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WO2000037971A1 - Articles pour verres de contact fabriques a partir de comonomeres perfluores - Google Patents

Articles pour verres de contact fabriques a partir de comonomeres perfluores Download PDF

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Publication number
WO2000037971A1
WO2000037971A1 PCT/US1999/028144 US9928144W WO0037971A1 WO 2000037971 A1 WO2000037971 A1 WO 2000037971A1 US 9928144 W US9928144 W US 9928144W WO 0037971 A1 WO0037971 A1 WO 0037971A1
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Prior art keywords
contact lens
lens
article
copolymer
perfluoro
Prior art date
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Ceased
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PCT/US1999/028144
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English (en)
Inventor
Joseph C. Salamone
James A. Bonafini, Jr.
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Bausch and Lomb Inc
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Bausch and Lomb Inc
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Publication date
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Priority to AU19248/00A priority Critical patent/AU1924800A/en
Publication of WO2000037971A1 publication Critical patent/WO2000037971A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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

Definitions

  • fluoropolymers in the class generally regarded as fluoroplastics, including amorphous fluoropolymers exhibiting optical transparency.
  • these conventional polymers have been developed to be stable at high temperature and resistant to chemical attack, with the degree of stability and inertness increasing with fluorine content in the molecule.
  • the physical and chemical properties of known fluoropolymers are highly desirable for many purposes, they are relatively difficult to manufacture and hence relatively expensive compared to other polymer materials. Their inertness makes them an unlikely choice for a biocompatible material.
  • highly fluorinated polymers especially those containing perfluorinated monomers, would not be a likely candidate for a contact lens to be made by finely controlled lathing and to be worn in the eye for an extended period of time.
  • the amorphous copolymers of PDD and TFE have certain properties that provide them with potential in a number of applications.
  • Representative examples include, in the electronics field, high-density integrated circuits (dielectric layers), packaging material, passivation coatings, encapsulation, and lithography; in the optical field, lens covers, optical fibers, coatings, UN-transmission devices, radar devices, and anti-reflective coatings; in the biomedical field, thin film membranes, biocompatible coatings, optical sensors, and integrated optics; and in the chemical industry, protective coatings, process sight glass, high-performance parts and non-stick surface-releasing agents.
  • U.S. Patent 5,147,417 to ⁇ emser discloses a membrane formed from an amorphous polymer of PDD (perfluoro-2,2-dimethyl-l,3-dioxole), the membrane exhibiting an oxygen-nitrogen selectivity of at least 1.4:1.
  • the membrane is part of an automotive air intake system for a mobile combustion engine.
  • the membrane preferably has an oxygen flux in excess of 100 Barrers, especially in excess of 500 Barrers.
  • the air intake system provides either oxygen-enriched air or oxygen-depleted air for the engine, depending on the mode of operation of the engine.
  • RGP rigid-gas-permeable contact lenses
  • high-Dk RGP materials have been commercially made from silicone-contaming monomers such as disclosed in U.S. Patent ⁇ os. 4,152,508; 4,330,383; 4,686,267; 4,826,889; 4,826,936; 4,861,850; 4,996,275; and 5,346,976.
  • the art has recognized that introducing fluorine-containing groups into contact lens polymers can increase oxygen-permeability. For example, U.S. Patent No. 4,996,275 to Ellis, et al.
  • U.S. Patent No. 3,389,012 to Hamm discloses a contact lens characterized by a modified edge portion surrounding a centrally located optical portion.
  • the modification of the lens comprises a coating formed on the interior surface of the lens in the edge portion thereof, which coating comprises a tetrafluoroethylene polymer, specifically a Teflon® (TFE) coating.
  • TFE Teflon®
  • U.S. Patent No. Re 29,299 to Girard et al. and US Patent No. 3,944,347 discloses contact lens made from copolymers and terpolymers of perfluoro-2-methylene-4-methyl- 1,3-dioxlane, referred to as PMD.
  • the copolymers of PMD and tetrafluoroethylene provide materials which are said to be especially suitable in that they exhibit refractive indices in the desired range, are characterized by good clarity and an absence of color and haze; further, they exhibit good hardness properties and permeability to oxygen and carbon dioxide, thus increasing the nutrition of the cornea.
