WO1995009878A1 - Compositions polymeres pouvant etre utilisees dans la fabrication de lentilles de contact - Google Patents

Compositions polymeres pouvant etre utilisees dans la fabrication de lentilles de contact Download PDF

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Publication number
WO1995009878A1
WO1995009878A1 PCT/US1994/011196 US9411196W WO9509878A1 WO 1995009878 A1 WO1995009878 A1 WO 1995009878A1 US 9411196 W US9411196 W US 9411196W WO 9509878 A1 WO9509878 A1 WO 9509878A1
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polymer composition
polymer
group
styrene
mol percent
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PCT/US1994/011196
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English (en)
Inventor
Nicholas T. Manesis
Patricia J. Fong
Gandhi Khushroo
Hermann Neidlinger
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Pilkington Barnes Hind, Inc.
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Priority to AU79266/94A priority Critical patent/AU7926694A/en
Publication of WO1995009878A1 publication Critical patent/WO1995009878A1/fr

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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G02B1/041—Lenses
    • G02B1/043—Contact lenses
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
    • C08F226/06—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
    • C08F226/10—N-Vinyl-pyrrolidone

Definitions

  • This invention is directed to polymer compositions t having properties particularly suited for use in the manufacture of ophthalmic devices, e.g., contact lenses, which compositions can also be used in other medical and non-medical devices.
  • this invention is directed to polymer 10 compositions comprising a vinyl amide monomer, a polysiloxanylalkyl acrylate or methacrylate monomer, a styrene and/or styrene related monomer, and a cross-linking agent.
  • copolymers such as hardness and strength, can be increased by copolymerizing the composition with a C, to C 20 ester of acrylic or methacrylic acid.
  • the tailoring of the amounts of components in a polymer for use as contact lenses requires a balancing of the amounts of each of the components so as to achieve overall requisite properties relating to hardness, oxygen permeability, water content, tensile strength, tear strength, and the like.
  • polymer compositions suitable for use as contact lenses are particularly critical characteristic of polymer compositions suitable for use as contact lenses.
  • the polymer contain sufficient hardness/strength to permit machining of the polymer composition into a contact lens.
  • a component can be included in the polymer composition to enhance the hardness/strength of the composition to suitable levels.
  • the added component does not so deleteriously affect other properties of the polymer composition as to render the polymer unsuitable for use as a contact lens.
  • polymer compositions which provide for more facile balancing of the desired properties are particularly desirable and especially those having enhanced hardness/strength so as to allow the polymer composition to be readily machined into contact lenses.
  • a polymer composition comprising a vinyl amide monomer, a polysiloxanylalkyl acrylate or methacrylate monomer, and styrene or a styrene related monomer provides the requisite balancing of properties for contact lenses relating to oxygen permeability, water content, tensile strength, tear strength, and the like while having sufficient hardness/strength so as to permit the composition to be machined into contact lenses.
  • a cross-linking agent is preferably employed in the polymer composition to enhance the rigidity or modulus of the composition. Accordingly, in one of its compositional aspects, this invention is directed to a polymer comprising:
  • R 1 , R 2 , and R 3 are independently selected from the group consisting of hydrogen and an alkyl group of from 1 to 4 carbon atoms
  • R 4 is selected from the group consisting of hydrogen and methyl
  • R 5 and R 6 are independently selected from the group consisting of hydrogen and an alkyl group of from 1 to 4 carbon atoms with the proviso that R 5 and R 6 are not both hydrogen;
  • X and Y are independently selected from the group consisting of alkyl substituents of from 1 to 4 carbon atoms, a phenyl substituent, and a substituent of the formula
  • A, B, C, A , B', and C are independently selected from the group consisting of alkyl substituents of from 1 to 4 carbon atoms and a phenyl substituent, R is selected from the group consisting of hydrogen and methyl, m and m' are independently integers of from 1 to 4, and n is an integer of from 1 to 5;
  • R I . 8 where R 7 is selected from the group consisting of phenyl and phenyl substituted with 1 to 3 alkyl substituents of from 1 to 6 carbon atoms and R 8 and R 9 are independently selected from the group consisting of hydrogen and methyl; and
  • this invention is directed to a hydrogel polymer composition which comprises the polymer composition described above and from about 10 to about 65 weight percent water based on the total weight of the polymer composition after hydration and preferably from about 10 to about 50 weight percent water.
