US20040186248A1 - Soft contact lenses - Google Patents

Soft contact lenses Download PDF

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US20040186248A1
US20040186248A1 US10/766,446 US76644604A US2004186248A1 US 20040186248 A1 US20040186248 A1 US 20040186248A1 US 76644604 A US76644604 A US 76644604A US 2004186248 A1 US2004186248 A1 US 2004186248A1
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alkyl
group
silicone hydrogel
monovalent
contact lens
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US10/766,446
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Douglas Vanderlaan
David Tumer
Marcie Hargiss
Annie Maiden
Robert Love
James Ford
Frank Molock
Robert Steffen
Azaam Alli
John Enns
Kevin McCabe
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Individual
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Priority claimed from US09/033,347 external-priority patent/US5998498A/en
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    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G02B1/041Lenses
    • G02B1/043Contact lenses
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F230/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F230/04Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
    • C08F230/08Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06Polymers provided for in subclass C08G
    • C08F290/068Polysiloxanes

Definitions

  • This invention relates to silicone hydrogels.
  • the invention relates to silicone hydrogels formed by curing a reaction mixture of silicone-containing monomers.
  • a hydrogel is a hydrated crosslinked polymeric system that contains water in an equilibrium state.
  • Hydrogels typically are oxygen permeable and biocompatible, making them preferred materials for producing biomedical devices and in particular contact or intraocular lenses.
  • Conventional hydrogels are prepared from monomeric mixtures predominantly containing hydrophilic monomers, such as 2-hydroxyethyl methacrylate (“HEMA”) or N-vinyl pyrrolidone (“NVP”).
  • HEMA 2-hydroxyethyl methacrylate
  • NDP N-vinyl pyrrolidone
  • U.S. Pat. Nos. 4,495,313, 4,889,664 and 5,039,459 disclose the formation of conventional hydrogels.
  • the oxygen permeability of these conventional hydrogel materials relates to the water content of the materials, and is typically below 20-30 barrers.
  • Silicone-containing polymers generally have higher oxygen permeabilities than conventional hydrogels.
  • Silicone hydrogels have typically been prepared by polymerizing mixtures containing at least one silicone-containing monomer and at least one hydrophilic monomer. Either the silicone-containing monomer or the hydrophilic monomer may function as a crosslinking agent (a crosslinking agent is a monomer having multiple polymerizable functionalities) or a separate crosslinking agent may be employed.
  • a crosslinking agent is a monomer having multiple polymerizable functionalities
  • U.S. Pat. No. 3,808,178 discloses the formation of copolymers of small silicone-containing monomers and various hydrophilic monomers.
  • U.S. Pat. No. 5,034,461 describes silicone hydrogels prepared from various combinations of silicone-polyurethane macromers and hydrophilic monomers such as HEMA or N,N-dimethyacrylamide (“DMA”).
  • HEMA silicone-polyurethane macromers
  • DMA N,N-dimethyacrylamide
  • TMS methacryloxypropyltris-(trimethylsiloxy)silane
  • TMS methacryloxypropyltris-(trimethylsiloxy)silane
  • U.S. Pat. Nos. 5,358,995 and 5,387,632 describe hydrogels made from various combinations of silicone macromers, TRIS, NVP and DMA. Replacing a substantial portion of the silicone macromer with TRIS reduced the modulus of the resulting hydrogels.
  • Two publications from the same author “The Role of Bulky Polysiloxanylalkyl Methacrylates in Polyurethane-Polysiloxane Hydrogels”, J. Appl. Poly. Sci., Vol. 60,1193-1199 (1996), and “The Role of Bulky Polysiloxanylalkyl Methacrylates in Oxygen-Permeable Hydrogel Materials”, J. Appl. Poly. Sci., Vol. 56, 317-324 (1995) also describe experimental results indicating that the modulus of hydrogels made from reaction mixtures of silicone-macromers and hydrophilic monomers such as DMA decreases with added TRIS.
  • MCM methacryloxypropylbis(trimethylsiloxy)methylsilane
  • This invention provides a silicone hydrogel prepared by curing a reaction mixture comprising either or both of the silicone-containing monomers of Structure I and II.
  • Structure I has the following structure:
  • R 51 is a monovalent group such as H, C 1-5 alkyl, or
  • Structure II has the following structure:
  • R 58 is a monovalent group containing at least one ethylenically unsaturated moiety, preferably a monovalent group containing a styryl, vinyl, or methacrylate moiety, more preferably a methacrylate moiety; each R 59 is independently a monovalent alkyl, or aryl group, which may be further substituted with alcohol, amine, ketone, carboxylic acid or ether groups, preferably unsubstituted monovalent alkyl or aryl groups, more preferably methyl; R 60 is a monovalent alkyl, or aryl group, which may be further substituted with alcohol, amine, ketone, carboxylic acid or ether groups, preferably unsubstituted monovalent alkyl or aryl groups, preferably a C 1-10 aliphatic or aromatic group which may include hetero
  • the silicone hydrogel comprises monomers of both Structure I and II. More preferably, the silicone hydrogel comprises silicone-containing monomer of Structure I and II and a hydrophilic monomer.
  • the use of the silicone-containing monomers of both Structure I and Structure II in a silicone hydrogel reduces the Young's modulus of the hydrogel especially in hydrogels which comprise these silicone-containing monomers and additional silicone-containing monomers which act as crosslinkers.
  • the monomers of Structure I and II are more effective at lowering the modulus of the silicone hydrogel than for monomers described in the prior art. Additionally, the tan ⁇ of the silicone hydrogels of this invention may be concurrently preserved.
  • the polymers produced according to this invention can be used to produce soft contact lenses that will provide high oxygen permeability, good elasticity, and can be produced economically and efficiently.
  • the polymer of this invention can be used to make biomedical devices which require biocompatability and high oxygen permeability, preferably contact lenses.
  • the term “monomer” used herein refers to lower molecular weight compounds that can be polymerized to higher molecular weight compounds, polymers, macromers, or prepolymers.
  • the term “macromer” as used herein refers to a high molecular weight polymerizable compound. Prepolymers are partially polymerized monomers or monomers which are capable of further polymerization.
  • a “silicone-containing monomer” is one that contains at least two [—Si—O—] repeating units in a monomer, macromer or prepolymer.
  • the total Si and attached O are present in the silicone-containing monomer in an amount greater than 20 weight percent, and more preferably greater than 30 weight percent of the total molecular weight of the silicone-containing monomer.
  • silicone-containing monomers of Structure I that can be used to form silicone hydrogels of this invention are, without limitation, methacryloxypropylbis(trimethylsiloxy)methylsilane, methacryloxypropyltris(trimethylsiloxy)silane, methacryloxypropylpentamethyldisiloxane, and (3-methacryloxy-2-hydroxypropyloxy) propylbis(trimethylsiloxy)methylsilane. While such silicone monomers may additionally be used, linear mono-alkyl terminated polydimethylsiloxanes (“mPDMS”) such as those shown in the following Structure II must be used:
  • mPDMS linear mono-alkyl terminated polydimethylsiloxanes
  • R 58 is a monovalent group containing at least one ethylenically unsaturated moiety, preferably a monovalent group containing a styryl, vinyl, or methacrylate moiety, more preferably a methacrylate moiety; each R 59 is independently a monovalent alkyl, or aryl group, which may be further substituted with alcohol, amine, ketone, carboxylic acid or ether groups, preferably unsubstituted monovalent alkyl or aryl groups, more preferably methyl; R 60 is a monovalent alkyl, or aryl group, which may be further substituted with alcohol, amine, ketone, carboxylic acid or ether groups, preferably unsubstituted monovalent alkyl or aryl groups, preferably a C 1-10 aliphatic or
  • the amount of mPDMS comprising the hydrogel is closely related to the modulus and tan ⁇ of the hydrogels made according to this invention.
  • Tan ⁇ is defined as the loss modulus of the material divided by its elastic modulus (G′′/G′).
  • modulus is defined as Young's modulus or it's equivalent tensile modulus where the measurement is recorded at the equilibrated hydrated state. It is desirable to lower both the modulus and tan ⁇ in silicone hydrogel lenses for a number of reasons. First, lower modulus and tan ⁇ in a lens are manifested as less stiffness, and after stress is relieved the lens quickly returns to its original shape.
  • SEALs superior epithelial arcurate lesions
  • silicone hydrogels made according to the invention comprise between about 2 and 70% wt mPDMS based on total weight of reactive monomer components from which the polymer is made. Depending upon the other monomers present, this will generally reduce the modulus of the polymer to between about 20 and 180 psi and a tan ⁇ of less than about 0.1 to no more than about 0.3 (measured at a frequency of 1 Hz and a temperature of 25° C., according to the method described in Example 21). Silicone hydrogels made according to the invention and comprising between about 4 and 50% wt mPDMS (same basis as above) are preferred.
  • Silicone hydrogels made according to the invention and comprising between about 8 and 40% wt mPDMS (same basis as above) are most preferred. These hydrogels will generally exhibit a modulus between about 40 and 130 psi and a tan ⁇ of about 0.2 or less (measured at a frequency of 1 Hz and a temperature of 25° C.). Hydrogels having tan ⁇ less than about 0.1 can also be made according to this invention as described more fully below.
  • Additional silicone-containing monomers may be combined with the silicone-containing monomers of Structures I and II to form the soft contact lenses of the invention.
  • Any known silicone-containing monomers useful for making silicone hydrogels can be used in combination with the silicone-containing monomer of Structure I and II to form the soft contact lenses of this invention.
  • Many silicone-containing monomers useful for this purpose are disclosed in U.S. Pat. No. 6,020,445 incorporated herein in its entirety by reference.
  • Useful additional silicone-containing monomers combined with the silicone-containing monomers of Structure I to form the silicone hydrogels of this invention are the hydroxyalkylamine-functional silicone-containing monomers disclosed in U.S. Pat. No. 5,962,548 incorporated herein in its entirety by reference.
  • the preferred silicone-containing linear or branched hydroxyalkylamine-functional monomers comprising a block or random monomer of the following structure:
  • R 2 , R 4 , R 5 , R 6 and R 7 are independently a monovalent alkyl, or aryl groups, which may be further substituted with alcohol, ester, amine, ketone, carboxylic acid or ether groups, preferably unsubstituted monovalent alkyl or aryl groups; and
  • R 1 , R 3 and R 8 are independently a monovalent alkyl, or aryl group, which may be further substituted with an alcohol, ester, amine, ketone, carboxylic acid or ether group, preferably unsubstituted monovalent alkyl or aryl groups, or are the following nitrogen-containing structure:
  • R 1 , R 3 , and R 8 are according to Structure IV, wherein R 9 is a divalent alkyl group such as —CH 2 ) n — where s is from 1 to 10, preferably 3 to 6 and most preferably 3;
  • R 10 and R 11 are independently H, a monovalent alkyl or aryl group which may be further substituted with an alcohol, ester, amine, ketone, carboxylic acid or ether group, or has the following structure:
  • R 14 is H, or a monovalent polymerizable group comprising acryloyl, methacryloyl, styryl, vinyl, allyl or N-vinyl lactam, preferably H or methacryloyl
  • R 16 is either H, a monovalent alkyl or aryl group which can be further substituted with alcohol, ester, amine, ketone, carboxylic acid or ether groups, or a polymerizable group comprising acrylate, methacrylate, styryl, vinyl, allyl or N-vinyl lactam, preferably alkyl substituted with an alcohol or methacrylate
  • R 12 , R 13 and R 15 are independently H, a monovalent alkyl or aryl, which can be further substituted with alcohol, ester, amine, ketone, carboxylic acid or ether groups, or R 12 and R 15 , or R 15 and R 13 can be bonded together to form a ring structure, with the provis
  • the silicone hydrogels of this invention comprising the silicone-containing monomers of either or both Structure I and Structure II may further comprise hydrophilic monomers.
  • the hydrophilic monomers optionally used to make the hydrogel polymer of this invention can be any of the known hydrophilic monomers disclosed in the prior art to make hydrogels.
  • the preferred hydrophilic monomers used to make the polymer of this invention may be either acrylic- or vinyl-containing. Such hydrophilic monomers may themselves be used as crosslinking agents.
  • the term “vinyl-type” or “vinyl-containing” monomers refer to monomers containing the vinyl grouping (—CH ⁇ CH 2 ) and are generally highly reactive. Such hydrophilic vinyl-containing monomers are known to polymerize relatively easily.
  • “Acrylic-type” or “acrylic-containing” monomers are those monomers containing the acrylic group: (CH 2 ⁇ CRCOX) wherein R is H or CH 3 , and X is O or N, which are also known to polymerize readily, such as N,N-dimethyl acrylamide (DMA), 2-hydroxyethyl methacrylate (HEMA), glycerol methacrylate, 2-hydroxyethyl methacrylamide, polyethyleneglycol monomethacrylate, methacrylic acid and acrylic acid.
  • DMA N,N-dimethyl acrylamide
  • HEMA 2-hydroxyethyl methacrylate
  • glycerol methacrylate 2-hydroxyethyl methacrylamide
  • polyethyleneglycol monomethacrylate methacrylic acid and acrylic acid.
  • Hydrophilic vinyl-containing monomers which may be incorporated into the silicone hydrogels of the present invention include monomers such as N-vinyl lactams (e.g. NVP), N-vinyl-N-methyl acetamide, N-vinyl-N-ethyl acetamide, N-vinyl-N-ethyl formamide, N-vinyl formamide, with NVP being preferred.
  • NVP N-vinyl lactams
  • hydrophilic monomers that can be employed in the invention include polyoxyethylene polyols having one or more of the terminal hydroxyl groups replaced with a functional group containing a polymerizable double bond.
  • examples include polyethylene glycol, ethoxylated alkyl glucoside, and ethoxylated bisphenol A reacted with one or more molar equivalents of an end-capping group such as isocyanatoethyl methacrylate (“IEM”), methacrylic anhydride, methacryloyl chloride, vinylbenzoyl chloride, or the like, to produce a polyethylene polyol having one or more terminal polymerizable olefinic groups bonded to the polyethylene polyol through linking moieties such as carbamate or ester groups.
  • IEM isocyanatoethyl methacrylate
  • hydrophilic vinyl carbonate or vinyl carbamate monomers disclosed in U.S. Pat. No. 5,070,215
  • hydrophilic oxazolone monomers disclosed in U.S. Pat. No. 4,910,277.
  • Other suitable hydrophilic monomers will be apparent to one skilled in the art.
  • hydrophilic monomers which may be incorporated into the polymer of the present invention include hydrophilic monomers such as DMA, HEMA, glycerol methacrylate, 2-hydroxyethyl methacrylamide, NVP, polyethyleneglycol monomethacrylate, methacrylic acid and acrylic acid with DMA being the most preferred.
  • Other monomers that can be present in the reaction mixture used to form the silicone hydrogel of this invention include ultra-violet absorbing monomers, reactive tints, pigments, and the like. Additional processing aids such as release agents or wetting agents can also be added to the reaction mixture.
  • a polymerization initiator is preferably included in the reaction mixture.
  • the polymerization initiator can be a compound such as lauryl peroxide, benzoyl peroxide, isopropyl percarbonate, azobisisobutyronitrile, or the like, that generates free radicals at moderately elevated temperatures, or the polymerization iniator can be a photoinitiator system such as an aromatic alpha-hydroxy ketone or a tertiary amine plus a diketone.
  • Illustrative examples of photoinitiator systems are 2-hydroxy-2-methyl-1-phenyl-propan-1-one, and a combination of camphorquinone and ethyl 4-(N,N-dimethylamino)benzoate.
  • the initiator is used in the reaction mixture in effective amounts, e.g., from about 0.1 to about 2 parts by weight per 100 parts of reactive monomer. Polymerization of the reaction mixture can be initiated using the appropriate choice of heat or visible or ultraviolet light or other means depending on the polymerization initiator used.
  • the preferred initiator is a 1:1 blend of 1-hydroxycyclohexyl phenyl ketone and bis(2,6-dimethoxybenzoyl)2, 4, 4-trimethylpentyl phosphine oxide and the preferred method of polymerization initiation is visible light.
  • the resulting polymer is treated with a solvent to remove the diluent (if used) or any traces of unreacted components, and hydrate the polymer to form the hydrogel.
  • the solvent used may be water (or an aqueous solution such as physiological saline), or depending on the solubility characteristics of the diluent (if used) used to make the hydrogel of this invention and the solubility characteristics of any residual unpolymerized monomers, the solvent initially used can be an organic liquid such as ethanol, methanol, isopropanol, mixtures thereof, or the like, or a mixture of one or more such organic liquids with water, followed by extraction with pure water (or physiological saline) to produce the silicone hydrogel comprising a polymer of said monomers swollen with water.
  • the silicone hydrogels after hydration of the polymers preferably comprise about 2 to 50 weight percent water, more preferably about 15 to 45 weight percent water, and most preferably about 20 to 40 weight percent water of the total weight of the silicone hydrogel. These silicone hydrogels are particularly suited for making contact lenses or intraocular lenses, preferably soft contact lenses.
  • a silicone hydrogel lens is made by reacting a macromer with a reaction mixture that includes silicone based monomers and hydrophilic monomers. This technique affords a high level of control of the structure of the ultimate product. Phase distribution can be controlled so that a more uniform coating or surface layer (if desired) can be applied to the lens.
  • surface layer is meant a distribution of material with a portion in contact with the environment and another portion in contact with a material having a different bulk property than that of the material from which the surface layer is formed. Additionally, it is easier to process the lenses because of greater uniformity of properties across the lens.
  • the macromers are made by combining a/an (meth)acrylate and a silicone in the presence of a Group Transfer Polymerization (“GTP”) catalyst.
  • GTP Group Transfer Polymerization
  • These macromers typically comprise copolymers of various monomers. They may be formed in such a way that the monomers come together in distinct blocks, or in a generally random distribution. These macromers may furthermore be linear, branched, or star shaped. Branched structures are formed for instance if polymethacrylates, or crosslinkable monomers such as ethyleneglycol dimethacrylate are included in the macromer. Initiators, reaction conditions, monomers, and catalysts that can be used to make GTP polymers are described in “Group-Transfer Polymerization” by O. W.
  • Hydroxyl-functional monomers like HEMA, can be incorporated as their trimethylsiloxy esters, with hydrolysis to form free hydroxyl group after polymerization.
  • GTP offers the ability to assemble macromers with control over molecular weight distribution and monomer distribution on the chains. This macromer is then reacted with a reaction mixture comprising predominantly polydimethylsiloxane (preferably, mPDMS), and hydrophilic monomers.
  • Preferred macromer components include mPDMS, TRIS, methyl methacrylate, HEMA, DMA, methacrylonitrile, ethyl methacrylate, butyl methacrylate, 2-hydroxypropyl-1-methacrylate, 2-hydroxyethyl methacrylamide and methacrylic acid. It is even more preferred that the macromer is made from a reaction mixture comprising HEMA, methyl methacrylate, TRIS, and mPDMS.
  • macromer is made from a reaction mixture comprising, consisting essentially of, or consisting of about 19.1 moles of blocked HEMA (2-(trimethylsiloxy)ethyl methacrylate) about 2.8 moles of methyl methacrylate, about 7.9 moles of TRIS, and about 3.3 moles of mono-methacryloxypropyl terminated mono-butyl terminated polydimethylsiloxane, and is completed by reacting the aforementioned material with about 2.0 moles per mole of 3-isopropenyl- ⁇ , ⁇ -dimethylbenzyl isocyanate using dibutyltin dilaurate as a catalyst.
  • a reaction mixture comprising, consisting essentially of, or consisting of about 19.1 moles of blocked HEMA (2-(trimethylsiloxy)ethyl methacrylate) about 2.8 moles of methyl methacrylate, about 7.9 moles of TRIS, and about 3.3 moles of mono-methacryloxypropyl terminated mono-but
  • Silicone hydrogels can be made by reacting blends of macromers, monomers, and other additives such as UV blockers, tints, polymerization inhibitors, and internal wetting agents.
  • Internal wetting agents are substances that are incorporated into the polymer blend of a lens prior to polymerization and due to their incorporation, the wettability of the lens increases.
  • the reactive components of these blends typically comprise a combination of hydrophobic silicone with hydrophilic components. Since these components are often immiscible because of their differences in polarity, it is particularly advantageous to incorporate a combination of hydrophobic silicone monomers with hydrophilic monomers, especially those with hydroxyl groups, into the macromer.
  • the macromer can then serve to compatibilize the additional silicone and hydrophilic monomers that are incorporated in the final reaction mixture. These blends typically also contain diluents to further compatibilize and solubilize all components.
  • the silicone based hydrogels are made by reacting the following monomer mix: macromer; an Si 8-10 monomethacryloxy terminated polydimethyl siloxane; and hydrophilic monomers together with minor amounts of additives and photoinitiators. It is more preferred that the hydrogels are made by reacting macromer; an Si 8-10 monomethacryloxy terminated polydimethyl siloxane; TRIS; DMA; HEMA; and tetraethyleneglycol dimethacrylate (“TEGDMA”).
  • TEGDMA tetraethyleneglycol dimethacrylate
  • the hydrogels are made from the reaction of (all amounts are calculated as weight percent of the total weight of the combination) macromer (about 18%); an Si 8-10 monomethacryloxy terminated polydimethyl siloxane (about 28%); TRIS (about 14%); DMA (about 26%); HEMA (about 5%); TEGDMA (about 1%), polyvinylpyrrolidone (“PVP”) (about 5%); with the balance comprising minor amounts of additives and photoinitiators, and that the reaction is conducted in the presence of 20% wt 3,7-dimethyl-3-octanol diluent.
  • the reaction mixture is subjected to conditions whereby the monomers polymerize, to thereby produce a polymer in the approximate shape of the final desired product.
  • this polymer mixture is optionally treated with a solvent and then water, producing a silicone hydrogel having a final size and shape which are quite similar to the size and shape of the original molded polymer article.
  • This method can be used to form contact lenses and is further described in U.S. Pat. Nos. 4,495,313; 4,680,336; 4,889,664; and 5,039,459, incorporated herein by reference.
  • the lens be may be coated with a hydrophilic coating.
  • the preferred range of the combined silicone-containing monomer of Structure II and additional silicone-containing monomers, if present in the reaction mixture, is from about 5 to 100 weight percent, more preferably about 10 to 90 weight percent, and most preferably about 15 to 80 weight percent of the reactive components in the reaction mixture.
  • the preferred range of optional hydrophilic monomer if present in the above invention is from about 5 to 80 weight percent, more preferably about 10 to 60 weight percent, and most preferably about 20 to 50 weight percent of the reactive components in the reaction mixture.
  • the preferred range of diluent is from about 0 to 70 weight percent, more preferably about 0 to 50 weight percent, and most preferably about 0 to 20 weight percent of the total reaction mixture. The amount of diluent required varies depending on the nature and relative amounts of the reactive components.
  • a preferred combination of reactive components about 10 to 60, more preferably about 15 to 50 weight percent of the reactive components is silicone-containing monomer, about 20 to 50 weight percent of the reactive components is silicone-containing monomer of Structure I or Structure II, about 10 to 50 percent of the reactive components is a hydrophilic monomer, more preferably DMA, about 0.1 to 1.0 percent of the reactive components is a UV or visible light-active photoinitiator and about 0 to 20 weight percent of the total reaction mixture is a secondary or tertiary alcohol diluent, more preferably a tertiary alcohol.
  • reaction mixtures of the present invention can be formed by any of the methods known to those skilled in the art, such as shaking or stirring, and used to form polymeric articles or devices by the methods described earlier.
  • temperatures such as 30-100° C., more preferably 50 to 80° C. or 60-70° C.
  • Silicone hydrogels of the instant invention have high oxygen permeability. They have O 2 Dk values between about 40 and 300 barrer determined by the polarographic method. Polarographic method measurements of oxygen permeability are made as follows. Lenses are positioned on the sensor then covered on the upper side with a mesh support. The oxygen which diffuses through the lens is measured using a polarographic oxygen sensor consisting of a 4 mm diameter gold cathode and a silver ring anode. The reference values are those measured on commercially available contact lenses using this method.
  • Etafilcon A lenses give a measurement of about 20 to 25 barrer.
  • Contact lenses made from the silicone hydrogels of the invention may be produced to include a hydrophilic surface layer.
  • Suitable materials for forming the surface layer are known in the art.
  • Preferred materials include poly(vinyl alcohol), polyethylene oxide, poly(2-hydroxyethyl methacrylate), poly(methyl methacrylate), poly(acrylic acid), poly(methacrylic acid), poly(maleic acid), poly(itaconic acid), poly(acrylamide), poly(methacrylamide), poly(dimethylacrylamide), poly(glycerol methacrylate), polystyrene sulfonic acid, polysulfonate polymers, poly(vinyl pyrrolidone), carboxymethylated polymers, such as carboxymethylcellulose, polysaccharides, glucose amino glycans, polylactic acid, polyglycolic acid, block or random copolymers of the aforementioned, and the like, and mixtures thereof.
  • the carboxyl functional hydrophilic polymer is poly(acrylic acid), poly(methacrylic acid), poly(meth)acrylamide, or poly(acrylamide). More preferably, poly(acrylic acid) or poly(acrylamide) is used.
  • Methods for coating contact lenses are disclosed in U.S. Pat. No. 6,087,415, and WO 00127662 incorporated herein in their entirety by reference.
  • mPDMS monomethacryloxypropyl terminated polydimethylsiloxane (MW 800-1000 unless otherwise indicated)
  • CGI 1850 1:1 (wt) blend of 1-hydroxycyclohexyl phenyl ketone and bis(2,6-dimethoxybenzoyl)2,4-4-trimethylpentyl phosphine oxide
  • PAA poly (acrylic acid)
  • DAROCUR 1173 2-hydroxy-2-methyl-1-phenyl-propan-1-one
  • the lenses were clear and had a tensile modulus of 205 ⁇ 12 psi, an elongation at break of 133 ⁇ 37%, and an equilibrium water content of 24.2 ⁇ 0.2%.
  • Tensile properties were determined using an InstronTM model 1122 tensile tester (tensile modulus is equivalent to Young's modulus).
  • Example Composition 1 2 3 4 Prep 1 38.2 33.5 27.6 22.3 MBM 28.8 33.5 39.4 44.7 DMA 33 33 33 33 33 35 Darocur 1173 0.4 0.4 0.4 0.4 % of Diluent* 9 7 5 4 EWC(%) 24.2 ⁇ 0.2 23.3 ⁇ 0.3 22.4 ⁇ 0.2 24.2 ⁇ 0.3 Modulus (psi) 205 ⁇ 12 178 ⁇ 11 136 ⁇ 4 109 ⁇ 3 % Elongation 133 ⁇ 37 156 ⁇ 39 168 ⁇ 48 200 ⁇ 58 Dk (barrers) 142.3 144.9 145.1 109.3
  • Example Composition 5 6 7 8 Prep 1 37.1 32.5 26.8 21.7 MBM 27.9 32.5 38.2 43.3 DMA 35 35 35 35 35 35 Darocur 1173 0.4 0.4 0.4 0.4 0.4 0.4 %
  • Lenses were made using the procedure and reaction mixture described in Example 17, but with MPD in place of MBM. The lens properties are shown in Table 2.
  • Example 17 A reaction mixture was made using the formulation of Example 17, but with TRIS in place of MBM, and with 20% diluent. Lenses were made following the procedure of Example 1. The lens properties, shown in Table 2, show that the use of MBM (Example 17) or MPD (Example 18) gave lower moduli when used in place of TRIS. TABLE 2 Compositions and Properties of Silicone Hydrogel Polymers. Example 17 Comp. Ex.
  • Example 19 Example 20 PDMS 29.0 29.0 T1 35.0 T2 35.0 DMA 35.0 35.0 DAROCUR 1.0 1.0 1173 %/Diluent 23.0 37.6 Modulus 193 ⁇ 15 psi 175 ⁇ 11 psi Elongation 87.9 ⁇ 42% 108 ⁇ 54% at break Dk 171 barrers 94 barrers EWC 31.1 ⁇ 0.2% 33.4 ⁇ 0.2%
  • the Examples show that the contact lenses made using the silicone-containing monomers of Structure I provide contact lenses which are clear and have a lower Young's modulus than the contact lenses made according to the Comparative Examples. A low modulus is desirable to provide contact lenses which are comfortable when worn.
  • compositions were prepared, and cured with UV light into flat sheets. These sheets were extracted with isopropanol to remove diluent and any unreacted monomer, then equilibrated in isotonic borate buffered saline.
  • the 25 mm diameter hydrogel disks (each approximately 0.7 mm thick) were held between the 25 mm diameter parallel plates (plated with a crystal clad 80/100 grit coating) of a controlled stress rheometer (ATS Stresstech) with a vertical force of 10 N.
  • the disks were immersed in water during the test to prevent dehydration.
  • a stress sweep from 100 to 10,000 Pa at 1 Hz and 25° C. was conducted on a disk of each material, to determine the range of the linear viscoelastic region for each formulation.
  • the rheometer was set in frequency sweep mode using a stress less than the predetermined limit, and G′, G′′, and tan ⁇ of the 25 mm diameter hydrated disks were measured as a function of frequency from 0.01-30 Hz at several temperatures (10, 25, 40 and 55° C.), all the while maintaining a vertical force of 10 N on the hydrogel disks.
  • the individual frequency scans of G′ and tan ⁇ were then combined to form master curves for each material.
  • the data for the shear modulus G′ and tan ⁇ of the hydrogels at a reference temperature of 25° C. are shown in tables 4 and 5.
  • sample A was greater than B in the frequency range in which they were tested (as would be expected since the only difference between them is the molecular weight between crosslinks: 1000 vs.
  • the shear modulus of sample D was greater than E in the frequency range in which they were tested (the only difference between them is the molecular weight of the dangling chains: 1000 vs. 5000), and their shear moduli gradually increased with increasing frequency.
  • the silicone-based macromer refers to a prepolymer in which one mole was made from an average of 19.1 moles of 2-hydroxyethyl methacrylate, 2.8 moles of methyl methacrylate, 7.9 moles of methacryloxypropyltris(trimethylsiloxy)silane, and 3.3 moles of mono-methacryloxypropyl terminated mono-butyl terminated polydimethylsiloxane.
  • the macromer was completed by reacting the aforementioned material with 2.0 moles per mole of 3-isopropenyl- ⁇ , ⁇ -dimethylbenzyl isocyanate using dibutyltin dilaurate as a catalyst.
  • Weight percentages are computed based on the total weight of all components; the balance of the compositions in Table 5 comprise initiators and additives.
  • Lenses were made from these compositions having a nominal base curve of 8.5 mm and a diameter of 14.0 mm at 22° C. They had a nominal center thickness of 0.110 mm and a measured center thickness of 0.119 mm (Lens A) and 0.085 mm (Lens B). Both lenses were coated with a hydrophilic coating (PAA as in Example 37). Lens A had a Young's modulus of 109.4 psi and Lens B had a Young's modulus of 88.5 psi.
  • PAA hydrophilic coating
  • Subjects participating in the study were given a baseline examination and fitted with lenses made from the compositions shown in Table 6. They then wore the lenses for one week. Lenses were wom for daily wear. The subjects returned for a clinical evaluation of the presence of SEALs and other clinical data (e.g. visual acuity).
  • Nineteen subjects (38 eyes) completed the study, eight of whom had a history of SEALs.
  • Ten (10) eyes wearing Lens A exhibited SEALs.
  • No eyes wearing Lens B exhibited SEALs.
  • reaction mixture was cooled to 15 C while stirring and purging with nitrogen. After the solution reaches 15° C., 191.75 g (1.100 mol) of 1-trimethylsiloxy-1-methoxy-2-methylpropene (1 equivalent) was injected into the reaction vessel. The reaction was allowed to exotherm to approximately 62° C. and then 30 ml of a 0.40 M solution of 154.4 g TBACB in 11 ml of dry THF was metered in throughout the remainder of the reaction. After the temperature of reaction reached 30° C.
  • the reaction flask was maintained at approximately 110° C. and a solution of 443 g (2.201 mol) TMI and 5.7 g (0.010 mol) dibutyltin dilaurate were added. The mixture, was reacted until the isocyanate peak was gone by IR. The toluene was evaporated under reduced pressure to yield an off-white, anhydrous, waxy reactive monomer.
  • the macromer was placed into acetone at a weight basis of approximately 2:1 acetone to macromer. After 24 hrs, water was added to precipitate out the macromer and the macromer was filtered and dried using a vacuum oven between 45 and 60° C. for 20-30 hrs.
  • Hydrogel were made from the monomer mixtures shown on Table 8. All amounts are calculated as weight percent of the total weight of the combination with the balance of the mixture being minor amounts of additives. Polymerization was conducted in the presence of the diluents listed.
  • Example 27 To lenses from Example 27 immersed in a solution of 1.0% 250,000 M w polyacrylic acid in water at 45° C. was added 0.1% 1-[3-(dimethylamino)propyl]-3-ethylcarbodiimide hydrochloride. After stirring for 30 minutes the lenses are rinsed in borate-buffered saline solution. The dynamic contact angles of the resulting poly(sodium acrylate)-coated lenses are 44° advancing and 42° receding.
  • Lenses were made by curing a blend of 57.5% TRIS, 40.0% DMA, 1.5% 1,3-bis(3-methacryloxypropyl)tetrakis(trimethylsiloxy)disiloxane and 1.0% 2-hydroxy-2-methyl-1-phenyl-propan-1-one (by weight) in contact lens molds under UV light.
  • the lenses were released into ethanol and transferred to borate-buffered saline solution.
  • the lenses had properties given in Table 9, but when extended they returned to their original shape very slowly due to their high tan ⁇ . In fact, even during ordinary lens handling, these lenses typically did not retain a their symmetrical shape. Further, they had less than desirable Dks and were very unwettable.

