WO2012016096A1 - Silicone hydrogel lenses with water-rich surfaces - Google Patents

Silicone hydrogel lenses with water-rich surfaces Download PDF

Info

Publication number
WO2012016096A1
WO2012016096A1 PCT/US2011/045808 US2011045808W WO2012016096A1 WO 2012016096 A1 WO2012016096 A1 WO 2012016096A1 US 2011045808 W US2011045808 W US 2011045808W WO 2012016096 A1 WO2012016096 A1 WO 2012016096A1
Authority
WO
WIPO (PCT)
Prior art keywords
contact lens
lens
μιη
anterior
silicone hydrogel
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/US2011/045808
Other languages
English (en)
French (fr)
Inventor
Yongxing Qiu
John Dallas Pruitt
Sibichen Thekveli
Robert Carey Tucker
Jared Nelson
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Novartis AG
Original Assignee
Novartis AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=45526406&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=WO2012016096(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Priority to RU2013108693/05A priority Critical patent/RU2540655C2/ru
Priority to MX2013001189A priority patent/MX382876B/es
Priority to BR122013012250-8A priority patent/BR122013012250B1/pt
Priority to EP25209874.4A priority patent/EP4657145A2/en
Priority to KR1020217003655A priority patent/KR102266815B1/ko
Priority to KR1020207011019A priority patent/KR102159909B1/ko
Priority to KR1020207026811A priority patent/KR102215955B1/ko
Priority to SI201130045T priority patent/SI2461767T1/sl
Priority to EP11813220.8A priority patent/EP2461767B1/en
Priority to CN201180037423.5A priority patent/CN103052364B/zh
Priority to RS20130337A priority patent/RS52882B/sr
Priority to BR112013002179-9A priority patent/BR112013002179B1/pt
Priority to JP2013521992A priority patent/JP5882322B2/ja
Priority to BR122020017231-2A priority patent/BR122020017231B1/pt
Priority to CA2802793A priority patent/CA2802793C/en
Priority to KR1020217017970A priority patent/KR102411923B1/ko
Priority to DK11813220.8T priority patent/DK2461767T3/da
Application filed by Novartis AG filed Critical Novartis AG
Priority to AU2011282602A priority patent/AU2011282602C1/en
Priority to KR1020187022807A priority patent/KR101990757B1/ko
Priority to KR1020137005040A priority patent/KR101413390B1/ko
Priority to EP25209870.2A priority patent/EP4657144A2/en
Priority to KR1020137016191A priority patent/KR101800059B1/ko
Priority to KR1020177031719A priority patent/KR101889246B1/ko
Priority to EP13160647.7A priority patent/EP2705808B1/en
Priority to HK12106456.0A priority patent/HK1165690B/en
Priority to PL11813220T priority patent/PL2461767T3/pl
Priority to BR122020017237-1A priority patent/BR122020017237B1/pt
Priority to SG2013006887A priority patent/SG187237A1/en
Priority to MYPI2018001205A priority patent/MY186340A/en
Priority to KR1020167030352A priority patent/KR101795983B1/ko
Priority to EP13160886.1A priority patent/EP2638878B1/en
Priority to ES11813220T priority patent/ES2423914T3/es
Priority to KR1020197016694A priority patent/KR102104222B1/ko
Publication of WO2012016096A1 publication Critical patent/WO2012016096A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D11/00—Producing optical elements, e.g. lenses or prisms
    • B29D11/00009—Production of simple or compound lenses
    • B29D11/00038—Production of contact lenses
    • B29D11/00067—Hydrating contact lenses
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D11/00—Producing optical elements, e.g. lenses or prisms
    • B29D11/00009—Production of simple or compound lenses
    • B29D11/00038—Production of contact lenses
    • B29D11/00048—Production of contact lenses composed of parts with dissimilar composition
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D11/00—Producing optical elements, e.g. lenses or prisms
    • B29D11/00865—Applying coatings; tinting; colouring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/38—Polysiloxanes modified by chemical after-treatment
    • C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
    • C08G77/388—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/056—Forming hydrophilic coatings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/12—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
    • C08L101/14—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity the macromolecular compounds being water soluble or water swellable, e.g. aqueous gels
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or 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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or 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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or 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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/24—Homopolymers or copolymers of amides or imides
    • C09D133/26—Homopolymers or copolymers of acrylamide or methacrylamide
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D171/02—Polyalkylene oxides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D177/00—Coating compositions based on polyamides obtained by reactions forming a carboxylic amide link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D177/06—Polyamides derived from polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
    • C09D5/1637—Macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1681—Antifouling coatings characterised by surface structure, e.g. for roughness effect giving superhydrophobic coatings or Lotus effect
    • 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
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • 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
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/18—Coatings for keeping optical surfaces clean, e.g. hydrophobic or photo-catalytic films
    • G—PHYSICS
    • G02—OPTICS
    • G02C—SPECTACLES; SUNGLASSES OR GOGGLES INSOFAR AS THEY HAVE THE SAME FEATURES AS SPECTACLES; CONTACT LENSES
    • G02C7/00—Optical parts
    • G02C7/02—Lenses; Lens systems ; Methods of designing lenses
    • G02C7/04—Contact lenses for the eyes
    • G—PHYSICS
    • G02—OPTICS
    • G02C—SPECTACLES; SUNGLASSES OR GOGGLES INSOFAR AS THEY HAVE THE SAME FEATURES AS SPECTACLES; CONTACT LENSES
    • G02C7/00—Optical parts
    • G02C7/02—Lenses; Lens systems ; Methods of designing lenses
    • G02C7/04—Contact lenses for the eyes
    • G02C7/049—Contact lenses having special fitting or structural features achieved by special materials or material structures
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2383/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2383/04—Polysiloxanes
    • C08J2383/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2433/00—Characterised by the use of homopolymers or 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 of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2433/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2433/00—Characterised by the use of homopolymers or 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 of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2433/24—Homopolymers or copolymers of amides or imides
    • C08J2433/26—Homopolymers or copolymers of acrylamide or methacrylamide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2487/00—Characterised by the use of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
    • G—PHYSICS
    • G02—OPTICS
    • G02C—SPECTACLES; SUNGLASSES OR GOGGLES INSOFAR AS THEY HAVE THE SAME FEATURES AS SPECTACLES; CONTACT LENSES
    • G02C2202/00—Generic optical aspects applicable to one or more of the subgroups of G02C7/00
    • G02C2202/06—Special ophthalmologic or optometric aspects
    • G—PHYSICS
    • G02—OPTICS
    • G02C—SPECTACLES; SUNGLASSES OR GOGGLES INSOFAR AS THEY HAVE THE SAME FEATURES AS SPECTACLES; CONTACT LENSES
    • G02C2202/00—Generic optical aspects applicable to one or more of the subgroups of G02C7/00
    • G02C2202/16—Laminated or compound lenses

Definitions

  • the present invention generally relates to an ophthalmic device, especially a silicone hydrogel contact lens which has a lens structural configuration creating a water content gradient and comprises: a silicone hydrogel bulk material having a water content (designated as WC S iH y ) of from about 10% to about 70% by weight and an outer surface layer that has a thickness of about 0.1 to about 20 ⁇ and completely covers the silicone hydrogel bulk material and is made of a hydrogel material totally or substantially free of silicone and having a higher water content characterized by a water-swelling ratio of at least about 100% if WC S iHy ⁇ 45% or by a water- swelling ratio of at least about [120 ⁇ WC SiHy /(l - WC SiHy )]% if WC Si H y > 45%, as measured by AFM with a cross section of the silicone hydrogel contact lens in fully hydrated state.
