silicone-free hydrophilic monomers and silicone-free hydrophobic monomers, in polymerizable compositions to form silicon-free hydrogels. In silicone hydrogels, the components of silicone-free hydrophilic monomers include those that are capable of providing at least about 10% (weight / weight), or even at least about 25% (weight / weight) content of water for the resulting hydrated lenses when combined with the other components of the polymerizable composition. For silicone hydrogels, the total silicone free monomers can be about 25% (weight / weight) to about 2-0 75% (weight / weight), or about 35% (weight / weight) to about from 65% (weight / weight), or from about 40% (weight / weight) to about 60% (weight / weight), 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, acrylic, methacrylic, acrylamide, methacrylamido, fumaric, maleic, styrene, isopropenylphenyl, O-vinylcarbonate, O-vinylcarbamate, allyl, O-vinylacetyl and N-vinyl double bonds lactam and N-vinylamido double bonds. In one example, hydrophilic monomers are vinyl-containing (for example, an acrylic-containing monomer or a non-acrylic vinyl-containing monomer). Such hydrophilic monomers alone can be used as crosslinking agents.
Such hydrophilic silicone-free monomers may, however, not necessarily be cross-linking agents. Considered as a subset of acryloyl fractions as described above, a monomer containing acrylate or "acrylic type" or "containing acrylic" is a monomer containing the acrylic group (CR'H = CRCOX) where R is H or CH3, R ' 35 is H, alkyl, or carbonyl, and X is O or N, which are also known to easily polymerize.
For silicone hydrogels, the hydrophilic silicone-free component may comprise non-silicon-containing monomer components that comprise an acrylic monomer (for example, a monomer with a vinyl group in the a-carbon position and a carboxylic acid terminal, a monomer with a vinyl group in the a-carbon position and an amide terminal, etc.) and a monomer containing hydrophilic vinyl (CH2 = CH-) (i.e., a monomer containing a vinyl group that is not part of an acrylic group).
Illustrative acrylic monomers include N, N-dimethylacrylamide (DMA), 2-hydroxyethyl acrylate, glycerol methacrylate, 2-hydroxyethyl methacrylate (HEMA), methacrylic acid, acrylic acid, methylmethacrylate (MMA), methacrylate and methacrylate ethylene glycol methyl (EGMA), and any mixtures thereof. In one example, the total acrylic monomer content is in an amount ranging from about 5% (weight / weight) to about 50% (weight / weight) of the polymerizable composition used to prepare a hydrogel lens product. silicone, and can be present in an amount ranging from about 10% (weight / weight) to about 40% (weight / weight), or from about 15% (weight / weight) to about 30% (weight / weight). weight) of the polymerizable composition.
As described above, silicone-free monomers can also comprise a monomer containing hydrophilic vinyl. Hydrophilic vinyl-containing monomers that can be incorporated into the materials of the present lenses include, without limitation, the following: N-vinyl lactans (eg, 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-β-alanine N-vinyl ester and the like and mixtures of themselves. An example of a vinyl-containing monomer is N-vinyl-methyl acetamide (VMA). The VMA structure corresponds to CH3C (O) N (CH3) -CH = CH2. In one example, the total vinyl-containing monomer content of the polymerizable composition is in an amount ranging from about 0% to about 50% (weight / weight), for example, up to about 50% (weight / volume), of the polymerizable composition used to prepare the silicone hydrogel lens product, and can be present in an amount ranging from about 20% (weight / weight) to about 45% (weight / weight), or about 28% ( weight / weight) to about 40% (weight / weight) of the polymerizable composition. Other silicone-free hydrophilic lens forming monomers known in the art may also be suitable.
Crosslinking agents useful in the production of the present contact lenses, such as the present silicone hydrogel contact lenses include, without limitation, the crosslinking agents indicated above. Examples of acrylate-functionalized ethylene oxide oligomers for use in crosslinking agents may include oligoethylene oxide dimethacrylate. The crosslinking agent can be TEGDMA, TEGDVE, EGDMA, TMGDMA, or any combination thereof. Typically, crosslinking agents are present in the polymerizable silicone hydrogel composition in relatively small total amounts in the polymerizable composition, such as in an amount ranging from about 0.1% (weight / weight) to about 10% ( weight / weight), or about 0.5% (weight / weight) to about 5% (weight / weight), or about 0.75% (weight / weight) to about 1.5 % (weight / weight), by weight of the polymerizable composition.
Additional Hydrogel Components. The polymerizable compositions of silicone hydrogel lenses described herein may also include additional components, for example, one or more initiators, such as one or more thermal initiators, one or more ultraviolet (UV) initiators, visible light initiators, combinations thereof , and the like, one or more UV absorbing compounds or agents, or energy absorbing or UV radiation, dyeing agent, pigments, release agents, antimicrobial compounds, and / or other additives. The term "additive" in the context of the present application refers to a compound or any chemical agent provided in the present polymerizable hydrogel contact lens compositions or polymerized hydrogel contact lens products, however it is not necessary for the manufacture of a hydrogel contact lens.
The polymerizable compositions can comprise one or more initiator compounds, that is, a compound capable of initiating the polymerization of the polymerizable composition. Thermal initiators, that is, initiators having an "outlet" temperature, can be used. For example, an exemplary thermal initiator employed in the present polymerizable compositions of the invention is 2,2'-azobiz (isobutyronitrile) (VAZO®-64). VAZO®-64 has an outlet temperature of about 62 ° C, which is the temperature at which the reactive components in the polymerizable composition will begin to polymerize. Another thermal initiator is 2,2'-azobis (2,4-dimethylpentanonitrile) (VAZO®-52), it has an outlet temperature of about 50 ° C. Yet another thermal initiator for use in the compositions of the invention is azo-bis-isobutyronitrile (VAZO®-88), which has an outlet temperature of about 90 ° C. All VAZO thermal initiators described here are available from DuPont (Wilmington, Del., USA). Additional thermal initiators include nitriles such as 1,1'-azobis (cyclohexanecarbonitrile) and 2,2'-azobis (2-methylpropionitrile), as well as other types of initiators such as those provided by Sigma Aldrich. Ophthalmically compatible silicone hydrogel contact lenses can be obtained from polymerizable compositions that comprise from about 0.05% (weight / weight) to about 0.8% (weight / weight), or about 0.1 % (weight / weight) to about 0.6% (weight / weight), of VAZ0®-64 or other thermal initiator.
A UV absorber can be, for example, a strong UV absorber that exhibits relatively high absorption values in the UV-A range of about 320-380 nanometers, but is reactively transparent above about 380 ran. Examples include photopolymerizable hydroxybenzophenones and photopolymerizable benzotriazoles, such as 2-hydroxy-4-acryloyloxyoxy benzophenone, commercially available as CYASORB UV416 from Cytec Industries, West Paterson, NJ, USA, 2-hydroxy-4- (2- hydroxy-3-methacrylyloxy) propoxybenzophenone, and photopolymerizable benzotriazoles, commercially available as NORBLOC® 7966 from Noramco, Athens, GA, USA. Other photopolymerizable UV absorbers suitable for use in accordance with the present invention include polymerizable, ethylenically unsaturated triazines, salicylates, aryl substituted acrylates, and mixtures thereof. In general, a UV absorber, if present, is supplied in an amount corresponding to about 0.5 weight percent of the polymerizable composition to about 1.5 weight percent of the composition. For example, the compositions can include from about 0.6% (weight / weight) to about 1.0% (weight / weight) of one or more UV absorbers.
Polymerizable compositions useful in accordance with the present invention may also include a dyeing agent, although both clear and colored lens products are contemplated. In one example, the dyeing agent is a reactive pigment or ink effective to provide color to the resulting lens product. Dyeing agents may include, for example, Blue 6 VAT (7,16-Dichloro-6,15-dihydroanthrazine-5,9,14,18-tetrone), 1-amino-4- [3- (beta- sulfatoethylsufonyl) anilio] -2-anthraquinonesulfonic (Reactive Blue 19 CI, RB-19), a copolymer of Reactive Blue 19 and hydroxyethylmethacrylate (RB-19 HEMA) 1, -bis [4- [(2-methacryl -oxyethyl) henylamino] anthraquinone (Reactive Blue 246, RB-246, available from Arran Chemical Company, Athlone, Ireland), 1,4-Bis [(2-hydroxyethyl) amino] -9,10- anthracenedodione bis (2-propenoic ester) (RB- 247), Reactive Blue 4, RB-4, or a copolymer of Reactive Blue 4 and hydroxyethyl methacrylate (RB-4 HEMA or "Azul HEMA"). Other exemplary dyeing agents are described, for example, in United States Patent Application Publication No. 2008/0048350, the description of which is incorporated in its entirety here by reference. Other dyeing agents suitable for use according to the present invention are phthalocyanine pigments such as phthalocyanine blue and phthalocyanine green, chromium-alumina-cobalt oxide, chromium oxides, and various iron oxides for the colors red, yellow, brown and black. Opacifying agents such as titanium oxide can also be incorporated. For certain applications, a mixture of colors can be used. If used, dyeing agents may be present in an amount ranging from about 0.1% (weight / weight) to about 15% (weight / weight), or about 1% (weight / weight) to about 10% (weight / weight), or about 4% (weight / weight) to about 8% (weight / weight).
Polymerizable compositions can also comprise a demoulding aid, that is, one or more effective ingredients in making it easier to remove cured contact lenses from their molds. Exemplary release agents include hydrophilic silicones, polyalkylene oxides, and combinations thereof. The polymerizable compositions can additionally comprise a diluent selected from the group consisting of hexanol, ethoxyethanol, isopropanol (IPA), propanol, decanol and combinations thereof. Diluents, if used, are typically present in amounts ranging from about 10% (weight / weight) to about 30% (weight / weight). Compositions having relatively higher concentrations of diluents tend, however, not necessarily to have lower ion flow values, reduced modulus, and increased elongation, as well as water dispersion times (WBUTs) greater than 20 seconds. Additional materials suitable for use in the preparation of hydrogel contact lenses are described in United States Patent No. 6,867,245, the description of which is incorporated in its entirety here by reference. In certain embodiments, however, the polymerizable composition is free of diluent.
Preparation Methods for Lenses. Various processes are known to cure a polymerizable composition in the production of contact lenses, including rotary casting and static casting. Rotary casting methods involve loading the polymerizable composition into a mold, and casting the mold in a controlled manner while exposing the polymerizable composition to UV light. Static casting methods involve providing the polymerizable composition between two mold sections, one mold section molded to form the front lens surface and the other mold section molded to form the rear lens surface, and curing the polymerizable composition by exposure UV light, heat, visible light or other radiation. Additional methods and details for forming contact lenses can be found, for example, in United States Patent Application Publications Nos. 2007/0296914 and 2008/0048350, the description of each of which is incorporated in its entirety here by reference.
After curing the reaction mixture, the resulting polymer is separated from the mold. In some situations, such as in static casting, the two mold members are first separated before separating the polymer from the mold.
The resulting polymer can also be treated with a washing liquid, including, but not limited to, water, aqueous solutions, organic solvents, and aqueous solutions including an organic solvent. Wash treatment can be used to remove diluent (if used), unreacted components, by-products, and the like, and hydrate the polymer to form a water-swollen 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. The lenses, without extraction of organic solvent, can be washed with water or an aqueous solution such as physiological saline or an aqueous solution of a surfactant or a 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 with water, followed by extraction with pure water (or physiological saline or a surfactant solution) to produce the silicone hydrogel that comprises a water-swollen polymer. In one embodiment, no diluents are present within or with the polymerizable composition. In any event, during or after washing, the lens is hydrated in water or an aqueous solution, such as a packaging solution. It will be understood that when a lens is washed with an aqueous solution, as described here, it will be at least partially hydrated. Washing / extraction processes, hydration processes, or both hydration and washing / extraction processes can be performed using a heated liquid, a pressurized liquid, or a liquid under a vacuum. Silicone hydrogels after hydration can comprise 20% (weight / weight) to 80% (weight / weight) of water, for example, 30% (weight / weight) 10 to 70% (weight / weight) of water, or 40 % (weight / weight) to 60% (weight / weight) of water of the total weight of the hydrogel.
Exemplary Polymerizable Compositions. The monomers of currently useful polymerizable compositions can be polymerized alone or copolymerized with other monomers to produce a contact lens material. TABLE
TABLE II
TABLE III
TABLE IV