Abstract

A soft contact lens containing a silicone-hydrogel made by curing a reaction mixture containing a silicone-containing monomer.

Description

    RELATED U.S. APPLICATIONS
  • This application is a continuation-in-part of U.S. Ser. No. 09/652,817, filed on Aug. 30, 2000, which is a continuation-in-part of U.S. Ser. No. 09/532,943, filed on Mar. 22, 2000, which is a continuation-in-part of U.S. Ser. No. 09/414,365, filed on Oct. 7, 1999, which is a continuation-in-part of U.S. Ser. No. 09/033,347, filed on Mar. 2, 1998, now issued as U.S. Pat. No. 5,998,498.[0001]
  • FIELD OF THE INVENTION
  • This invention relates to silicone hydrogels. In particular, the invention relates to silicone hydrogels formed by curing a reaction mixture of silicone-containing monomers. [0002]
  • BACKGROUND OF THE INVENTION
  • A hydrogel is a hydrated crosslinked polymeric system that contains water in an equilibrium state. Hydrogels typically are oxygen permeable and biocompatible, making them preferred materials for producing biomedical devices and in particular contact or intraocular lenses. [0003]
  • Conventional hydrogels are prepared from monomeric mixtures predominantly containing hydrophilic monomers, such as 2-hydroxyethyl methacrylate (“HEMA”) or N-vinyl pyrrolidone (“NVP”). U.S. Pat. Nos. 4,495,313, 4,889,664 and 5,039,459 disclose the formation of conventional hydrogels. The oxygen permeability of these conventional hydrogel materials relates to the water content of the materials, and is typically below 20-30 barrers. For contact lenses made of the conventional hydrogel materials, that level of oxygen permeability is suitable for short-term wear of the contact lenses; however, that level of oxygen permeability may be insufficient to maintain a healthy comea during long-term wear of contact lenses (e.g., 30 days without removal). Therefore, efforts have been made and continue to be made to increase the oxygen permeability of conventional hydrogels. [0004]
  • One known way to increase the oxygen permeability of hydrogels is to add silicone-containing monomers to the hydrogel formulations to produce silicone hydrogels. Silicone-containing polymers generally have higher oxygen permeabilities than conventional hydrogels. Silicone hydrogels have typically been prepared by polymerizing mixtures containing at least one silicone-containing monomer and at least one hydrophilic monomer. Either the silicone-containing monomer or the hydrophilic monomer may function as a crosslinking agent (a crosslinking agent is a monomer having multiple polymerizable functionalities) or a separate crosslinking agent may be employed. The formation of silicone hydrogels has been disclosed in U.S. Pat. Nos. 4,954,587, 5,010,141, 5,079,319, 5,115,056, 5,260,000, 5,336,797, 5,358,995, 5,387,632, 5,451,617, 5,486,579, WO 96/31792, U.S. Pat. Nos. 5,789,461, 5,776,999, 5,760,100 and U.S. Pat. No. 5,849,811. Group Transfer Polymerization techniques for polymerizing acrylic and methacrylic monomers with terminal silyl containing monomers is described in various patents including U.S. Pat. Nos. 4,414,372, 4,417,034, 4,508,880, 4,524,196, 4,581,428, 4,588,795, 4,598,161, 4,605,716, 4,622,372,4,656,233, 4,659,782, 4,659,783, 4,681,918, 4,695,607, 4,711,942, 4,771,116, 5,019,634 and 5,021,524 each of which is incorporated in its entirety herein by reference. [0005]
  • U.S. Pat. No. 3,808,178 discloses the formation of copolymers of small silicone-containing monomers and various hydrophilic monomers. U.S. Pat. No. 5,034,461 describes silicone hydrogels prepared from various combinations of silicone-polyurethane macromers and hydrophilic monomers such as HEMA or N,N-dimethyacrylamide (“DMA”). The addition of methacryloxypropyltris-(trimethylsiloxy)silane (“TRIS”) reduced the modulus of such hydrogels, but in many examples the modulus was still higher than may be desired. [0006]
  • U.S. Pat. Nos. 5,358,995 and 5,387,632 describe hydrogels made from various combinations of silicone macromers, TRIS, NVP and DMA. Replacing a substantial portion of the silicone macromer with TRIS reduced the modulus of the resulting hydrogels. Two publications from the same author, “The Role of Bulky Polysiloxanylalkyl Methacrylates in Polyurethane-Polysiloxane Hydrogels”, J. Appl. Poly. Sci., Vol. 60,1193-1199 (1996), and “The Role of Bulky Polysiloxanylalkyl Methacrylates in Oxygen-Permeable Hydrogel Materials”, J. Appl. Poly. Sci., Vol. 56, 317-324 (1995) also describe experimental results indicating that the modulus of hydrogels made from reaction mixtures of silicone-macromers and hydrophilic monomers such as DMA decreases with added TRIS. [0007]
  • The use of methacryloxypropylbis(trimethylsiloxy)methylsilane (“MBM”) to make hard contact lenses was described in WO 9110155 and in JP 61123609. [0008]
  • When relatively high levels of bulky silicone-containing monomers such as TRIS are incorporated into the hydrogels made from silicone-containing macromers and hydrophilic monomers, time at which the polymer returns to its original shape after applied stress is relieved increases to an extent that is unacceptable to the contact lens wearer. [0009]
  • There still remains a need in the art for silicone hydrogels that are soft enough to make soft contact lenses, which possess high oxygen permeability, suitable water content, and sufficient elasticity, and are comfortable to the contact lens wearer. [0010]
  • SUMMARY OF THE INVENTION
  • This invention provides a silicone hydrogel prepared by curing a reaction mixture comprising either or both of the silicone-containing monomers of Structure I and II. Structure I has the following structure: [0011]
    Figure US20040186248A1-20040923-C00001
  • wherein R[0012] 51 is a monovalent group such as H, C1-5alkyl, or an ethylenically unsaturated moiety (such as styryl, C1-5alkenyl and the like) where H, CH3 are preferred, q is 1, 2, or 3 and for each q, R52, R53 and R54 are independently alkyl or aromatic, preferably ethyl, methyl, benzyl, phenyl, or a monovalent siloxane chain comprising from 1 to 100 repeating Si—O units, p is 1 to 10, r=(3−q), X is O or NR55, where R55 is H or a monovalent alkyl group with 1 to 4 carbons, a is 0 or 1, and L is a divalent linking group which preferably comprises from 2 to 5 carbons, which may also optionally comprise ether or hydroxyl groups, for example, a polyethylene glycol chain.
  • Structure II has the following structure: [0013]
    Figure US20040186248A1-20040923-C00002
  • where b=0 to 100, where it is understood that b is a distribution having a mode equal to a stated value, preferably 8 to 10; R[0014] 58 is a monovalent group containing at least one ethylenically unsaturated moiety, preferably a monovalent group containing a styryl, vinyl, or methacrylate moiety, more preferably a methacrylate moiety; each R59 is independently a monovalent alkyl, or aryl group, which may be further substituted with alcohol, amine, ketone, carboxylic acid or ether groups, preferably unsubstituted monovalent alkyl or aryl groups, more preferably methyl; R60 is a monovalent alkyl, or aryl group, which may be further substituted with alcohol, amine, ketone, carboxylic acid or ether groups, preferably unsubstituted monovalent alkyl or aryl groups, preferably a C1-10aliphatic or aromatic group which may include hetero atoms, more preferably C3-8alkyl groups, most preferably butyl, and R61 is independently alkyl or aromatic, preferably ethyl, methyl, benzyl, phenyl, or a monovalent siloxane chain comprising from 1 to 100 repeating Si—O units.
  • In the preferred embodiment, the silicone hydrogel comprises monomers of both Structure I and II. More preferably, the silicone hydrogel comprises silicone-containing monomer of Structure I and II and a hydrophilic monomer. [0015]
  • Among the advantages of this invention is that the use of the silicone-containing monomers of both Structure I and Structure II in a silicone hydrogel reduces the Young's modulus of the hydrogel especially in hydrogels which comprise these silicone-containing monomers and additional silicone-containing monomers which act as crosslinkers. The monomers of Structure I and II are more effective at lowering the modulus of the silicone hydrogel than for monomers described in the prior art. Additionally, the tan δ of the silicone hydrogels of this invention may be concurrently preserved. [0016]
  • The polymers produced according to this invention can be used to produce soft contact lenses that will provide high oxygen permeability, good elasticity, and can be produced economically and efficiently. The polymer of this invention can be used to make biomedical devices which require biocompatability and high oxygen permeability, preferably contact lenses.[0017]
  • DETAILED DESCRIPTION OF THE INVENTION AND PREFERRED EMBODIMENTS
  • The term “monomer” used herein refers to lower molecular weight compounds that can be polymerized to higher molecular weight compounds, polymers, macromers, or prepolymers. The term “macromer” as used herein refers to a high molecular weight polymerizable compound. Prepolymers are partially polymerized monomers or monomers which are capable of further polymerization. [0018]
  • A “silicone-containing monomer” is one that contains at least two [—Si—O—] repeating units in a monomer, macromer or prepolymer. Preferably, the total Si and attached O are present in the silicone-containing monomer in an amount greater than 20 weight percent, and more preferably greater than 30 weight percent of the total molecular weight of the silicone-containing monomer. [0019]
  • Examples of the silicone-containing monomers of Structure I that can be used to form silicone hydrogels of this invention are, without limitation, methacryloxypropylbis(trimethylsiloxy)methylsilane, methacryloxypropyltris(trimethylsiloxy)silane, methacryloxypropylpentamethyldisiloxane, and (3-methacryloxy-2-hydroxypropyloxy) propylbis(trimethylsiloxy)methylsilane. While such silicone monomers may additionally be used, linear mono-alkyl terminated polydimethylsiloxanes (“mPDMS”) such as those shown in the following Structure II must be used: [0020]
    Figure US20040186248A1-20040923-C00003
  • where b=0 to 100, where it is understood that b is a distribution having a mode equal to a stated value, preferably 4 to 16, more preferably 8 to 10; R[0021] 58 is a monovalent group containing at least one ethylenically unsaturated moiety, preferably a monovalent group containing a styryl, vinyl, or methacrylate moiety, more preferably a methacrylate moiety; each R59 is independently a monovalent alkyl, or aryl group, which may be further substituted with alcohol, amine, ketone, carboxylic acid or ether groups, preferably unsubstituted monovalent alkyl or aryl groups, more preferably methyl; R60 is a monovalent alkyl, or aryl group, which may be further substituted with alcohol, amine, ketone, carboxylic acid or ether groups, preferably unsubstituted monovalent alkyl or aryl groups, preferably a C1-10aliphatic or aromatic group which may include hetero atoms, more preferably C3-8alkyl groups, most preferably butyl; and R61 is independently alkyl or aromatic, preferably ethyl, methyl, benzyl, phenyl, or a monovalent siloxane chain comprising from 1 to 100 repeating Si-O units.
  • The amount of mPDMS comprising the hydrogel is closely related to the modulus and tan δ of the hydrogels made according to this invention. Tan δ is defined as the loss modulus of the material divided by its elastic modulus (G″/G′). For purposes of this invention, modulus is defined as Young's modulus or it's equivalent tensile modulus where the measurement is recorded at the equilibrated hydrated state. It is desirable to lower both the modulus and tan δ in silicone hydrogel lenses for a number of reasons. First, lower modulus and tan δ in a lens are manifested as less stiffness, and after stress is relieved the lens quickly returns to its original shape. This improves comfort over traditional silicone hydrogel lenses and makes them more aesthetically appealing given their ability to retain their round shape. Further, the incidence of superior epithelial arcurate lesions (“SEALs”) is either or both lessened and eliminated by using lenses made from a polymer having a sufficiently low modulus and tan δ. Thus, replacing lenses made from high modulus, high tan d polymers with those of the instant invention is a means for reducing or eliminating the occurrence of SEALs. This is particularly the case for contact lens wearers that are prone to SEALs. [0022]
  • Desirably, silicone hydrogels made according to the invention comprise between about 2 and 70% wt mPDMS based on total weight of reactive monomer components from which the polymer is made. Depending upon the other monomers present, this will generally reduce the modulus of the polymer to between about 20 and 180 psi and a tan δ of less than about 0.1 to no more than about 0.3 (measured at a frequency of 1 Hz and a temperature of 25° C., according to the method described in Example 21). Silicone hydrogels made according to the invention and comprising between about 4 and 50% wt mPDMS (same basis as above) are preferred. These will generally exhibit a modulus between about 30 and 160 psi and a tan δ of about 0.05 to about 0.3 (measured at a frequency of 1 Hz and a temperature of 25° C.). Silicone hydrogels made according to the invention and comprising between about 8 and 40% wt mPDMS (same basis as above) are most preferred. These hydrogels will generally exhibit a modulus between about 40 and 130 psi and a tan δ of about 0.2 or less (measured at a frequency of 1 Hz and a temperature of 25° C.). Hydrogels having tan δ less than about 0.1 can also be made according to this invention as described more fully below. [0023]
  • Additional silicone-containing monomers may be combined with the silicone-containing monomers of Structures I and II to form the soft contact lenses of the invention. Any known silicone-containing monomers useful for making silicone hydrogels can be used in combination with the silicone-containing monomer of Structure I and II to form the soft contact lenses of this invention. Many silicone-containing monomers useful for this purpose are disclosed in U.S. Pat. No. 6,020,445 incorporated herein in its entirety by reference. Useful additional silicone-containing monomers combined with the silicone-containing monomers of Structure I to form the silicone hydrogels of this invention are the hydroxyalkylamine-functional silicone-containing monomers disclosed in U.S. Pat. No. 5,962,548 incorporated herein in its entirety by reference. The preferred silicone-containing linear or branched hydroxyalkylamine-functional monomers comprising a block or random monomer of the following structure: [0024]
    Figure US20040186248A1-20040923-C00004
  • Structure III [0025]
  • wherein: [0026]
  • n is 0 to 500 and m is 0 to 500 and (n+m)=10 to 500 and more preferably 20 to 250; R[0027] 2, R4, R5, R6 and R7 are independently a monovalent alkyl, or aryl groups, which may be further substituted with alcohol, ester, amine, ketone, carboxylic acid or ether groups, preferably unsubstituted monovalent alkyl or aryl groups; and R1, R3 and R8 are independently a monovalent alkyl, or aryl group, which may be further substituted with an alcohol, ester, amine, ketone, carboxylic acid or ether group, preferably unsubstituted monovalent alkyl or aryl groups, or are the following nitrogen-containing structure:
    Figure US20040186248A1-20040923-C00005
  • Structure IV [0028]
  • with the proviso that at least one of R[0029] 1, R3, and R8 are according to Structure IV, wherein R9 is a divalent alkyl group such as —CH2)n— where s is from 1 to 10, preferably 3 to 6 and most preferably 3;
  • R[0030] 10 and R11 are independently H, a monovalent alkyl or aryl group which may be further substituted with an alcohol, ester, amine, ketone, carboxylic acid or ether group, or has the following structure:
    Figure US20040186248A1-20040923-C00006
  • Structure V [0031]
  • where R[0032] 14, is H, or a monovalent polymerizable group comprising acryloyl, methacryloyl, styryl, vinyl, allyl or N-vinyl lactam, preferably H or methacryloyl; R16 is either H, a monovalent alkyl or aryl group which can be further substituted with alcohol, ester, amine, ketone, carboxylic acid or ether groups, or a polymerizable group comprising acrylate, methacrylate, styryl, vinyl, allyl or N-vinyl lactam, preferably alkyl substituted with an alcohol or methacrylate; R12, R13 and R15 are independently H, a monovalent alkyl or aryl, which can be further substituted with alcohol, ester, amine, ketone, carboxylic acid or ether groups, or R12 and R15, or R15 and R13 can be bonded together to form a ring structure, with the proviso that at least some of the Structure IV groups on the monomer comprises polymerizable groups. R12, R13 and R15 are preferably H.
  • In alternative embodiments, the silicone hydrogels of this invention, comprising the silicone-containing monomers of either or both Structure I and Structure II may further comprise hydrophilic monomers. The hydrophilic monomers optionally used to make the hydrogel polymer of this invention can be any of the known hydrophilic monomers disclosed in the prior art to make hydrogels. [0033]
  • The preferred hydrophilic monomers used to make the polymer of this invention may be either acrylic- or vinyl-containing. Such hydrophilic monomers may themselves be used as crosslinking agents. The term “vinyl-type” or “vinyl-containing” monomers refer to monomers containing the vinyl grouping (—CH═CH[0034] 2) and are generally highly reactive. Such hydrophilic vinyl-containing monomers are known to polymerize relatively easily.
  • “Acrylic-type” or “acrylic-containing” monomers are those monomers containing the acrylic group: (CH[0035] 2═CRCOX) wherein R is H or CH3, and X is O or N, which are also known to polymerize readily, such as N,N-dimethyl acrylamide (DMA), 2-hydroxyethyl methacrylate (HEMA), glycerol methacrylate, 2-hydroxyethyl methacrylamide, polyethyleneglycol monomethacrylate, methacrylic acid and acrylic acid.
  • Hydrophilic vinyl-containing monomers which may be incorporated into the silicone hydrogels of the present invention include monomers such as N-vinyl lactams (e.g. NVP), N-vinyl-N-methyl acetamide, N-vinyl-N-ethyl acetamide, N-vinyl-N-ethyl formamide, N-vinyl formamide, with NVP being preferred. [0036]
  • Other hydrophilic monomers that can be employed in the invention include polyoxyethylene polyols having one or more of the terminal hydroxyl groups replaced with a functional group containing a polymerizable double bond. Examples include polyethylene glycol, ethoxylated alkyl glucoside, and ethoxylated bisphenol A reacted with one or more molar equivalents of an end-capping group such as isocyanatoethyl methacrylate (“IEM”), methacrylic anhydride, methacryloyl chloride, vinylbenzoyl chloride, or the like, to produce a polyethylene polyol having one or more terminal polymerizable olefinic groups bonded to the polyethylene polyol through linking moieties such as carbamate or ester groups. [0037]
  • Still further examples are the hydrophilic vinyl carbonate or vinyl carbamate monomers disclosed in U.S. Pat. No. 5,070,215, and the hydrophilic oxazolone monomers disclosed in U.S. Pat. No. 4,910,277. Other suitable hydrophilic monomers will be apparent to one skilled in the art. [0038]
  • More preferred hydrophilic monomers which may be incorporated into the polymer of the present invention include hydrophilic monomers such as DMA, HEMA, glycerol methacrylate, 2-hydroxyethyl methacrylamide, NVP, polyethyleneglycol monomethacrylate, methacrylic acid and acrylic acid with DMA being the most preferred. [0039]