  • a silicone hydrogel bulk material having a water content (designated as WC S iH y ) of from about 10%
  • Silicone hydrogel (SiHy) contact lenses are widely used for correcting many different types of vision deficiencies. They are made of a hydrated, crosslinked polymeric material that contains silicone and a certain amount of water within the lens polymer matrix at equilibrium. According to the FDA's contact lens classification, hydrogel contact lenses are generally classified into two main categories: low water content contact lenses (containing less than 50% of water) and high water content contact lenses (containing greater than 50% of water). For SiHy contact lenses, high oxygen permeability, which is required for a contact lens to have minimal adverse effects upon corneal health, is achieved by incorporating silicone, not by increasing water content, in the crosslinked polymeric material.
  • SiHy contact lenses can have a low water content while still having a relatively high oxygen permeability (Dk), for example, Focus® Night & Day® from CIBA Vision Corporation (ca. 23.5% H 2 0 and Dk ⁇ 140 Barrers; Air Optix® from CIBA Vision Corporation (ca. 33% H 2 0 and Dk ⁇ 1 10 Barrers); PureVision® from Bausch & Lomb (ca. 36% H 2 0 and Dk ⁇ 100 Barrers); Acuvue® Oasys® from Johnson & Johnson (ca. 38% H 2 0, Dk ⁇ 105 Barrers); Acuvue®
  • Dk oxygen permeability
  • Water in a SiHy contact lens can provide the desirable softness that enable a SiHy lens to be worn for sufficiently long periods of time and provides patients with the benefits including adequate initial comfort (i.e., immediately after lens insertion), relatively short period of adapting time required for a patient to become accustomed to them, and/or proper fit.
  • Higher water content would be desirable for providing SiHy contact lenses with biocompatibility and comfort.
  • high water content could also have undesired consequences. For instance, oxygen permeability of a SiHy contact lens could be compromised by increasing water content.
  • in-eye dehydration may be derived from evaporation (i.e., water loss) at the anterior surface of the contact lens and such water loss is primarily controlled by water diffusion through a lens from the posterior surface to the anterior surface, and that the rate of diffusion is closely proportional to the water content of the lens bulk material at equilibrium (L. Jones et al., Contact Lens & Anterior Eye 25 (2002) 147-156, herein incorporated by reference in its entirety).
  • a SiHy contact lens will generally require a surface modification process to eliminate or minimize the exposure of silicone of the contact lens and to maintain a hydrophilic surface, including, for example, various plasma treatments (e.g., Focus® Night & Day® and Air Optix® from CIBA Vision Corporation;
  • SiHy polymer matrix e.g., Acuvue® Oasys®, Acuvue® Advance® and Acuvue® TruEyeTM from Johnson & Johnson; Biofinity® and AvairaTM from CooperVision.
  • surface modification techniques used in the commercial SiHy lens production may provide fresh (unused) SiHy lenses with adequately hydrophilic surfaces
  • a SiHy lenses worn in the eye may have dry spots and/or hydrophobic surface areas created due to air exposure, shearing forces of the eyelids, silicone migration, and/or partial failure to prevent silicone from exposure. Those dry spots and/or hydrophobic surface areas are non-wettable and susceptible to adsorbing lipids or proteins from the ocular environment and may adhere to the eye, causing patient discomfort.
  • the invention can satisfy the needs for SiHy contact lenses with hydrophilic surfaces that have a persistent surface hydrophilicity, surface wettability and surface lubricity in the eye throughout the entire day.
  • the invention provides a hydrated silicone hydrogel contact lens which comprises: an anterior (convex) surface and an opposite posterior (concave) surface; and a layered structural configuration from the anterior surface to the posterior surface, wherein the layered structural configuration includes an anterior outer hydrogel layer, an inner layer of a silicone hydrogel material, and a posterior outer hydrogel layer, wherein the silicone hydrogel material has an oxygen permeability (Dk) of at least about 50, preferably at least about 60, more preferably at least about 70, even more preferably at least about 90 barrers, most preferably at least about 1 10 Barrers, and a first water content (designated as WC S iH y ) of from about 10% to about 70%, preferably from about 10% to about 65%, more preferably from about 10% to about 60%, even more preferably from about 15% to about 5
  • each of the anterior and posterior outer hydrogel layers is from about 0.1 ⁇ to about 20 ⁇ , preferably from about 0.25 ⁇ to about 15 ⁇ , more preferably from about 0.5 ⁇ to about 12.5 ⁇ , even more preferably from about 1 ⁇ to about 10 ⁇ (as measured with atomic force microscopy across a cross section from the posterior surface to the anterior surface of the silicone hydrogel contact lens in fully hydrated state).
  • a hydrated silicone hydrogel contact lens of the invention comprises: a silicone hydrogel material as bulk material, an anterior surface and an opposite posterior surface; wherein the contact lens has an oxygen transmissibility of at least about 40, preferably at least about 60, more preferably at least about 80, even more preferably at least about 1 10 barrers/mm, and a cross-sectional surface-modulus profile which comprises, along a shortest line between the anterior and posterior surfaces on the surface of a cross section of the contact lens, an anterior outer zone including and near the anterior surface, an inner zone including and around the center of the shortest line, and a posterior outer zone including and near the posterior surface, wherein the anterior outer zone has an average anterior surface modulus (designated as SM ⁇ ) while the posterior outer zone has an average posterior surface modulus (designated as SM Post ), wherein the inner zone has an average inner surface modulus (designated as SM Inner ), wherein at least
  • Inner - SM Ant xl00% is at least about 20%, preferably at
  • a hydrated silicone hydrogel contact lens of the invention comprises: a silicone hydrogel material as bulk material, an anterior surface and an opposite posterior surface; wherein the contact lens has (1 ) an oxygen transmissibility of at least about 40, preferably at least about 60, more preferably at least about 80, even more preferably at least about 1 10 barrers/mm, and (2) a surface lubricity characterized by having a critical coefficient of friction (designated as CCOF) of about 0.046 or less, preferably about 0.043 or less, more preferably about 0.040 or less, wherein the anterior and posterior surfaces have a low surface concentration of negatively-charged groups including carboxylic acid groups as characterized by attracting at most about 200, preferably at most about 160, more preferably at most about 120, even more preferably at most about 90, most preferably at most about 60 positively-charged particles in positively-charged- particles-adhesion test.