  • compositions of this invention comprise a vinyl amide monomer, a polysiloxanylalkyl acrylate or methacrylate monomer, and a styrene or styrene related monomer.
  • the polymer compositions described herein further comprise a cross-linking agent.
  • cross-linking agent refers to a monomer containing at least two reactive groups capable of forming covalent linkages with functional groups found on at least one of the monomers used to prepare the polymer compositions described herein.
  • Suitable reactive groups include, for example, vinyl groups which can participate in the polymerization reaction.
  • the reactive groups are typically substituents on a suitable backbone such as a polyoxy lkylene backbone (including halogenated derivatives thereof) , a polyalkylene backbone, a glycol backbone, a glycerol backbone, a polyester backbone, a polyamide backbone, polyurea backbone, a polycarbonate backbone, and the like.
  • Cross-linking agents for use in the compositions described herein are well known in the art and the particular cross-linking agent employed is not critical.
  • the reactive vinyl group is attached to the backbone of the cross-linking agent via an ester bond such as that found in acrylate and methacrylate derivatives such as urethane diacrylate, urethane di ethacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, polyoxyethylene diacrylate, polyoxyethylene dimethacrylate, and the like.
  • suitable vinyl compounds include, by way of example, di- and higher- vinyl carbonates, di- and higher-vinyl amides (e.g. ,
  • cross-linking agents include, by way of example, ethylene glycol dimethacrylate, ethylene glycol diacrylate, diethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, triethylene glycol diacrylate, tetradecaethylene glycol dimethacrylate, tetradecaethylene glycol diacrylate, allyl methacrylate, allyl acrylate, trimethylol-propane trimethacrylate, trimethylolpropane triacrylate, 1,3-butanediol dimethacrylate, 1,3-butanediol diacrylate, l,4-butanediol dimethacrylate, 1,4- butanediol diacrylate, 1,6-hexanediol dimethacrylate, 1,6- hexanediol diol diacrylate, 1,6- hexanediol diol diacrylate, 1,6- he
  • the cross-linking agent preferably has at least 2 and more preferably from 2 to about 6 vinyl functionalities and preferably has a number average molecular weight of from about 100 to about 2,500. More preferably, the vinyl functionalities are acrylate or methacrylate groups attached to a polyoxyalkylene backbone (including halogenated derivatives thereof) , a polyalkylene backbone, a glycol backbone, a glycerol backbone, a polyester backbone, or a polycarbonate backbone.
  • hydrogel polymer composition refers to polymer compositions described herein which, after polymer formation, are hydratable when treated with water and, accordingly, can incorporate water into the polymeric matrix without itself dissolving in water.
  • water incorporation is effected by soaking the polymer cor ⁇ position in a water solution for a sufficient period so as to incorporate from about 10 to about 65 weight percent water, and preferably from about 10 to about 50 weight percent water, into the polymer composition based on the total weight of the polymer composition.
  • dry polymer composition refers to the composition formed in the absence of added water wherein any water in the polymer composition is typically due to water impurities present in one or more of the reagents used to prepare the polymer composition and such water is typically less than 1 weight percent of the total polymer composition and preferably less than 0.1 weight percent. Such compositions are also referred to as "xerogel polymer compositions”.
  • the polymeric compositions of this invention comprise at least three components; namely, a vinyl amide monomer, a polysiloxanylalkyl acrylate or methacrylate monomer, and a styrene or a styrene related monomer.
  • the polymeric compositions further comprise a cross-linking agent.
  • Vinyl amide monomers suitable for use herein are defined by the formula:
  • R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 are as defined above.
  • the preparation of each of these monomers is well known in the art and some of these monomers are commercially available.
  • Particularly suitable vinyl amide monomers for use in this invention include, by way of example, N,N-dimethyl acrylamide, N,N-dimethyl methacryla ide, and N-vinyl pyrrolidone. Mixtures of such vinyl amide monomers can also be used.
  • the vinyl amide monomer is employed at from about 30 to about 85 mol percent based on the total number of mols of all components found in the dry polymer composition, preferably from about 50 to about 85 mol percent, and more preferably, from about 65 to about 75 mol percent.
  • Polysiloxanylalkyl acrylate or methacrylate monomers suitable for use herein are defined by the formula
  • A, B, C, R, X, Y, m and n are as defined above.