  • Other monomers that can be present in the reaction mixture used to form the silicone hydrogel of this invention include ultra-violet absorbing monomers, reactive tints, pigments, and the like. Additional processing aids such as release agents or wetting agents can also be added to the reaction mixture. [0040]
  • A polymerization initiator is preferably included in the reaction mixture. The polymerization initiator can be a compound such as lauryl peroxide, benzoyl peroxide, isopropyl percarbonate, azobisisobutyronitrile, or the like, that generates free radicals at moderately elevated temperatures, or the polymerization iniator can be a photoinitiator system such as an aromatic alpha-hydroxy ketone or a tertiary amine plus a diketone. Illustrative examples of photoinitiator systems are 2-hydroxy-2-methyl-1-phenyl-propan-1-one, and a combination of camphorquinone and ethyl 4-(N,N-dimethylamino)benzoate. The initiator is used in the reaction mixture in effective amounts, e.g., from about 0.1 to about 2 parts by weight per 100 parts of reactive monomer. Polymerization of the reaction mixture can be initiated using the appropriate choice of heat or visible or ultraviolet light or other means depending on the polymerization initiator used. The preferred initiator is a 1:1 blend of 1-hydroxycyclohexyl phenyl ketone and bis(2,6-dimethoxybenzoyl)2, 4, 4-trimethylpentyl phosphine oxide and the preferred method of polymerization initiation is visible light. [0041]
  • Typically after curing of the reaction mixture of the silicone-containing monomers of either or both Structure I and II and optional hydrophilic monomers and any other optional ingredients such as additional silicone-containing monomers, diluents, crosslinking agents, catalysts, release agents, tints etc. which are blended together prior to polymerization, the resulting polymer is treated with a solvent to remove the diluent (if used) or any traces of unreacted components, and hydrate the polymer to form the hydrogel. The solvent used may be water (or an aqueous solution such as physiological saline), or depending on the solubility characteristics of the diluent (if used) used to make the hydrogel of this invention and the solubility characteristics of any residual unpolymerized monomers, the solvent initially used can be an organic liquid such as ethanol, methanol, isopropanol, mixtures thereof, or the like, or a mixture of one or more such organic liquids with water, followed by extraction with pure water (or physiological saline) to produce the silicone hydrogel comprising a polymer of said monomers swollen with water. The silicone hydrogels after hydration of the polymers preferably comprise about 2 to 50 weight percent water, more preferably about 15 to 45 weight percent water, and most preferably about 20 to 40 weight percent water of the total weight of the silicone hydrogel. These silicone hydrogels are particularly suited for making contact lenses or intraocular lenses, preferably soft contact lenses. [0042]
  • In another preferred embodiment, a silicone hydrogel lens is made by reacting a macromer with a reaction mixture that includes silicone based monomers and hydrophilic monomers. This technique affords a high level of control of the structure of the ultimate product. Phase distribution can be controlled so that a more uniform coating or surface layer (if desired) can be applied to the lens. By “surface layer” is meant a distribution of material with a portion in contact with the environment and another portion in contact with a material having a different bulk property than that of the material from which the surface layer is formed. Additionally, it is easier to process the lenses because of greater uniformity of properties across the lens. [0043]
  • The macromers are made by combining a/an (meth)acrylate and a silicone in the presence of a Group Transfer Polymerization (“GTP”) catalyst. These macromers typically comprise copolymers of various monomers. They may be formed in such a way that the monomers come together in distinct blocks, or in a generally random distribution. These macromers may furthermore be linear, branched, or star shaped. Branched structures are formed for instance if polymethacrylates, or crosslinkable monomers such as ethyleneglycol dimethacrylate are included in the macromer. Initiators, reaction conditions, monomers, and catalysts that can be used to make GTP polymers are described in “Group-Transfer Polymerization” by O. W. Webster, in Encyclopedia of Polymer Science and Engineering Ed. (John Wiley & Sons) p. 580, 1987. These polymerizations are conducted under anhydrous conditions. Hydroxyl-functional monomers, like HEMA, can be incorporated as their trimethylsiloxy esters, with hydrolysis to form free hydroxyl group after polymerization. GTP offers the ability to assemble macromers with control over molecular weight distribution and monomer distribution on the chains. This macromer is then reacted with a reaction mixture comprising predominantly polydimethylsiloxane (preferably, mPDMS), and hydrophilic monomers. [0044]
  • Preferred macromer components include mPDMS, TRIS, methyl methacrylate, HEMA, DMA, methacrylonitrile, ethyl methacrylate, butyl methacrylate, 2-hydroxypropyl-1-methacrylate, 2-hydroxyethyl methacrylamide and methacrylic acid. It is even more preferred that the macromer is made from a reaction mixture comprising HEMA, methyl methacrylate, TRIS, and mPDMS. It is most preferred that macromer is made from a reaction mixture comprising, consisting essentially of, or consisting of about 19.1 moles of blocked HEMA (2-(trimethylsiloxy)ethyl methacrylate) about 2.8 moles of methyl methacrylate, about 7.9 moles of TRIS, and about 3.3 moles of mono-methacryloxypropyl terminated mono-butyl terminated polydimethylsiloxane, and is completed by reacting the aforementioned material with about 2.0 moles per mole of 3-isopropenyl-ω,ω-dimethylbenzyl isocyanate using dibutyltin dilaurate as a catalyst. [0045]
  • Silicone hydrogels can be made by reacting blends of macromers, monomers, and other additives such as UV blockers, tints, polymerization inhibitors, and internal wetting agents. Internal wetting agents are substances that are incorporated into the polymer blend of a lens prior to polymerization and due to their incorporation, the wettability of the lens increases. The reactive components of these blends typically comprise a combination of hydrophobic silicone with hydrophilic components. Since these components are often immiscible because of their differences in polarity, it is particularly advantageous to incorporate a combination of hydrophobic silicone monomers with hydrophilic monomers, especially those with hydroxyl groups, into the macromer. The macromer can then serve to compatibilize the additional silicone and hydrophilic monomers that are incorporated in the final reaction mixture. These blends typically also contain diluents to further compatibilize and solubilize all components. Preferably, the silicone based hydrogels are made by reacting the following monomer mix: macromer; an Si[0046] 8-10 monomethacryloxy terminated polydimethyl siloxane; and hydrophilic monomers together with minor amounts of additives and photoinitiators. It is more preferred that the hydrogels are made by reacting macromer; an Si8-10 monomethacryloxy terminated polydimethyl siloxane; TRIS; DMA; HEMA; and tetraethyleneglycol dimethacrylate (“TEGDMA”). It is most preferred that the hydrogels are made from the reaction of (all amounts are calculated as weight percent of the total weight of the combination) macromer (about 18%); an Si8-10 monomethacryloxy terminated polydimethyl siloxane (about 28%); TRIS (about 14%); DMA (about 26%); HEMA (about 5%); TEGDMA (about 1%), polyvinylpyrrolidone (“PVP”) (about 5%); with the balance comprising minor amounts of additives and photoinitiators, and that the reaction is conducted in the presence of 20% wt 3,7-dimethyl-3-octanol diluent.
  • Various processes are known for molding the reaction mixture in the production of contact lenses, including spincasting and static casting. Spincasting methods are disclosed in U.S. Pat. Nos. 3,408,429 and 3,660,545, and static casting methods are disclosed in U.S. Pat. Nos. 4,113,224 and 4,197,266. The preferred method for producing contact lenses comprising the polymer of this invention is by the direct molding of the silicone hydrogels, which is economical, and enables precise control over the final shape of the hydrated lens. For this method, the reaction mixture is placed in a mold having the shape of the final desired silicone hydrogel, i.e. water-swollen polymer, and the reaction mixture is subjected to conditions whereby the monomers polymerize, to thereby produce a polymer in the approximate shape of the final desired product. Then, this polymer mixture is optionally treated with a solvent and then water, producing a silicone hydrogel having a final size and shape which are quite similar to the size and shape of the original molded polymer article. This method can be used to form contact lenses and is further described in U.S. Pat. Nos. 4,495,313; 4,680,336; 4,889,664; and 5,039,459, incorporated herein by reference. After producing the silicone hydrogel, the lens be may be coated with a hydrophilic coating. Some methods of adding hydrophilic coatings to a lens have been disclosed in the prior art, including U.S. Pat. Nos. 3,854,982, 3,916,033, 4,920,184, 5,002,794, 5,779,943, 6,087,415; WO 91/04283, and EPO 93/810,399. [0047]
  • The preferred range of the combined silicone-containing monomer of Structure II and additional silicone-containing monomers, if present in the reaction mixture, is from about 5 to 100 weight percent, more preferably about 10 to 90 weight percent, and most preferably about 15 to 80 weight percent of the reactive components in the reaction mixture. The preferred range of optional hydrophilic monomer if present in the above invention is from about 5 to 80 weight percent, more preferably about 10 to 60 weight percent, and most preferably about 20 to 50 weight percent of the reactive components in the reaction mixture. The preferred range of diluent is from about 0 to 70 weight percent, more preferably about 0 to 50 weight percent, and most preferably about 0 to 20 weight percent of the total reaction mixture. The amount of diluent required varies depending on the nature and relative amounts of the reactive components. [0048]
  • In a preferred combination of reactive components about 10 to 60, more preferably about 15 to 50 weight percent of the reactive components is silicone-containing monomer, about 20 to 50 weight percent of the reactive components is silicone-containing monomer of Structure I or Structure II, about 10 to 50 percent of the reactive components is a hydrophilic monomer, more preferably DMA, about 0.1 to 1.0 percent of the reactive components is a UV or visible light-active photoinitiator and about 0 to 20 weight percent of the total reaction mixture is a secondary or tertiary alcohol diluent, more preferably a tertiary alcohol. [0049]
  • The reaction mixtures of the present invention can be formed by any of the methods known to those skilled in the art, such as shaking or stirring, and used to form polymeric articles or devices by the methods described earlier. For some monomer reaction mixtures it is preferred to polymerize the reaction mixtures at temperatures such as 30-100° C., more preferably 50 to 80° C. or 60-70° C. [0050]
  • Silicone hydrogels of the instant invention have high oxygen permeability. They have O[0051] 2 Dk values between about 40 and 300 barrer determined by the polarographic method. Polarographic method measurements of oxygen permeability are made as follows. Lenses are positioned on the sensor then covered on the upper side with a mesh support. The oxygen which diffuses through the lens is measured using a polarographic oxygen sensor consisting of a 4 mm diameter gold cathode and a silver ring anode. The reference values are those measured on commercially available contact lenses using this method. Balafilcon A lenses available from Bausch & Lomb give a measurement of approximately 79 barrer (1 barrer=10−10 (cm3 of gas×cm2)/(cm3 of polymer×s×cm Hg). Etafilcon A lenses give a measurement of about 20 to 25 barrer.
  • Contact lenses made from the silicone hydrogels of the invention may be produced to include a hydrophilic surface layer. Suitable materials for forming the surface layer are known in the art. Preferred materials include poly(vinyl alcohol), polyethylene oxide, poly(2-hydroxyethyl methacrylate), poly(methyl methacrylate), poly(acrylic acid), poly(methacrylic acid), poly(maleic acid), poly(itaconic acid), poly(acrylamide), poly(methacrylamide), poly(dimethylacrylamide), poly(glycerol methacrylate), polystyrene sulfonic acid, polysulfonate polymers, poly(vinyl pyrrolidone), carboxymethylated polymers, such as carboxymethylcellulose, polysaccharides, glucose amino glycans, polylactic acid, polyglycolic acid, block or random copolymers of the aforementioned, and the like, and mixtures thereof. Preferably, the carboxyl functional hydrophilic polymer is poly(acrylic acid), poly(methacrylic acid), poly(meth)acrylamide, or poly(acrylamide). More preferably, poly(acrylic acid) or poly(acrylamide) is used. Methods for coating contact lenses are disclosed in U.S. Pat. No. 6,087,415, and WO 00127662 incorporated herein in their entirety by reference. [0052]
  • The non-limiting examples below further describe this invention. In the examples the following abbreviations are used: [0053]
  • EXAMPLES
  • MBM 3-methacryloxypropylbis(trimethylsiloxy)methylsilane [0054]
  • MPD methacryloxypropylpentamethyl disiloxane [0055]
  • TRIS 3-methacryloxypropyltris (trimethylsiloxy) silane [0056]
  • DMA N,N-dimethylacrylamide [0057]
  • THF tetrahydrofuran [0058]
  • TMI dimethyl meta-isopropenyl benzyl isocyanate [0059]
  • HEMA 2-hydroxyethyl methacrylate [0060]
  • TEGDMA tetraethyleneglycol dimethacrylate [0061]
  • EGDMA ethyleneglycol dimethacrylate [0062]
  • MMA methyl methacrylate [0063]
  • TBACB tetrabutyl ammonium-m-chlorobenzoate [0064]
  • mPDMS monomethacryloxypropyl terminated polydimethylsiloxane (MW 800-1000 unless otherwise indicated) [0065]
  • PDMS polydimethylsiloxane [0066]
  • 3M3P 3-methyl-3-pentanol [0067]
  • Norbloc 2-(2′-hydroxy-5-methacrylyloxyethylphenyl)-2H-benzotriazole [0068]
  • CGI 1850 1:1 (wt) blend of 1-hydroxycyclohexyl phenyl ketone and bis(2,6-dimethoxybenzoyl)2,4-4-trimethylpentyl phosphine oxide [0069]
  • PAA poly (acrylic acid) [0070]
  • PVP poly(N-vinyl pyrrolidone) [0071]
  • IPA isopropyl alcohol [0072]
  • DAROCUR 1173 2-hydroxy-2-methyl-1-phenyl-propan-1-one [0073]
  • D30 3, 7-dimethyl-3-octanol [0074]
  • HOAc acetic acid [0075]
  • TAA t-amyl alcohol [0076]
  • blocked Hema 2-(trimethylsiloxy)ethyl methacrylate [0077]
  • Blue HEMA the reaction product of reactive blue number 4 and HEMA, as described in Example 4 or U.S. Pat. No. 5,944,853 [0078]
  • Preparation 1—Preparation of Polysiloxane Macromer
  • 500 grams of α,ω-bisaminopropyl polydimethylsiloxane (5000 MW) and 68 grams of glycidyl methacrylate were combined and heated with stirring at 100° C. for 10 hours. The product was extracted five times with 1500 ml of acetonitrile to remove residual glycidyl methacrylate to give a clear oil. IR: 3441, 2962, 1944, 1725, 1638, 1612, 1412 cm[0079] −1. This product will be referred to as “Prep 1” or alternatively bis(N,N-bis-2-hydroxy-3-methacryloxypropyl)aminopropyl polydimethylsiloxane.
  • Example 1
  • 38.2 parts by weight of the product of PREPARATION 1 was combined with 28.8 parts MBM, 33 parts DMA and 1 part DAROCUR 1173 and diluted with 3-methyl-3-pentanol to make a reaction mixture in which the diluent made up 9% of the mass of the complete reaction mixture. The resulting reaction mixture was a clear, homogeneous solution. Polypropylene contact lens molds were filled, closed and irradiated with a total of 3.2 J/cm[0080] 2 UV light from a fluorescent UV source over a 30-minute period. The molds were opened and the lenses were released into isopropanol and then transferred into deionized water.
  • The lenses were clear and had a tensile modulus of 205±12 psi, an elongation at break of 133±37%, and an equilibrium water content of 24.2 ±0.2%. Tensile properties were determined using an Instron™ model 1122 tensile tester (tensile modulus is equivalent to Young's modulus). Equilibrium Water Contents (EWC) were determined gravimetrically and are expressed as: % EWC=100×(mass of hydrated lens—mass of dry lens)/mass of hydrated lens [0081]
  • Examples 2-16
  • Reaction mixtures were made using the formulation of Example 1, but with amounts listed in Table 1. All reaction mixtures and lenses were clear. [0082]
    TABLE 1
    Silicone Hydrogel Formulations and Properties.
    Example
    Composition 1 2 3 4
    Prep 1  38.2  33.5  27.6  22.3
    MBM  28.8  33.5  39.4  44.7
    DMA  33  33  33  33
    Darocur 1173  0.4  0.4  0.4  0.4
    % of Diluent*  9  7  5  4
    EWC(%) 24.2 ± 0.2 23.3 ± 0.3 22.4 ± 0.2 24.2 ± 0.3
    Modulus (psi)  205 ± 12  178 ± 11  136 ± 4  109 ± 3
    % Elongation  133 ± 37  156 ± 39  168 ± 48  200 ± 58
    Dk (barrers) 142.3 144.9 145.1 109.3
    Example
    Composition 5 6 7 8
    Prep 1  37.1  32.5  26.8  21.7
    MBM  27.9  32.5  38.2  43.3
    DMA  35  35  35  35
    Darocur 1173  0.4  0.4  0.4  0.4
    % of Diluent* 10  7  5 11
    EWC(%) 26.1 ± 0.3 25.8 ± 0.3 25.8 ± 0.3 25.8 ± 0.1
    Modulus (psi)  179 ± 5  215 ± 7  132 ± 6  101 ± 4
    % Elongation  151 ± 42  106 ± 30  195 ± 65  179 ± 47
    Dk (barrers) 118.8 129.6 116.5 107.9
    Example
    Composition 9 10 11 12
    Prep 1  35.4  31  25.5  20.7
    MBM  26.6  31  36.5  41.3
    DMA  38  38  38  38
    Darocur 1173  0.4  0.4  0.4  0.4
    % of Diluent* 12  7  7  5
    EWC(%) 29.4 ± 0.3 30.0 ± 0.3 26.6 ± 0.2 26.7 ± 0.3
    Modulus (psi)  215 ± 7  175 ± 7  132 ± 51  106 ± 4
    % Elongation   99 ± 22  132 ± 40  166 ± 51  204 ± 55
    Dk (barrers) 106.6 115.7 104.9 100.3
    Example
    Composition 13 14 15 16
    Prep 1  34.2  30  24.7  20
    MBM  25.8  30  35.3  40
    DMA  40  40  40  40
    Darocur  0.4  0.4  0.4  0.4
    % of Diluent* 12 11  8  9
    EWC(%) 32.1 ± 0.1 31.2 ± 0.2 31.6 ± 0.3 31.7 ± 0.2
    Modulus (psi)  218 ± 11  170 ± 6  131 ± 4   95 ± 3
    % Elongation  110 ± 34  130 ± 51  185 ± 53  203 ± 47
    Dk (barrers) 112.4 104.6  90.8  92.3
  • Example 17
  • 21.5% of α,ω-bismethacryloxypropyl polydimethylsiloxane with an average molecular weight of 5000 g/mol was combined with 42.5% MBM, 35% DMA and 1% DAROCUR 1173 and diluted with 3-methyl-3-pentanol to give a clear solution containing 22 weight % diluent. Lenses were made following the procedure of Example 1. The lens properties are shown in Table 2. [0083]
  • Example 18
  • Lenses were made using the procedure and reaction mixture described in Example 17, but with MPD in place of MBM. The lens properties are shown in Table 2. [0084]
  • Comparative Example 1
  • A reaction mixture was made using the formulation of Example 17, but with TRIS in place of MBM, and with 20% diluent. Lenses were made following the procedure of Example 1. The lens properties, shown in Table 2, show that the use of MBM (Example 17) or MPD (Example 18) gave lower moduli when used in place of TRIS. [0085]
    TABLE 2
    Compositions and Properties of Silicone Hydrogel Polymers.
    Example 17 Comp. Ex. 1 Example 18
    PDMS* 21.5 21.5 21.5
    TRIS 42.5
    MBM 42.5
    MPD 42.5
    DMA 35 35 35
    Monomer/Diluent 78/22 80/20 78/22
    Modulus   65 ± 2 psi   87 ± 3 psi   55 ± 2 psi