  • CCOF critical coefficient of friction
  • Figure 1 schematically depicts a sectional view of the structural configuration of a SiHy contact lens according to a preferred embodiment of the invention.
  • Figure 2 schematically depicts a sectional view of the structural configuration of a SiHy contact lens according to another preferred embodiment of the invention.
  • Figure 3 shows the fluorescence intensity profiles across the cross sections of a SiHy contact lens in a con-focal laser fluorescence microscopy.
  • Figure 4 shows the SEM (scanning electron microscopy) images of a SiHy contact lens of the invention in a freeze-dried state.
  • Figure 5 schematically illustrates the set up of the inclined plate method according to a preferred embodiment.
  • Figure 6 shows optical microscopic images of the contact lenses having different coatings thereon after being immersed in a dispersion of positively charged particles (DOWEXTM 1x4 20-50 Mesh resins).
  • Figure 7 schematically illustrates how to mount vertically in a metal clamp a cross-section piece of a SiHy contact lens of the invention for AFM testing.
  • Figure 8 shows the AFM (atomic force microscopy) image of a portion of a cross section of a SiHy contact lens in fully hydrated state (in phosphate buffered saline, pH -7.3) according to a preferred embodiment of the invention.
  • Figure 9 shows a cross sectional surface modulus profile of a SiHy contact lens of the invention in fully hydrated state (in phosphate-buffered saline, pH ⁇ 7.3), along two shortest line between the anterior and posterior surfaces on the surface of a cross section of a SiHy contact lens, according to a preferred embodiment of the invention as represented approximately by the plots of the cantilever deflection as function of the distance.
  • silicone hydrogel contact lens refers to a contact lens comprising a silicone hydrogel material.
  • hydrogel or “hydrogel material” refers to a crosslinked polymeric material which is not water-soluble and can contains at least 10% by weight of water within its polymer matrix when fully hydrated.
  • non-silicone hydrogel refers to a hydrogel that is theoretically free of silicon.
  • silicone hydrogel refers to a hydrogel containing silicone.
  • a silicone hydrogel typically is obtained by copolymerization of a polymerizable composition comprising at least one silicone-containing vinylic monomer or at least one silicone- containing vinylic macromer or at least one silicone-containing prepolymer having ethylenically unsaturated groups.
  • vinylenically unsaturated group refers to a compound that has one sole ethylenically unsaturated group and can be polymerized actinically or thermally.
  • exemplary ethylenically unsaturated groups include without limitation (meth)acryloyl (— CH— CH 2 ) ; aiiyi, vinyl
  • (meth)acrylamide refers to methacrylamide and/or acrylamide.
  • (meth)acrylate refers to methacrylate and/or acrylate.
  • hydrophilic vinylic monomer refers to a vinylic monomer which as a homopolymer typically yields a polymer that is water-soluble or can absorb at least 10 percent by weight water.
  • hydrophobic vinylic monomer refers to a vinylic monomer which as a homopolymer typically yields a polymer that is insoluble in water and can absorb less than 10 percent by weight water.
  • the term “macromer” or “prepolymer” refers to a medium and high molecular weight compound or polymer that contains two or more ethylenically unsaturated groups. Medium and high molecular weight typically means average molecular weights greater than 700 Daltons.
  • the term “crosslinker” refers to a compound having at least two ethylenically unsaturated groups.
  • a “crosslinking agent” refers to a crosslinker having a molecular weight of about 700 Daltons or less.
  • polymer means a material formed by
  • molecular weight of a polymeric material refers to the weight-average molecular weight unless otherwise specifically noted or unless testing conditions indicate otherwise.
  • amino group refers to a primary or secondary amino group of formula -NHR', where R' is hydrogen or a C C 2 o unsubstituted or substituted, linear or branched alkyl group, unless otherwise specifically noted.
  • epichlorohydrin-functionalized polyamine or "epichlorohydrin-functionalized polyamidoamine” refers to a polymer obtained by reacting a polyamine or polyamidoamine with epichlorohydrin to convert all or a substantial percentage of amine groups of the polyamine or polyamidoamine into azetidinium groups.
  • azetidinium group refers to a positively charged group
  • thermally-crosslinkable in reference to a polymeric material or a functional group means that the polymeric material or the functional group can undergo a crosslinking (or coupling) reaction with another material or functional group at a relatively-elevated temperature (from about 40°C to about 140°C), whereas the polymeric material or functional group cannot undergo the same crosslinking reaction (or coupling reaction) with another material or functional group at room temperature (i.e., from about 22°C to about 28°C, preferably from about 24°C to about 26°C, in particular at about 25°C) to an extend detectable (i.e., greater than about 5%) for a period of about one hour.
  • phosphorylcholine refers to a zwitterionic group of in which n is an integer of 1 to 5 and R-i , R 2 and R 3 independently of each other are C C 8 alkyl or C C 8 hydroxyalkyl.
  • reactive vinylic monomer refers to a vinylic monomer having a carboxyl group or an amino group (i.e., a primary or secondary amino group).
  • non-reactive hydrophilic vinylic monomer refers to a hydrophilic vinylic monomer which is free of any carboxyl group or amino group (i.e., primary or secondary amino group).
  • a non-reactive vinylic monomer can include a tertiary or quaternium amino group.
  • water-soluble in reference to a polymer means that the polymer can be dissolved in water to an extent sufficient to form an aqueous solution of the polymer having a concentration of up to about 30% by weight at room temperature (defined above).
  • water contact angle refers to an average water contact angle (i.e., contact angles measured by Sessile Drop method), which is obtained by averaging measurements of contact angles.
  • the term "intactness" in reference to a coating on a SiHy contact lens is intended to describe the extent to which the contact lens can be stained by Sudan Black in a Sudan Black staining test described in Example 1. Good intactness of the coating on a SiHy contact lens means that there is practically no Sudan Black staining of the contact lens.
  • the term "durability" in reference to a coating on a SiHy contact lens is intended to describe that the coating on the SiHy contact lens can survive a digital rubbing test.
  • the term "surviving a digital rubbing test” or “surviving a durability test” in reference to a coating on a contact lens means that after digitally rubbing the lens according to a procedure described in Example 1 , water contact angle on the digitally rubbed lens is still about 100 degrees or less, preferably about 90 degrees or less, more preferably about 80 degrees or less, most preferably about 70 degrees or less.
  • the intrinsic "oxygen permeability", Dk, of a material is the rate at which oxygen will pass through a material.
  • oxygen permeability (Dk) in reference to a hydrogel (silicone or non-silicone) or a contact lens means a measured oxygen permeability (Dk) which is corrected for the surface resistance to oxygen flux caused by the boundary layer effect according to the procedures shown in Examples hereinafter.
  • Oxygen permeability is conventionally expressed in units of barrers, where “barrer” is defined as [(cm 3 oxygen)(mm) / (cm 2 )(sec)(mm Hg)] x 10 "10 .