  • a copolymer containing 92 parts by weight of tetrafluoroethylene with eight parts by weight of PMD is characterized by an index of refraction of 1.349, a Knoop hardness of 4.9, and a molding temperature of 350°C.
  • the patent states that copolymers of PMD and tetrafluoroethylene are characterized by optimum indices of refraction, since the optimum index, that of human tears, is 1.336.
  • contact lens materials with such a low index of refraction have not been commercialized, because they may be impractical or require thicker lenses to achieve the same refractive correction as lenses with a higher index of refraction. A thicker lens may be less comfortable or negate the improved oxygen-transmissibility of the lens material.
  • the aforementioned highly fluorinated polymers have not been able to compete with the more economical, more easily designed and manufactured, more biocompatible materials on the market for use in RGP contact lenses.
  • fluoropolymers may be able to provide improved oxygen transmissibility or other desirable properties.
  • New polymers are sought which not only provide improved oxygen transmissibility, but which provide an acceptable and advantageous combination of other contact lens properties, including biocompatibility and a sufficiently high modulus or rigidity, to mask corneal astigmatism, that would allow economic manufacture into the final lens design.
  • a further object of the invention is to provide an ophthalmic lens capable of extended, continuous wear periods of at least 24 hours without substantial adverse impact on the cornea, and more preferably, to provide a lens capable of continuous wear for about one week to about thirty days or more without unacceptable corneal swelling or other adverse effects.
  • the present invention involves a high-Dk, fluoropolymeric contact lens article, including both contact lenses and the buttons from which contact lenses are produced.
  • the subject copolymer for use in a high-Dk, rigid-gas-permeable contact lens is made from certain perfluorinated cyclic monomers.
  • the present invention further includes methods for making the contact lenses from such copolymers and for rendering the surface biocompatible with eye tissue.
  • An advantage of the subject invention is that the above-described material not only can improve the oxygen transmissibility of the resulting contact lens, but can be injection molded and/or lathed from buttons or other blanks of the molded material.
  • the present invention is related to a high-Dk fluoropolymeric contact lens or a precursor article.
  • article as used herein is intended to include lenses and buttons or blanks from which contact lenses are produced by lathing.
  • button as used herein refers to stock material from which lens surfaces are cut by way of a lathe.
  • the improved contact lens compositions are achieved through incorporation of certain perfluorinated, heterocyclic comonomers in extended-wear or specialty rigid, gas- permeable (RGP) contact lenses.
  • Contact lenses made from such comonomers have been found amenable to lathing for economic manufacture.
  • a highly advantageous combination of high oxygen transmissibility, optical transparency, and acceptable flexural modulus of has been found for forming a contact lens.
  • lens design results in a sufficiently thin series of lenses.
  • treatment of the finally-shaped lens has been successfully accomplished to render the surface of the lens wettable and biocompatible in the eye.
  • modulus will be understood to herein refer to the flexural modulus of the material.
  • the RGP material has a relatively high modulus, ranging from about 1000 to 2500, preferably 1200 to 2400 megapascals (MPa). It is more preferable to provide lenses having moduli in the range of about 1400 to about 2200, and most preferably from about 1600 to about 1900 MPa .
  • the modulus of a lens material can have a significant impact upon lens comfort. Lenses possessing too high a moduli or stiffness will tend to be brittle, whereas lenses possessing too low a moduli or stiffness will have too much lens flexure on the eye, thus not masking astigmatism.
  • gas- permeable refers specifically to the oxygen permeability through the lens from the atmosphere to the cornea.
  • RGP materials applicable to the present invention suitably have an oxygen-permeability (Dk) that is suitably 100 to 1200 Barrers, preferably 200 to 1000 Barrers, more preferably 200 to 500 Barrers.
  • Dk oxygen-permeability
  • the oxygen-permeability Dk of a lens material does not depend on lens thickness.
  • the oxygen-permeability is the rate at which oxygen will pass through a material.
  • a Barrer is defined as: ((cm 3 oxygen)(mm)/(cm 2 )(sec)(mm Hg))xl0 "10 or, alternatively, ((cm 3 oxygen)(cm)/(cm 2 )(sec)(mm Hg))xlO "u