    Elongation at  278 ± 60%  307 ± 88%  263 ± 81%
    break
    Dk 110 barrers 147 barrers 75.6 barrers
    EWC 28.2 ± 0.3% 28.9 ± 0.3% 31.0 ± 0.3%
  • Example 19
  • 29.0% of α,ω-bismethacryloxypropyl polydimethylsiloxane with an average molecular weight of 5000 g/mol was combined with 35% mono-methacryloxypropyl terminated PDMS (T1, Structure II, MW=800 to 1000), 35% DMA and 1% DAROCUR 1173 and diluted with 3-methyl-3-pentanol to give a clear solution containing 23.0 weight % diluent. Lenses were made following the procedure of Example 1. The lens properties are shown in Table 3. [0086]
  • Example 20
  • 29.0% of α,ω-bismethacryloxypropyl polydimethylsiloxane with an average molecular weight of 5000 g/mol was combined with 35% (3-methacryloxy-2-hydroxypropyloxy)propylbis(trimethylsiloxy)methylsilane (T2), 35% DMA and 1% DAROCUR 1173 and diluted with 3M3P to give a clear solution containing 37.6 weight % diluent. Lenses were made following the procedure of Example 1. The lens properties are shown in Table 3. [0087]
    TABLE 3
    Compositions and Properties of Silicone Hydrogel Polymers.
    Example 19 Example 20
    PDMS 29.0 29.0
    T1 35.0
    T2 35.0
    DMA 35.0 35.0
    DAROCUR  1.0  1.0
    1173
    %/Diluent 23.0 37.6
    Modulus  193 ± 15 psi  175 ± 11 psi
    Elongation 87.9 ± 42%  108 ± 54%
    at break
    Dk 171 barrers 94 barrers
    EWC 31.1 ± 0.2% 33.4 ± 0.2%
  • The Examples show that the contact lenses made using the silicone-containing monomers of Structure I provide contact lenses which are clear and have a lower Young's modulus than the contact lenses made according to the Comparative Examples. A low modulus is desirable to provide contact lenses which are comfortable when worn. [0088]
  • Example 21
  • The following compositions were prepared, and cured with UV light into flat sheets. These sheets were extracted with isopropanol to remove diluent and any unreacted monomer, then equilibrated in isotonic borate buffered saline. [0089]
    A* B* C* D E
    PDMS 11.41 g 0 g 0 g 0 g 0 g
    1000 MW
    PDMS 0 g 11.38 g 0 g 0 g 0 g
    3000 MW
    TRIS 0 g 0 g 11.38 g 0 g 0 g
    mPDMS 0 g 0 g 0 g 11.38 g 0 g
    1000 MW**
    mPDMS 0 g 0 g 0 g 0 g 11.38 g
    5000
    MW***
    DMA 6.13 g 6.15 g 6.13 g 6.13 g 6.13 g
    EGDMA 0 g 0 g 0.35 g 0.37 g 0.35 g
    Darocur 0.08 g 0.08 g 0.08 g 0.08 g 0.08 g
    1173
    Diluent\ 7.50 g 10.40 g 7.50 g 7.50 g 15.42 g
  • †3M3P [0090]
  • The structure of PDMS was: [0091]
    Figure US20040186248A1-20040923-C00007
  • (Molecular weights for mPDMS and PDMS shown above are number average molecular weights). [0092]
  • The structure of mPDMS used in this example was: [0093]
    Figure US20040186248A1-20040923-C00008
  • For the determination of the properties after hydration, the 25 mm diameter hydrogel disks (each approximately 0.7 mm thick) were held between the 25 mm diameter parallel plates (plated with a crystal clad 80/100 grit coating) of a controlled stress rheometer (ATS Stresstech) with a vertical force of 10 N. The disks were immersed in water during the test to prevent dehydration. A stress sweep from 100 to 10,000 Pa at 1 Hz and 25° C. was conducted on a disk of each material, to determine the range of the linear viscoelastic region for each formulation. [0094]
  • Once the limit of the linear viscoelastic region had been determined, the rheometer was set in frequency sweep mode using a stress less than the predetermined limit, and G′, G″, and tan δ of the 25 mm diameter hydrated disks were measured as a function of frequency from 0.01-30 Hz at several temperatures (10, 25, 40 and 55° C.), all the while maintaining a vertical force of 10 N on the hydrogel disks. The individual frequency scans of G′ and tan δ were then combined to form master curves for each material. The data for the shear modulus G′ and tan δ of the hydrogels at a reference temperature of 25° C. are shown in tables 4 and 5. [0095]
  • The shear modulus of sample A was greater than B in the frequency range in which they were tested (as would be expected since the only difference between them is the molecular weight between crosslinks: 1000 vs. [0096]
  • 3000), and their shear moduli gradually increased with increasing frequency. At the high frequency extreme, sample A appeared to be approaching a transition, since the modulus appeared to be approaching a region of more rapid increase. [0097]
  • The tan δ of samples A and B were below 0.2 for the most part, with the tan δ of sample A increasing at the high frequencies in anticipation of a transition at higher frequencies. [0098]
  • Similarly, the shear modulus of sample D was greater than E in the frequency range in which they were tested (the only difference between them is the molecular weight of the dangling chains: 1000 vs. 5000), and their shear moduli gradually increased with increasing frequency. [0099]
  • The tan δ of samples D and E was below 0.1 for the entire frequency range in which they were tested, with the tan δ of sample E below that of sample D. [0100]
  • The shear modulus of sample C increased rapidly in the frequency range in which it was tested, indicating a transition from a rubbery to a more rigid state. The bulky TRIS moiety reduced the internal molecular mobility of the hydrogel (relative to the PDMS and mPDMS polymers), and caused the “glass” transition to shift to lower frequencies (=higher temperatures). [0101]
  • The tan δ of sample C reach d a maximum at 100 Hz at the reference temperature of 40° C., indicative of the transition. [0102]
  • The addition of mPDMS was more effective than, the addition of di-capped PDMS in reducing the tan δ of the hydrogel. The elastic properties of a material were controlled by the judicious addition of mPDMS while maintaining the homogeneity of the material. On the other hand, the addition of TRIS increased the tan δ of a material. [0103]
    TABLE 4
    Frequency G′ (Pa)
    (Hz) A B C D E
    30.0000 5.84E+05 2.89E+05 2.03E+06 3.41E+05 2.22E+05
    20.0000 5.70E+05 2.92E+05 1.81E+06 3.43E+05 2.24E+05
    15.0000 5.56E+05 2.92E+05 1.63E+06 3.42E+05 2.23E+05
    10.0000 5.37E+05 2.90E+05 1.42E+06 3.39E+05 2.24E+05
    9.0000 5.34E+05 2.89E+05 1.37E+06 3.37E+05 2.24E+05
    8.0000 5.27E+05 2.89E+05 1.35E+06 3.38E+05 2.24E+05
    6.9971 5.22E+05 2.88E+05 1.29E+06 3.38E+05 2.22E+05
    6.0000 5.16E+05 2.86E+05 1.22E+06 3.35E+05 2.22E+05
    5.0000 5.08E+05 2.85E+05 1.13E+06 3.34E+05 2.22E+05
    4.0000 4.96E+05 2.82E+05 1.07E+06 3.31E+05 2.20E+05
    3.0000 4.84E+05 2.81E+05 9.88E+05 3.28E+05 2.20E+05
    2.0000 4.74E+05 2.76E+05 8.49E+05 3.24E+05 2.20E+05
    1.5000 4.63E+05 2.73E+05 7.85E+05 3.21E+05 2.20E+05
    1.0000 4.48E+05 2.71E+05 6.96E+05 3.16E+05 2.19E+05
    0.9000 4.46E+05 2.70E+05 6.72E+05 3.18E+05 2.19E+05
    0.8000 4.43E+05 2.69E+05 6.62E+05 3.15E+05 2.17E+05
    0.7001 4.39E+05 2.68E+05 6.33E+05 3.12E+05 2.18E+05
    0.6000 4.35E+05 2.65E+05 6.07E+05 3.12E+05 2.18E+05
    0.5000 4.32E+05 2.65E+05 5.78E+05 3.10E+05 2.17E+05
    0.4000 4.25E+05 2.62E+05 5.48E+05 3.07E+05 2.16E+05
    0.3000 4.18E+05 2.60E+05 5.06E+05 3.06E+05 2.15E+05
    0.2000 4.07E+05 2.58E+05 4.59E+05 3.01E+05 2.14E+05
    0.1500 4.00E+05 2.56E+05 4.31E+05 2.99E+05 2.18E+05
    0.1000 3.91E+05 2.53E+05 3.93E+05 2.94E+05 2.12E+05
    0.0900 3.90E+05 2.54E+05 3.82E+05 2.94E+05 2.12E+05
    0.0800 3.86E+05 2.52E+05 3.75E+05 2.91E+05 2.13E+05
    0.0700 3.86E+05 2.52E+05 3.63E+05 2.90E+05 2.13E+05
    0.0600 3.83E+05 2.51E+05 3.52E+05 2.89E+05 2.12E+05
    0.0500 3.80E+05 2.50E+05 3.39E+05 2.87E+05 2.12E+05
    0.0400 3.75E+05 2.49E+05 3.27E+05 2.88E+05 2.13E+05
    0.0300 3.74E+05 2.49E+05 3.07E+05 2.83E+05 2.11E+05
    0.0200 3.64E+05 2.44E+05 2.87E+05 2.79E+05 2.09E+05
    0.0150 3.60E+05 2.44E+05 2.76E+05 2.75E+05 2.07E+05
    0.0100 3.53E+05 2.41E+05 2.58E+05 2.71E+05 2.08E+05
  • [0104]
    TABLE 5
    Frequency tan δ
    (Hz) A B C D E
    30.0000 0.2371 0.1084 0.5259 0.1025 0.0500
    20.0000 0.2107 0.0964 0.5392 0.0869 0.0394
    15.0000 0.1925 0.0917 0.5584 0.0767 0.0347
    10.0000 0.1804 0.0917 0.5664 0.0725 0.0326
    9.0000 0.1690 0.0877 0.5745 0.0671 0.0270
    8.0000 0.1622 0.0871 0.5540 0.0704 0.0290
    6.9971 0.1631 0.0876 0.5534 0.0702 0.0240
    6.0000 0.1594 0.0883 0.5381 0.0682 0.0298
    5.0000 0.1538 0.0872 0.5690 0.0656 0.0260
    4.0000 0.1471 0.0839 0.5568 0.0635 0.0284
    3.0000 0.1461 0.0879 0.5192 0.0633 0.0226
    2.0000 0.1472 0.0902 0.5352 0.0607 0.0240
    1.5000 0.1219 0.0892 0.5221 0.0654 0.0172
    1.0000 0.1199 0.0953 0.5070 0.0648 0.0259
    0.9000 0.1209 0.0915 0.4974 0.0553 0.0242
    0.8000 0.1294 0.0978 0.4892 0.0601 0.0267
    0.7001 0.1230 0.0898 0.4852 0.0647 0.0260
    0.6000 0.1160 0.0953 0.4742 0.0640 0.0310
    0.5000 0.1096 0.0939 0.4754 0.0664 0.0150
    0.4000 0.1133 0.0969 0.4641 0.0626 0.0254
    0.3000 0.1113 0.0976 0.4469 0.0651 0.0147
    0.2000 0.1083 0.1019 0.4256 0.0653 0.0270
    0.1500 0.1067 0.1047 0.4039 0.0699 0.0244
    0.1000 0.1039 0.1066 0.3895 0.0744 0.0277
    0.0900 0.1045 0.1084 0.3848 0.0761 0.0300
    0.0800 0.1042 0.1066 0.3831 0.0774 0.0234
    0.0700 0.0988 0.1076 0.3749 0.0709 0.0155
    0.0600 0.0969 0.1112 0.3705 0.0755 0.0262
    0.0500 0.1024 0.1137 0.3496 0.0765 0.0209
    0.0400 0.0887 0.1117 0.3349 0.0782 0.0257
    0.0300 0.0914 0.1160 0.3282 0.0830 0.0322
    0.0200 0.1060 0.1185 0.3248 0.0792 0.0241
    0.0150 0.1038 0.1270 0.2978 0.0753 0.0391
    0.0100 0.1038 0.1326 0.2800 0.0846 0.0285
  • Example 22 SEALs Study
  • A double masked, contralateral, randomized, complete block clinical study was conducted to determine the relationship between SEALs and the Young's modulus of contact lenses. Lenses were made from two different silicone hydrogel compositions as follows. [0105]
    TABLE 6
    Component Lens A (Wt %) Lens B(Wt %)
    Silicone based 17.98 17.98
    macromer
    TRIS 21 14
    mPDMS 21 28
    DMA 25.5 26
    blocked HEMA 5 5
    PVP K90 5 5
    TEGDMA 1.5 1
  • The silicone-based macromer refers to a prepolymer in which one mole was made from an average of 19.1 moles of 2-hydroxyethyl methacrylate, 2.8 moles of methyl methacrylate, 7.9 moles of methacryloxypropyltris(trimethylsiloxy)silane, and 3.3 moles of mono-methacryloxypropyl terminated mono-butyl terminated polydimethylsiloxane. The macromer was completed by reacting the aforementioned material with 2.0 moles per mole of 3-isopropenyl-ω,ω-dimethylbenzyl isocyanate using dibutyltin dilaurate as a catalyst. [0106]
  • Weight percentages are computed based on the total weight of all components; the balance of the compositions in Table 5 comprise initiators and additives. [0107]
  • Lenses were made from these compositions having a nominal base curve of 8.5 mm and a diameter of 14.0 mm at 22° C. They had a nominal center thickness of 0.110 mm and a measured center thickness of 0.119 mm (Lens A) and 0.085 mm (Lens B). Both lenses were coated with a hydrophilic coating (PAA as in Example 37). Lens A had a Young's modulus of 109.4 psi and Lens B had a Young's modulus of 88.5 psi. [0108]
  • Subjects participating in the study were given a baseline examination and fitted with lenses made from the compositions shown in Table 6. They then wore the lenses for one week. Lenses were wom for daily wear. The subjects returned for a clinical evaluation of the presence of SEALs and other clinical data (e.g. visual acuity). Nineteen subjects (38 eyes) completed the study, eight of whom had a history of SEALs. Ten (10) eyes wearing Lens A exhibited SEALs. No eyes wearing Lens B exhibited SEALs. [0109]
  • Example 23 SEALs Study
  • A study similar to that of Example 22 was conducted using lenses of different center thicknesses. The lenses had the following characteristics and gave the results shown in Table 7. In Table 7, column 4, “E” represents 20 Young's modulus and “CT” represents the center thickness. [0110]
    TABLE 7
    Modulus CT E(CT)2 SEALs
    Lens Type (psi) (μm) (psi · mm2) (%)
    Etafilcon 40 110 0.48 1
    Lens A* 110 124 1.69 10
    Lens B* 88 105 0.97 0
    Lens B* 88 170 2.54 24
    Lotrafilcon A 238 80 1.52 5
    Balafilcon A 155 90 1.26 5
  • This examples shows the combined effect of lens center thickness and modulus on SEALs. [0111]
  • Example 24 (Prophetic)
  • A set of lens characteristics is established for lenses that will not result in SEALs. This is accomplished by comparing the relative deflection (k(Et[0112] 2)−1, where k=constant, E=Young's modulus, and t=center thickness of lenses having different moduli with those of the moduli and thicknesses of the lenses of Example 22 that did not induce SEALs. This range is used to establish mPDMS concentration ranges that will result in lenses whose use will not induce SEALs.
    E (psi) Thickness (μm) [mPDMS] (wt %)*
    45 <149 40
    60 <129 30
    100 <100 20
    130 <88 5
  • Example 25 (GTP Macromer Preparation)
  • Macromer A: [0113]
  • To a dry container housed in a dry box under nitrogen at ambient temperature was added 30.0 g (0.277 mol) of bis(dimethylamino)methylsilane, a solution of 13.75 ml of a 1 M solution of TBACB (386.0 g TBACB in 1000 ml dry THF), 61.39 g (0.578 mol) of p-xylene, 154.28 g (1.541 mol) methyl methacrylate (1.4 equivalents relative to initiator), 1892.13 (9.352 mol) 2-(trimethylsiloxy)ethyl methacrylate (8.5 equivalents relative to initiator) and 4399.78 g (61.01 mol) of THF. To a dry, three-necked, round-bottomed flask equipped with a thermocouple and condenser, all connected to a nitrogen source, was charged the above mixture prepared in the dry box. [0114]
  • The reaction mixture was cooled to 15 C while stirring and purging with nitrogen. After the solution reaches 15° C., 191.75 g (1.100 mol) of 1-trimethylsiloxy-1-methoxy-2-methylpropene (1 equivalent) was injected into the reaction vessel. The reaction was allowed to exotherm to approximately 62° C. and then 30 ml of a 0.40 M solution of 154.4 g TBACB in 11 ml of dry THF was metered in throughout the remainder of the reaction. After the temperature of reaction reached 30° C. and the metering began, a solution of 467.56 g (2.311 mol) 2-(trimethylsiloxy)ethyl methacrylate (2.1 equivalents relative to the initiator), 3636.6 g (3.463 mol) n-butyl monomethacryloxypropyl-polydimethylsiloxane (3.2 equivalents relative to the initiator), 3673.84 g (8.689 mol) TRIS (7.9 equivalents relative to the initiator) and 20.0 g bis(dimethylamino)methylsilane was added. [0115]
  • The mixture was allowed to exotherm to approximately 38-42° C. and then allowed to cool to 30° C. At that time, a solution of 10.0 g (0.076 mol) bis(dimethylamino)methylsilane, 154.26 g (1.541 mol) methyl methacrylate (1.4 equivalents relative to the initiator) and 1892.13 g (9.352 mol) 2-trimethylsiloxy)ethyl methacrylate (8.5 equivalents relative to the initiator) was added and the mixture again allowed to exotherm to approximately 40° C. The reaction temperature dropped to approximately 30° C. and 2 gallons of THF were added to decrease the viscosity. A solution of 439.69 g water, 740.6 g methanol and 8.8 g (0.068 mol) dichloroacetic acid was added and the mixture refluxed for 4.5 hours to de-block the protecting groups on the HEMA. Volatiles were then removed and toluene added to aid in removal of the water until a vapor temperature of 110° C. was reached. [0116]
  • The reaction flask was maintained at approximately 110° C. and a solution of 443 g (2.201 mol) TMI and 5.7 g (0.010 mol) dibutyltin dilaurate were added. The mixture, was reacted until the isocyanate peak was gone by IR. The toluene was evaporated under reduced pressure to yield an off-white, anhydrous, waxy reactive monomer. The macromer was placed into acetone at a weight basis of approximately 2:1 acetone to macromer. After 24 hrs, water was added to precipitate out the macromer and the macromer was filtered and dried using a vacuum oven between 45 and 60° C. for 20-30 hrs. [0117]
  • Macromer B: [0118]
  • The procedure for Macromer A used except that 19.1 mole parts HEMA, 5.0 mole parts MM, 2.8 mole parts MMA; 7.9 mole parts TRIS, 3.3, mole parts mPDMS, and 2.0 mole parts TMI were used. [0119]
  • Macromer C: [0120]
  • The procedure for Macromer A was used except that 19.1 mole parts HEMA, 7.9 mole parts TRIS, 3.3 mole parts mPDMS, and 2.0 mole parts TMI were used. [0121]
  • Examples 26-36 (Lens Formation)
  • Hydrogel were made from the monomer mixtures shown on Table 8. All amounts are calculated as weight percent of the total weight of the combination with the balance of the mixture being minor amounts of additives. Polymerization was conducted in the presence of the diluents listed. [0122]
  • Contact lenses were formed by adding about 0.10 g of the monomer mix to the cavity of an eight cavity lens mold of the type described in U.S. Pat. No. 4,640,489 and curing for 1200 sec. Polymerization occurred under a nitrogen purge and was photoinitiated with visible light generated with a Philips TL 20W/03T fluorescent bulb. After curing, the molds were opened, and the lenses were either released in a 1:1 blend of water and ethanol, then leached in ethanol to remove any residual monomers and diluent, or released in a 60% IPA/water, then leached in IPA/DI to remove any residual monomers and diluent. Finally the lenses were equilibrated in physiological borate-buffered saline. The lenses had the properties described in Table 8 [0123]
    TABLE 8
    EXAMPLE
    26 27 28 29 30 31 32 33 34 35 36
    Macromer B A A C C A A A A A A
    Macromer 30.00 17.98 25.00 60.00 20.00 17.98 17.98 19.98 17.98 17.98 19.98
    TRIS 0.00 14.00 18.00 0.00 40.00 21.00 21.00 8.00 20.00 25.00 20.00
    DMA 27.00 26.00 28.00 36.00 36.00 25.50 25.50 26.00 22.00 9.00 23.00
    MPDMS 39.00 28.00 18.00 0.00 0.00 21.00 21.00 28.50 25.50 30.00 28.50
    Norbloc 2.00 2.00 2.00 3.00 3.00 2.00 2.00 2.00 2.00 2.00 2.00
    CGI 1850 2.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00
    TEGDMA 0.00 1.00 0.00 0.00 0.00 1.50 1.50 1.50 1.50 0.50 1.50
    HEMA 0.00 5.00 0.00 0.00 0.00 5.00 5.00 5.00 5.00 7.00 5.00
    Blue 0.00 0.02 0.00 0.00 0.00 0.02 0.02 0.02 0.02 0.02 0.02
    HEMA
    PVP (K90) 0.00 5.00 8.00 0.00 0.00 5.00 5.00 8.00 5.00 7.50 9.00
    Diluent % 41 20 20 20 None 20 50.00 37.50 20.00 40.00 50.00
    Diluent 3M3P *D3O 3M3P 3M3P NA D3O TAA 3M3P ethyl 3M3P 3M3P
    lactate
    % EWC 49.2 39.1 48.5 40.9 37.1
    Modulus 73 85.3 59 273 102
    (psi)
    % 200 251 261 74 384
    Elongation
    Dk (edge 109.4 109 97.9 34.5 79.8
    corrected)
  • Example 37
  • To lenses from Example 27 immersed in a solution of 1.0% 250,000 M[0124] w polyacrylic acid in water at 45° C. was added 0.1% 1-[3-(dimethylamino)propyl]-3-ethylcarbodiimide hydrochloride. After stirring for 30 minutes the lenses are rinsed in borate-buffered saline solution. The dynamic contact angles of the resulting poly(sodium acrylate)-coated lenses are 44° advancing and 42° receding.
  • Comparative Example 2
  • Lenses were made by curing a blend of 57.5% TRIS, 40.0% DMA, 1.5% 1,3-bis(3-methacryloxypropyl)tetrakis(trimethylsiloxy)disiloxane and 1.0% 2-hydroxy-2-methyl-1-phenyl-propan-1-one (by weight) in contact lens molds under UV light. The lenses were released into ethanol and transferred to borate-buffered saline solution. The lenses had properties given in Table 9, but when extended they returned to their original shape very slowly due to their high tan δ. In fact, even during ordinary lens handling, these lenses typically did not retain a their symmetrical shape. Further, they had less than desirable Dks and were very unwettable. [0125]
    TABLE 9
    Properties of Lenses From Comparative Example 2.
    Tensile Modulus 67
    (psi)
    Elongation at 674
    break (%)
    Water Content (%) 40.2
    Edge corrected Dk 70.2
    (barrers)