  • the "oxygen transmissibility", Dk/t, of a lens or material is the rate at which oxygen will pass through a specific lens or material with an average thickness of t [in units of mm] over the area being measured.
  • Oxygen transmissibility is conventionally expressed in units of barrers/mm, where "barrers/mm” is defined as [(cm 3 oxygen) / (cm 2 )(sec)(mm Hg)] x 10 "9 .
  • the "ion permeability" through a lens correlates with the lonoflux Diffusion Coefficient.
  • the lonoflux Diffusion Coefficient, D is determined by applying Fick's law as follows:
  • n' rate of ion transport [mol/min]
  • A area of lens exposed [mm 2 ]
  • dc concentration difference [mol/L]
  • dx thickness of lens [mm].
  • ophthalmically compatible refers to a material or surface of a material which may be in intimate contact with the ocular environment for an extended period of time without significantly damaging the ocular environment and without significant user discomfort.
  • ophthalmically safe with respect to a packaging solution for sterilizing and storing contact lenses is intended to mean that a contact lens stored in the solution is safe for direct placement on the eye without rinsing after autoclave and that the solution is safe and sufficiently comfortable for daily contact with the eye via a contact lens.
  • An ophthalmically-safe packaging solution after autoclave has a tonicity and a pH that are compatible with the eye and is substantially free of ocularly irritating or ocularly cytotoxic materials according to international ISO standards and U.S. FDA regulations.
  • cross section of a SiHy contact lens refers to a lens section obtained by cutting through the lens with a knife or cutting tool at an angle substantially normal to either of the anterior and posterior surfaces of the lens.
  • a person skilled in the art knows well to cut manually (i.e., hand cut), or with Cryosta Microtome or with a lath, a contact lens to obtain a cross section of the contact lens.
  • a resultant cross section of a contact lens can be polished by using ion etching or similar techniques.
  • surface modulus means a nanomechnical property (elastic property) which is measured by atomic force microscopy (AFM) on a surface of a material or a cross section of a contact lens in fully hydrated state (in a phosphate buffered solution, pH ⁇ 7.3 ⁇ 0.2), using contact mode, nanoindentation method, Peakforce QNM method, or Harmonic Force method, as known to a person skilled in the art.
  • AMF atomic force microscopy
  • AFM nanoindentation can be performed according to the experimental protocol described by Gonzalez-Meijome JM, Almeida JB and Parafita MA in Microscopy: Science, Technology, Applications and Education, "Analysis of Surface Mechanical Properties of Unworn and Worn Silicone Hydrogel Contact Lenses Using Nanoindentation with AFM", pp554-559, A. Mendez-Vilas and J. Diaz (Eds.), Formatex Research Center, Badajoz, Spain (2010), herein incorporated by reference in its entirety.
  • Nanoindentation method Peakforce QNM method and Harmonic Force method are described in the paper by Kim Sweers, et al. in Nanoscale Research Letters 201 1 , 6:270, entitled "Nanomechanical properties of a-synuclein amyloid fibrils: a comparative study by nanoindentation, harmonic force microscopy, and Peakforce QNM” (herein incorporated by reference in its entirety.
  • a surface modulus profile across a cross section of a contact lens can be established along a shortest line between the anterior and posterior surfaces on the surface of the cross section of the contact lens. It is further understood that as a good approximation, any experimentally and directly measured quantity can be used to represent the surface modulus so long as the measured quantity is proportional to the surface modulus.
  • anterior outer hydrogel layer in reference to a SiHy contact lens of the invention means a hydrogel layer that includes the anterior surface of the contact lens, is substantially uniform in thickness (i.e., variation in thickness is not more than about 10% from the average thickness of that layer), and has an average thickness of at least about 0.1 ⁇ .
  • the "average thickness" of an anterior outer hydrogel layer is simply referred to as the “thickness of an anterior outer hydrogel layer” in this application.
  • the term "posterior outer hydrogel layer” in reference to a SiHy contact lens of the invention means a hydrogel layer that includes the posterior surface of the contact lens, is substantially uniform in thickness (i.e., variation in thickness is not more than about 10% from the average thickness of that layer), and has an average thickness of at least about 0.1 ⁇ .
  • the "average thickness" of a posterior outer hydrogel layer is simply referred to as the “thickness of a posterior outer hydrogel layer” in this application.
  • the term "inner layer” in reference to a SiHy contact lens of the invention means a layer that includes a central curved plane (which divides the contact lens into two parts, one containing the anterior surface and the other containing the posterior surface) and has a variable thickness.
  • crosslinked coating or “hydrogel coating” interchangeably is used to describe a crosslinked polymeric material having a three-dimensional network that can contain water when fully hydrated.
  • the three-dimensional network of a crosslinked polymeric material can be formed by crosslinking of two or more linear or branched polymers through crosslinkages.
  • L We t is the average thickness of that outer hydrogel layer of the SiHy contact lens in fully hydrated state as measured with AFM on a cross section of the SiHy contact lens in fully hydrated state (i.e., in a phosphate buffered solution, pH ⁇ 7.3 ⁇ 0.2)
  • L Dry is the average thickness of that outer hydrogel layer of the SiHy contact lens in dry state as measured with AFM on a cross section of the SiHy contact lens in dry state (dried without preserving the porosity of the hydrogel material, e.g., vacuum dried) and in substantially dry atmosphere.
  • each outer hydrogel layer (of a SiHy contact lens of the invention) is proportional to the water content possessed by each outer hydrogel layer and a water-swelling ratio of at least about 100% 120 » WC SiHv
  • WC S iH y is the water content of the bulk (or inner layer of )
  • silicone hydrogel material of a SiHy contact lens of the invention can be served as a good indicator of the nature of the outer hydrogel layers having a higher water content relative to the bulk (or inner layer of) silicone hydrogel material of a SiHy contact lens of the invention.
  • the term "reduced surface modulus”, in reference to either or both of the anterior and posterior outer hydrogel layers of a SiHy contact lens of the invention, is intended to mean a value calculated based on the following equation
  • RSM SM imer " SM ° ⁇ r x 100%
  • RSM is the reduced modulus of the anterior or posterior outer hydrogel layer relative to the inner layer
  • SM 0uter is the average surface modulus of the posterior or anterior outer hydrogel layer
  • SM Inner is the average surface modulus of the inner layer.
  • SM 0uter and SM Inner are obtained from a cross-sectional surface modulus profile of the SiHy contact lens in fully hydrated state (as measured by analyzing surface mechanic properties, i.e., surface moduli of a cross section of the fully hydrated SiHy contact lens using AFM), as described above. It is expected that the cross-sectional surface modulus profile (i.e., a graph of surface modulus vs.
  • the average surface modulus for the outer zone is obtained by averaging all surface moduli in the outer zone excluding a region of about 1 to about 2 microns between the outer zone and the inner zone (i.e., in and/or near the boundary region or transition zone).