  • the oxygen transmissibility of a lens is the rate at which oxygen will pass through a specific lens.
  • Oxygen transmissibility, Dk/t is conventionally expressed in units of Barrers/mm, where t is the average thickness of the material (in units of mm) over the area being measured.
  • a lens having a Dk of 90 Barrers (oxygen-permeability barrers) and a thickness of 90 microns (0.090 mm) would have a Dk/t or 100 Barrers/mm (oxygen transmissibility Barrers/mm).
  • Contact lens materials with high refractive indices are desirable from a lens design standpoint. Additionally, a high refractive index material is preferred when constructing certain types of lenses such as a segmented bifocal lens.
  • the copolymers of PDD and tetrafluorethylene provide materials that exhibit refractive indices less than 1.40, as for example, in the range of about 1.32.
  • the relatively low refractive index of Teflon AF makes it advantageous for use in cladding for optical fibers in which the greatest difference in refractive index between the cladding and the optical fiber is advantageous for keeping light within the optical fiber.
  • an index of refraction of 1.336 that of tears, may be ideal in terms of biocompatibility, higher values are generally used in order to provide the desired refractive lenses with a relatively thin lens.
  • the relatively low refractive index of PDD can, in fact, be adequately compensated by lens design, for example, a steeper curve in the lens at the anterior surface thereof, such that unduly or disadvantageously thick lenses generally can be avoided.
  • contact lens according to the invention capable of providing refractive correction with a diopter range of-20.00D to +20.00D.
  • the contact lens of the invention can be made by a variety of methods known to those skilled in the art, particularly in light of the versatile processability of the perfluorodioxole polymers. These methods include molding into a form such as a rod, button, or other, preferably cylindrical, shape.
  • the copolymer of the present invention after first being molded and/or cut into a button or the like, can be lathed. It has been found that amorphous copolymers of monomer (I) have the necessary mechanical stability, rigidity/modulus, and response to cutting motion to be lathed, preferably normal or conventional lathing at ambient temperatures.
  • the material of the present invention is polymerized from a monomer mix including 20 to 75 mole percent, and more preferably from about 30 to about 50 mole percent of monomers represented by Formula I. Below 20 mole percent, the composition tends to become cloudy and about 75 mole percent, the modulus tends to become too low for a contact lens. A higher modulus, tending to more resistant to flexing, is necessary to mask an astigmatism of the eye.
  • TFE tetrafluorethylene
  • CTFE chlorotrifluoroethylene
  • PAVE ⁇ erfluoro(alkyl vinyl) ethers
  • suitable comonomers include but are not limited to perfluoro(alkyl vinyl ethers) such as perfluoro(methyl vinyl ether), perfluoro(ethyl vinyl ether), and perfluoro( «-propyl vinyl ether).
  • Other ethers include, for example, methyl perfluoro(3,6- dioxa-4-methyl-8-nonenoate), further referred to as EVE, represented by the following formula:
  • CF 2 CFOCF 2 CFOCF 2 CF 2 COOCH 3
  • PSEPVE perfluoro(4-methyl-3,6-dioxa-7-octenyl) sulfonyl fluoride
  • CF 2 CFOCF 2 CFOCF 2 CF 2 SO 2 F
  • TFE is made in large quantities by E.I. du Pont de Nemours and Company; other suitable representative monomers are available from the following sources: vinylidene difluoride, chlorotrifluoroethylene (CTFE), hexafluoropropylene (HFP), vinyl fluoride, and trifluoroethylene from SCM Specialty Chemicals, Gainesville, Fla.; perfluoro(methyl vinyl ether) (PMVE), and perfluoro(propyl vinyl ether) (PPVE) can be made as described in U.S. Pat. No. 3,1810,8950; (EVE) can be made as described in U.S.
  • PDD is described in the above-mentioned U.S. Pat. No. 3,978,030.
  • Other suitable comonomers are functional fluorovinyl ethers having the general formula:
  • CF 2 CF — [OCF 2 CF(CF 3 )] m — O- ⁇ CF 2 ) n — (CH 2 ) p — O— COR
  • CF 2 CF — [OCF 2 CF(CF 3 )] m — 0- ⁇ CF 2 ) n - ⁇ CH 2 ) p -OH
  • This reaction can be conducted in glassware, for example, at atmospheric pressure and at cool temperatures such as 0°-25°C, preferably 5°-15°C.
  • the product (IV) can be isolated from the reaction mass by conventional means.
  • the polymers of the invention contain units derived from functional fluorovinyl ether monomers having the general formula:
  • CF 2 CF — [OCF 2 CF(CF 3 )] m — O-(CF 2 ) n -COOR
  • (VI) but which may require post-polymerization esterification because of partial hydrolysis of COOR during aqueous polymerization.
  • the esterification can be carried out by treatment of the polymer; for example, with trimethyl orthoformate.