  • the preparation of polysiloxanylalkyl acrylate or methacrylate monomers of the formula set forth above is described, for example, in U.S. Patent Nos. 3,808,178 and 4,182,822 the disclosures of which are incorporated herein by reference in their entirety. Several of these monomers are commercially available.
  • the polysiloxanylalkyl acrylate or methacrylate monomers are employed at from about 15 to about 45 mol percent based on the total number of mols of all components found in the dry polymer composition, preferably from about 15 to about 35 mol percent, and more preferably, from about 25 to about 30 mol percent. Mixtures of such esters can also be employed.
  • Suitable polysiloxanylalkyl acrylate and methacrylate monomers include, by way of example, tris(trimethylsiloxy) silylpropyl acrylate, tris(trimethylsiloxy) silylpropyl methacrylate, methylbis(trimethylsiloxy) silyljpropyl methacrylate, methylbis(trimethylsiloxy)silyl]propyl acrylate, tris(pentamethyldisiloxy) silyl]propyl acrylate, tris(pentamethyldisiloxy)silyl]propyl methacrylate, bis(trimethylsiloxy)mono(pentamethyldisiloxy)-silyl]propyl acrylate, bis(trimethylsiloxy)mono(pentamethyldisiloxy)-silyl]propyl methacrylate, mono(trimethylsiloxy)bis(pentamethyldisiloxy)-silyl]propyl acrylate, mono
  • Styrene and styrene related monomers suitable for use in this invention are selected from a compound of the formula:
  • the styrene or styrene related monomer is selected from styrene or styrene having from 1 to 3 alkyl substituents on the phenyl ring wherein each alkyl substituent is independently of from 1 to 6 carbon atoms. Still more preferably, the styrene component is selected from 4-t-butylstyrene and 2,4,6- trimethylstyrene. Mixtures of styrene and styrene related monomers can be used.
  • the styrene component is preferably employed in the polymer composition at from about 0.5 to about 15 mol percent based on the total number of mols of all components found in the dry polymer composition, preferably from about 1 to about 10 mol percent, and more preferably, from about 1 to about 5 mol percent.
  • the cross-linking agent is employed in the polymer composition at from about 0.1 to about 2 mol percent based on the total number of mols of components found in the dry polymer compositions.
  • the polymer composition of this invention can optionally contain additional components such as fluorinated alkyl acrylates having from 1 to 12 fluoro atoms and 4 to 12 carbon atoms (e.g., hexafluoroisopropyl methacrylate) , which is employed at from about 0.1 to about 2 mol percent based on the total number of mols of all components found in the dry polymer composition and preferably from about 0.1 to about 1 mol percent.
  • fluorinated alkyl acrylates having from 1 to 12 fluoro atoms and 4 to 12 carbon atoms (e.g., hexafluoroisopropyl methacrylate) , which is employed at from about 0.1 to about 2 mol percent based on the total number of mols of all components found in the dry polymer composition and preferably from about 0.1 to about 1 mol percent.
  • the mol percent of each of the vinyl amide monomer, the polysiloxanylalkyl acrylate or methacrylate monomer, the styrene or styrene related monomer and the cross-linking agent are selected so that the resulting polymer has a oxygen permeability as measured by a Dk value of greater than 60 [cm 3 (0 2 )cm]/[cm 2 sec cm Hg] ; a Shore D hardness of greater than 75; a modulus of greater than 3 Mdynes per square centimeter; a percent elongation of greater than 75%, a tear strength of greater than 3 grams per square millimeter, and an effective water concentration of from about 10 to about 65 weight percent.
  • the polymer compositions described herein are readily prepared from a mixture comprising requisite amounts of a vinyl amide monomer (or mixtures thereof) , a polysiloxanylalkyl acrylate or methacrylate monomer (or mixtures thereof) , a styrene or a styrene related monomer (or mixtures thereof) and a cross-linking agent.
  • the reagents employed are typically stored and formulated in containers which prevent premature polymerization of one or more of the reagents. For example, the use of amber bottles for storing reagents inhibits photo- induced polymerization.
  • thermal induced polymerization can be achieved by combining a suitable polymerization initiator into the mixture of monomers under an inert atmosphere (e.g., argon) and maintaining the mixture at an elevated temperature of from about 20°C to about 75°C for a period of time from about 1 to about 48 hours.
  • inert atmosphere e.g., argon
  • UV induced polymerization can be achieved by combining a suitable polymerization initiator into the mixture of monomers under an inert atmosphere (e.g., argon) and maintaining the mixture under a suitable UV source.
  • a suitable polymerization initiator e.g., argon
  • UV induced polymerization is conducted at ambient conditions for a period of from about 5 minutes to about 24 hours.
  • Suitable polymerization initiators are well known in the art including thermal initiators such as t-butyl peroxy pivalate (TBPP) , t-butyl peroxy neodecanoate (TBPN) , benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl peroxycarbonate and the like and UV initiators such as benzophenone, Darocur 1173 (available from Ciba Geigy, Ardsley, New York) and the like.