  • a "critical coefficient of friction” is the tangent of the critical angle which is the highest inclined angle of an inclined plate at which a lens begins sliding on the inclined plate after being pushed, but stops, or takes longer than 10 seconds, before reaching the end.
  • the procedures for determining the critical coefficient of friction (CCOF) are described in Example 29. It is believed that the critical coefficient of friction (CCOF) of a contact lens correlates with the surface lubricity of that contact lens and can be used to quantify the surface lubricity of a contact lens.
  • the "positively-charged-particles-adhesion test” refers a test for characterizing the surface concentration of negatively-charged groups (e.g., carboxylic acid groups) of a hydrated SiHy contact lens.
  • the positively-charged-particles-adhesion test is performed as follows. An aqueous dispersion of DOWEXTM 1x4 20-50 Mesh resins, which are spherical, Type I strong base resins (styrene/divinylbenzene copolymers containing N + (CH 3 ) 3 C functional groups and 4% divinylbenzene) is prepared by dispersing a given amount of
  • Hydrated silicone hydrogel contact lenses are immersed in the aqueous dispersion of DOWEXTM 1x4 20-50 Mesh resins prepared above and stirred vortexed at an rpm of about 1000-1 100 for 1 about minute, followed by rinsing with Dl water and vortexing in Dl water for about 1 minute. Then, the lenses are placed in water in glass Petri dishes and images of lenses are taken with Nikon optical microscope, using bottom lighting.
  • the number of positively-charged particles adhered onto the surface of each lens can be counted.
  • the number of positively-charged particles adhered onto the surface of the lens is proportional to the surface concentration of negatively-charged groups of a contact lens.
  • carboxylic acid content in reference to the crosslinked coating or an outer hydrogel layer of a SiHy contact lens of the invention, means the weight percentage of carboxylic group (COOH) based on the weight of the crosslinked coating or the outer hydrogel layer of the SiHy contact lens.
  • the carboxylic acid content of a crosslinked coating or an outer hydrogel layer can be estimated theoretically based on the composition of starting materials for making the crosslinked coating or the outer hydrogel layer and on the carboxylic acid content of each starting materials.
  • the invention is related to a SiHy contact lens having a layered structural configuration and unique water gradient from inside to outside of the SiHy contact lens: a lower water content silicone hydrogel core (or bulk material) completely covered with an outer (surface) hydrogel layer having a higher water content and adequate thickness (at least about 0.1 ⁇ ) and being substantially free of silicone (preferably totally free of silicone); and the water content of the outer hydrogel layer being at least about 1.2 folds (or 120%), preferably at least about 1.3 folds (or 130%), more preferably at least about 1.4 folds (or 140%), even more preferably at least about 1.5 folds (150%), most preferably at least about 2 folds (or 200%) of the water content of the bulk material.
  • Figure 1 schematically illustrates a SiHy contact lens having a layered structural configuration, according to a preferred embodiment. In accordance with this preferred
  • the SiHy contact lens 100 has an anterior surface (or front curve or convex surface) 101 and an opposite posterior surface (or base curve or concave surface) 102 which is rest on the cornea of the eye when worn by a user.
  • the SiHy contact lens 100 has an anterior surface (or front curve or convex surface) 101 and an opposite posterior surface (or base curve or concave surface) 102 which is rest on the cornea of the eye when worn by a user.
  • the inner layer 110 is the bulk material of SiHy contact lens 100 and has a 3-dimensional shape very close to the SiHy contact lens 100.
  • the inner layer 110 is preferably made of a lower water content silicone hydrogel.
  • the two outer layers 120 substantially identical to each other, are substantially uniform in thickness and made of a hydrogel material substantially free of silicone (preferably totally free of silicone) having a higher water content relative to that of the inner layer 110.
  • the two outer layers 120 merge at the peripheral edge 103 of the contact lens 100 and cover completely the inner layer 110.
  • a SiHy contact lens with a layered structural configuration of the invention can offer several advantages over contact lenses in the prior art.
  • First, such a SiHy contact lens can still possess high oxygen permeability, which is required to maintain the corneal health of the eye.
  • the outer hydrogel layers can provide the contact lens with a skin super-enriched with water or a water content gradient in the lens structural configuration (highest water content in the region near and including the lens surface and lowest water content in the lens core).
  • a SiHy contact lens with a layered structural configuration of the invention may have low in-eye dehydration, may cause less dryness sensation in the eye, and consequently can have enhanced end-day wearing comfort. It is believed that the inner layer (i.e., the bulk material of the lens) with low water content will control (limit) the rate of water diffusion through a lens from the posterior surface to the anterior surface and in turn the evaporation (water loss) at the anterior surface of the lens.
  • a layered structural configuration of the invention may create an inward water concentration gradient (i.e., the water content decreasing as going inwardly from the anterior surface toward the lens core), which is unfavorable for water diffusion through a lens from the posterior surface to the anterior surface based on Fick's laws of diffusion.
  • a SiHy contact lens with a layered structural configuration of the invention may provide high biocompatibility, because water is highly biocompatible with the tear and because high water content (e.g., preferably > 75% H 2 0) in the outer hydrogel layers is located in and nears the anterior and posterior surfaces with which the eye is in direct contact and where the biocompatibility counts most.
  • high water content in the outer hydrogel layers with adequate thickness may provide a SiHy contact lens with a highly soft surface, i.e., a "water cushion.”
  • a SiHy contact lens with a layered structural configuration of the invention may have a highly lubricious surface. It is believed that the outer hydrogel layer with much higher water content and with adequate thickness would provide a "water-loving" surface which can attract tears to be spread on the lens surface.
  • the outer hydrogel layer with much higher softness than that of the bulk lens material may be very susceptible to deformation under pressure (i.e., shearing forces of the eyelids) and may provide elastohydrodynamic lubrication when such a SiHy contact lens is worn in the eye.
  • a layered structural configuration in a SiHy contact lens of the invention may prevent silicone from exposure. It is believed that the three dimensional mesh network (i.e., polymeric matrix) of the outer hydrogel layers with adequate thickness can sheath silicone and prevent silicone from migrating onto the lens surface.
  • a SiHy contact lens of the invention can have a low surface concentration of negatively-charged groups (e.g., carboxylic acid groups) and is less susceptible to high debris adhesion during patient handling and high protein adhesion during wearing (a majority of proteins in tears is believed to be positively charged).