Copolymers can be prepared by combining one or more monomers, macromers or prepolymers containing silicone, for example, first and second monomers, macromers or prepolymers containing silicone, as well as combining monomers, macromers or prepolymers of Structures (A) and (B), with one or more silicone-free monomers, such as those described in Table II and a cross-linking agent, such as those described in Table III. A polymerization initiator, such as those described in Table IV, is added to the mixture.
Copolymers are prepared in the form of contact lenses using lens molds, for example, made of a non-polar material, such as polypropylene, for example, a nucleated thermoplastic polypropylene resin, or in the form of films made between lined glass sheets of Teflon, first combining the components listed in Table I. The monomer mixtures are distributed in molds or in the wells of the slides and then the initiator is "started", for example, by heating the appropriate outlet temperature . Upon completion of molding, the molds are opened, and the polymers are separated from the molds. The lenses are then contacted with water or an aqueous solution, as described elsewhere here, to wash the lenses. The lenses can be hydrated in water or an aqueous solution, as described elsewhere here. The lenses can then be packaged in blisters or blister packs, such as blisters using a PBS solution. The present contact lens bodies are not subjected to a form of plasma treatment and / or are not treated with a polymerizable wetting agent after the lens body is formed.
The present contact lenses can have acceptable wettability as shown, for example, by various properties of the same such as, for example, contact angle in advance, water dispersion time (WBUT), capture of wetting solution, and other techniques.
Contact lenses can have at least one of the front and rear surfaces of the lens body when wet comprising a plurality of depressions with an average diameter between about 150 nanometers and less than 1500 nanometers, or a plurality of depressions with a average diameter between about 130 nanometers and less than about 630 nanometers, or a plurality of depressions with an average diameter between about 150 nanometers and less than about 550 nanometers.
A plurality of depressions can have an average depth of about 4 nanometers to about 100 nanometers, or a plurality of depressions can have an average depth of about 4 nanometers to about 4 nanometers, from about 4 nanometers to about 40 nanometers, or a plurality of depressions can have an average depth of about 4 nanometers to about 20 nanometers. In one embodiment, a plurality of depressions can have an average depth of about 8 nanometers to about 20 nanometers, or a plurality of depressions can have an average depth of about 15 nanometers to about 90 nanometers.
Contact lenses according to the present invention can have an average surface roughness of about 5 nanometers of square root mean (RMS) to about 30 nanometers of RMS, or the average surface roughness can be about 7 nanometers of RMS to about 25 nanometers of RMS, or the average surface roughness can be from about 10 nanometers of RMS to about 20 nanometers of RMS.
A plurality of depressions can have an average density or density, meaning the number of depressions per 900 square micrometers of surface or the average number of depressions per 900 square micrometers of surface, from about 5 depressions per 900 square micrometers of surface to about 1500 depressions per 900 square micrometers of surface, or a plurality of depressions can have an average density of about 80 depressions per 900 square micrometers of surface to about 1500 depressions per 900 square micrometers of surface, or a plurality of depressions can have an average density of about 200 depressions per 900 square micrometers of surface to about 1000 depressions per 900 square micrometers of surface. In one embodiment, a plurality of depressions can have an average density of about 100 depressions per 900 square micrometers of surface to about 1200 depressions per 900 square micrometers of surface.
The present contact lenses, immediately following hydration in water or an aqueous solution, can have at least one between the front surface and the rear surface of the lens body that has a contact angle in advance of less than 100 ° and one water dispersion time (WBUT) greater than five (5) seconds. A contact lens of the present invention can have, at least 12 hours after hydration in water or an aqueous solution, at least one between the front surface and the rear surface of the lens body that has a contact angle in advance less than 100 ° and a water dispersion time greater than five (5) seconds. In one embodiment, immediately following hydration in water and the aqueous solution, at least one of the front and rear surfaces of the lens body has a contact angle in advance of less than 100 ° and a water dispersion time greater than 5 seconds and at least 12 hours after hydration in water or the aqueous solution at least one of the front surface and the rear surface of the lens body has a contact angle in advance of less than 100 ° and a dispersion time of water longer than 5 seconds.
Contact lenses according to the present invention may have, immediately following hydration in water or in aqueous solution, at least one of the front and rear surfaces of the lens body having a first contact angle in advance which differs in no more than 30 ° from a second contact angle in advance of the anterior surface or the posterior surface of the lens body at least 12 hours after hydration in water or the aqueous solution, or a first contact angle in advance which differs by no more than 20 ° of a second contact angle in advance of the anterior surface or posterior surface of the lens body at least 12 hours after hydration in water or an aqueous solution, or a first contact angle in advance which differs by no more than 10 ° of a second contact angle in advance of the anterior surface or posterior surface of the lens body at least 12 hours after hydration in water or an aqueous solution.
The present contact lenses can have, immediately after hydration in water or an aqueous solution, the anterior surface or posterior surface of the lens body having a first water dispersion time that differs in no more than 15 seconds from a second time dispersion of water from the anterior or posterior surface of the lens body at least 12 hours after hydration in water or an aqueous solution or a first water dispersion time that differs by no more than 10 seconds from a second dispersion time of water from the front or back surface of the lens body at least 12 hours after hydration in water or an aqueous solution, or a first water dispersion time that differs by no more than 5 seconds from a second water dispersion time from anterior or posterior surface of the lens body at least 12 hours after hydration in water or an aqueous solution.
Contact lens packaging. A contact lens package is provided which comprises the contact lens body, as described above, and a packaging solution. The packaging solution can comprise a wetting agent or an agent to help prevent or eliminate the lenses from adhering to the blister package such as, for example, a surfactant or a hydrophilic polymer. The surfactant can be a nonionic surfactant such as polysorbate 80, a poloxamer, or a saccharide. The hydrophilic polymer can be a form of polyvinylpyrrolidone, polyethylene glycol, polyvinyl alcohol, or combinations thereof.
With respect to the contact lens packaging, the packaging may also comprise a base member with a cavity configured to hold the contact lens body and the packaging solution, and a seal attached to the base member configured to hold the contact lens. contact and packaging solution in a stereo condition for a period of time equivalent to a contact lens shelf life. EXAMPLES
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 = A monomethacryloxypropyl-terminated polydimethylsiloxane, as previously illustrated (Gelest, Morrisville, PA, USA). MCS-M11 = A monomethacryloxypropyl-terminated polydimethylsiloxane (Gelest, Morrisville, PA, USA). A structure like this is:
MCS-M11 FMM = A component containing silicone as previously illustrated (Shin-Etsu Silicones of America, Akron, OH, USA). M5A = A component containing silicone equal to, or similar in structure to, the hydrophilic polysiloxane A macromonomers described in Example 2 of United States Patent Application Publication No. 2009/0234089 (Asahi Kasei Aime Co., Ltd., Kanagawa , Japan). X22-1622 = A component containing silicone as previously illustrated (Shin-Etsu Silicones of America, Akron, OH, USA). X22-1625 = A component containing silicone as previously illustrated (Shin-Etsu Silicones of America, Akron, OH, USA). SiGMA = (3-Methacryloxy-2-hydroxypropyloxy) propylbis (trimethylsiloxy) methylsilane. A structure of the same
SiGMA Tris = 3- [Tris (trimethylsilyloxy) silyl] propyl methacrylate. A structure of the same is:
Tris DMS-R18 = A methacryloxypropyl-terminated polydimethylsiloxane, as previously illustrated (Gelest, Morrisville, PA, USA). 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 = Divinyl ether of tri (ethylene glycol). VAZO® 64 = 2,2'-Azobiz (isobutyronitrile). PBS = phosphate buffered saline (20mM, pH = 7.3) MPC = 2-methacryloyloxyethyl phosphorylcholine (HEMA-PC, LIPIDURE®, NOF Corporation, Tokyo, Japan). VB6 = VAT Blue 6 (7,16-Dichloro-6,15-dihydroanthrazine-5,9,14,18-tetrone). EHMA = 2-Ethylhexyl methacrylate. IBM = Isobornyl methacrylate. AE = Aloxy ethanol Preparation of Contact Lenses
The polymerizable lens compositions were prepared by mixing various combinations of ingredients and components as indicated by some in Table AB below. The lens formulations are formed on lenses in the following general manner.
Contact lens molds were molded by injection of non-polar polypropylene resin using conventional injection molding equipment and techniques. Each contact lens mold includes a female mold member that includes a concave optical quality surface to form the front surface of the contact lens, and a male mold member that includes a convex optical quality surface to form the rear lens surface. contact. The female mold member can be understood to be a frontal surface mold, and the male mold member can be understood to be a posterior surface mold.
A quantity (about 60 pl) of the polymerizable lens composition was placed on the female mold member concave surface. The male mold member was placed in contact with the female mold member such that the polymerizable lens composition was located in a molded cavity of the contact lens formed between the concave surface of the female mold member and the convex surface of the mold member male. The male mold member was held in position by an interference fit between the peripheral region of the female and male mold members. The contact lens mold containing the polymerizable lens composition was then placed in an oven where the polymerizable lens composition was cured at a temperature of about 100 ° C for about 30 minutes. After curing, the contact lens mold contained a polymerized contact lens product in the molded contact lens cavity. The contact lens mold was removed from the oven and allowed to cool to room temperature (about 20 ° C). The contact lens mold was mechanically demoulded to separate the male and female mold members from one another. The polymerized contact lens product remained attached to the male mold member. The polymerized contact lens product was then mechanically removed from the male mold member to separate the contact lens product from the male mold member. The separate contact lens product was then washed in water, hydrated in PBS and subjected to various test procedures to characterize the hydrated contact lens product. In certain cases, the contact lens product has been tested dry, that is, with the contact lens product in the dry state, for example, prior, for washing, extraction or hydration, or after drying to remove the solvent or retained water . Methods for Characterizing Lens Products
The topography of the anterior and posterior surfaces of contact lens products, in particular the contact lens bodies of such products, was analyzed using atomic force microscopy (AFM). The instrument employed was a Veeco Model CP II Atomic Force Microscope, sold by Veeco Instrument, Inc., Santa Barbara, CA USA. This instrument was used running in touch mode, with a scan rate of 0.5 Hz and scan sizes of 10x10 microns, 20x20 microns, 30x30 microns and 40x40 microns. The data were analyzed using the following software: Image analysis version 2.1 provided by Veeco Instrument, Inc. The following procedure was followed:
Veeco CP II atomic force microscopy operating in touch mode was used to take images from dry and wet lenses. The tested wet lenses were in PBS solution. For specific types of lenses, 3 lenses were tested to take atomic force microscopy (AFM) images. At least 3 different areas were scanned in a lens sample to collect AFM data. A wet lens sample was removed from the blister or bottle package, and mounted on top of a polypropylene mold submerged in the PBS solution. Surface topography images were subsequently taken in a liquid environment at different scan sizes (10pm x 10pm, 20pm x 20pm, 30ym x 30pm, 40pm x 40pm) with a scan rate of 0.5Hz. The dry lens samples were fixed on a clean stainless steel sheet using double sided carbon tape and tested in a dry condition at different scan sizes (10pm x 10pm, 20pm x 20pm, 30pm x 30pm, 40pm x 40pm) with a scan rate of 0.5Hz. Surface depressions were also analyzed using Image Analysis V2.1 (Veeco Instrument Inc.). The number of periodicity or distribution of the surface depression was counted from the AFM images in an area of 30pm x 30pm. 50 Surface depressions were also analyzed to obtain the mean diameter and mean depth of the depression in the AFM images. In addition, the mean square root roughness (RMS) was calculated using the same software for different types of lenses.
Water dispersion time (WBUT). Before testing, a lens is soaked in 3 ml of fresh PBS for at least 24 hours. Immediately before testing, the lens is shaken to remove excess PBS, and the amount of time in seconds it takes for the water film to leak from the lens surface is determined (for example, water dispersion time (water BUT , or WBUT)).
Forward contact angle. The forward contact angle can be determined using routine methods known to persons of ordinary skill in the art. For example, the forward contact angles of the contact lenses provided here can be measured using a captive bubble method. The forward contact angles of silicone hydrogel contact lenses can be determined using a Kruss DSA 100 instrument (Kruss GmbH, Hamburg), and as described in DA Brandreth: "Dynamic contact angles and contact angle hysteresis", Journal of Colloid and Interface Science, vol. 62, 1977, pp. 205-212 and R. Knapikowski, M. Kudra: Kontaktwinkelmessungen nach dem Wil-helmy-Prinzip-Ein statistischer Ansatz zur Fehierbeurteilung ", Chem. Technik, vol. 45, 1993, pp. 179-185, and United States Patent No. 6,436,481, all of which are incorporated in their entirety here by reference.
As an example, the forward contact angle can be determined using a captive bubble method using phosphate buffered saline (PBS; pH = 7.2). Before testing, the solution is soaked in a pH 7.2 PBS solution for at least 30 minutes or overnight. The lens is flattened on a quartz surface and rehydrated with PBS for 10 minutes before testing. An air bubble is placed on a lens surface using an automatic syringe system. The size of the air bubble can be increased and decreased to obtain the recoil angle (the plateau obtained by increasing the bubble size) and the lead angle (the plateau obtained by decreasing the bubble size).
Static contact angle. The angle of static contact can be determined using routine methods known to persons of ordinary skill in the art. For example, the static contact angle can be determined using a captive bubble method 20, or using a DSA 100 drop shape analysis system (Kruss, Hamburg, Germany). Before testing, the lens is soaked in a pH 7.2 PBS solution for at least 30 minutes or overnight.
Module. The module of a lens body can be determined using methods known to persons of ordinary skill in the art. For example, pieces of a contact lens having about 4 mm in width can be cut from a central part of a lens, and the module (unit; MPa) can be determined from a strain strain curve obtained by the test tensile strength at a rate of 10 mm / min in air at a humidity of at least 75% at 25 ° C, using an Instron 3342 (Instron Corporation, Norwood, MA, USA).
Ion flow. The ion flow of the lens bodies of the present lenses can be terminated using routine methods known to persons of ordinary skill in the art. For example, the ion flow from a contact lens or lens body can be measured using a technique substantially similar to the "Ion Flow Technique" described in United States Patent No. 5,849,811. For example, the lens to be measured can be placed in a lens holding device between the male and female parts. The male and female parts include flexible sealing rings that are positioned between the lenses and the respective male or female parts. After placing the lens on the lens holding device, the lens holding device is placed in a screw cap. The cap is screwed over a glass tube to define the donor chamber. The donor chamber can be filled with 16 ml of 0.1 molar NaCI solution. A receiving chamber can be filled with 80 ml of deionized water. The lead of the conductivity meter is immersed in the deionized water of the receiving chamber and a stir bar is added to the receiving chamber. The receiving chamber is placed in a thermostat and the temperature is maintained at about 35 ° C. Finally, the donor chamber is immersed in the receiving chamber. Conductivity measurements can be taken every 2 minutes for about 20 minutes, starting 10 minutes after immersing the donor chamber in the receiving chamber. Conductivity versus time data must be substantially linear.
Tensile strength. The tensile strength of a lens body can be determined using routine methods known to people of ordinary skill in the art. For example, parts of a contact lens about 4 mm wide can be cut from a central part of a lens, and the tensile strength (unit; MPa) can be determined from the test using an Instron 3342 (Instron Corporation, Norwood, MA, USA).
Stretching. The elongation of a lens body can be determined using routine methods known to persons of ordinary skill in the art. For example, elongation (%) can be determined using an Instron 3342 (Instron Corporation, Norwood, MA, USA).
Oxygen Permeability (Dk). The Dk of the present lenses can be determined using routine methods known to persons of ordinary skill in the art. For example, the Dk value can be determined using a modified polarographic method, as described in A single-lens polarographic measurement of oxygen permeability (Dk) for hypertransmissible soft contact lenses, M. Chhabra et al., Biomaterials 28 (2007) 4331 - 4342.
Equilibrium Water Content (EWC). The water content of the present lenses can be determined using routine methods known to persons of ordinary skill in the art. For example, a hydrated silicone hydrogel contact lens can be removed from an aqueous liquid, wiped to remove excess surface water, and weighed. The heavy lens can then be dried in an oven at 80 ° C under a vacuum, and the dry lens can then be weighed. The weight difference is determined by subtracting the dry lens weight from the hydrated lens weight. The water content (%) is the (difference in weight / hydrated weight) x 100.
Lens Center Thickness (CT). CT can be determined using routine methods known to persons of ordinary skill in the art. For example, CT can be determined using a Rehder ET gauge (Rehder Development Company, Castro Valley, CA, USA).
A series of 16 contact lenses were formed and tested as described above. These 16 lenses were formed in polypropylene (nucleated) molds of the polymerizable compositions 5 listed in Table AB. TABLE AB