  • thermal or UV initiator employed is not critical and sufficient initiator is employed to catalyze the polymerization reaction.
  • the initiator is employed at up to about 1 weight percent based on the total weight of the composition.
  • Polymerization is typically conducted in a manner so as to facilitate manufacture of the finished contact lens.
  • polymerization can be conducted in molds which correspond to the structure of the contact lens.
  • polymerization can be conducted so as to form a polymer rod which can be machined (lathed) to provide contact lenses of suitable dimensions.
  • polymerization is conducted in a silylated glass test tube and after polymerization, the test tube is broken to provide for the polymeric rod.
  • a post-curing procedure is preferably employed to increase the hardness of the polymer.
  • the post-curing procedure can comprise heating the polymer to a temperature of from about 60°C to 120°C for a period of from about 2 to about 24 hours.
  • the post-curing procedure can comprise irradiation of the polymer composition with from 0.1 to about 3 MRads of gamma (7) rays.
  • the post-curing procedure can comprise both heating and 7 radiation of the polymer (i.e., first heating the polymer in the manner described above followed by 7 radiation or first 7 irradiating the polymer followed by heating) .
  • the contact lenses prepared from the polymer compositions described herein are then soaked in a water composition (e.g., a phosphate buffered saline solution) in order to incorporate water into the polymer composition. Soaking is continued until the polymer incorporates from about 10 to about 65 weight percent water based on the total weight of the polymer composition after hydration and preferably from about 20 to about 50 weight percent water. Because of the incorporation of this amount of water, the resulting polymer composition is referred to as a "hydrogel polymer composition".
  • a water composition e.g., a phosphate buffered saline solution
  • Hydration of the xerogel polymer composition is necessarily conducted after contact lens formation because the hydrogel composition lacks suitable physical characteristics, e.g., strength, to permit lathing, etc. of the composition necessary to provide for a contact lens.
  • the xerogel polymer compositions described herein are suitable for use in medical and non-medical applications such as water absorbent materials useful in a variety of applications. After water incorporation, the polymer compositions described herein are particularly suitable for use as contact lenses providing requisite water content, transparency, oxygen permeability, and mechanical properties.
  • Equilibrium Water Content is determined by soaking the polymer samples in phosphate buffered saline solution for overnight. The samples are removed, lightly blotted dry with a tissue and subsequently weighed. The hydrated samples are then placed in a vacuum oven at 100°C overnight. The next day, the sample is reweighed. Equilibrium Water Content is calculated using the following equation:
  • Linear Expansion factor is determined by measuring the diameter of the polymer sample using the Nikon Profile Projector V - 12 (available from Nippon Kogaku K.K., Tokyo, Japan) . The sample is then soaked overnight in phosphate buffered saline solution. The diameter is subsequently remeasured in phosphate buffered saline. Linear Expansion is calculated using the following equation:
  • the oxygen permeability of a contact lens is measured polarographically using a dissolved oxygen meter (available from Rosemont Analytical, Irvine, California, USA) .
  • This dissolved oxygen meter consists of a electrode probe which has a gold cathode. The gold cathode is covered with a thin Teflon membrane.
  • the probe is placed in a jacketed jar containing isotonic buffered saline.
  • the saline is kept at 35°C by hot water circulating through the outside jacket of the jar.
  • the saline is constantly stirred using a magnetic stirrer.
  • the probe is placed in the saline solution and allowed to equilibrate.
  • the reading on the dissolved oxygen meter should correspond to 6.7 ppm oxygen. If not the calibration knob is turned till it does so.
  • the probe is taken out of the saline and the contact lens or disc is placed flat on the tip of the probe.
  • the lens/disc is held against the Teflon membrane by a screw type device.
  • the probe is then inserted back into the saline and allowed to equilibrate. Once the dissolved oxygen meter has reached a constant reading, this reading is noted.
  • the lens or disc is then taken out and the average thickness of the lens/disc is measured.
  • the oxygen permeability is then calculated using conventional methodology.
  • buttons which are at least 5 mm thick and about 12 mm in diameter.
  • the buttons should have flat faces.
  • the button is placed on a rigid flat surface for measurement.