  • Caboxylic and sulfonic acid derivatives of the above monomers may also be used to from a copolymerization compatible mixture.
  • TFE is an especially preferred comonomer, either alone or with other fluoromonomers, especially such a polymer with the above-indicated proportion of perfluoro-2,2-dimethyl-l,3-dioxole.
  • Teflon AF may be represented by the following formula:
  • Teflon AF The glass transition temperature of Teflon AF depends on its composition: T g decreases with increasing content of TFE.
  • T g decreases with increasing content of TFE.
  • ⁇ MR nuclear resonance
  • Teflon AF polymer properties suggest the presence of "microvoids," or considerable free volume in the Teflon AF polymer structure. This has been substantiated by position annihilation lifetime experiments.
  • the amorphous polymer preferably has a glass transition temperature of at least 110° C, and more preferably at least 140°C.
  • Glass transition temperature (T g ) is known in the art and is the temperature at which the polymer changes from a brittle, vitreous or glassy state to a rubbery or plastic state. Examples of such copolymers are described in further detail in the U.S. Pat. No. 4,754,009 to Squire.
  • the glass transition temperature of the .amorphous polymer will vary with the actual polymer, especially the amount of tetrafluoroethylene or other comonomers that may be present.
  • T g are shown in FIG. 1 of the aforementioned U.S. Pat. No. 4,754,009 to Squire as ranging from about 260° C for copolymers with tetrafluoroethylene having low amounts of tetrafluoroethylene comonomer, down to less than 100° C for the copolymers containing at least 60 mole % of tetrafluoroethylene.
  • the addition of other comonomers may also function to decrease T g or to provide other desirable properties, such as modulus or hydrophilicity to increase surface wetting.
  • T g glass transition temperature
  • the perfluoropolymers of the present invention can be processed by several methods. Polymerization can be achieved using free radical polymerization initiators commonly used in polymerizing unsaturated compounds known in the art. Representative polymerization initiators include 2,2-azobis(isobutyronitrile) (AIBN); 2,2'-azobis(2,4-di-methylvaleronitrile) (ADVN); l,l-azobis(cyanocyclohexane) and 2,2'- azobis(2-methylbutyronitrile).
  • AIBN 2,2-azobis(isobutyronitrile)
  • ADVN 2,2'-azobis(2,4-di-methylvaleronitrile)
  • l,l-azobis(cyanocyclohexane) 2,2'- azobis(2-methylbutyronitrile).
  • ALBN .and ADVN are used together at combined concentrations of 0.01 to 0.4 weight percent, with preferably 0.01 to 0.1 weight percent ADVN and 0.1 to 0.3 weight
  • the polymers are melt-processable by conventional methods such as extrusion or compression molding and injection molding can be used to fabricate polymers into shaped articles.
  • the processing temperature is usually about 100° C above the polymer T g , although longer than usual heating times may be necessary because of their lower thermal conductivities.
  • Lens buttons prepared by molding or cutting of rods can be processed into the high-Dk fluoropolymeric contact lenses using means well established in the ophthalmic lens arts, including lathing and polishing of the lens surfaces to yield a contact lens of the appropriate thickness.
  • the perfluorodioxole copolymer of the present invention when made into contact lenses, has good mechanical properties and exhibit the unusually high oxygen-permeability generally associated with the polymer.
  • the gas-permeability increases with the dioxole monomer content, and contact lenses made from the present polymers are characterized, as indicated above, by an oxygen-permeability that is prefererably a Dk of about 200 to 1000.
  • the lens is subjected to surface treatment, preferably by means of reductive RF plasma-treatment, employing an hydrogen-containing gas.
  • Plasma-treatment involves passing an electrical discharge through a gas at low pressure.
  • the electrical discharge is usually at radio frequency (typically, 13.56 MHz), although microwave and other frequencies can be used.
  • This electrical discharge is absorbed by atoms and molecules in their gas state, thus forming a plasma that interacts with the surface of the contact lens.
  • This plasma treatment with hydrogen-containing gas is believed to reduce the fluorine content and increase the carbon content, allowing sites for subsequent oxidation, as proposed in commonly assigned copending application S.N. (docket no. P01565), hereby incorported by reference in its entirety.
  • oxidizing plasma e.g., employing O 2 (oxygen gas), water, hydrogen peroxide, air, ammonia, etc., or mixtures thereof, creating radicals and oxidized functional groups.
  • O 2 oxygen gas
  • further surface treatment can be carried out; for example, by the attachment of biocompatible or hydrophilic polymers or macromonomers.