A series of commercially available silicone hydrogel contact lenses have also been tested using AFM to analyze surface topography. These lenses include commercially available lenses that have not undergone a form of plasma treatment as part of their manufacturing processes, including AVAIRA® lenses and 5 BIOFINITY® lenses (CooperVision, Pleasanton, CA), CLARITI ™ lenses (Sauflon, Twickenham , UK) and ACUVUE® OASYS ™ lenses, ACUVUE® ADVANCE® lenses, and ACUVUE® TRUEYE ™ lenses (Johnson & Johnson Vision Care, Inc., Jacksonville, FL, USA). The lenses also include commercially available lenses that have undergone a form of plasma treatment as part of their manufacturing processes, including PUREVISION® lenses (Bausch & Lomb, Rochester, NY, USA), PREMIO ™ lenses (Menicon, JP), and NIGHT & DAY® lenses, 020PTIX® lenses, and AIR OPTIX® lenses (Ciba Vision, Duluth, GA, USA).
Certain results of these AFM tests are shown in Figures 1-4, as well as in Table AC. In addition, Figures 5-18 show pictures of the lens surfaces.
The size, depth and density of the depressions, as well as the RMS roughness of the anterior / posterior surfaces of each of the test lenses, remained substantially the same, for example, ± between 10% and 15%, whether the AFM analysis was conducted immediately after hydration or 12 hours after hydration or 24 hours after hydration.
As shown in Table AC below, and Figure 1, the average diameter of the surface depressions in contact lenses produced from formulations 1-14 and 16 is in a range between 175.7 nm to 615.8 nm. Some of the formulations of the present invention have average diameters of surface depressions in the range, for example, between about 150 nm and about 1500 nm, between about 130 nm and about 630 nm, between about 150 nm and about 1500 nm, between about 170 nm and about 570 nm, between about 180 nm and about 380 nm, or between about 250 nm and about 390 nm. The contact lenses of formulation 15 have an average depression diameter of 1174.6 nm. Of the tested commercially available lenses, lenses that have not undergone a form of plasma treatment (i.e., AVAIRA® lenses, BIOFINITY® lenses, CLARITI ™ lenses and ACUVUE® lenses) or have no detectable surface depressions or surface depressions with average diameters larger than the lenses of formulations 1-14 and 16. Lenses that have undergone a form of plasma treatment (ie, PUREVISION® lenses, PRIZE® lenses, NIGHT lenses & DAY®, 020PTIX® lenses, and AIR OPTIX® lenses) either have no surface depression or surface depressions with slightly larger average diameters, for example, between about 400 nm and about 800 nm. TABLE AC