  • a calibrated Shore D durometer available from Pacific Transducer Corp., Los Angeles,
  • the durometer is placed on the flat face of the button and the durometer is lowered quickly till the flat face of the durometer meets the button surface. At this point, the durometer reading is taken. Usually, the durometer has a mechanism by which the maximum reading is recorded. This reading is then the Shore D hardness of the material.
  • the durometer is reset before the next measurement. An average of 5 readings is usually taken and reported.
  • a "dumb-bell" shaped specimen is cut.
  • the sample is inspected under a microscope for nicks and cuts. If these are observed the sample is discarded.
  • the thickness of the specimen is then measured.
  • the sample is then placed between the clamps on an
  • Instron tensile tester available from Intron Corp., Canton, Massachusetts, USA
  • the initial grip separation used is 10 mm.
  • the sample is placed under saline during measurement to prevent drying out.
  • the experiment is then started with the cross-head speed set to 5 mm/min.
  • the Instron records the force required to pull on the sample as a function of cross-head displacement. This information is then converted into a stress-strain plot. The experiment continues until the sample breaks. From the stress strain plot are calculated the following:
  • Tensile strength The maximum stress the sample can withstand before breaking.
  • Elongation The amount of extension (expressed as a percent of original length/grip separation) the sample undergoes before breaking.
  • the experiment is usually repeated with 5 samples from the same batch of polymer and the average and standard deviation are reported.
  • Each leg of the trouser is placed in each of the grips of an Instron testing machine (available from Instron Corp., Canton, Massachusetts, USA).
  • the initial grip separation used is 6 mm.
  • the experiment is started with the speed of cross-head movement set at 20 mm/min.
  • the Instron records the force required to tear the sample. Since an initial split has already been cut in the sample, the test measures the propagational tear strength.
  • the average force during tearing is calculated. This force when divided by the width and thickness of the sample gives the tear strength.
  • the preparation of the polymers of this invention in contact lens form involves polymerization of a formulation containing requisite amount of each of the monomers in a suitable mold. Initially, the formulation of monomers is prepared, the molds are then casted with the formulation and polymerization is initiated. Afterwards, the molds are decasted to provide for the polymer in lens form.
  • the preparation of a formulation containing such monomers employs amber bottles which were used to store the requisite amount of each of the monomers, cross-linking agent and the thermal initiator. After each of these reagents are weighed (to an accuracy of 0.001 grams), they are added to the amber bottle.
  • the bottle Upon completion of the addition of all of the reagents including the initiator, the bottle is sealed with a rubber stopper and an aluminum cap. The bottle is degassed with argon for at least 10 minutes. Afterwards, the bottle is placed in the freezer for storage prior to use.
  • the mold base curve is Corona treated for 0.45 seconds in air at a distance of 25 mm from the top of the mold base curve to the bottom of the Corona treatment ball and casting is accomplished by conventional techniques and the molds are processed by exposure to UV radiation for 10 minutes whereupon the molds are post-cured by heating to about 90°C for 3-24 hours (e.g., 3 hours or 24 hours). Upon cooling to room temperature the polymer composition is then de olded and are ready for physico-chemical analysis.
  • the test tube was fitted with a rubber septum and purged with Argon for 5 minutes.
  • Each sample was then polymerized in a water bath at 40°C to 45°C for approximately 24 hours.
  • the resulting polymer was post-cured by heating at 90° to 110°C for approximately 24 hours in a forced air oven. Afterwards, the rods were machined into buttons and disks for physico chemical analysis.
  • Examples 3-7 the curing conditions were 45°C for 24 hours and the post-curing conditions were 110°C for 24 hours; whereas in Examples 8-10, the curing conditions were 40°C for 24 hours and the post-curing conditions were 110°C for 24 hours. Additionally, in each of these examples, TBPP was used as the initiator (0.75 weight percent in Examples 3-7 and 0.50 weight percent in Examples 8-10 based on the total weight of the composition) . TABLE I
  • TMS 2,4,6-trimethylstyrene
  • DMA N,N-dimethylacrylamide
  • T-1 was obtained from Huls-America, Piscataway, New Jersey, USA
  • ethylene glycol dimethylacrylate was obtained from Esschem Co., Essington, Pennsylvania, USA
  • TBPP t-butyl peroxy pivalate
  • Oxygen permeability (Dk) is reported in [x 10" 10 cm3(02) cm]/[cm2 sec cm Hg]
  • the polymer compositions of Examples 3-7 were subjected to a post-curing procedure comprising heating the composition at a temperature of approximately 110°C for 24 hours.