  • negatively-charged groups e.g., carboxylic acid groups
  • the invention provides a hydrated silicone hydrogel contact lens which comprises: an anterior (convex) surface and an opposite posterior (concave) surface; and a layered structural configuration from the anterior surface to the posterior surface, wherein the layered structural configuration includes an anterior outer hydrogel layer, an inner layer of a silicone hydrogel material, and a posterior outer hydrogel layer, wherein the silicone hydrogel material has an oxygen permeability (Dk) of at least about 50, preferably at least about 60, more preferably at least about 70, even more preferably at least about 90, most preferably at least about 1 10 barrers, and a first water content (designated as WC S iH y ) of from about 10% to about 70%, preferably from about 10% to about 65%, more preferably from about 10% to about 60%, even more preferably from about 15% to about 55%, most preferably from about 15% to about 50% by weight, wherein the anterior and posterior outer hydrogel layers are substantially uniform in thickness and merge at the peripheral edge of the contact lens to completely enclose the inner layer of the
  • layer is from about 0.1 ⁇ to about 20 ⁇ , preferably from about 0.25 ⁇ to about 15 ⁇ , more preferably from about 0.5 ⁇ to about 12.5 ⁇ , even more preferably from about 1 ⁇ to about 10 ⁇ (as measured with atomic force microscopy across a cross section from the posterior surface to the anterior surface of the silicone hydrogel contact lens in fully hydrated state).
  • the anterior and posterior surfaces have a low surface concentration of negatively- charged groups (e.g., carboxylic acid groups) as characterized by attracting at most about 200, preferably at most about 160, more preferably at most about 120, even more preferably at most about 90, most preferably at most about 60 positively-charged particles in positively-charged- particles-adhesion test.
  • the hydrated silicone hydrogel contact lens has a surface lubricity characterized by having a critical coefficient of friction (designated as CCOF) of about 0.046 or less, preferably about 0.043 or less, more preferably about 0.040 or less.
  • the inner layer of a SiHy contact lens is practically the bulk material of the lens. It can be derived directly from a preformed SiHy contact lens in a surface modification process where two outer hydrogel layers are applied and attached directly and/or indirectly onto the preformed SiHy contact lenses.
  • a preformed SiHy contact lens can be any commercial SiHy lens, such as, one of those described above.
  • a preformed SiHy can be made according to any methods well known to a person skilled in the art.
  • preformed contact lenses can be produced in a conventional "spin-casting mold," as described for example in U.S. Patent No. 3,408,429, or by the full cast-molding process in a static form, as described in U.S.
  • a lens formulation typically is dispensed into molds and cured (i.e., polymerized and/or crosslinked) in molds for making contact lenses.
  • a SiHy lens formulation for cast-molding or spin-cast molding or for making SiHy rods used in lathe-cutting of contact lenses generally comprises at least one components selected from the group consisting of a silicone-containing vinylic monomer, a silicone- containing vinylic macromer, a silicone-containing prepolymer, a hydrophilic vinylic monomer, a hydrophobic vinylic monomer, a crosslinking agent (a compound having a molecular weight of about 700 Daltons or less and containing at least two ethylenically unsaturated groups), a free- radical initiator (photoinitiator or thermal initiator), a hydrophilic vinylic macromer/prepolymer, and combination thereof, as well known to a person skilled in the art.
  • a SiHy contact lens formulation can also comprise other necessary components known to a person skilled in the art, such as, for example, a UV-absorbing agent, a visibility tinting agent (e.g., dyes, pigments, or mixtures thereof), antimicrobial agents (e.g., preferably silver nanoparticles), a bioactive agent, leachable lubricants, leachable tear-stabilizing agents, and mixtures thereof, as known to a person skilled in the art.
  • Resultant preformed SiHy contact lenses then can be subjected to extraction with an extraction solvent to remove unpolymerized components from the resultant lenses and to hydration process, as known by a person skilled in the art.
  • a preformed SiHy contact lens can be a colored contact lens (i.e., a SiHy contact lens having at least one colored patterns printed thereon as well known to a person skilled in the art).
  • Any suitable silicone-containing vinylic monomers can be used in the invention.
  • silicone-containing vinylic monomers include without limitation N- [tris(trimethylsiloxy)silylpropyl]-(meth)acrylamide, N-[tris(dimethylpropylsiloxy)-silylpropyl]- (meth)acrylamide, N-[tris(dimethylphenylsiloxy)silylpropyl] (meth)acrylamide, N- [tris(dimethylethylsiloxy)silylpropyl] (meth)acrylamide, N-(2-hydroxy-3-(3- (bis(trimethylsilyloxy)methylsilyl)propyloxy)-2- methyl acrylamide; N-(2-hydroxy-3-(3- (bis(trimethylsilyloxy)methylsilyl)propyloxy)propyl) acrylamide; N,N-bis[2-hydroxy-3-(3- (bis(trimethylsilyloxy)methylsilyl)propyloxy)propyl]-2-methyl acrylamide
  • siloxane-containing (meth)acrylamide monomers of formula (1 ) are N-[tris(trimethylsiloxy)silylpropyl]acrylamide, TRIS, N-[2-hydroxy-3- (3-(t-butyldimethylsilyl)propyloxy)propyl]acrylamide, or combinations thereof.
  • a class of preferred silicone-containing vinylic monomers or macromers is polysiloxane- containing vinylic monomers or macromers.
  • polysiloxane-containing vinylic monomers or macromers are monomethacrylated or monoacrylated polydimethylsiloxanes of various molecular weight (e.g., mono-3-methacryloxypropyl terminated, mono-butyl terminated polydimethylsiloxane or mono-(3-methacryloxy-2-hydroxypropyloxy)propyl terminated, mono- butyl terminated polydimethylsiloxane); dimethacrylated or diacrylated polydimethylsiloxanes of various molecular weight; vinyl carbonate-terminated polydimethylsiloxanes; vinyl carbamate- terminated polydimethylsiloxane; vinyl terminated polydimethylsiloxanes of various molecular weight; methacrylamide-terminated polydimethylsiloxanes; acrylamide-terminated
  • polydimethylsiloxanes acrylate-terminated polydimethylsiloxanes; methacrylate-terminated polydimethylsiloxanes; bis-3-methacryloxy-2-hydroxypropyloxypropyl polydimethylsiloxane; N,N,N N' etrakis(3-methacryloxy-2-hydroxypropyl)-alpha,omega-bis-3-aminopropyl- polydimethylsiloxane; polysiloxanylalkyl (meth)acrylic monomers; siloxane-containing macromer selected from the group consisting of Macromer A, Macromer B, Macromer C, and Macromer D described in US 5,760,100 (herein incorporated by reference in its entirety); the reaction products of glycidyl methacrylate with amino-functional polydimethylsiloxanes; hydroxyl- functionalized siloxane-containing vinylic monomers or macromers; polysiloxane-containing macromers disclosed in
  • polyethyleneoxide-block-polydimethylsiloxane-block-polyethyleneoxide to enhance oxygen permeability.
  • Suitable monofunctional hydroxyl-functionalized siloxane-containing vinylic monomers/macromers and suitable multifunctional hydroxyl-functionalized siloxane-containing vinylic monomers/macromers are commercially available from Gelest, Inc, Morrisville, PA.
  • Another class of preferred silicone-containing macromers is silicon-containing
  • prepolymers comprising hydrophilic segments and hydrophobic segments.