As shown in Table AC and Figure 2, the average depth of the surface depressions in contact lenses produced from formulations 1-14 and 16 is in a range between 5.1 nm and 48.1 nm. The contact lenses of formulation 15 have an average surface depression depth of 61.6 nm. Some of the formulations of the present invention 5 have average depths of surface depressions in the range, for example, between about 4 nm and about 60 nm, between about 4 nm and about 20 nm, between about 8 nm and about 40 nm, between about 8 nm and about 20 nm, between about 15 nm and about 90 nm, or between about 15 nm and about 30 nm.
As shown in Table AC and Figure 3, the density or distribution of surface depression 10 in contact lenses produced from formulations 1-14 and 16 is in a range between 135 and 1062 depressions by 900 pm2. The contact lenses of formulation 15 have a density of 5 depressions per 900 pm2. Some of the formulations of the present invention have densities in a range between about 5 depressions by 900 pm2 and about 1500 depressions by 900 pm2, between about 80 depressions by 900 pm2 and about 1500 depressions by 900 pm2, between about 200 depressions for 900 pm2 and about 1000 depressions for 900 pm2, between about 100 depressions for 900 pm2 and about 1200 depressions for 900 pm2, between 2 depressions for 900 pm2 and 700 depressions for 900 nm2, or between about 100 depressions for 900 pm2 and about 600 depressions for 900 pm2. Tested commercially available lenses that have not undergone a form of plasma treatment either have no surface depression or have a surface depression density that is substantially less than that of formulations 1-14 and 16.
As shown in Table AC, and Figure 4, the average RMS surface roughness of contact lenses produced from formulations 1-16 is in a range between 6.9 and 19.7. Some of the formulations of the present invention have an average RMS surface roughness in the range between about 5 nm and about 30 nm, between about 5 nm and about 20 nm, between about 5 nm and about 15 nm, between about 7 nm and about 25 nm, between about 10 nm and about 30 nm, between about 15 nm and 30 nm, or between 15 nm and 20 nm. The tested commercially available lenses that were not subjected to a form of plasma treatment had an average RMS surface roughness that tends to be slightly smaller, for example, in a range between about 5 nm and about 10 nm.
In addition, Table AD below includes results of the lens property characterization tests performed using the present formulations. Table AD


FIGURES 5-18 comprise a set of photographs showing the surface morphology of lenses as determined by atomic force microscopy (AFM) using touch mode. FIGURES 5-10 show the lenses produced from formulations 1-16 after hydration in PBS. FIGURES 11-14 show morphology photographs of several commercially available lenses, including AVAIRA®, BIOFINITY®, CLARITI ™, PREMIUM ™, PUREVISION®, ACUVUE® OASYS ™, ACUVUE® ADVANCE®, ACUVUE® TRUEYE ™, NIGHT & DAY® 020PTIX®, and AIR OPTIX® as determined using touch mode AFM after hydrating the lens in PBS.
In FIGURES 16-18, the results of touch mode AFM are presented for contact lenses of formulations 1,5, 15 and the commercially available AVAIRA® lenses tested in both wet and hydrated (hydrated in PBS) and dry conditions . These results show that the surface depressions are present in both wet and dry lenses. Thus, the surface depressions do not result, for example, not only result, from the hydration of the lenses.
Several publications, patents and patent applications have been cited previously. Each of these publications, patents and patent applications cited is hereby incorporated by reference in their entirety.
At the same time that this invention has been described with respect to the various specific embodiments and examples, it should be understood that the invention is not limited to this and that it can be varied in practice within the scope of the following claims.