  • a further post-cure procedure separate samples of these compositions were exposed to 1, 2, and 3 MRads of radiation.
  • the resulting compositions were then evaluated for their equilibrium water content (EWC) , linear expansion (LE) and Hardness (Shore D) and percent weight loss in methanol. This last evaluation is conducted for the purpose of determining the amount of extractables removed from the composition. Compositions having smaller amounts of extractables correspond to "harder" compositions.
  • Percent weight loss in methanol is determined by the following procedure. Preweighed dry polymer samples are placed in a Soxhlet extraction system using methanol as the solvent. Extraction is allowed to occur overnight. The next day, the samples are removed and placed in a vacuum oven at 50°C for 24 hours. The polymer materials are then reweighed. Weight loss values are determined using the following equation:
  • Table V below sets forth additional polymer compositions which were prepared in the manner similar to that described in Examples 1 and 2 above with the exceptions that in each of the examples, the curing conditions were 40°C for 24 hours and the post-curing conditions were 110°C for 24 hours. Additionally, in each of these examples, TBPP was used as the initiator (0.50 weight percent).
  • TMS 2,4,6-trimethylstyrene
  • DMA N,N-dimethylacrylamide
  • T-1 was obtained from Huls- America, Piscataway, New Jersey, USA
  • ethylene glycol dimethylacrylate was obtained from Esschem Co. , Essington, Pennsylvania, USA
  • TBPP t-butyl peroxy pivalate
  • Example 12 the polymer of Example 12 was evaluated for its tensile strength, percent elongation, modulus, tear strength, oxygen permeability, and hardness in the manner described above. The results of this evaluation are reported in Table VII below:
  • Oxygen permeability (Dk) is reported in [x 10 " '° cm3(02) cm]/[cm2 sec cm Hg]
  • Table VIII below sets forth additional polymer compositions which were prepared in the manner similar to that described in Example 1 above which composition was prepared in a mold so as to provide for a product in the shape of a contact lens with the exception that the curing conditions employed in this method involved exposure of the molds to UV radiation for 10 minutes followed by a post-cure procedure of heating the polymer composition at about 50°C for about 24 hours followed by further heating the composition at 90°C for about an additional 24 hrs.
  • 0.40 weight percent of VAZO 52 available from E.I. Dupont de Nemoures and Company, Wilmington, Delaware, USA
  • BME available from Aldrich Chemical Company, Milwaukee, Wisconsin, USA
  • TMS 2,4,6-trimethylstyrene
  • DMA 2,4,6-trimethyl-acrylamide
  • T-1 2,4,6-trimethyl-acrylamide
  • Oxygen permeability (Dk) is reported in [x 10 " '° cm3(02) cm]/[cm2 sec cm Hg]
  • compositions were prepared in a manner similar to Examples 1 and 2 above with the exceptions that in each of the examples, the curing conditions were about 40°C for 24 hours and the post-curing conditions were about 110°C for 24 hours. Additionally, in each of these examples, TBPP was used as the initiator (0.50 weight percent). Table XI sets forth the polymer compositions used in these examples:
  • TMS 2,4,6-trimethylstyrene
  • DMA 2,4,6-trimethyl-acrylamide
  • T-1 2,4,6-trimethyl-acrylamide
  • ethylene glycol dimethylacrylate were obtained as described above.
  • Each of the polymers of Examples 22-24 was evaluated for its oxygen permeability in the manner described above. The results of this evaluation are reported in Table XII below:
  • TBS 4-t-butylstyrene
  • DMA N,N-dimethylacrylamide
  • T-1 was obtained from Huls- America, Piscataway, New Jersey, USA
  • ethylene glycol dimethylacrylate was obtained from Esschem Co., Essington, Pennsylvania, USA.
  • Oxygen permeability (Dk) is reported in [x 10"'° cm3(02) cm]/[cm2 sec cm Hg]
  • Table XVI sets forth several polymer compositions which were prepared in the manner similar to that described in Example 1 above with the exceptions that in each of the examples, the curing conditions were UV exposure for 10 minutes followed by post-curing conditions of heating the polymer composition at 50°C for 24 hours and then at 90°C for an additional 24 hours. Additionally, in each of these examples, 0.40 weight percent of BME (available from Aldrich Chemical Company, Milwaukee, Wisconsin, USA) and 0.40 weight percent of VAZO 52 (available from E.I. Dupont de Nemoures and Company, Wilmington, Delaware, USA) were used as the initiator.
  • BME available from Aldrich Chemical Company, Milwaukee, Wisconsin, USA
  • VAZO 52 available from E.I. Dupont de Nemoures and Company, Wilmington, Delaware, USA
  • TMS 2,4,6-trimethylstyrene
  • DMA N,N-dimethylacrylamide
  • T-1 was obtained from Huls- America, Piscataway, New Jersey, USA
  • ethylene glycol dimethylacrylate was obtained from Esschem Co. , Essington, Pennsylvania, USA.
  • Oxygen permeability (Dk) is reported in [x 10 " '° cm3(02) cm]/[cm2 sec cm Hg]