Claims (80)

We claim:
1. A method of lowering the Young's modulus or tan δ of a silicone hydrogel comprising the step of incorporating in said hydrogel, a mono-alkyl terminated polydimethylsiloxane monomer having the structure:
Figure US20040186248A1-20040923-C00009
where b=0 to 100; R58 is a monovalent group containing at least one ethylenically unsaturated moiety; R59 is independently a monovalent alkyl, or aryl group, which may be further substituted with alcohol, amine, ketone, carboxylic acid or ether group; R60 is a monovalent alkyl, or aryl group, which may be further substituted with alcohol, amine, ketone, carboxylic acid or ether groups; and R61 is independently alkyl or aromatic, or a monovalent siloxane chain comprising from 1 to 100 repeating Si—O units.
2. The method of claim 1, wherein b is about 4 to about 16, R58 is a monovalent group containing at least one styryl, vinyl, or methacrylate moiety, R59 is methyl, R60 is C3-8alkyl group, and R61 is methyl.
3. The method of claim 1, wherein b is about 8 to about 10, R58 is a monovalent group containing at least one styryl, vinyl, or methacrylate moiety, R59 is methyl, R60 is C3-8alkyl group, and R61 is methyl.
4. The method of claim 1, wherein b is about 4 to about 16, R58 is a methacrylate moiety; each R59 is methyl; and R60 is a butyl group.
5. The method of claim 1, wherein b is about 8 to about 10, R58 is a methacrylate moiety; each R59 is methyl, R60 is a butyl group, and R61 is methyl.
6. The method of claim 1, wherein about 2 to about 70% wt, based on the total weight of reactive monomer, of the mono-alkyl terminated polydimethylsiloxane is incorporated in said silicone hydrogel.
7. The method of claim 1, wherein about 4 to about 50% wt, based on the total weight of reactive monomer, of the mono-alkyl terminated polydimethylsiloxane is incorporated in said silicone hydrogel.
8. The method of claim 1, wherein about 8 to about 40% wt, based on the total weight of reactive monomer, of the mono-alkyl terminated polydimethylsiloxane is incorporated in said silicone hydrogel.
9. The method of claim 1, wherein said silicone hydrogel additionally comprises a silicone-containing monomer other than that of claim 1 and having the structure:
Figure US20040186248A1-20040923-C00010
wherein R51 is H, C1-5alkyl, or an ethylenically unsaturated moiety, q is 1, 2, or 3 and for each q, R52, R53 and R54 is independently an alkyl group, an aromatic group or a monovalent siloxane chain comprising from 1 to 100 repeating Si—O units, p is 1 to 10, r=(3−q), X is O or NR55, where R55 is H or a monovalent alkyl group with 1 to 4 carbons, a is 0 or 1, and L is a divalent linking group.
10. The method of claim 1, wherein said silicone hydrogel additionally comprises 3-methacryloxypropyltris (trimethylsiloxy) silane.
11. The method of claim 9, wherein each of R52, R53, and R54 is independently ethyl, methyl, benzyl or phenyl.
12. A silicone hydrogel having a Young's modulus of less than about 154 psi and a tan δ of equal to or less than about 0.3 at a frequency of 1 Hz at 25° C.
13. The silicone hydrogel of claim 12, wherein the Young's modulus is less than about 130 psi.
14. The silicone hydrogel of claim 12, wherein the Young's modulus is less than about 100 psi.
15. The silicone hydrogel of claim 12, wherein the Young's modulus is less than about 70 psi.
16. The silicone hydrogel of claim 12, wherein the Young's modulus is less than about 45 psi.
17. The silicone hydrogel of claim 12, further comprising an O2 Dk greater than about 40 barrer.
18. The silicone hydrogel of claim 12, 13, or 17, further comprising about 2-70% wt, based on the total weight of reactive monomer, of a mono-alkyl terminated polydimethylsiloxane having the structure:
Figure US20040186248A1-20040923-C00011
where b=0 to 100, where it is understood that b is a distribution having a mode equal to a stated value, preferably 8 to 10; R58 is a monovalent group containing at least one ethylenically unsaturated moiety, preferably a monovalent group containing a styryl, vinyl, or methacrylate moiety, more preferably a methacrylate moiety; each R59 is independently a monovalent alkyl, or aryl group, which may be further substituted with alcohol, amine, ketone, carboxylic acid or ether groups, preferably unsubstituted monovalent alkyl or aryl groups, more preferably methyl; R60 is a monovalent alkyl, or aryl group, which may be further substituted with alcohol, amine, ketone, carboxylic acid or ether groups, preferably unsubstituted monovalent alkyl or aryl groups, preferably a C1-10aliphatic or aromatic group which may include hetero atoms, more preferably C3-8alkyl groups, most preferably butyl, and R61 is independently alkyl or aromatic, preferably ethyl, methyl, benzyl, phenyl, or a monovalent siloxane chain comprising from 1 to 100 repeating Si—O units.
19. The silicone hydrogel of claim 18, wherein b=4 to 16, R58 is a monovalent group containing at least one styryl, vinyl, or methacrylate moiety, each R59 is methyl, R60 is a C3-8alkyl group, and R61 is methyl.
20. The silicone hydrogel of claim 18, wherein b=8 to 10, R58 is a methacrylate moiety; each R59 is methyl; R60 is a butyl group, and R61 is methyl.
21. The silicone hydrogel of claim 18, wherein the mono-alkyl terminated polydimethylsiloxane is a monomethacryloxypropyl terminated polydimethylsiloxane.
22. The silicone hydrogel of claim 18, having a Young's modulus of about 30-160 psi.
23. The silicone hydrogel of claim 18, having a Young's modulus of about 40-130 psi.
24. A contact lens comprising a silicone hydrogel having a Young's modulus less than about 180 psi and a tan δ of equal to or less than about 0.25 at a frequency of 1 Hz at 25° C.
25. The contact lens of claim 24, having a Young's modulus of less than about 100 psi.
26. The contact lens of claim 24, further comprising an O2 Dk greater than about 40 barrer.
27. The contact lens of claim 24, 25, or 26, further comprising about 2-70% wt, based on the total weight of reactive monomer, of a mono-alkyl terminated polydimethylsiloxane having the structure:
Figure US20040186248A1-20040923-C00012
where b=0 to 100, where it is understood that b is a distribution having a mode equal to a stated value, preferably 8 to 10; R58 is a monovalent group containing at least one ethylenically unsaturated moiety, preferably a monovalent group containing a styryl, vinyl, or methacrylate moiety, more preferably a methacrylate moiety; each R59 is independently a monovalent alkyl, or aryl group, which may be further substituted with alcohol, amine, ketone, carboxylic acid or ether groups, preferably unsubstituted monovalent alkyl or aryl groups, more preferably methyl; R60 is a monovalent alkyl, or aryl group, which may be further substituted with alcohol, amine, ketone, carboxylic acid or ether groups, preferably unsubstituted monovalent alkyl or aryl groups, preferably a C1-10aliphatic or aromatic group which may include hetero atoms, more preferably C3-8alkyl groups, most preferably butyl, and R61 is independently alkyl or aromatic, preferably ethyl, methyl, benzyl, phenyl, or a monovalent siloxane chain comprising from 1 to 100 repeating Si—O units.
28. The contact lens of claim 27, wherein b=4 to 16, R58 is a monovalent group containing at least one styryl, vinyl, or methacrylate moiety, each R59 is methyl, R60 is C3-8alkyl group, and R61 is methyl.
29. The contact lens of claim 27, wherein b=8 to 10, R58 is a methacrylate moiety; each R59 is methyl, R60 is a butyl group, and R61 is methyl.
30. The contact lens of claim 27, wherein the mono-alkyl terminated polydimethylsiloxane is a monomethacryloxypropyl terminated polydimethylsiloxane.
31. The contact lens of claim 27, wherein said silicone hydrogel has a Young's modulus of about 30-160 psi.
32. The contact lens of claim 27, wherein said silicone hydrogel has a Young's modulus of about 40-130 psi.
33. The contact lens of claim 27, further comprising a surface layer that is more hydrophilic than said silicone hydrogel.
34. The contact lens of claim 33, further comprising a coating that is more hydrophilic than said silicone hydrogel.
35. The contact lens of claim 33, wherein the surface layer comprises poly(acrylic acid).
36. A silicone hydrogel contact lens comprising a (CT) of about 50 to about 160 μm and a Young's modulus (E) of about 40 to about 300 pSi, wherein (E)(CT)2 is less than about 1 psi·mm2.
37. The silicone hydrogel contact lens of claim 36, further comprising a tan δ of equal to or less than about 0.3 at a frequency of 1 Hz at 25° C.
38. The silicone hydrogel contact lens of claim 36, further comprising a O2Dk greater than about 40 barrer.
39. The silicone hydrogel contact lens of claim 36, 37, or 38, further comprising at least 5% wt of a mono-alkyl terminated polydimethylsiloxane having the structure:
Figure US20040186248A1-20040923-C00013
where b=0 to 100; R58 is a monovalent group comprising at least one ethylenically unsaturated moiety; each R59 is independently a monovalent alkyl, or aryl group, which may be further substituted with alcohol, amine, ketone, carboxylic acid or ether groups; R60 is a monovalent alkyl, or aryl group, which may be further substituted with alcohol, amine, ketone, carboxylic acid or ether groups, and R61 is independently alkyl or aromatic, or a monovalent siloxane chain comprising from 1 to 100 repeating Si—O units.
40. The silicone hydrogel contact lens of claim 39, wherein b=4 to 16, R58 is a monovalent group containing at least one styryl, vinyl, or methacrylate moiety, each R59 is methyl, and R60 is C3-8alkyl group.
41. The silicone hydrogel contact lens of claim 39, wherein b=8 to 10, R58 is a methacrylate moiety; each R59 is methyl; R60 is a butyl group, and R61 is methyl.
42. The silicone hydrogel contact lens of claim 39, wherein the mono-alkyl terminated polydimethylsiloxane is a monomethacryloxypropyl terminated polydimethylsiloxane.
43. The silicone hydrogel contact lens of claim 39, wherein the center thickness is less than about 85 μm.
44. The silicone hydrogel contact lens of claim 39 wherein the thickness is less than about 100 μm and the Young's modulus is less than about 100 psi.
45. The silicone hydrogel contact lens of claim 39, wherein the amount of mono-alkyl terminated polydimethylsiloxane is about 20% wt.
46. The silicone hydrogel contact lens of claim 39, wherein the center thickness is less than 129 μm and the Young's modulus is less than about 60 psi.
47. The silicone hydrogel contact lens of claim 39, wherein the amount of mono-alkyl terminated polydimethylsiloxane is about 30% wt.
48. A method of making a polymer comprising preparing a silicone based macromer by Group Transfer Polymerization and reacting said macromer with a polymerization mixture comprising a mono-alkyl terminated polydimethylsiloxane monomer having the structure:
Figure US20040186248A1-20040923-C00014
where b=0 to 100; R58 is a monovalent group containing at least one ethylenically unsaturated moiety; R59 is independently a monovalent alkyl, or aryl group, which may be further substituted with alcohol, amine, ketone, carboxylic acid or ether group; R60 is a monovalent alkyl, or aryl group, which may be further substituted with alcohol, amine, ketone, carboxylic acid or ether groups; and R61 is independently alkyl or aromatic, or a monovalent siloxane chain comprising from 1 to 100 repeating Si—O units.
49. The method of claim 48 wherein said silicone based macromer comprises a mono-alkyl terminated polydimethylsiloxane monomer having the structure:
Figure US20040186248A1-20040923-C00015
where b=0 to 100; R58 is a monovalent group containing at least one ethylenically unsaturated moiety; R59 is independently a monovalent alkyl, or aryl group, which may be further substituted with alcohol, amine, ketone, carboxylic acid or ether group; R60 is a monovalent alkyl, or aryl group, which may be further substituted with alcohol, amine, ketone, carboxylic acid or ether groups; and R61 is independently alkyl or aromatic, or a monovalent siloxane chain comprising from 1 to 100 repeating Si—O units.
50. The method of claim 48 wherein said polymerizable mixture comprises Si8-10 monomethacryloxy terminated polydimethyl siloxane, a polydimethylsiloxane other than Si8-10 monomethacryloxy terminated polydimethyl siloxane, and a hydrophilic monomer.
51. The method of claim 48, wherein said macromer is the reaction product of a reaction mixture comprising 2-(trimethylsiloxy)ethyl methacrylate, methyl methacrylate, methacryloxypropyltris(trimethylsiloxy)silane, and mono-methacryloxypropyl terminated mono-butyl terminated polydimethylsiloxane.
52. The method of claim 48, wherein the macromer is functionalized with a free radical polymerizable group.
53. The method of claim 48, wherein the reaction mixture of claim 48 is treated with a catalyst and a molecule containing both an isocyanate group and a free radical polymerizable group.
54. The method of claim 53 wherein said catalyst comprises, tin, bismuth or a tertiary amine and said molecule containing both an isocyanate group and said free radical polymerizable group is dimethyl meta-isopropenyl benzyl isocyanate.
55. A macromer useful for making silicone hydrogels comprising a Group Transfer Polymerization product of a reaction mixture comprising 2-(trimethylsiloxy)ethyl methacrylate, methyl methacrylate, methacryloxypropyltris(trimethylsiloxy)silane, and mono-methacryloxypropyl terminated mono-butyl terminated polydimethylsiloxane.
56. The macromer of claim 55, wherein the Group Transfer Polymerization product reaction mixture comprises about 19.1 moles of 2-(trimethylsiloxy)ethyl methacrylate, about 2.8 moles of methyl methacrylate, about 7.9 moles of methacryloxypropyltris(trimethylsiloxy)silane, and about 3.3 moles of mono-methacryloxypropyl terminated mono-butyl terminated polydimethylsiloxane.
57. A silicone hydrogel comprising the reaction product of a silicone based macromer Group Transfer Polymerization product and a polymerizable mixture comprising Si8-10 monomethacryloxy terminated polydimethyl siloxane, a polydimethylsiloxane other than Si8-10 monomethacryloxy terminated polydimethyl siloxane, and a hydrophilic monomer.
58. The silicone hydrogel of claim 57, wherein the macromer is the Group Transfer Product of a reaction mixture 2-(trimethylsiloxy)ethyl methacrylate, methyl methacrylate, methacryloxypropyltris(trimethylsiloxy)silane, and mono-methacryloxypropyl terminated mono-butyl terminated polydimethylsiloxane.
59. The silicone hydrogel of claim 57, wherein the macromer is the Group Transfer Polymerization product of reaction mixture comprising about 19.1 moles of 2-(trimethylsiloxy)ethyl methacrylate, about 2.8 moles of methyl methacrylate, about 7.9 moles of methacryloxypropyltris(trimethylsiloxy)silane, and about 3.3 moles of mono-methacryloxypropyl terminated mono-butyl terminated polydimethylsiloxane
60. The silicone hydrogel of claim 57, 58, or 59 wherein the polymerizable mixture comprises Si8-10 monomethacryloxy terminated polydimethyl siloxane; methacryloxypropyl tris(trimethyl siloxy) silane; N,N-dimethyl acrylamide; 2-(trimethylsiloxy)ethyl methacrylate; and tetraethyleneglycol dimethacrylate.
61. The silicone hydrogel of claim 60, wherein the macromer is present in an amount of about 10 to about 60 wt percent, the Si8-10 monomethacryloxy terminated polydimethyl siloxane is present in an amount of about 0 to about 45 wt percent; the methacryloxypropyl tris(trimethyl siloxy) silane is present in an amount of about 0 to about 40 wt percent; the N,N-dimethyl acrylamide is present in an amount of about 5 to about 40 wt percent; the 2-hydroxy ethyl methacrylate is present in an amount of about 0 to about 10 wt percent; and the tetraethyleneglycol dimethacrylate is present in an amount of about 0 to about 5 wt percent.
62. The silicone hydrogel of claim 60, wherein the macromer is present in an amount of about 15 to about 25 wt percent, the Si8-10 monomethacryloxy terminated polydimethyl siloxane is present in an amount of about 20 to about 30 wt percent; the methacryloxypropyl tris(trimethyl siloxy) silane is present in an amount of about 15 to about 25 wt percent; the N,N-dimethyl acrylamide is present in an amount of about 20 to about 30 wt percent; the 2-hydroxy ethyl methacrylate is present in an amount of about 2 to about 7 wt percent; and the tetraethyleneglycol dimethacrylate is present in an amount of about 0 to about 5 wt percent.
63. The silicone hydrogel of claim 60, 61, or 62 wherein the polymerizable mixture further comprises poly(N-vinyl pyrrolidinone).
64. The silicone hydrogel of claim 61, wherein the polymerizable mixture further comprises about 0 to about 10 wt percent poly(N-vinyl pyrrolidinone).
65. The silicone hydrogel of claim 62, wherein the polymerizable mixture further comprises about 2 to about 7 wt percent poly(N-vinyl pyrrolidinone).
66. A contact lens comprising the reaction product of a silicone based macromer Group Transfer Polymerization product and a polymerizable mixture comprising Si8-10 monomethacryloxy terminated polydimethyl siloxane, a polydimethylsiloxane other than Si8-10 monomethacryloxy terminated polydimethyl siloxane, and a hydrophilic monomer.
67. The contact lens of claim 66, wherein the macromer is the Group Transfer Product of a reaction mixture, comprising 2-(trimethylsiloxy)ethyl methacrylate, methyl methacrylate, methacryloxypropyltris(trimethylsiloxy)silane, and mono-methacryloxypropyl terminated mono-butyl terminated polydimethylsiloxane.
68. The contact lens of claim 66, wherein the macromer is the Group Transfer Polymerization product of reaction mixture comprising about 19.1 moles of 2-(trimethylsiloxy)ethyl methacrylate, about 2.8 moles of methyl methacrylate, about 7.9 moles of methacryloxypropyltris(trimethylsiloxy)silane, and about 3.3 moles of mono-methacryloxypropyl terminated mono-butyl terminated polydimethylsiloxane
69. The contact lens of claim 66, 67, or 68 wherein the polymerizable mixture comprises Si8-10 monomethacryloxy terminated polydimethyl siloxane; methacryloxypropyl tris(trimethyl siloxy) silane; N,N-dimethyl acrylamide; 2-hydroxy ethyl methacrylate; and tetraethyleneglycol dimethacrylate.
70. The contact lens of claim 69, wherein the macromer is present in an amount of about 10 to about 60 wt percent, the Si5-10monomethacryloxy terminated polydimethyl siloxane is present in an amount of about 0 to about 45 wt percent; the methacryloxypropyl tris(trimethyl siloxy) silane is present in an amount of about 0 to about 40 wt percent; the N,N-dimethyl acrylamide is present in an amount of about 5 to about 40 wt percent; the 2-hydroxy ethyl methacrylate is present in an amount of about 0 to about 10 wt percent; and the tetraethyleneglycol dimethacrylate is present in an amount of about 0 to about 5 wt percent.
71. The contact lens of claim 69, wherein the macromer is present in an amount of about 15 to about 25 wt percent, the Si8-10 monomethacryloxy terminated polydimethyl siloxane is present in an amount of about 20 to about 30 wt percent; the methacryloxypropyl tris(trimethyl siloxy) silane is present in an amount of about 15 to about 25 wt percent; the N,N-dimethyl acrylamide is present in an amount of about 20 to about 30 wt percent; the 2-hydroxy ethyl methacrylate is present in an amount of about 2 to about 7 wt percent; and the tetraethyleneglycol dimethacrylate is present in an amount of about 0 to about 5 wt percent.
72. The contact lens of claim 69, wherein the polymerizable mixture further comprises poly(N-vinyl pyrrolidinone).
73. The contact lens of claim 70, wherein the polymerizable mixture further comprises about 0 to about 10 wt percent poly(N-vinyl pyrrolidinone).
74. The contact lens of claim 71, wherein the polymerizable mixture further comprises about 2 to about 7 wt percent poly(N-vinyl pyrrolidinone).
75. A method of lowering the Young's modulus and tan δ of a silicone hydrogel comprising the step of incorporating in said hydrogel, a mono-alkyl terminated polydimethylsiloxane monomer having the structure:
Figure US20040186248A1-20040923-C00016
where b=0 to 100; R58 is a monovalent group containing at least one ethylenically unsaturated moiety; R59 is independently a monovalent alkyl, or aryl group, which may be further substituted with alcohol, amine, ketone, carboxylic acid or ether group; R60 is a monovalent alkyl, or aryl group, which may be further substituted with alcohol, amine, ketone, carboxylic acid or ether groups; and R61 is independently alkyl or aromatic, or a monovalent siloxane chain comprising from 1 to 100 repeating Si—O units.
76. The method of claim 75, wherein said silicone hydrogel additionally comprises a silicone-containing monomer other than that of claim 1 and having the structure:
Figure US20040186248A1-20040923-C00017
wherein R51 is H, C1-5alkyl, or an ethylenically unsaturated moiety, q is 1, 2, or 3 and for each q, R52, R53 and R54 is independently an alkyl group, an aromatic group or a monovalent siloxane chain comprising from 1 to 100 repeating Si—O units, p is 1 to 10, r=(3−q), X is O or NR55, where R55 is H or a monovalent alkyl group with 1 to 4 carbons, a is 0 or 1, and L is a divalent linking group.
77. The method of claim 75, wherein said silicone hydrogel additionally comprises 3-methacryloxypropyltris (trimethylsiloxy) silane.
78. The method of claim 76, wherein each of R52, R53, and R54 is independently ethyl, methyl, benzyl or phenyl.
79. The method of claim 75 wherein Young's modulus is lowered to less than about 100 psi and tan δ of equal to or less than about 0.25 at a frequency of 1 Hz at 25° C.
80. The method of claim 75 wherein Young's modulus is lowered to less than about 80 psi and tan δ of equal to or less than about 0.25 at a frequency of 1 Hz at 25° C.
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Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1601723A2 (en) * 2003-03-07 2005-12-07 J &amp; J Vision Care, Inc. Diluents for forming clear, wettable silicone hydrogel articles
US20070291223A1 (en) * 2006-06-15 2007-12-20 Charlie Chen Wettable Silicone Hydrogel Contact Lenses and Related Compositions and Methods
US20070296914A1 (en) * 2006-06-15 2007-12-27 Ye Hong Wettable Silicone Hydrogel Contact Lenses and Related Compositions and Methods
US20080048350A1 (en) * 2006-06-15 2008-02-28 Charlie Chen Wettable Silicone Hydrogel Contact Lenses and Related Compositions and Methods
US20080094570A1 (en) * 2004-09-30 2008-04-24 Takehisa Kamiya Highly Oxygen-Permeable Hydrated Ocular Lens
US20090111905A1 (en) * 2007-10-31 2009-04-30 Ture Kindt-Larsen Process for forming random (meth)acrylate containing prepolymers
US20100120939A1 (en) * 2008-11-13 2010-05-13 John Christopher Phelan Silicone hydrogel materials with chemically bound wetting agents
US20100280146A1 (en) * 2002-09-06 2010-11-04 Vanderlaan Douglas C Forming clear, wettable silicone hydrogel articles without surface treatments
US7858000B2 (en) 2006-06-08 2010-12-28 Novartis Ag Method of making silicone hydrogel contact lenses
US8003710B2 (en) 2006-12-13 2011-08-23 Novartis Ag Production of ophthalmic devices based on photo-induced step growth polymerization
US8404783B2 (en) 2006-07-12 2013-03-26 Novartis Ag Polymers
US8557940B2 (en) 2010-07-30 2013-10-15 Novartis Ag Amphiphilic polysiloxane prepolymers and uses thereof
US8835525B2 (en) 2010-10-06 2014-09-16 Novartis Ag Chain-extended polysiloxane crosslinkers with dangling hydrophilic polymer chains
US8993651B2 (en) 2010-10-06 2015-03-31 Novartis Ag Polymerizable chain-extended polysiloxanes with pendant hydrophilic groups
US9187601B2 (en) 2010-10-06 2015-11-17 Novartis Ag Water-processable silicone-containing prepolymers and uses thereof
US20190049751A1 (en) * 2015-09-30 2019-02-14 Menicon Co., Ltd. Contact lens package and method for producing the same