权利要求:
Claims (18)
[0001]
1. Silicone hydrogel contact lenses CHARACTERIZED by the fact that they comprise: a body of silicone hydrogel lenses comprising an anterior surface and a posterior surface, where, after hydration in water or an aqueous solution, at least one between the anterior surface and the posterior surface of the lens body when wet it is substantially smooth and comprises a plurality of depressions extending internally into the lens body from the substantially smooth surface, the plurality of depressions having an average diameter between 150 nanometers and less than 1500 nanometers and an average density of 100 depressions per 900 pm2 to 1200 depressions per 900 pm2, and where the lens body was not subjected to a form of plasma treatment, the lens body was not treated with a polymerizable wetting agent after the lens body is formed, or both, at least one of the front and rear surfaces of the lens body lenses have an average surface roughness of 5 nanometers RMS to 30 nanometers RMS, and the lens body has a swelling factor of at least 20%.
[0002]
2. Contact lenses, according to claim 1, CHARACTERIZED by the fact that the plurality of depressions have an average diameter between 130 nanometers and less than 630 nanometers.
[0003]
3. Contact lenses, according to claim 1, CHARACTERIZED by the fact that the plurality of depressions have an average depth of 4 nanometers to 100 nanometers.
[0004]
4. Contact lenses, according to claim 1, CHARACTERIZED by the fact that the plurality of depressions has an average density of 5 depressions per 900 pm2 to 1500 depressions per 900 pm2.
[0005]
5. Contact lenses, according to claim 1, CHARACTERIZED by the fact that, at least 12 hours after hydration in water or in aqueous solution, at least one of the front and rear surfaces of the lens body has a contact angle in advance less than 100 ° and a water dispersion time greater than five seconds.
[0006]
6. Contact lenses according to claim 1, CHARACTERIZED by the fact that the lens body is completely or partially cured while in direct contact with a contact lens mold that comprises a non-polar material.
[0007]
7. Contact lenses according to claim 1, CHARACTERIZED by the fact that the lens body comprises a reaction product of a polymerizable composition comprising: reactive ingredients comprising at least one monomer containing silicone, at least one macromer containing silicone, at least one prepolymer containing silicone, or mixtures thereof, at least one hydrophilic monomer, and at least one cross-linking agent which cross-links reactive ingredients during polymerization to form a polymer.
[0008]
8. Method of making silicone hydrogel contact lenses, CHARACTERIZED by the fact that it comprises: forming a body of silicone hydrogel contact lenses as defined in claim 1.
[0009]
9. Method according to claim 8, CHARACTERIZED by the fact that the formation step comprises polymerizing a polymerizable composition comprising reactive ingredients comprising at least one silicone-containing monomer, at least one silicone-containing macromer, at least one pre- polymer containing silicone, or mixtures thereof; at least one hydrophilic monomer and at least one crosslinking agent effective to crosslink reactive ingredients.
[0010]
10. Method according to claim 9, CHARACTERIZED by the fact that the polymerization step occurs at least partially in a contact lens mold comprising a non-polar material.
[0011]
11. Method according to claim 10, CHARACTERIZED by the fact that the non-polar material comprises polypropylene.
[0012]
12. Method, according to claim 10, CHARACTERIZED by the fact that the non-polar material is a nucleated thermoplastic polypropylene resin.
[0013]
13. Method according to claim 9, CHARACTERIZED by the fact that the reactive ingredients comprise a silicone-containing monomer with a molecular weight less than 700 Daltons.
[0014]
14. Method according to claim 9, CHARACTERIZED by the fact that the reactive ingredients comprise a silicone-containing macromer with a molecular weight between 700 Daltons and 2,000 Daltons.
[0015]
15. Method according to claim 9, CHARACTERIZED by the fact that the reactive ingredients comprise a silicone-containing prepolymer with a molecular weight greater than 2,000 Daltons.
[0016]
16. Method according to claim 8, CHARACTERIZED by the fact that the formation step comprises the polymerization of a polymerizable composition in the absence of a diluent.
[0017]
17. Method, according to claim 8, CHARACTERIZED by the fact that the lens body is not subjected to extraction with an organic solvent or an aqueous solution including a component of the organic solvent before hydration in the water or in the aqueous solution.
[0018]
18. Method, according to claim 8, CHARACTERIZED by the fact that, after hydration in water or an aqueous solution, at least one of the front and rear surfaces of the lens body when wet comprises a plurality of 5 depression with an average diameter between 150 nanometers and less than 1500 nanometers, and an average density of 100 depressions per 900 pm2 to 1200 depressions per 900 pm2.

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同族专利:

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公开号 | 公开日

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GB2481761B|2012-09-12|

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US20110085128A1|2011-04-14|

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HUE030443T2|2017-05-29|

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EP2483737A4|2015-06-03|

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EP2483737B1|2016-07-06|

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MY159465A|2017-01-13|

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CA2773223C|2015-11-24|

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ES2593406T3|2016-12-09|

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SG175812A1|2011-12-29|

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HK1170311A1|2013-02-22|

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BR112012007373A2|2016-10-11|

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CA2773223A1|2011-04-07|

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GB2481761A|2012-01-04|

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GB201118233D0|2011-12-07|

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KR20120002609A|2012-01-06|

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CN102576158A|2012-07-11|

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TWI509312B|2015-11-21|

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JP6023589B2|2016-11-09|

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WO2011041523A3|2011-09-29|

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MX2012003436A|2012-05-22|

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JP2013506875A|2013-02-28|

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EP2483737A2|2012-08-08|

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US8672475B2|2014-03-18|

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KR101197842B1|2012-11-05|

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TW201122618A|2011-07-01|

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WO2011041523A2|2011-04-07|

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CN102576158B|2014-07-16|

引用文献:

---

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

---

---

US2393266A|1943-12-07|1946-01-22|Donald J Riddell|Contact lens|

---

US2989894A|1959-06-22|1961-06-27|Contact Lens Guild Inc|Corneal contact lens with spiral vent ducts|

---

US3246941A|1962-02-28|1966-04-19|Herbert L Moss|Contact lens with upper crescent shaped scleral flange and having vent channels and apertures|

---

US3228741A|1962-06-29|1966-01-11|Mueller Welt Contact Lenses In|Corneal contact lens fabricated from transparent silicone rubber|

---

US3431046A|1964-02-14|1969-03-04|Studies Inc|Flexible polyethylene corneal contact lens|

---

US3594074A|1969-06-16|1971-07-20|Mencher Alexander|Contact lens with flexible central portion|

---

US3907851A|1971-03-30|1975-09-23|Union Carbide Corp|Novel process for producing organosilicon hydroxy compounds and novel organosilicon adducts|

---

CA983230A|1972-01-03|1976-02-10|Lawrence Stark|Physiologically compatible plastic contact lenses and a method for their production|

---

US3808178A|1972-06-16|1974-04-30|Polycon Laboratories|Oxygen-permeable contact lens composition,methods and article of manufacture|

---

US4099859A|1974-12-02|1978-07-11|High Voltage Engineering Corporation|Contact lens having a smooth surface layer of a hydrophilic polymer|

---

DE2546692C3|1975-10-17|1978-10-19|American Optical Corp., Framingham, Mass. |Method and apparatus for finishing and producing groove-like or groove-like depressions on the edge portion of a silicone rubber contact lens|

---

US4121896A|1976-03-24|1978-10-24|Shepherd Thomas H|Apparatus for the production of contact lenses|

---

US4120570A|1976-06-22|1978-10-17|Syntex Inc.|Method for correcting visual defects, compositions and articles of manufacture useful therein|

---

US4182822A|1976-11-08|1980-01-08|Chang Sing Hsiung|Hydrophilic, soft and oxygen permeable copolymer composition|

---

US4136250A|1977-07-20|1979-01-23|Ciba-Geigy Corporation|Polysiloxane hydrogels|

---

US4153641A|1977-07-25|1979-05-08|Bausch & Lomb Incorporated|Polysiloxane composition and contact lens|

---

JPS5640324B2|1977-11-08|1981-09-19|

---

US4217038A|1978-06-05|1980-08-12|Bausch & Lomb Incorporated|Glass coated polysiloxane contact lens|

---

US4208365A|1978-12-20|1980-06-17|National Patent Development Corporation|Method and apparatus for molding toric contact lenses|

---

JPS5734849B2|1979-02-23|1982-07-26|

---

US4246389A|1979-06-25|1981-01-20|American Optical Corporation|Contact lens composition having increased oxygen permeability|