  • Any suitable of silicone-containing prepolymers with hydrophilic segments and hydrophobic segments can be used in the invention.
  • silicone-containing prepolymers include those described in commonly-owned US Patent Nos. 6,039,913, 7,091 ,283, 7,268,189 and 7,238,750, 7,521 ,519; commonly-owned US patent application publication Nos. US 2008-0015315 A1 , US 2008- 0143958 A1 , US 2008-0143003 A1 , US 2008-0234457 A1 , US 2008-0231798 A1 , and commonly-owned US patent application Nos. 61/180,449 and 61/180,453; all of which are incorporated herein by references in their entireties.
  • hydrophilic vinylic monomers are N,N-dimethylacrylamide (DMA), ⁇ , ⁇ -dimethylmethacrylamide (DMMA), 2-acrylamidoglycolic acid, 3-acryloylamino-1-propanol, N-hydroxyethyl acrylamide, /V-[tris(hydroxymethyl)methyl]-acrylamide, N-methyl-3-methylene-2- pyrrolidone, 1-ethyl-3-methylene-2-pyrrolidone, 1-methyl-5-methylene-2-pyrrolidone, 1 -ethyl-5- methylene-2-pyrrolidone, 5-methyl-3-methylene-2-pyrrolidone, 5-ethyl-3-methylene-2-pyrrolidone, 1 -n-propyl-3-methylene-2-pyrrolidone, 1 -n-propyl-5-methylene-2-pyrrolidone, 1 -isopropyl-3- methylene-2-pyrrolidone, 1 -isopropy
  • hydrophobic vinylic monomers examples include methylacrylate, ethyl- acrylate, propylacrylate, isopropylacrylate, cyclohexylacrylate, 2-ethylhexylacrylate,
  • cross-linking agents include without limitation tetraethyleneglycol diacrylate, triethyleneglycol diacrylate, ethyleneglycol diacylate, diethyleneglycol diacrylate, tetraethyleneglycol dimethacrylate, triethyleneglycol dimethacrylate, ethyleneglycol
  • dimethacylate diethyleneglycol dimethacrylate, trimethylopropane trimethacrylate,
  • a preferred cross-linking agent is tetra(ethyleneglycol) diacrylate, tri(ethyleneglycol) diacrylate, ethyleneglycol diacrylate, di(ethyleneglycol) diacrylate, methylenebisacrylamide, triallyl isocyanurate, or triallyl cyanurate.
  • the amount of a cross-linking agent used is expressed in the weight content with respect to the total polymer and is preferably in the range from about 0.05% to about 4%, and more preferably in the range from about 0.1 % to about 2%.
  • thermal initiators examples include, but are not limited to, 2,2'-azobis (2,4- dimethylpentanenitrile), 2,2'-azobis (2-methylpropanenitrile), 2,2'-azobis (2-methylbutanenitrile), peroxides such as benzoyl peroxide, and the like.
  • the thermal initiator is 2,2'- azobis(isobutyronitrile) (AIBN).
  • Suitable photoinitiators are benzoin methyl ether, diethoxyacetophenone, a
  • benzoylphosphine oxide 1 -hydroxycyclohexyl phenyl ketone and Darocur and Irgacur types, preferably Darocur 1 173® and Darocur 2959®.
  • benzoylphosphine initiators include 2,4,6-trimethylbenzoyldiphenylophosphine oxide; bis-(2,6-dichlorobenzoyl)-4-N- propylphenylphosphine oxide; and bis-(2,6-dichlorobenzoyl)-4-N-butylphenylphosphine oxide.
  • Reactive photoinitiators which can be incorporated, for example, into a macromer or can be used as a special monomer are also suitable.
  • reactive photoinitiators are those disclosed in EP 632 329, herein incorporated by reference in its entirety.
  • the polymerization can then be triggered off by actinic radiation, for example light, in particular UV light of a suitable wavelength.
  • actinic radiation for example light, in particular UV light of a suitable wavelength.
  • the spectral requirements can be controlled accordingly, if appropriate, by addition of suitable photosensitizers.
  • a polymerizable UV-absorbing agent comprises a benzotriazole-moiety or a benzophenone- moiety.
  • preferred polymerizable UV absorbers include without limitation 2-(2- hydroxy-5-vinylphenyl)-2H-benzotriazole, 2-(2-hydroxy-5-acrylyloxyphenyl)-2H-benzotriazole, 2- (2-hydroxy-3-methacrylamido methyl-5-tert octylphenyl)benzotriazole, 2-(2'-hydroxy-5'- methacrylamidophenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-5'-methacrylamidophenyl)-5- methoxybenzotriazole, 2-(2'-hydroxy-5'-methacryloxypropyl-3'-t-butyl-phenyl)-5- chlorobenzotriazo le, 2-(2'-hydroxy-5'-hydroxy-5'-
  • the bioactive agent is any compound that can prevent a malady in the eye or reduce the symptoms of an eye malady.
  • the bioactive agent can be a drug, an amino acid (e.g., taurine, glycine, etc.), a polypeptide, a protein, a nucleic acid, or any combination thereof.
  • amino acid e.g., taurine, glycine, etc.
  • polypeptide e.g., a polypeptide
  • protein e.g., glycine, etc.
  • nucleic acid e.g., a nucleic acid
  • examples of drugs useful herein include, but are not limited to, rebamipide, ketotifen, olaptidine,
  • bioactive agents include 2- pyrrolidone-5-carboxylic acid (PCA), alpha hydroxyl acids (e.g., glycolic, lactic, malic, tartaric, mandelic and citric acids and salts thereof, etc.), linoleic and gamma linoleic acids, and vitamins (e.g., B5, A, B6, etc.).
  • PCA 2- pyrrolidone-5-carboxylic acid
  • alpha hydroxyl acids e.g., glycolic, lactic, malic, tartaric, mandelic and citric acids and salts thereof, etc.
  • linoleic and gamma linoleic acids e.g., B5, A, B6, etc.
  • leachable lubricants include without limitation mucin-like materials (e.g., polyglycolic acid) and non-crossllinkable hydrophilic polymers (i.e., without ethylenically unsaturated groups). Any hydrophilic polymers or copolymers without any ethylenically unsaturated groups can be used as leachable lubricants.
  • non- crosslinkable hydrophilic polymers include, but are not limited to, polyvinyl alcohols (PVAs), polyamides, polyimides, polylactone, a homopolymer of a vinyl lactam, a copolymer of at least one vinyl lactam in the presence or in the absence of one or more hydrophilic vinylic
  • the weight-average molecular weight M w of the non-crosslinkable hydrophilic polymer is preferably from 5,000 to 1 ,00,000.
  • leachable tear-stabilizing agents include, without limitation, phospholipids, monoglycerides, diglycerides, triglycerides, glycolipids, glyceroglycolipids, sphingolipids, sphingo-glycolipids, fatty alcohols, fatty acids, mineral oils, and mixtures thereof.