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Abstract

Compositions polymères qui comprennent un monomère de vinylamide, un monomère de méthacrylate ou d'acrylate de polysiloxanylalkyle, un monomère de styrène et/ou apparenté à un styrène et un agent de réticulation. Lesdites compositions polymères peuvent contenir d'environ 10 à environ 65 pour cent en poids d'eau et sont utiles dans la fabrication de lentilles de contact.
PCT/US1994/011196 1993-10-05 1994-10-04 Compositions polymeres pouvant etre utilisees dans la fabrication de lentilles de contact WO1995009878A1 (fr)

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AU79266/94A AU7926694A (en) 1993-10-05 1994-10-04 Polymer compositions suitable for use as contact lens

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US13137493A 1993-10-05 1993-10-05
US08/131,374 1993-10-05

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WO1995009878A1 true WO1995009878A1 (fr) 1995-04-13

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PCT/US1994/011196 WO1995009878A1 (fr) 1993-10-05 1994-10-04 Compositions polymeres pouvant etre utilisees dans la fabrication de lentilles de contact

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009073321A1 (fr) 2007-12-03 2009-06-11 Bausch & Lomb Incorporated Hydrogels de silicone à teneur élevée en eau
US9507172B2 (en) 1998-03-02 2016-11-29 Johnson & Johnson Vision Care, Inc. Contact lenses

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4182822A (en) * 1976-11-08 1980-01-08 Chang Sing Hsiung Hydrophilic, soft and oxygen permeable copolymer composition
US4661573A (en) * 1986-04-14 1987-04-28 Paragon Optical Inc. Lens composition articles and method of manufacture

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4182822A (en) * 1976-11-08 1980-01-08 Chang Sing Hsiung Hydrophilic, soft and oxygen permeable copolymer composition
US4661573A (en) * 1986-04-14 1987-04-28 Paragon Optical Inc. Lens composition articles and method of manufacture

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9507172B2 (en) 1998-03-02 2016-11-29 Johnson & Johnson Vision Care, Inc. Contact lenses
WO2009073321A1 (fr) 2007-12-03 2009-06-11 Bausch & Lomb Incorporated Hydrogels de silicone à teneur élevée en eau
US7934830B2 (en) 2007-12-03 2011-05-03 Bausch & Lomb Incorporated High water content silicone hydrogels
EP2397505A1 (fr) * 2007-12-03 2011-12-21 Bausch & Lomb Incorporated Hydrogels de silicone à teneur élevée en eau

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