Families Citing this family (122)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7052131B2 (en) * 2001-09-10 2006-05-30 J&J Vision Care, Inc. Biomedical devices containing internal wetting agents
US6822016B2 (en) 2001-09-10 2004-11-23 Johnson & Johnson Vision Care, Inc. Biomedical devices containing internal wetting agents
US6891010B2 (en) * 2001-10-29 2005-05-10 Bausch & Lomb Incorporated Silicone hydrogels based on vinyl carbonate endcapped fluorinated side chain polysiloxanes
DE10216608A1 (en) * 2002-04-15 2003-10-30 Wacker Polymer Systems Gmbh Extrudable, low-migration silicone organocopolymers with high transparency, their production and use
JP4708023B2 (en) * 2002-08-16 2011-06-22 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 Mold for contact lens manufacturing
US20070138692A1 (en) * 2002-09-06 2007-06-21 Ford James D Process for forming clear, wettable silicone hydrogel articles
EP2283877B1 (en) * 2002-12-23 2015-06-17 Johnson and Johnson Vision Care, Inc. Contact lens packages containing additives
US20060051454A1 (en) * 2004-08-26 2006-03-09 Ansell Scott F Molds for producing ophthalmic lenses
WO2006026474A2 (en) * 2004-08-27 2006-03-09 Asahikasei Aime Co. Ltd. Silicone hydrogel contact lenses
US9322958B2 (en) 2004-08-27 2016-04-26 Coopervision International Holding Company, Lp Silicone hydrogel contact lenses
US9804295B2 (en) * 2005-05-05 2017-10-31 Novartis Ag Ophthalmic devices for sustained delivery of active compounds
ATE526597T1 (en) 2005-08-09 2011-10-15 Coopervision Int Holding Co Lp MANUFACTURING PROCESS AND CONDITIONS FOR SILICONE HYDROGEL POLYMER CONTACT LENSES
US20070138670A1 (en) * 2005-12-20 2007-06-21 Bausch And Lomb Incorporated Method and Apparatus for the Dry Release of a Compliant Opthalmic Article from a Mold Surface
RU2008129775A (en) * 2005-12-20 2010-01-27 Джонсон Энд Джонсон Вижн Кэа, Инк. (Us) METHODS AND SYSTEMS FOR THE PROCESSING OF COMPLEX FORMED DEVICES PRODUCED FROM HYDROGELS
US8414804B2 (en) 2006-03-23 2013-04-09 Johnson & Johnson Vision Care, Inc. Process for making ophthalmic lenses
US7838698B2 (en) 2006-09-29 2010-11-23 Johnson & Johnson Vision Care, Inc. Hydrolysis-resistant silicone compounds
WO2008076736A2 (en) 2006-12-13 2008-06-26 Novartis Ag Actinically curable silicone hydrogel copolymers and uses thereof
MX2009010116A (en) * 2007-03-22 2009-10-12 Novartis Ag Prepolymers with dangling polysiloxane-containing polymer chains.
BRPI0809151A2 (en) * 2007-03-22 2014-09-16 Novartis Ag PREPOLYMERS CONTAINING SILICON WITH PENDING HYDROPHILIC POLYMER CHAINS
US7799888B2 (en) * 2007-04-27 2010-09-21 Gelest, Inc. Low molecular weight siloxanes with one functional group
US8044111B2 (en) 2007-11-30 2011-10-25 Novartis Ag Actinically-crosslinkable silicone-containing block copolymers
ATE552517T1 (en) * 2007-12-10 2012-04-15 Novartis Ag METHOD FOR PRODUCING SILICONE HYDROGEL CONTACT LENSES
US7802883B2 (en) 2007-12-20 2010-09-28 Johnson & Johnson Vision Care, Inc. Cosmetic contact lenses having a sparkle effect
US8470906B2 (en) 2008-09-30 2013-06-25 Johnson & Johnson Vision Care, Inc. Ionic silicone hydrogels having improved hydrolytic stability
US20130203812A1 (en) 2008-09-30 2013-08-08 Johnson & Johnson Vision Care, Inc. Ionic silicone hydrogels comprising pharmaceutical and/or nutriceutical components and having improved hydrolytic stability
EP2452212B1 (en) * 2009-07-09 2015-03-25 Bausch & Lomb Incorporated Mono ethylenically unsaturated polymerizable group containing polycarbosiloxane monomers
US7915323B2 (en) * 2009-07-09 2011-03-29 Bausch & Lamb Incorporated Mono ethylenically unsaturated polycarbosiloxane monomers
US8827447B2 (en) 2009-07-09 2014-09-09 Bausch & Lomb Incorporated Mono ethylenically unsaturated polymerizable group containing polycarbosiloxane monomers
US7994356B2 (en) * 2009-07-09 2011-08-09 Bausch & Lomb Incorporated Mono ethylenically unsaturated polycarbosiloxane monomers
US9039174B2 (en) 2009-07-09 2015-05-26 Bausch & Lomb Incorporated Ethylenically unsaturated polymerizable groups comprising polycarbosiloxane monomers
MY158359A (en) * 2009-09-15 2016-09-30 Novartis Ag Prepolymers suitable for making ultra-violet absorbing contact lenses
EP2480928B1 (en) * 2009-09-22 2017-01-25 CooperVision International Holding Company, LP Materials for use in ophthalmic applications and methods
HUE030443T2 (en) * 2009-10-01 2017-05-29 Coopervision Int Holding Co Lp Silicone hydrogel contact lenses and methods of making silicone hydrogel contact lenses
US8877103B2 (en) 2010-04-13 2014-11-04 Johnson & Johnson Vision Care, Inc. Process for manufacture of a thermochromic contact lens material
US8697770B2 (en) 2010-04-13 2014-04-15 Johnson & Johnson Vision Care, Inc. Pupil-only photochromic contact lenses displaying desirable optics and comfort
WO2011133408A2 (en) * 2010-04-23 2011-10-27 Henkel Corporation Silicone-acrylic copolymer
US11364695B2 (en) * 2010-07-30 2022-06-21 Alcon Inc. Silicone hydrogel lenses with water-rich surfaces
EP2638878B1 (en) * 2010-07-30 2019-10-23 Novartis AG Silicone hydrogel lenses with water-rich surfaces
MY161370A (en) 2011-02-28 2017-04-14 Coopervision Int Holding Co Lp Wettable silicon hydrogel contact lenses
SG192245A1 (en) 2011-02-28 2013-09-30 Coopervision Int Holding Co Lp Silicone hydrogel contact lenses
KR101743801B1 (en) 2011-02-28 2017-06-05 쿠퍼비젼 인터내셔날 홀딩 캄파니, 엘피 Silicone hydrogel contact lenses having acceptable levels of energy loss
TWI512355B (en) 2011-02-28 2015-12-11 Coopervision Int Holding Co Lp Silicone hydrogel contact lenses and related compositions and methods
EP2492718B1 (en) 2011-02-28 2014-01-08 CooperVision International Holding Company, LP Silicone Hydrogel Contact Lenses
KR101742351B1 (en) 2011-02-28 2017-05-31 쿠퍼비젼 인터내셔날 홀딩 캄파니, 엘피 Phosphine-containing hydrogel contact lenses
MY151110A (en) 2011-02-28 2014-04-15 Coopervision Int Holding Co Lp Dimensionally stable silicone hydrogel contact lenses
US9125808B2 (en) 2011-12-23 2015-09-08 Johnson & Johnson Vision Care, Inc. Ionic silicone hydrogels
US9156934B2 (en) 2011-12-23 2015-10-13 Johnson & Johnson Vision Care, Inc. Silicone hydrogels comprising n-vinyl amides and hydroxyalkyl (meth)acrylates or (meth)acrylamides
US8937111B2 (en) * 2011-12-23 2015-01-20 Johnson & Johnson Vision Care, Inc. Silicone hydrogels comprising desirable water content and oxygen permeability
US8937110B2 (en) 2011-12-23 2015-01-20 Johnson & Johnson Vision Care, Inc. Silicone hydrogels having a structure formed via controlled reaction kinetics
US9140825B2 (en) 2011-12-23 2015-09-22 Johnson & Johnson Vision Care, Inc. Ionic silicone hydrogels
US9588258B2 (en) 2011-12-23 2017-03-07 Johnson & Johnson Vision Care, Inc. Silicone hydrogels formed from zero diluent reactive mixtures
US10209534B2 (en) 2012-03-27 2019-02-19 Johnson & Johnson Vision Care, Inc. Increased stiffness center optic in soft contact lenses for astigmatism correction
US9423528B2 (en) 2012-06-25 2016-08-23 Johnson & Johnson Vision Care, Inc. Method of making silicone containing contact lens with reduced amount of diluents
US8937133B2 (en) 2012-09-25 2015-01-20 National Chiao Tung University Dissoluble PDMS-modified p(HEMA-MAA) amphiphilic copolymer and method for fabricating the same
TWI496838B (en) 2012-11-30 2015-08-21 Pegavision Corp Silicone hydrogel composition and silicone hydrogel contact lenses made of the composition
US9250357B2 (en) 2013-03-15 2016-02-02 Johnson & Johnson Vision Care, Inc. Silicone-containing contact lens having reduced amount of silicon on the surface
US20140268028A1 (en) 2013-03-15 2014-09-18 Johnson & Johnson Vision Care, Inc. Silicone-containing contact lens having clay treatment applied thereto
JP6351384B2 (en) * 2014-06-03 2018-07-04 株式会社メニコン Contact lens and manufacturing method thereof
JP6351385B2 (en) * 2014-06-03 2018-07-04 株式会社メニコン Contact lens manufacturing method
WO2015198919A1 (en) * 2014-06-27 2015-12-30 東レ株式会社 Silicone hydrogel, medical device, ocular lens and contact lens
GB2536410A (en) * 2015-03-06 2016-09-21 The Queen's Univ Of Belfast Coating composition and uses thereof
US10370476B2 (en) 2016-07-06 2019-08-06 Johnson & Johnson Vision Care, Inc. Silicone hydrogels comprising high levels of polyamides
RU2720005C1 (en) 2016-07-06 2020-04-23 Джонсон Энд Джонсон Вижн Кэа, Инк. Central optical zone of increased stiffness in soft contact lenses for astigmatism correction
US10371865B2 (en) 2016-07-06 2019-08-06 Johnson & Johnson Vision Care, Inc. Silicone hydrogels comprising polyamides
US11125916B2 (en) 2016-07-06 2021-09-21 Johnson & Johnson Vision Care, Inc. Silicone hydrogels comprising N-alkyl methacrylamides and contact lenses made thereof
US11021558B2 (en) 2016-08-05 2021-06-01 Johnson & Johnson Vision Care, Inc. Polymer compositions containing grafted polymeric networks and processes for their preparation and use
US10676575B2 (en) * 2016-10-06 2020-06-09 Johnson & Johnson Vision Care, Inc. Tri-block prepolymers and their use in silicone hydrogels
US10752720B2 (en) 2017-06-26 2020-08-25 Johnson & Johnson Vision Care, Inc. Polymerizable blockers of high energy light
US10723732B2 (en) 2017-06-30 2020-07-28 Johnson & Johnson Vision Care, Inc. Hydroxyphenyl phenanthrolines as polymerizable blockers of high energy light
US10526296B2 (en) 2017-06-30 2020-01-07 Johnson & Johnson Vision Care, Inc. Hydroxyphenyl naphthotriazoles as polymerizable blockers of high energy light
EP3724696A1 (en) 2017-12-13 2020-10-21 Alcon Inc. Weekly and monthly disposable water gradient contact lenses
US10961341B2 (en) 2018-01-30 2021-03-30 Johnson & Johnson Vision Care, Inc. Ophthalmic devices derived from grafted polymeric networks and processes for their preparation and use
US11034789B2 (en) 2018-01-30 2021-06-15 Johnson & Johnson Vision Care, Inc. Ophthalmic devices containing localized grafted networks and processes for their preparation and use
US10935695B2 (en) 2018-03-02 2021-03-02 Johnson & Johnson Vision Care, Inc. Polymerizable absorbers of UV and high energy visible light
US20210061934A1 (en) 2019-08-30 2021-03-04 Johnson & Johnson Vision Care, Inc. Contact lens displaying improved vision attributes
US10996491B2 (en) 2018-03-23 2021-05-04 Johnson & Johnson Vision Care, Inc. Ink composition for cosmetic contact lenses
US11046636B2 (en) 2018-06-29 2021-06-29 Johnson & Johnson Vision Care, Inc. Polymerizable absorbers of UV and high energy visible light
US10932902B2 (en) 2018-08-03 2021-03-02 Johnson & Johnson Vision Care, Inc. Dynamically tunable apodized multiple-focus opthalmic devices and methods
US20200073145A1 (en) 2018-09-05 2020-03-05 Johnson & Johnson Vision Care, Inc. Vision care kit
US11493668B2 (en) 2018-09-26 2022-11-08 Johnson & Johnson Vision Care, Inc. Polymerizable absorbers of UV and high energy visible light
US11724471B2 (en) 2019-03-28 2023-08-15 Johnson & Johnson Vision Care, Inc. Methods for the manufacture of photoabsorbing contact lenses and photoabsorbing contact lenses produced thereby
US11578176B2 (en) * 2019-06-24 2023-02-14 Johnson & Johnson Vision Care, Inc. Silicone hydrogel contact lenses having non-uniform morphology
US20200407324A1 (en) 2019-06-28 2020-12-31 Johnson & Johnson Vision Care, Inc. Polymerizable fused tricyclic compounds as absorbers of uv and visible light
US20200407337A1 (en) 2019-06-28 2020-12-31 Johnson & Johnson Vision Care, Inc. Photostable mimics of macular pigment
US20210003754A1 (en) 2019-07-02 2021-01-07 Johnson & Johnson Vision Care, Inc. Core-shell particles and methods of making and using thereof
US11543683B2 (en) 2019-08-30 2023-01-03 Johnson & Johnson Vision Care, Inc. Multifocal contact lens displaying improved vision attributes
US11891526B2 (en) 2019-09-12 2024-02-06 Johnson & Johnson Vision Care, Inc. Ink composition for cosmetic contact lenses
US11360240B2 (en) 2019-12-19 2022-06-14 Johnson & Johnson Vision Care, Inc. Contact lens containing photosensitive chromophore and package therefor
US20210301088A1 (en) 2020-03-18 2021-09-30 Johnson & Johnson Vision Care, Inc. Ophthalmic devices containing transition metal complexes as high energy visible light filters
CN111607043B (en) * 2020-05-22 2022-06-24 广州悦清再生医学科技有限公司 Contact lens material, preparation method thereof and contact lens
US11853013B2 (en) 2020-06-15 2023-12-26 Johnson & Johnson Vision Care, Inc. Systems and methods for indicating the time elapsed since the occurrence of a triggering event
US20210388141A1 (en) 2020-06-16 2021-12-16 Johnson & Johnson Vision Care, Inc. Imidazolium zwitterion polymerizable compounds and ophthalmic devices incorporating them
TW202225787A (en) 2020-09-14 2022-07-01 美商壯生和壯生視覺關懷公司 Single touch contact lens package
TW202231215A (en) 2020-09-14 2022-08-16 美商壯生和壯生視覺關懷公司 Single touch contact lens case
US20220113558A1 (en) 2020-10-13 2022-04-14 Johnson & Johnson Vision Care, Inc. Contact lens position and rotation control using the pressure of the eyelid margin
AU2021396636A1 (en) 2020-12-13 2023-01-19 Johnson & Johnson Vision Care, Inc. Contact lens packages and methods of opening
WO2022130089A1 (en) 2020-12-18 2022-06-23 Johnson & Johnson Vision Care, Inc. Photostable mimics of macular pigment
US20220220417A1 (en) 2021-01-12 2022-07-14 Johnson & Johnson Vision Care, Inc. Compositions for Ophthalmologic Devices
US20230037781A1 (en) 2021-06-30 2023-02-09 Johnson & Johnson Vision Care, Inc. Transition metal complexes as visible light absorbers
CA3173598A1 (en) 2021-09-13 2023-03-13 Johnson & Johnson Vision Care, Inc. Contact lens packages and methods of handling and manufacture
US11912800B2 (en) 2021-09-29 2024-02-27 Johnson & Johnson Vision Care, Inc. Amide-functionalized polymerization initiators and their use in the manufacture of ophthalmic lenses
WO2023052889A1 (en) 2021-09-29 2023-04-06 Johnson & Johnson Vision Care, Inc. Amide-functionalized polymerization initiators and their use in the manufacture of ophthalmic lenses
WO2023052890A1 (en) 2021-09-29 2023-04-06 Johnson & Johnson Vision Care, Inc. Anthraquinone-functionalized polymerization initiators and their use in the manufacture of ophthalmic lenses
US20230176251A1 (en) 2021-09-29 2023-06-08 Johnson & Johnson Vision Care, Inc. Ophthalmic lenses and their manufacture by in-mold modification
US11708209B2 (en) 2021-11-05 2023-07-25 Johnson & Johnson Vision Care, Inc. Touchless contact lens packages and methods of handling
WO2023105470A1 (en) 2021-12-08 2023-06-15 Johnson & Johnson Vision Care, Inc. Slotted contact lens packages and methods of handling
TW202335928A (en) 2021-12-08 2023-09-16 美商壯生和壯生視覺關懷公司 Contact lens packages having lens lifting arms and methods of handling
TW202340053A (en) 2021-12-13 2023-10-16 美商壯生和壯生視覺關懷公司 Contact lens packages with sliding or tilting lens transfer and methods of handling
WO2023111853A1 (en) 2021-12-14 2023-06-22 Johnson & Johnson Vision Care, Inc. Contact lens packages having twisting or thimble levers and methods of handling
WO2023111852A1 (en) 2021-12-15 2023-06-22 Johnson & Johnson Vision Care, Inc. No-touch contact lens packages and methods of handling
WO2023111851A1 (en) 2021-12-15 2023-06-22 Johnson & Johnson Vision Care, Inc. Solutionless contact lens packages and methods of manufacture
WO2023111939A1 (en) 2021-12-16 2023-06-22 Johnson & Johnson Vision Care, Inc. Pressurized or vacuum-sealed contact lens packages
TW202337347A (en) 2021-12-16 2023-10-01 美商壯生和壯生視覺關懷公司 No-touch contact lens packages and methods of handling
WO2023111943A1 (en) 2021-12-17 2023-06-22 Johnson & Johnson Vision Care, Inc. Contact lens packages having a pivot mechanism and methods of handling
WO2023111947A1 (en) 2021-12-17 2023-06-22 Johnson & Johnson Vision Care, Inc. Contact lens dispenser
US20230296807A1 (en) 2021-12-20 2023-09-21 Johnson & Johnson Vision Care, Inc. Contact lenses containing light absorbing regions and methods for their preparation
US20230350230A1 (en) 2022-04-28 2023-11-02 Johnson & Johnson Vision Care, Inc. Using particles for light filtering
US20230350099A1 (en) 2022-04-28 2023-11-02 Johnson & Johnson Vision Care, Inc. Shape engineering of particles to create a narrow spectral filter against a specific portion of the light spectrum
US20230348717A1 (en) 2022-04-28 2023-11-02 Johnson & Johnson Vision Care, Inc. Particle surface modification to increase compatibility and stability in hydrogels
US11733440B1 (en) 2022-04-28 2023-08-22 Johnson & Johnson Vision Care, Inc. Thermally stable nanoparticles and methods thereof
US20230348718A1 (en) 2022-04-28 2023-11-02 Johnson & Johnson Vision Care, Inc. Light-filtering materials for biomaterial integration and methods thereof
WO2023242688A1 (en) 2022-06-16 2023-12-21 Johnson & Johnson Vision Care, Inc. Ophthalmic devices containing photostable mimics of macular pigment and other visible light filters