---

US4401371A|1979-09-24|1983-08-30|Neefe Charles W|Hydrogel oxygen generator with improved fluid flow|

---

US4259467A|1979-12-10|1981-03-31|Bausch & Lomb Incorporated|Hydrophilic contact lens made from polysiloxanes containing hydrophilic sidechains|

---

US4260725A|1979-12-10|1981-04-07|Bausch & Lomb Incorporated|Hydrophilic contact lens made from polysiloxanes which are thermally bonded to polymerizable groups and which contain hydrophilic sidechains|

---

US4353849A|1981-06-19|1982-10-12|Lawrence Lewison|Manufacture of soft contact lenses having vent passageways|

---

US4640594A|1982-01-07|1987-02-03|Richard Berger|Tear pump contact lens|

---

US4440918A|1982-01-18|1984-04-03|Minnesota Mining And Manufacturing Company|Contact lens containing a fluorinated telechelic polyether|

---

US4487905A|1983-03-14|1984-12-11|Dow Corning Corporation|Wettable silicone resin optical devices and curable compositions therefor|

---

US4605712A|1984-09-24|1986-08-12|Ciba-Geigy Corporation|Unsaturated polysiloxanes and polymers thereof|

---

JPH0155653B2|1984-12-10|1989-11-27|Toyo Contact Lens Co Ltd|

---

US4711943A|1985-04-26|1987-12-08|Sola U.S.A. Inc.|Hydrophilic siloxane monomers and dimers for contact lens materials, and contact lenses fabricated therefrom|

---

DE3708308A1|1986-04-10|1987-10-22|Bayer Ag|CONTACT OPTICAL ITEMS|

---

JP2532406B2|1986-09-30|1996-09-11|ホ−ヤ株式会社|Oxygen permeable hard contact lens material with excellent impact resistance|

---

FR2617763B1|1987-07-07|1989-12-01|Essilor Int|METHOD OF MANUFACTURING CONTACT LENS IN A NATURAL PROTEIN POLYMER, BY MOLDING BEFORE CROSS-LINKING|

---

US4740533A|1987-07-28|1988-04-26|Ciba-Geigy Corporation|Wettable, flexible, oxygen permeable, substantially non-swellable contact lens containing block copolymer polysiloxane-polyoxyalkylene backbone units, and use thereof|

---

US5009497A|1987-11-12|1991-04-23|Cohen Allen L|Contact lenses utilizing keel orientation|

---

US5258490A|1987-12-14|1993-11-02|Chang Sing Hsiung|Non-irritating soft gas permeable contact lens and process for producing same|

---

EP0330617B1|1988-02-26|1991-07-03|Ciba-Geigy Ag|Wettable, flexible, oxygen permeable contact lens containing block copolymer polysiloxane-polyoxyalkylene backbone units|

---

DE68900100D1|1988-02-26|1991-07-11|Ciba Geigy Ag|Wettable, flexible, oxygen-permeable contact lens, consisting of block copolymers with polysiloxane-polyoxyalkylene links in the main chain, and use here.|

---

US5070169A|1988-02-26|1991-12-03|Ciba-Geigy Corporation|Wettable, flexible, oxygen permeable contact lens containing block copolymer polysiloxane-polyoxyalkylene backbone units and use thereof|

---

GB2217869A|1988-04-22|1989-11-01|Ceskoslovenska Akademie Ved|Contact lenses|

---

US4954586A|1989-01-17|1990-09-04|Menicon Co., Ltd|Soft ocular lens material|

---

US5104213A|1989-01-17|1992-04-14|Wolfson Leonard G|Polymer buttons having holes therein and contact lenses manufactured therefrom and method of manufacture|

---

US5034461A|1989-06-07|1991-07-23|Bausch & Lomb Incorporated|Novel prepolymers useful in biomedical devices|

---

US5010141A|1989-10-25|1991-04-23|Ciba-Geigy Corporation|Reactive silicone and/or fluorine containing hydrophilic prepolymers and polymers thereof|

---

US5079319A|1989-10-25|1992-01-07|Ciba-Geigy Corporation|Reactive silicone and/or fluorine containing hydrophilic prepolymers and polymers thereof|

---

EP0431881B1|1989-12-05|1995-06-28|Shin-Etsu Chemical Co., Ltd.|Fabric material coated with a self-adhesive silicone rubber|

---

AU629725B2|1990-01-24|1992-10-08|Novartis Ag|Contact lens and process for the manufacture thereof|

---

US5314960A|1990-04-10|1994-05-24|Permeable Technologies, Inc.|Silicone-containing polymers, oxygen permeable hydrophilic contact lenses and methods for making these lenses and treating patients with visual impairment|

---

US5158717A|1990-11-27|1992-10-27|Bausch & Lomb Incorporated|Method of molding shaped polymeric articles|

---

US5274008A|1990-11-27|1993-12-28|Bausch & Lomb Incorporated|Mold materials for silicone containing lens materials|

---

US5483304A|1991-07-26|1996-01-09|Hanita Lenses|Multifocal contact lens|

---

BR9206601A|1991-09-12|1995-10-17|Bausch & Lob Inc|Method for making a wettable hydrogel composition containing silicone, hydrogel composition containing silicone, biomedical device and contact lens|

---

US5621083A|1991-11-04|1997-04-15|Xoma Corporation|Immunotoxins comprising ribosome-inactivating proteins|

---

JP3354571B2|1991-11-05|2002-12-09|ボシュ・アンド・ロム・インコーポレイテッド|Wettable silicone hydrogel composition and method for producing the same|

---

US5352714A|1991-11-05|1994-10-04|Bausch & Lomb Incorporated|Wettable silicone hydrogel compositions and methods for their manufacture|

---

US5358995A|1992-05-15|1994-10-25|Bausch & Lomb Incorporated|Surface wettable silicone hydrogels|

---

US5260000A|1992-08-03|1993-11-09|Bausch & Lomb Incorporated|Process for making silicone containing hydrogel lenses|

---

US5347326A|1992-10-05|1994-09-13|Volk Donald A|Diagnostic or therapeutic contact lens|

---

US5321108A|1993-02-12|1994-06-14|Bausch & Lomb Incorporated|Fluorosilicone hydrogels|

---

US5374662A|1993-03-15|1994-12-20|Bausch & Lomb Incorporated|Fumarate and fumaramide siloxane hydrogel compositions|

---

US5598233A|1994-08-18|1997-01-28|Harold A. Gell|Soft contact lens with contamination indicator|

---

US7468398B2|1994-09-06|2008-12-23|Ciba Vision Corporation|Extended wear ophthalmic lens|

---

DE29624309U1|1995-04-04|2002-01-03|Novartis Ag|Duration supporting lenses|

---

US5760100B1|1994-09-06|2000-11-14|Ciba Vision Corp|Extended wear ophthalmic lens|

---

TW585882B|1995-04-04|2004-05-01|Novartis Ag|A method of using a contact lens as an extended wear lens and a method of screening an ophthalmic lens for utility as an extended-wear lens|

---

TW393498B|1995-04-04|2000-06-11|Novartis Ag|The preparation and use of Polysiloxane-comprising perfluoroalkyl ethers|

---

DE69611161T2|1995-04-04|2001-05-17|Novartis Ag|POLYMERIZABLE PERFLUOROALKYL ETHER SILOXANE MACROMER|

---

US5641437A|1995-09-29|1997-06-24|Johnson & Johnson Vision Products, Inc.|Marking of mold inserts to produce marked contact lenses|

---

US5807944A|1996-06-27|1998-09-15|Ciba Vision Corporation|Amphiphilic, segmented copolymer of controlled morphology and ophthalmic devices including contact lenses made therefrom|

---

AR009439A1|1996-12-23|2000-04-12|Novartis Ag|AN ARTICLE THAT INCLUDES A SUBSTRATE WITH A PRIMARY POLYMERIC COATING THAT CARRIES REACTIVE GROUPS PREDOMINANTLY ON ITS SURFACE, A METHOD FOR PREPARING SUCH AN ARTICLE, AN ARTICLE THAT HAS A HYBRID-TYPE COATING AND A CONTACT LENS|

---

GB9711818D0|1997-06-06|1997-08-06|Bausch & Lomb|Contact lens packing solutions and methods for improving the comfort of disposable contact lenses|

---

US6020445A|1997-10-09|2000-02-01|Johnson & Johnson Vision Products, Inc.|Silicone hydrogel polymers|

---

US6310116B1|1997-10-09|2001-10-30|Kuraray Co., Ltd.|Molded polymer article having a hydrophilic surface and process for producing the same|

---

US5817924A|1998-01-21|1998-10-06|Modern Controls, Inc.|Method and apparatus for measuring oxygen transmission through contact lenses|