  • contact lenses may be surface-treated by placing them within an electric glow discharge reaction vessel (e.g., a vacuum chamber). Such reaction vessels are commercially available.
  • the lenses may be supported within the vessel on an aluminum tray (which acts as an electrode) or with other support devices designed to adjust the position of the lenses.
  • the use of specialized support devices which permit the surface treatment of both sides of a lens is known in the art and may be used in the present invention.
  • the plasma treatment with a hydrogen-containing atmosphere is conducted at a wattage of 100 to 1000 watts at a electric discharge frequency of 13.56 MHz,, preferably about 200 to 800 watts, and a pressure of 0.1 to 1.0 torr, and the plasma treatment with an oxygen- or nitrogen- containing compound is conducted at a wattage of 25 to 1000 watts and a pressure of 0.1 to 1.0 torr.
  • the lens is plasma-treatment with hydrogen at 200 to 500 watts for a period of 2 to 20 minutes, and then subsequently plasma treated with air at about 50 to 200 watts for a period of 2 to 20 minutes.
  • the gas employed in the plasma-treatment can additionally comprise an inert gas such as argon.
  • the plasma treatment time is preferably at a flow rate of 50 to 500 seem (standard cubic centimeters).
  • the thickness of the surface treatment is sensitive to plasma flow rate and chamber temperature, as will be understood by the skilled artisan. Since the coating is dependent on a number of variables, the optimal variables for obtaining the desired or optimal coating may require some adjustment. If one parameter is adjusted, a compensatory adjustment of one or more other parameters may be appropriate, so that some routine trial and error experiments and iterations thereof may be necessary in order to achieve the coating according to the present invention. However, such adjustment of process parameters, in light of the present disclosure and the state of the art in plasma treatment, should not involve undue experimentation. As indicated above, general relationships among process parameters are known by the skilled artisan, and the art of plasma-treatment has become well developed in recent years. The Examples below provide the Applicants' best mode for forming the coating on a highly fluorinated RGP lens.
  • the contact lenses of the present invention are especially advantageous for extended-wear or specialty uses, such as for relatively thick lenses.
  • Extended wear lenses are lenses capable of being worn overnight, preferably capable of being worn for at least one week, most preferably capable of wear for a continuous period of one week to one month.
  • capable is meant lenses approved by one or more governmental regulatory authorities for such consumer use, for example, the U.S. Food & Drug Administration (USFDA) in the U.S. or its equivalent in other countries.
  • EXAMPLE 1 A number of high-Dk fluoropolymeric contact lens articles were made according to the subject invention and are described below. Molded rods of the material were obtained from Random Technologies (San Franciso, California), which were made from Teflon AF 1600, comprising 65 mole percent PDD and 45 mole percent TFE, supplied by DuPont. The rods' dimensions were 12.7 mm diameter and 4 mm thick. Buttons were cut from the rods and lathed into contact lenses by techniques well known in the art. An exemplary contact lens exhibited the characteristics in Table 1 below. TABLE 1
  • Teflon® AF is a registered tradmark of E.I duPont de Nemours (Wilmington, DE)
  • This Example illustrates a process for the surface modification of a contact lens according to the present invention.
  • High-Dk fluoropolymeric lenses made according to Example 1 above from Teflon® AF 1600 polymeric material were plasma treated as follows: The lenses were placed concave side up on an aluminum coated tray and the tray placed into a plasma treatment chamber.
  • the plasma treatment chamber was a direct current DC RFGD chamber manufactured by Branson GaSonics Division (Model 7104). This chamber was a cold equilibrium planar configuration which had a maximum power of 500 watts. All lenses were prepumped to 0.01 torr prior to any plasma treatment from residual air in the chamber. This process reduced the relative treatment level of the polymer by controlling gas pressure.
  • the lens was first treated by passing hydrogen gas at 50 seem into the chamber.
  • the lenses were plasma treated for a period of 10 minutes (300 watts, 0.3 torr). Subsequently, the lenses were treated by passing air at 250 seem into the chamber while plasma treating the lenses for a period of 5 minutes (100 watts, 0.3 torr).
  • the contact angle of the lens with water was, before the plasma treatment, 115 degrees and, after the plasma treatment, was 0 degrees