Citations (91)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3408429A (en) * 1963-09-11 1968-10-29 Ceskoslovenska Akademie Ved Method for centrifugal casting a contact lens
US3660545A (en) * 1961-12-27 1972-05-02 Ceskoslovenska Akademie Ved Method of centrifugally casting thin edged corneal contact lenses
US3808178A (en) * 1972-06-16 1974-04-30 Polycon Laboratories Oxygen-permeable contact lens composition,methods and article of manufacture
US3854982A (en) * 1972-05-12 1974-12-17 Hydroplastics Inc Method for preparing hydrophilic polymer grafts including irradiation
US3916033A (en) * 1971-06-09 1975-10-28 High Voltage Engineering Corp Contact lens
US4113224A (en) * 1975-04-08 1978-09-12 Bausch & Lomb Incorporated Apparatus for forming optical lenses
US4136250A (en) * 1977-07-20 1979-01-23 Ciba-Geigy Corporation Polysiloxane hydrogels
US4139513A (en) * 1977-11-08 1979-02-13 Toyo Contact Lens Co., Ltd. Copolymer for soft contact lens, its preparation and soft contact lens made thereof
US4153641A (en) * 1977-07-25 1979-05-08 Bausch & Lomb Incorporated Polysiloxane composition and contact lens
US4182822A (en) * 1976-11-08 1980-01-08 Chang Sing Hsiung Hydrophilic, soft and oxygen permeable copolymer composition
US4189546A (en) * 1977-07-25 1980-02-19 Bausch & Lomb Incorporated Polysiloxane shaped article for use in biomedical applications
US4197266A (en) * 1974-05-06 1980-04-08 Bausch & Lomb Incorporated Method for forming optical lenses
US4246389A (en) * 1979-06-25 1981-01-20 American Optical Corporation Contact lens composition having increased oxygen permeability
US4254248A (en) * 1979-09-13 1981-03-03 Bausch & Lomb Incorporated Contact lens made from polymers of polysiloxane and polycyclic esters of acrylic acid or methacrylic acid
US4259467A (en) * 1979-12-10 1981-03-31 Bausch & Lomb Incorporated Hydrophilic contact lens made from polysiloxanes containing hydrophilic sidechains
US4260725A (en) * 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
US4261875A (en) * 1979-01-31 1981-04-14 American Optical Corporation Contact lenses containing hydrophilic silicone polymers
US4276402A (en) * 1979-09-13 1981-06-30 Bausch & Lomb Incorporated Polysiloxane/acrylic acid/polcyclic esters of methacrylic acid polymer contact lens
US4293397A (en) * 1979-02-23 1981-10-06 Shin-Etsu Chemical Co., Ltd. Photocurable organopolysiloxane compositions
US4327203A (en) * 1981-02-26 1982-04-27 Bausch & Lomb Incorporated Polysiloxane with cycloalkyl modifier composition and biomedical devices
US4341889A (en) * 1981-02-26 1982-07-27 Bausch & Lomb Incorporated Polysiloxane composition and biomedical devices
US4343927A (en) * 1976-11-08 1982-08-10 Chang Sing Hsiung Hydrophilic, soft and oxygen permeable copolymer compositions
US4355147A (en) * 1981-02-26 1982-10-19 Bausch & Lomb Incorporated Polysiloxane with polycyclic modifier composition and biomedical devices
US4414372A (en) * 1982-06-17 1983-11-08 E. I. Du Pont De Nemours & Co. Process for preparing living polymers
US4417034A (en) * 1981-06-30 1983-11-22 E. I. Du Pont De Nemours & Co. Living polymers and process for their preparation
US4486577A (en) * 1982-10-12 1984-12-04 Ciba-Geigy Corporation Strong, silicone containing polymers with high oxygen permeability
US4495313A (en) * 1981-04-30 1985-01-22 Mia Lens Production A/S Preparation of hydrogel for soft contact lens with water displaceable boric acid ester
US4508880A (en) * 1981-06-30 1985-04-02 E. I. Du Pont De Nemours And Company "Living" polymers and process for their preparation
US4543398A (en) * 1983-04-28 1985-09-24 Minnesota Mining And Manufacturing Company Ophthalmic devices fabricated from urethane acrylates of polysiloxane alcohols
US4588795A (en) * 1985-03-01 1986-05-13 E. I. Du Pont De Nemours And Company Oxyanion-catalyzed polymerization
US4598161A (en) * 1983-04-04 1986-07-01 E. I. Du Pont De Nemours And Company Tris(dialkylamino)sulfonium bifluoride catalysts
US4605716A (en) * 1985-02-14 1986-08-12 E. I. Du Pont De Nemours And Company Lewis base-catalyzed polymerization
US4605712A (en) * 1984-09-24 1986-08-12 Ciba-Geigy Corporation Unsaturated polysiloxanes and polymers thereof
US4622372A (en) * 1985-03-01 1986-11-11 E. I. Du Pont De Nemours And Company Polymer life enhancement in oxyanion-catalyzed polymerization
US4656233A (en) * 1984-11-29 1987-04-07 E. I. Du Pont De Nemours And Company "Living" polymers and chain transfer-regulated polymerization process
US4659783A (en) * 1984-07-05 1987-04-21 E. I. Du Pont De Nemours And Company Acrylic star polymers containing multifunctional monomers in the core
US4661575A (en) * 1982-01-25 1987-04-28 Hercules Incorporated Dicyclopentadiene polymer product
US4680336A (en) * 1984-11-21 1987-07-14 Vistakon, Inc. Method of forming shaped hydrogel articles
US4681918A (en) * 1981-06-30 1987-07-21 E. I. Du Pont De Nemours And Company "Living" polymers and process for their preparation
US4695607A (en) * 1984-07-05 1987-09-22 E. I. Du Pont De Nemours And Company Group transfer processes for acrylic star polymers
US4703097A (en) * 1986-04-10 1987-10-27 Bayer Aktiengesellschaft Optical contact objects
US4711942A (en) * 1983-11-07 1987-12-08 E. I. Du Pont De Nemours And Company "Living" polymers and process for their preparation
US4771116A (en) * 1987-04-30 1988-09-13 E. I. Du Pont De Nemours And Company Silylamines as additives in group transfer polymerization
US4786657A (en) * 1987-07-02 1988-11-22 Minnesota Mining And Manufacturing Company Polyurethanes and polyurethane/polyureas crosslinked using 2-glyceryl acrylate or 2-glyceryl methacrylate
US4837289A (en) * 1987-04-30 1989-06-06 Ciba-Geigy Corporation UV- and heat curable terminal polyvinyl functional macromers and polymers thereof
US4871785A (en) * 1986-08-13 1989-10-03 Michael Froix Clouding-resistant contact lens compositions
US4889664A (en) * 1988-11-25 1989-12-26 Vistakon, Inc. Method of forming shaped hydrogel articles including contact lenses
US4910277A (en) * 1988-02-09 1990-03-20 Bambury Ronald E Hydrophilic oxygen permeable polymers
US4920184A (en) * 1985-05-15 1990-04-24 Ciba-Geigy Corporation Hydrophilic silicone rubber article and process for its preparation
US4954586A (en) * 1989-01-17 1990-09-04 Menicon Co., Ltd Soft ocular lens material
US4954587A (en) * 1988-07-05 1990-09-04 Ciba-Geigy Corporation Dimethylacrylamide-copolymer hydrogels with high oxygen permeability
US5002794A (en) * 1989-08-31 1991-03-26 The Board Of Regents Of The University Of Washington Method of controlling the chemical structure of polymeric films by plasma
US5010141A (en) * 1989-10-25 1991-04-23 Ciba-Geigy Corporation Reactive silicone and/or fluorine containing hydrophilic prepolymers and polymers thereof
US5018849A (en) * 1988-11-16 1991-05-28 Ciba-Geigy Corporation Colored contact lens and methods of making the same
US5019634A (en) * 1988-02-16 1991-05-28 E. I. Du Pont De Nemours And Company Group transfer living polymer grafted to an initiator support
US5024524A (en) * 1989-08-11 1991-06-18 Raf Electronics Corp. Reflective image plane module
US5034461A (en) * 1989-06-07 1991-07-23 Bausch & Lomb Incorporated Novel prepolymers useful in biomedical devices
US5039459A (en) * 1988-11-25 1991-08-13 Johnson & Johnson Vision Products, Inc. Method of forming shaped hydrogel articles including contact lenses
US5057578A (en) * 1990-04-10 1991-10-15 E. I. Du Pont De Nemours And Company Silicone-containing block copolymers and macromonomers
US5070215A (en) * 1989-05-02 1991-12-03 Bausch & Lomb Incorporated Novel vinyl carbonate and vinyl carbamate contact lens material monomers
US5079319A (en) * 1989-10-25 1992-01-07 Ciba-Geigy Corporation Reactive silicone and/or fluorine containing hydrophilic prepolymers and polymers thereof
US5115056A (en) * 1989-06-20 1992-05-19 Ciba-Geigy Corporation Fluorine and/or silicone containing poly(alkylene-oxide)-block copolymers and contact lenses thereof
US5258490A (en) * 1987-12-14 1993-11-02 Chang Sing Hsiung Non-irritating soft gas permeable contact lens and process for producing same
US5260000A (en) * 1992-08-03 1993-11-09 Bausch & Lomb Incorporated Process for making silicone containing hydrogel lenses
US5314961A (en) * 1990-10-11 1994-05-24 Permeable Technologies, Inc. Silicone-containing polymers, compositions and improved oxygen permeable hydrophilic contact lenses
US5314960A (en) * 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
US5336797A (en) * 1992-12-30 1994-08-09 Bausch & Lomb Incorporated Siloxane macromonomers
US5346946A (en) * 1992-08-26 1994-09-13 Menicon Co., Ltd Ocular lens material
US5358995A (en) * 1992-05-15 1994-10-25 Bausch & Lomb Incorporated Surface wettable silicone hydrogels
US5371147A (en) * 1990-10-11 1994-12-06 Permeable Technologies, Inc. Silicone-containing acrylic star polymers, block copolymers and macromonomers
US5387662A (en) * 1993-02-12 1995-02-07 Bausch & Lomb Incorporated Fluorosilicone hydrogels
US5401508A (en) * 1992-01-15 1995-03-28 Allergan, Inc. Hydrogel compositions and structures made from same
US5451617A (en) * 1991-09-12 1995-09-19 Bausch & Lomb Incorporated Wettable silicone hydrogel compositions and methods for their manufacture
US5485479A (en) * 1990-11-07 1996-01-16 Fuji Electric Co., Ltd. Semiconductor laser device encapsulated in a transparent resin layer
US5486579A (en) * 1991-11-05 1996-01-23 Bausch & Lomb Incorporated Wettable silicone hydrogel compositions and methods for their manufacture
US5710302A (en) * 1995-12-07 1998-01-20 Bausch & Lomb Incorporated Monomeric units useful for reducing the modules of silicone hydrogels
US5714557A (en) * 1995-12-07 1998-02-03 Bausch & Lomb Incorporated Monomeric units useful for reducing the modulus of low water polymeric silicone compositions
US5760100A (en) * 1994-09-06 1998-06-02 Ciba Vision Corporation Extended wear ophthalmic lens
US5776999A (en) * 1994-09-06 1998-07-07 Ciba Vision Corporation Methods of using and screening extended wear ophthalmic lenses
US5779943A (en) * 1996-03-19 1998-07-14 Johnson & Johnson Vision Products, Inc. Molded polymeric object with wettable surface made from latent-hydrophilic monomers
US5807944A (en) * 1996-06-27 1998-09-15 Ciba Vision Corporation Amphiphilic, segmented copolymer of controlled morphology and ophthalmic devices including contact lenses made therefrom
US5944853A (en) * 1992-10-26 1999-08-31 Johnson & Johnson Vision Products, Inc. Method for preparing halotriazine dye- and vinyl sulfone dye-monomer compounds
US5958440A (en) * 1992-05-19 1999-09-28 Westaim Technologies, Inc. Anti-microbial materials
US5959117A (en) * 1998-08-10 1999-09-28 Bausch & Lomb Monomers useful for contact lens materials
US5962548A (en) * 1998-03-02 1999-10-05 Johnson & Johnson Vision Products, Inc. Silicone hydrogel polymers
US5981675A (en) * 1998-12-07 1999-11-09 Bausch & Lomb Incorporated Silicone-containing macromonomers and low water materials
US5981615A (en) * 1995-06-14 1999-11-09 Ciba Vision Corporation Polymerizable siloxane macromonomers
US6020445A (en) * 1997-10-09 2000-02-01 Johnson & Johnson Vision Products, Inc. Silicone hydrogel polymers
US6039913A (en) * 1998-08-27 2000-03-21 Novartis Ag Process for the manufacture of an ophthalmic molding
US6087415A (en) * 1998-06-11 2000-07-11 Johnson & Johnson Vision Care, Inc. Biomedical devices with hydrophilic coatings
US20030109637A1 (en) * 1999-07-27 2003-06-12 Bausch & Lomb Incorporated Contact lens material