---

US6849671B2|1998-03-02|2005-02-01|Johnson & Johnson Vision Care, Inc.|Contact lenses|

---

US6367929B1|1998-03-02|2002-04-09|Johnson & Johnson Vision Care, Inc.|Hydrogel with internal wetting agent|

---

US5998498A|1998-03-02|1999-12-07|Johnson & Johnson Vision Products, Inc.|Soft contact lenses|

---

US6943203B2|1998-03-02|2005-09-13|Johnson & Johnson Vision Care, Inc.|Soft contact lenses|

---

US5962548A|1998-03-02|1999-10-05|Johnson & Johnson Vision Products, Inc.|Silicone hydrogel polymers|

---

US6203156B1|1998-03-31|2001-03-20|Johnson & Johnson Vision Care, Inc.|Contact lenses bearing marks|

---

US6024448A|1998-03-31|2000-02-15|Johnson & Johnson Vision Products, Inc.|Contact lenses bearing identifying marks|

---

US6193369B1|1998-05-05|2001-02-27|Bausch & Lomb Incorporated|Plasma surface treatment of silicone hydrogel contact lenses|

---

US6348507B1|1998-05-05|2002-02-19|Bausch & Lomb Incorporated|Surface treatment of silicone hydrogel contact lenses|

---

US5969076A|1998-05-15|1999-10-19|Bausch & Lomb Incorporated|Thermoplastic silicone-containing hydrogels|

---

US6359024B2|1998-05-15|2002-03-19|Bausch & Lomb Incorporated|Method for polymerizing contact lenses|

---

US5959117A|1998-08-10|1999-09-28|Bausch & Lomb|Monomers useful for contact lens materials|

---

US5981675A|1998-12-07|1999-11-09|Bausch & Lomb Incorporated|Silicone-containing macromonomers and low water materials|

---

US6042230A|1998-12-14|2000-03-28|Johnson & Johnson Vision Products, Inc.|Markings for contact lenses|

---

EP1176454B1|1999-05-12|2003-07-30|Menicon Co., Ltd.|Ocular lens materials and process for producing the same|

---

US6630243B2|1999-05-20|2003-10-07|Bausch & Lomb Incorporated|Surface treatment of silicone hydrogel contact lenses comprising hydrophilic polymer chains attached to an intermediate carbon coating|

---

US6440571B1|1999-05-20|2002-08-27|Bausch & Lomb Incorporated|Surface treatment of silicone medical devices with reactive hydrophilic polymers|

---

JP2003505728A|1999-07-27|2003-02-12|ボシュ・アンド・ロム・インコーポレイテッド|Contact lens material|

---

US6478423B1|1999-10-12|2002-11-12|Johnson & Johnson Vison Care, Inc.|Contact lens coating selection and manufacturing process|

---

US6488375B2|1999-10-28|2002-12-03|Ocular Sciences, Inc.|Tinted contact lens and method for making same|

---

US6649722B2|1999-12-10|2003-11-18|Novartis Ag|Contact lens|

---

AU779729B2|1999-12-16|2005-02-10|Coopervision International Limited|Soft contact lens capable of being worn for a long period|

---

EP1197782B1|2000-03-22|2004-06-02|Menicon Co., Ltd.|Material for ocular lens|

---

US6372815B1|2000-04-18|2002-04-16|Ocular Sciences Inc|Ophthalmic lenses and compositions, and methods for producing same|

---

US6689480B2|2000-05-10|2004-02-10|Toray Industries, Inc.|Surface-treated plastic article and method of surface treatment|

---

AT346323T|2000-05-25|2006-12-15|Novartis Pharma Gmbh|CONTACT LENS WITH PRESSED INVERSION MARKING|

---

US6779888B2|2000-07-28|2004-08-24|Ocular Sciences, Inc.|Contact lenses with microchannels|

---

US6886936B2|2000-07-28|2005-05-03|Ocular Sciences, Inc.|Contact lenses with blended microchannels|

---

AU8175801A|2000-08-23|2002-03-04|Surfarc Aps|Biocompatible materials|

---

US6652095B2|2000-11-17|2003-11-25|Hsiao-Ching Tung|Orthokeratology and bi-focal contact lens|

---

US6861123B2|2000-12-01|2005-03-01|Johnson & Johnson Vision Care, Inc.|Silicone hydrogel contact lens|

---

US6774178B2|2001-01-05|2004-08-10|Novartis Ag|Tinted, high Dk ophthalmic molding and a method for making same|

---

US6815074B2|2001-05-30|2004-11-09|Novartis Ag|Polymeric materials for making contact lenses|

---

US7461937B2|2001-09-10|2008-12-09|Johnson & Johnson Vision Care, Inc.|Soft contact lenses displaying superior on-eye comfort|

---

US7052131B2|2001-09-10|2006-05-30|J&J Vision Care, Inc.|Biomedical devices containing internal wetting agents|

---

US6822016B2|2001-09-10|2004-11-23|Johnson & Johnson Vision Care, Inc.|Biomedical devices containing internal wetting agents|

---

US6891010B2|2001-10-29|2005-05-10|Bausch & Lomb Incorporated|Silicone hydrogels based on vinyl carbonate endcapped fluorinated side chain polysiloxanes|

---

JP3881221B2|2001-11-16|2007-02-14|石根 三井|Contact lenses for myopia and / or astigmatism correction|

---

TWI255224B|2002-01-09|2006-05-21|Novartis Ag|Polymeric articles having a lubricious coating and method for making the same|

---

CN1320004C|2002-03-11|2007-06-06|庄臣及庄臣视力保护公司|Low polydispersity poly-HEMA compositions|

---

US6846892B2|2002-03-11|2005-01-25|Johnson & Johnson Vision Care, Inc.|Low polydispersity poly-HEMA compositions|

---

US7695775B2|2004-06-04|2010-04-13|Applied Microstructures, Inc.|Controlled vapor deposition of biocompatible coatings over surface-treated substrates|

---

US9248614B2|2004-06-30|2016-02-02|Novartis Ag|Method for lathing silicone hydrogel lenses|

---

CN1734314A|2004-08-11|2006-02-15|李冰|Contact lens with micropore|

---

SG155241A1|2004-08-27|2009-09-30|Asahikasei Aime Co Ltd|Silicone hydrogel contact lenses|

---

US7247692B2|2004-09-30|2007-07-24|Johnson & Johnson Vision Care, Inc.|Biomedical devices containing amphiphilic block copolymers|

---

US7249848B2|2004-09-30|2007-07-31|Johnson & Johnson Vision Care, Inc.|Wettable hydrogels comprising reactive, hydrophilic, polymeric internal wetting agents|

---

US7319133B2|2005-08-09|2008-01-15|Coopervision, Inc.|Contact lens extraction/hydration systems and methods of reprocessing fluids used therein|

---

US7320587B2|2005-08-09|2008-01-22|Cooper Vision, Inc.|Contact lens molds and systems and methods for producing same|

---

US7731873B2|2005-08-09|2010-06-08|Coopervision International Holding Company, Lp|Contact lens mold assemblies and systems and methods of producing same|

---

US7785092B2|2005-08-09|2010-08-31|Coopervision International Holding Company, Lp|Systems and methods for producing contact lenses from a polymerizable composition|

---

US7799249B2|2005-08-09|2010-09-21|Coopervision International Holding Company, Lp|Systems and methods for producing silicone hydrogel contact lenses|

---

CN101535353B|2005-08-09|2011-07-27|库柏维景国际控股公司|Compositions and methods for producing silicone hydrogel contact lenses|

---

US7426993B2|2005-08-09|2008-09-23|Coopervision International Holding Company, Lp|Contact lens package|

---

MY141143A|2005-08-11|2010-03-15|Coopervision Int Holding Co Lp|Contact lenses and methods for reducing conjunctival pressure in contact lens wearers|

---

CN101389364A|2005-12-30|2009-03-18|庄臣及庄臣视力保护公司|Silicone containing polymers formed from non-reactive silicone containing prepolymers|

---

US20070155851A1|2005-12-30|2007-07-05|Azaam Alli|Silicone containing polymers formed from non-reactive silicone containing prepolymers|

---

US7572841B2|2006-06-15|2009-08-11|Coopervision International Holding Company, Lp|Wettable silicone hydrogel contact lenses and related compositions and methods|

---

TWI443116B|2006-06-15|2014-07-01|Coopervision Int Holding Co Lp|Wettable silicone hydrogel contact lenses and related compositions and methods|

---

US8231218B2|2006-06-15|2012-07-31|Coopervision International Holding Company, Lp|Wettable silicone hydrogel contact lenses and related compositions and methods|

---

US7540609B2|2006-06-15|2009-06-02|Coopervision International Holding Company, Lp|Wettable silicone hydrogel contact lenses and related compositions and methods|