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Eyeglasses (AREA)

Abstract

L'invention concerne un article pour verres de contact rigide, perméable au gaz, fluoropolymère à haut Dk comprenant à la fois les verres de contact et la matière à partir de laquelle sont fabriqués les verres de contact. L'invention concerne plus particulièrement l'article pour verres de contact renfermant des copolymères de certaines unités comonomères hétérocycliques perfluorées améliorant l'équilibre entre les propriétés, à savoir l'augmentation de la capacité de transmission d'oxygène, nécessaire pour un port prolongé de verres ou pour des verres de contact spéciaux. De tels copolymères se sont avérés suffisamment rigides pour un tournage normal et peu coûteux en termes de fabrication. Les verres de contact sont biocompatibles lorsque leur surface est traitée.
PCT/US1999/028144 1998-12-21 1999-11-29 Articles pour verres de contact fabriques a partir de comonomeres perfluores Ceased WO2000037971A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU19248/00A AU1924800A (en) 1998-12-21 1999-11-29 Contact lens articles made from perfluorinated comonomers

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US22000298A 1998-12-21 1998-12-21
US09/220,002 1998-12-21

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006023795A3 (fr) * 2004-08-18 2006-04-27 Du Pont Revetement proteinique amphipathique sur polymere nanoporeux
WO2007005335A1 (fr) * 2005-07-01 2007-01-11 Bausch & Lomb Incorporated Dispositifs biomédicaux
EP1839687A3 (fr) * 2006-03-31 2007-10-10 Cordis Development Corporation Dispositifs et procédés d'occlusion vasculaire à traitement plasma
WO2017194095A1 (fr) * 2016-05-10 2017-11-16 Carl Zeiss Vision International Gmbh Moule et procédé de préparation de verres de lunettes

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0443986A1 (fr) * 1990-02-23 1991-08-28 Ciba-Geigy Ag Lentilles ophthalmiques à base de fluoropolymères amorphes
EP0950672A1 (fr) * 1998-04-17 1999-10-20 Asahi Glass Company Ltd. Procédé de préparation de polymères contenant du fluor

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0443986A1 (fr) * 1990-02-23 1991-08-28 Ciba-Geigy Ag Lentilles ophthalmiques à base de fluoropolymères amorphes
EP0950672A1 (fr) * 1998-04-17 1999-10-20 Asahi Glass Company Ltd. Procédé de préparation de polymères contenant du fluor

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006023795A3 (fr) * 2004-08-18 2006-04-27 Du Pont Revetement proteinique amphipathique sur polymere nanoporeux
US7147912B2 (en) 2004-08-18 2006-12-12 E. I. Du Pont De Nemours And Company Amphipathic proteinaceous coating on nanoporous polymer
WO2007005335A1 (fr) * 2005-07-01 2007-01-11 Bausch & Lomb Incorporated Dispositifs biomédicaux
US7582704B2 (en) 2005-07-01 2009-09-01 Bausch & Lomb Incorporated Biomedical devices
EP1839687A3 (fr) * 2006-03-31 2007-10-10 Cordis Development Corporation Dispositifs et procédés d'occlusion vasculaire à traitement plasma
US7927676B2 (en) 2006-03-31 2011-04-19 Codman & Shurtleff, Inc. Plasma-treated vascular occlusion devices and methods
WO2017194095A1 (fr) * 2016-05-10 2017-11-16 Carl Zeiss Vision International Gmbh Moule et procédé de préparation de verres de lunettes

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Designated state(s): AE AL AU BA BB BG BR CA CN CU CZ EE GD GE HR HU ID IL IN IS JP KP KR LC LK LR LT LV MG MK MN MW MX NO NZ PL RO SG SI SK SL TR TT UA UZ VN YU ZA

AL Designated countries for regional patents

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Designated state(s): GH GM KE LS MW SD SL SZ TZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
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122 Ep: pct application non-entry in european phase