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5262109A (en) 1975-11-18 1977-05-23 Kawasaki Steel Co Process for production of highhdensity metallic material and metallic powder filling container for its practice
US4321889A (en) 1981-01-05 1982-03-30 Michaelsen Marcus H Livestock loading device
US4495303A (en) 1983-11-29 1985-01-22 Mobil Oil Corporation Process for making zeolite ZSM-45 with a dimethyldiethylammonium directing agent
US4681575A (en) 1984-01-23 1987-07-21 Lewis Knox Method of chemical deodorization of articles and solutions used in medical and biological procedures
US5998498A (en) 1998-03-02 1999-12-07 Johnson & Johnson Vision Products, Inc. Soft contact lenses

Patent Citations (102)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3660545A (en) * 1961-12-27 1972-05-02 Ceskoslovenska Akademie Ved Method of centrifugally casting thin edged corneal contact lenses
US3408429A (en) * 1963-09-11 1968-10-29 Ceskoslovenska Akademie Ved Method for centrifugal casting a contact lens
US3916033A (en) * 1971-06-09 1975-10-28 High Voltage Engineering Corp Contact lens
US3854982A (en) * 1972-05-12 1974-12-17 Hydroplastics Inc Method for preparing hydrophilic polymer grafts including irradiation
US3808178A (en) * 1972-06-16 1974-04-30 Polycon Laboratories Oxygen-permeable contact lens composition,methods and article of manufacture
US4197266A (en) * 1974-05-06 1980-04-08 Bausch & Lomb Incorporated Method for forming optical lenses
US4113224A (en) * 1975-04-08 1978-09-12 Bausch & Lomb Incorporated Apparatus for forming optical lenses
US4343927A (en) * 1976-11-08 1982-08-10 Chang Sing Hsiung Hydrophilic, soft and oxygen permeable copolymer compositions
US4182822A (en) * 1976-11-08 1980-01-08 Chang Sing Hsiung Hydrophilic, soft and oxygen permeable copolymer composition
US4136250A (en) * 1977-07-20 1979-01-23 Ciba-Geigy Corporation Polysiloxane hydrogels
US4153641A (en) * 1977-07-25 1979-05-08 Bausch & Lomb Incorporated Polysiloxane composition and contact lens
US4189546A (en) * 1977-07-25 1980-02-19 Bausch & Lomb Incorporated Polysiloxane shaped article for use in biomedical applications
US4139513A (en) * 1977-11-08 1979-02-13 Toyo Contact Lens Co., Ltd. Copolymer for soft contact lens, its preparation and soft contact lens made thereof
US4261875A (en) * 1979-01-31 1981-04-14 American Optical Corporation Contact lenses containing hydrophilic silicone polymers
US4293397A (en) * 1979-02-23 1981-10-06 Shin-Etsu Chemical Co., Ltd. Photocurable organopolysiloxane compositions
US4246389A (en) * 1979-06-25 1981-01-20 American Optical Corporation Contact lens composition having increased oxygen permeability
US4276402A (en) * 1979-09-13 1981-06-30 Bausch & Lomb Incorporated Polysiloxane/acrylic acid/polcyclic esters of methacrylic acid polymer contact lens
US4254248A (en) * 1979-09-13 1981-03-03 Bausch & Lomb Incorporated Contact lens made from polymers of polysiloxane and polycyclic esters of acrylic acid or methacrylic acid
US4259467A (en) * 1979-12-10 1981-03-31 Bausch & Lomb Incorporated Hydrophilic contact lens made from polysiloxanes containing hydrophilic sidechains
US4260725A (en) * 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
US4327203A (en) * 1981-02-26 1982-04-27 Bausch & Lomb Incorporated Polysiloxane with cycloalkyl modifier composition and biomedical devices
US4341889A (en) * 1981-02-26 1982-07-27 Bausch & Lomb Incorporated Polysiloxane composition and biomedical devices
US4355147A (en) * 1981-02-26 1982-10-19 Bausch & Lomb Incorporated Polysiloxane with polycyclic modifier composition and biomedical devices
US4495313A (en) * 1981-04-30 1985-01-22 Mia Lens Production A/S Preparation of hydrogel for soft contact lens with water displaceable boric acid ester
US4417034A (en) * 1981-06-30 1983-11-22 E. I. Du Pont De Nemours & Co. Living polymers and process for their preparation
US4681918A (en) * 1981-06-30 1987-07-21 E. I. Du Pont De Nemours And Company "Living" polymers and process for their preparation
US4508880A (en) * 1981-06-30 1985-04-02 E. I. Du Pont De Nemours And Company "Living" polymers and process for their preparation
US4661575A (en) * 1982-01-25 1987-04-28 Hercules Incorporated Dicyclopentadiene polymer product
US4414372A (en) * 1982-06-17 1983-11-08 E. I. Du Pont De Nemours & Co. Process for preparing living polymers
US4524196A (en) * 1982-06-17 1985-06-18 E. I. Du Pont De Nemours And Company Process for preparing "living" polymers
US4581428A (en) * 1982-06-17 1986-04-08 E. I. Du Pont De Nemours And Company Process for preparing "living" polymers using tetracoordinate organosilicon, organotin or organogermanium polymerization initiator with bifluoride ion source co-catalyst
US4486577A (en) * 1982-10-12 1984-12-04 Ciba-Geigy Corporation Strong, silicone containing polymers with high oxygen permeability
US4598161A (en) * 1983-04-04 1986-07-01 E. I. Du Pont De Nemours And Company Tris(dialkylamino)sulfonium bifluoride catalysts
US4543398A (en) * 1983-04-28 1985-09-24 Minnesota Mining And Manufacturing Company Ophthalmic devices fabricated from urethane acrylates of polysiloxane alcohols
US4711942A (en) * 1983-11-07 1987-12-08 E. I. Du Pont De Nemours And Company "Living" polymers and process for their preparation
US4659783A (en) * 1984-07-05 1987-04-21 E. I. Du Pont De Nemours And Company Acrylic star polymers containing multifunctional monomers in the core
US4659782A (en) * 1984-07-05 1987-04-21 E. I. Du Pont De Nemours And Company Acrylic star polymers containing single-and multi-functional monomers in the core
US4695607A (en) * 1984-07-05 1987-09-22 E. I. Du Pont De Nemours And Company Group transfer processes for acrylic star polymers
US4605712A (en) * 1984-09-24 1986-08-12 Ciba-Geigy Corporation Unsaturated polysiloxanes and polymers thereof
US4680336A (en) * 1984-11-21 1987-07-14 Vistakon, Inc. Method of forming shaped hydrogel articles
US4656233A (en) * 1984-11-29 1987-04-07 E. I. Du Pont De Nemours And Company "Living" polymers and chain transfer-regulated polymerization process
US4605716A (en) * 1985-02-14 1986-08-12 E. I. Du Pont De Nemours And Company Lewis base-catalyzed polymerization
US4622372A (en) * 1985-03-01 1986-11-11 E. I. Du Pont De Nemours And Company Polymer life enhancement in oxyanion-catalyzed polymerization
US4588795A (en) * 1985-03-01 1986-05-13 E. I. Du Pont De Nemours And Company Oxyanion-catalyzed polymerization
US4920184A (en) * 1985-05-15 1990-04-24 Ciba-Geigy Corporation Hydrophilic silicone rubber article and process for its preparation
US4703097A (en) * 1986-04-10 1987-10-27 Bayer Aktiengesellschaft Optical contact objects
US4871785A (en) * 1986-08-13 1989-10-03 Michael Froix Clouding-resistant contact lens compositions
US4837289A (en) * 1987-04-30 1989-06-06 Ciba-Geigy Corporation UV- and heat curable terminal polyvinyl functional macromers and polymers thereof
US4771116A (en) * 1987-04-30 1988-09-13 E. I. Du Pont De Nemours And Company Silylamines as additives in group transfer polymerization
US4786657A (en) * 1987-07-02 1988-11-22 Minnesota Mining And Manufacturing Company Polyurethanes and polyurethane/polyureas crosslinked using 2-glyceryl acrylate or 2-glyceryl methacrylate
US5258490A (en) * 1987-12-14 1993-11-02 Chang Sing Hsiung Non-irritating soft gas permeable contact lens and process for producing same
US4910277A (en) * 1988-02-09 1990-03-20 Bambury Ronald E Hydrophilic oxygen permeable polymers
US5019634A (en) * 1988-02-16 1991-05-28 E. I. Du Pont De Nemours And Company Group transfer living polymer grafted to an initiator support
US4954587A (en) * 1988-07-05 1990-09-04 Ciba-Geigy Corporation Dimethylacrylamide-copolymer hydrogels with high oxygen permeability
US5018849A (en) * 1988-11-16 1991-05-28 Ciba-Geigy Corporation Colored contact lens and methods of making the same
US5039459A (en) * 1988-11-25 1991-08-13 Johnson & Johnson Vision Products, Inc. Method of forming shaped hydrogel articles including contact lenses
US4889664A (en) * 1988-11-25 1989-12-26 Vistakon, Inc. Method of forming shaped hydrogel articles including contact lenses
US4954586A (en) * 1989-01-17 1990-09-04 Menicon Co., Ltd Soft ocular lens material
US5070215A (en) * 1989-05-02 1991-12-03 Bausch & Lomb Incorporated Novel vinyl carbonate and vinyl carbamate contact lens material monomers
US5034461A (en) * 1989-06-07 1991-07-23 Bausch & Lomb Incorporated Novel prepolymers useful in biomedical devices
US5115056A (en) * 1989-06-20 1992-05-19 Ciba-Geigy Corporation Fluorine and/or silicone containing poly(alkylene-oxide)-block copolymers and contact lenses thereof
US5024524A (en) * 1989-08-11 1991-06-18 Raf Electronics Corp. Reflective image plane module
US5002794A (en) * 1989-08-31 1991-03-26 The Board Of Regents Of The University Of Washington Method of controlling the chemical structure of polymeric films by plasma
US5010141A (en) * 1989-10-25 1991-04-23 Ciba-Geigy Corporation Reactive silicone and/or fluorine containing hydrophilic prepolymers and polymers thereof
US5079319A (en) * 1989-10-25 1992-01-07 Ciba-Geigy Corporation Reactive silicone and/or fluorine containing hydrophilic prepolymers and polymers thereof
US5057578A (en) * 1990-04-10 1991-10-15 E. I. Du Pont De Nemours And Company Silicone-containing block copolymers and macromonomers
US5314960A (en) * 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
US5371147A (en) * 1990-10-11 1994-12-06 Permeable Technologies, Inc. Silicone-containing acrylic star polymers, block copolymers and macromonomers
US5314961A (en) * 1990-10-11 1994-05-24 Permeable Technologies, Inc. Silicone-containing polymers, compositions and improved oxygen permeable hydrophilic contact lenses
US5485479A (en) * 1990-11-07 1996-01-16 Fuji Electric Co., Ltd. Semiconductor laser device encapsulated in a transparent resin layer
US5451617A (en) * 1991-09-12 1995-09-19 Bausch & Lomb Incorporated Wettable silicone hydrogel compositions and methods for their manufacture
US5486579A (en) * 1991-11-05 1996-01-23 Bausch & Lomb Incorporated Wettable silicone hydrogel compositions and methods for their manufacture
US5401508A (en) * 1992-01-15 1995-03-28 Allergan, Inc. Hydrogel compositions and structures made from same
US5358995A (en) * 1992-05-15 1994-10-25 Bausch & Lomb Incorporated Surface wettable silicone hydrogels
US5387632A (en) * 1992-05-15 1995-02-07 Bausch & Lomb Incorporated Surface wettable silicone hydrogels
US5958440A (en) * 1992-05-19 1999-09-28 Westaim Technologies, Inc. Anti-microbial materials
US5260000A (en) * 1992-08-03 1993-11-09 Bausch & Lomb Incorporated Process for making silicone containing hydrogel lenses
US5346946A (en) * 1992-08-26 1994-09-13 Menicon Co., Ltd Ocular lens material
US5944853A (en) * 1992-10-26 1999-08-31 Johnson & Johnson Vision Products, Inc. Method for preparing halotriazine dye- and vinyl sulfone dye-monomer compounds
US5336797A (en) * 1992-12-30 1994-08-09 Bausch & Lomb Incorporated Siloxane macromonomers
US5387662A (en) * 1993-02-12 1995-02-07 Bausch & Lomb Incorporated Fluorosilicone hydrogels
US5539016A (en) * 1993-02-12 1996-07-23 Bausch & Lomb Incorporated Fluorosilicone hydrogels
US5789461A (en) * 1994-09-06 1998-08-04 Ciba Vision Corporation Methods of forming an extended wear ophthalmic lens having a hydrophilic surface
US5776999A (en) * 1994-09-06 1998-07-07 Ciba Vision Corporation Methods of using and screening extended wear ophthalmic lenses
US5760100A (en) * 1994-09-06 1998-06-02 Ciba Vision Corporation Extended wear ophthalmic lens
US5789461B1 (en) * 1994-09-06 2000-11-21 Ciba Vision Corp Methods of forming an extended wear ophthalmic lens having a hydrophilic surface
US5776999B1 (en) * 1994-09-06 2000-11-21 Ciba Vision Corp Methods of using and screening extended wear opthalmic lenses
US5965631A (en) * 1994-09-06 1999-10-12 Ciba Vision Corporation Extended wear ophthalmic lens
US5760100B1 (en) * 1994-09-06 2000-11-14 Ciba Vision Corp Extended wear ophthalmic lens
US5981615A (en) * 1995-06-14 1999-11-09 Ciba Vision Corporation Polymerizable siloxane macromonomers
US5908906A (en) * 1995-12-07 1999-06-01 Bausch & Lomb Incorporated Monomeric units useful for reducing the modulus of silicone hydrogels
US5714557A (en) * 1995-12-07 1998-02-03 Bausch & Lomb Incorporated Monomeric units useful for reducing the modulus of low water polymeric silicone compositions
US5710302A (en) * 1995-12-07 1998-01-20 Bausch & Lomb Incorporated Monomeric units useful for reducing the modules of silicone hydrogels
US5779943A (en) * 1996-03-19 1998-07-14 Johnson & Johnson Vision Products, Inc. Molded polymeric object with wettable surface made from latent-hydrophilic monomers
US5807944A (en) * 1996-06-27 1998-09-15 Ciba Vision Corporation Amphiphilic, segmented copolymer of controlled morphology and ophthalmic devices including contact lenses made therefrom
US6020445A (en) * 1997-10-09 2000-02-01 Johnson & Johnson Vision Products, Inc. Silicone hydrogel polymers
US5962548A (en) * 1998-03-02 1999-10-05 Johnson & Johnson Vision Products, Inc. Silicone hydrogel polymers
US6087415A (en) * 1998-06-11 2000-07-11 Johnson & Johnson Vision Care, Inc. Biomedical devices with hydrophilic coatings
US5959117A (en) * 1998-08-10 1999-09-28 Bausch & Lomb Monomers useful for contact lens materials
US6039913A (en) * 1998-08-27 2000-03-21 Novartis Ag Process for the manufacture of an ophthalmic molding
US5981675A (en) * 1998-12-07 1999-11-09 Bausch & Lomb Incorporated Silicone-containing macromonomers and low water materials
US20030109637A1 (en) * 1999-07-27 2003-06-12 Bausch & Lomb Incorporated Contact lens material

Cited By (39)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8158695B2 (en) 2002-09-06 2012-04-17 Johnson & Johnson Vision Care, Inc. Forming clear, wettable silicone hydrogel articles without surface treatments
US20100280146A1 (en) * 2002-09-06 2010-11-04 Vanderlaan Douglas C Forming clear, wettable silicone hydrogel articles without surface treatments
EP1601723A4 (en) * 2003-03-07 2007-06-20 Johson & Johnson Vision Care I Diluents for forming clear, wettable silicone hydrogel articles
EP1601723A2 (en) * 2003-03-07 2005-12-07 J &amp; J Vision Care, Inc. Diluents for forming clear, wettable silicone hydrogel articles
US7781536B2 (en) * 2004-09-30 2010-08-24 Seed Co., Ltd. Highly oxygen-permeable hydrated ocular lens
US20080094570A1 (en) * 2004-09-30 2008-04-24 Takehisa Kamiya Highly Oxygen-Permeable Hydrated Ocular Lens
US7858000B2 (en) 2006-06-08 2010-12-28 Novartis Ag Method of making silicone hydrogel contact lenses
US8231218B2 (en) * 2006-06-15 2012-07-31 Coopervision International Holding Company, Lp Wettable silicone hydrogel contact lenses and related compositions and methods
US8476337B2 (en) 2006-06-15 2013-07-02 Coopervision International Holding Company, Lp Wettable silicone hydrogel contact lenses and related compositions and methods
US7572841B2 (en) 2006-06-15 2009-08-11 Coopervision International Holding Company, Lp Wettable silicone hydrogel contact lenses and related compositions and methods
US9804417B2 (en) 2006-06-15 2017-10-31 Coopervision International Holding Company, Lp Wettable silicone hydrogel contact lenses and related compositions and methods
US9272473B2 (en) 2006-06-15 2016-03-01 Coopervision International Holding Company, Lp Wettable silicone hydrogel contact lenses and related compositions and methods
US8552085B2 (en) 2006-06-15 2013-10-08 Coopervision International Holding Company, Lp Wettable silicone hydrogel contact lenses and related compositions and methods
US7540609B2 (en) 2006-06-15 2009-06-02 Coopervision International Holding Company, Lp Wettable silicone hydrogel contact lenses and related compositions and methods
US20070291223A1 (en) * 2006-06-15 2007-12-20 Charlie Chen Wettable Silicone Hydrogel Contact Lenses and Related Compositions and Methods
US20080048350A1 (en) * 2006-06-15 2008-02-28 Charlie Chen Wettable Silicone Hydrogel Contact Lenses and Related Compositions and Methods
US20070296914A1 (en) * 2006-06-15 2007-12-27 Ye Hong Wettable Silicone Hydrogel Contact Lenses and Related Compositions and Methods
US8703875B2 (en) 2006-07-12 2014-04-22 Novartis Ag Polymers
US8404783B2 (en) 2006-07-12 2013-03-26 Novartis Ag Polymers
US8003710B2 (en) 2006-12-13 2011-08-23 Novartis Ag Production of ophthalmic devices based on photo-induced step growth polymerization
US8357771B2 (en) 2006-12-13 2013-01-22 Novartis Ag Production of ophthalmic devices based on photo-induced step growth polymerization
US8609745B2 (en) 2006-12-13 2013-12-17 Novartis Ag Production of ophthalmic devices based on photo-induced step growth polymerization
WO2009058207A1 (en) * 2007-10-31 2009-05-07 Johnson & Johnson Vision Care, Inc. Process for forming random (meth)acrylate containing prepolymers
US20090111905A1 (en) * 2007-10-31 2009-04-30 Ture Kindt-Larsen Process for forming random (meth)acrylate containing prepolymers
US8404759B2 (en) 2008-11-13 2013-03-26 Novartis Ag Silicone hydrogel materials with chemically bound wetting agents
WO2010056687A3 (en) * 2008-11-13 2010-07-22 Novartis Ag Silicone hydrogel materials with chemically bound wetting agents
WO2010056687A2 (en) * 2008-11-13 2010-05-20 Novartis Ag Silicone hydrogel materials with chemically bound wetting agents
US20100120939A1 (en) * 2008-11-13 2010-05-13 John Christopher Phelan Silicone hydrogel materials with chemically bound wetting agents
US8557940B2 (en) 2010-07-30 2013-10-15 Novartis Ag Amphiphilic polysiloxane prepolymers and uses thereof
US8987403B2 (en) 2010-07-30 2015-03-24 Novartis Ag Amphiphilic polysiloxane prepolymers and uses thereof
US9341744B2 (en) 2010-07-30 2016-05-17 Novartis Ag Amphiphilic polysiloxane prepolymers and uses thereof
US8835525B2 (en) 2010-10-06 2014-09-16 Novartis Ag Chain-extended polysiloxane crosslinkers with dangling hydrophilic polymer chains
US9187601B2 (en) 2010-10-06 2015-11-17 Novartis Ag Water-processable silicone-containing prepolymers and uses thereof
US9109091B2 (en) 2010-10-06 2015-08-18 Novartis Ag Polymerizable chain-extended polysiloxanes with pendant hydrophilic groups
US9052440B2 (en) 2010-10-06 2015-06-09 Novartis Ag Chain-extended polysiloxane crosslinkers with dangling hydrophilic polymer chains
US8993651B2 (en) 2010-10-06 2015-03-31 Novartis Ag Polymerizable chain-extended polysiloxanes with pendant hydrophilic groups
US9921340B2 (en) 2010-10-06 2018-03-20 Novartis Ag Water-processable silicone-containing prepolymers and uses thereof
US20190049751A1 (en) * 2015-09-30 2019-02-14 Menicon Co., Ltd. Contact lens package and method for producing the same
US11181753B2 (en) * 2015-09-30 2021-11-23 Menicon Co., Ltd. Contact lens package and method for producing the same

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