---

US8003024B2|2006-09-18|2011-08-23|Coopervision International Holding Company, Lp|Polyolefin contact lens molds and uses thereof|

---

US7625598B2|2006-12-15|2009-12-01|Bausch & Lomb Incorporated|Silicone contact lenses with wrinkled surface|

---

WO2008087859A1|2007-01-16|2008-07-24|Menicon Co., Ltd.|Contact lens and process for producing the same|

---

US7968018B2|2007-04-18|2011-06-28|Coopervision International Holding Company, Lp|Use of surfactants in extraction procedures for silicone hydrogel ophthalmic lenses|

---

US7799888B2|2007-04-27|2010-09-21|Gelest, Inc.|Low molecular weight siloxanes with one functional group|

---

US8011784B2|2008-01-14|2011-09-06|Coopervision International Holding Company, Lp|Polymerizable contact lens formulations and contact lenses obtained therefrom|

---

MY153130A|2008-02-08|2014-12-31|Coopervision Int Holding Co Lp|Hydrophilic polysiloxane monomer, and production method and application thereof|

---

JP4646152B2|2008-05-27|2011-03-09|信越化学工業株式会社|Monomers for ophthalmic device manufacturing|JP5154231B2|2005-02-14|2013-02-27|ジョンソン・アンド・ジョンソン・ビジョン・ケア・インコーポレイテッド|Comfortable ophthalmic device and its manufacturing method|

---

US9052529B2|2006-02-10|2015-06-09|Johnson & Johnson Vision Care, Inc.|Comfortable ophthalmic device and methods of its production|

---

JP6010832B2|2010-07-30|2016-10-19|クーパーヴィジョン インターナショナル ホウルディング カンパニー リミテッド パートナーシップ|Ophthalmic device mold and related methods|

---

US9217813B2|2011-02-28|2015-12-22|Coopervision International Holding Company, Lp|Silicone hydrogel contact lenses|

---

EP2681594B1|2011-02-28|2015-01-14|CooperVision International Holding Company, LP|Phosphine-containing hydrogel contact lenses|

---

HUE024483T2|2011-02-28|2016-01-28|Coopervision Int Holding Co Lp|Dimensionally stable silicone hydrogel contact lenses|

---

CN103620480B|2011-02-28|2015-12-09|库柏维景国际控股公司|There is the silicone hydrogel contact lenses of the energy loss of acceptable level|

---

WO2012154268A1|2011-02-28|2012-11-15|Coopervision International Holding Company, Lp|Silicone hydrogel contact lenses|

---

ES2732681T3|2011-02-28|2019-11-25|Coopervision Int Holding Co Lp|Silicone Hydrogel Contact Lenses|

---

SG192236A1|2011-02-28|2013-09-30|Coopervision Int Holding Co Lp|Wettable silicone hydrogel contact lenses|

---

CA2827205C|2011-02-28|2014-08-26|Coopervision International Holding Company, Lp|Dimensionally stable silicone hydrogel contact lenses|

---

US9164298B2|2011-02-28|2015-10-20|Coopervision International Holding Company, Lp|Wettable silicone hydrogel contact lenses|

---

CN103764724B|2011-02-28|2016-04-06|库柏维景国际控股公司|Silicone hydrogel contact lenses and compositions related and method|

---

MY161159A|2011-02-28|2017-04-14|Coopervision Int Holding Co Lp|Silicone hydrogel contact lenses|

---

EP2681613B1|2011-02-28|2018-10-24|CooperVision International Holding Company, LP|Silicone hydrogel contact lenses|

---

EP2718751B1|2011-06-09|2015-07-22|Novartis AG|Silicone hydrogel lenses with nano-textured surfaces|

---

US9125808B2|2011-12-23|2015-09-08|Johnson & Johnson Vision Care, Inc.|Ionic silicone hydrogels|

---

US9140825B2|2011-12-23|2015-09-22|Johnson & Johnson Vision Care, Inc.|Ionic silicone hydrogels|

---

US8937111B2|2011-12-23|2015-01-20|Johnson & Johnson Vision Care, Inc.|Silicone hydrogels comprising desirable water content and oxygen permeability|

---

US9588258B2|2011-12-23|2017-03-07|Johnson & Johnson Vision Care, Inc.|Silicone hydrogels formed from zero diluent reactive mixtures|

---

US9156934B2|2011-12-23|2015-10-13|Johnson & Johnson Vision Care, Inc.|Silicone hydrogels comprising n-vinyl amides and hydroxyalkyl acrylates or acrylamides|

---

US8937110B2|2011-12-23|2015-01-20|Johnson & Johnson Vision Care, Inc.|Silicone hydrogels having a structure formed via controlled reaction kinetics|

---

TWI500992B|2012-05-11|2015-09-21|Benq Materials Corp|Method for forming contact lenses and contact lenses therefrom|

---

WO2014012016A1|2012-07-13|2014-01-16|University Of Florida Research Foundation, Inc.|Contact lens with spatially heterogeneous surface patterns for improved lubricity|

---

MY180770A|2012-08-28|2020-12-09|Coopervision Int Ltd|Contact lenses made with hema-compatible polysiloxane macromers|

---

JP6088191B2|2012-10-05|2017-03-01|株式会社ダイセル|Adhesive, method of using the same, and back grind film|

---

TWI496838B|2012-11-30|2015-08-21|Pegavision Corp|Silicone hydrogel composition and silicone hydrogel contact lenses made of the composition|

---

JP5452756B1|2013-07-02|2014-03-26|Ｈｏｙａ株式会社|Method for producing silicone-containing copolymer molded article having hydrophilic surface and silicone hydrogel contact lens having hydrophilic surface|

---

EP3090007B1|2014-02-28|2017-06-07|CooperVision International Holding Company, LP|Contact lenses made with hema-compatible polysiloxane macromers|

---

CN103941419B|2014-04-18|2015-05-13|江苏海伦隐形眼镜有限公司|Hydrogel cornea contact lens and preparation method thereof|

---

TWI628485B|2014-08-01|2018-07-01|開眼光學研發股份有限公司|Color image patch for contact lenses|

---

CN105713153B|2014-12-05|2019-05-10|晶硕光学股份有限公司|Obstruct the silicon glue composition of ultraviolet light and the silicon glue eyeglass comprising it|

---

US9789654B2|2014-12-05|2017-10-17|Coopervision International Holding Company, Lp|Method of manufacturing wettable silicone hydrogel contact lenses|

---

TWI551616B|2016-01-05|2016-10-01|望隼科技股份有限公司|A fabricating method of silicone hydrogel for ophthalmic application|

---

KR101943288B1|2016-04-20|2019-01-28|쿠퍼비젼 인터내셔날 홀딩 캄파니, 엘피|Silicone elastomer - silicone hydrogel hybrid contact lens|

---

US10139521B2|2016-04-20|2018-11-27|Coopervision International Holding Company, Lp|Silicone elastomer-hydrogel hybrid contact lenses|

---

US10422927B2|2016-07-14|2019-09-24|Coopervision International Holding Company, Lp|Method of manufacturing silicone hydrogel contact lenses having reduced rates of evaporation|

---

CN108264609B|2017-01-04|2020-08-11|北京赛特超润界面科技有限公司|Method for preparing bionic super-hydrophilic oxygen-permeable nano contact lens|

---

WO2018224975A1|2017-06-07|2018-12-13|Novartis Ag|Silicone hydrogel contact lenses|

---

EP3928967A4|2017-06-07|2021-12-29|Alcon Inc|Silicone hydrogel contact lenses|

---

HUE055667T2|2017-06-07|2021-12-28|Alcon Inc|Method for producing silicone hydrogel contact lenses|

---

EP3794388A1|2018-05-15|2021-03-24|Bausch & Lomb Incorporated|Water extractable ophthalmic devices|

法律状态:
2019-01-08| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2019-07-16| B06T| Formal requirements before examination [chapter 6.20 patent gazette]|

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2020-03-10| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application [chapter 6.1 patent gazette]|

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2020-07-14| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2020-11-03| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 10 (DEZ) ANOS CONTADOS A PARTIR DE 03/11/2020, OBSERVADAS AS CONDICOES LEGAIS. |

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2021-08-24| B25G| Requested change of headquarter approved|Owner name: COOPERVISION INTERNATIONAL HOLDING COMPANY, LP (BB) |

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2021-09-14| B25A| Requested transfer of rights approved|Owner name: COOPERVISION INTERNATIONAL LIMITED (GB) |

优先权:

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申请号 | 申请日 | 专利标题

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US27807209P| true| 2009-10-01|2009-10-01|

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US61/278.072|2009-10-01|

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PCT/US2010/050879|WO2011041523A2|2009-10-01|2010-09-30|Silicone hydrogel contact lenses and methods of making silicone hydrogel contact lenses|

---