  • a tear stabilizing agent is a phospholipid, a monoglyceride, a diglyceride, a triglyceride, a glycolipid, a glyceroglycolipid, a sphingolipid, a sphingo-glycolipid, a fatty acid having 8 to 36 carbon atoms, a fatty alcohol having 8 to 36 carbon atoms, or a mixture thereof.
  • a SiHy lens formulation can be a solution or a melt at a temperature from about 20°C to about 85°C.
  • a polymerizable composition is a solution of all desirable components in a suitable solvent, or a mixture of suitable solvents.
  • a SiHy lens formulation can be prepared by dissolving all of the desirable components in any suitable solvent, such as, water, a mixture of water and one or more organic solvents miscible with water, an organic solvent, or a mixture of one or more organic solvents, as known to a person skilled in the art.
  • suitable solvent such as, water, a mixture of water and one or more organic solvents miscible with water, an organic solvent, or a mixture of one or more organic solvents, as known to a person skilled in the art.
  • Example of preferred organic solvents includes without limitation, tetrahydrofuran, tripropylene glycol methyl ether, dipropylene glycol methyl ether, ethylene glycol n-butyl ether, ketones (e.g., acetone, methyl ethyl ketone, etc.), diethylene glycol n-butyl ether, diethylene glycol methyl ether, ethylene glycol phenyl ether, propylene glycol methyl ether, propylene glycol methyl ether acetate, dipropylene glycol methyl ether acetate, propylene glycol n-propyl ether, dipropylene glycol n-propyl ether, tripropylene glycol n-butyl ether, propylene glycol n-butyl ether, dipropylene glycol n-butyl ether, tripropylene glycol n-butyl ether, propylene glycol n-butyl ether, diprop
  • SiHy lens formulations have been described in numerous patents and patent applications published by the filing date of this application. All of them can be used in obtaining a preformed SiHy lens which in turn becomes the inner layer of a SiHy contact lens of the invention, so long as they will yield a SiHy material having a Dk and water content specified above.
  • a SiHy lens formulation for making commercial SiHy lenses such as, lotrafilcon A, lotrafilcon B, balafilcon A, galyfilcon A, senofilcon A, narafilcon A, narafilcon B, comfilcon A, enfilcon A, asmofilcon A, filcon II 3, can also be used in making preformed SiHy contact lenses (the inner layer of a SiHy contact lens of the invention).
  • a mold for cast molding
  • a mold generally comprises at least two mold sections (or portions) or mold halves, i.e. first and second mold halves.
  • the first mold half defines a first molding (or optical) surface and the second mold half defines a second molding (or optical) surface.
  • the first and second mold halves are configured to receive each other such that a lens forming cavity is formed between the first molding surface and the second molding surface.
  • the molding surface of a mold half is the cavity-forming surface of the mold and in direct contact with lens-forming material.
  • Methods of manufacturing mold sections for cast-molding a contact lens are generally well known to those of ordinary skill in the art.
  • the process of the present invention is not limited to any particular method of forming a mold. In fact, any method of forming a mold can be used in the present invention.
  • the first and second mold halves can be formed through various techniques, such as injection molding or lathing. Examples of suitable processes for forming the mold halves are disclosed in U.S. Patent Nos. 4,444,71 1 to Schad; 4,460,534 to Boehm et al.; 5,843,346 to Morrill; and 5,894,002 to Boneberqer et al., which are also incorporated herein by reference.
  • Virtually all materials known in the art for making molds can be used to make molds for making contact lenses.
  • polymeric materials such as polyethylene, polypropylene, polystyrene, PMMA, Topas ® COC grade 8007-S10 (clear amorphous copolymer of ethylene and norbornene, from Ticona GmbH of Frankfurt, Germany and Summit, New Jersey), or the like can be used.
  • Other materials that allow UV light transmission could be used, such as quartz glass and sapphire.
  • reusable molds are used and the silicone-hydrogel lens- forming composition is cured actinically under a spatial limitation of actinic radiation to form a SiHy contact lens.
  • preferred reusable molds are those disclosed in U.S. patent application Nos. 08/274,942 filed July 14, 1994, 10/732,566 filed December 10, 2003,
  • Reusable molds can be made of quartz, glass, sapphire, CaF 2 , a cyclic olefin copolymer (such as for example, Topas ® COC grade 8007-S10 (clear amorphous copolymer of ethylene and norbornene) from Ticona GmbH of Frankfurt, Germany and Summit, New Jersey, Zeonex® and Zeonor® from Zeon Chemicals LP, Louisville, KY),
  • a cyclic olefin copolymer such as for example, Topas ® COC grade 8007-S10 (clear amorphous copolymer of ethylene and norbornene) from Ticona GmbH of Frankfurt, Germany and Summit, New Jersey, Zeonex® and Zeonor® from Zeon Chemicals LP, Louisville, KY
  • PMMA polymethylmethacrylate
  • Polyoxymethylene from DuPont DuPont
  • Ultem® polymethylmethacrylate
  • the silicone hydrogel (bulk material) of the inner layer has an oxygen permeability of at least about 50, preferably at least about 60, more preferably at least about 70, even more preferably at least about 90 barrers, most preferably at least about 110 Barrers.
  • the silicone hydrogel material can also have a (first) water content WC S iH y of from about 10% to about 70%, preferably from about 10% to about 65%, more preferably from about 10% to about 60%; even more preferably from about 15% to about 55%, most preferably from about 15% to about 50% by weight.
  • the silicone hydrogel material can further have a bulk elastic modulus or bulk Young Modulus (hereinafter the terms, “softness,” “elastic modulus,” and “Young's modulus” are interchangeably used in this application to mean bulk elastic modulus if the term is not modified by the word "surface.") of from about 0.3 MPa to about 1.8 MPa, preferably from 0.4 MPa to about 1.5 MPa, more preferably from about 0.5 MPa to about 1.2 MPa.
  • the oxygen permeability, elastic modulus and water content of the inner layer of the silicone hydrogel material of a SiHy contact lens of the invention can be determined by measuring the oxygen permeability, the elastic modulus and water content of the preformed SiHy lens from which the inner layer is derived.
  • the elastic modulus of a SiHy contact lens of the invention can be considered to be the elastic modulus of the silicone hydrogel material of the inner layer, because of the much thinner outer hydrogel layers.
  • a person skilled in the art knows well how to determine the elastic modulus and water content of a silicone hydrogel material or a SiHy contact lens. For example, all commercial SiHy contact lenses have reported values of elastic modulus and water content.
  • the two outer hydrogel layers of a SiHy contact lens of the invention preferably are substantially identical to each other and are a crosslinked coating which is applied onto a preformed SiHy contact lens having a desired Dk, water content, and bulk elastic modulus.
  • the layered structure configuration of a SiHy contact lens of the invention can be established by analysis with atomic force microscopy (AFM) of a cross section of a SiHy contact lens in fully hydrated state (i.e., directly in water or a buffered saline) as described above and shown in Examples.
  • AFM atomic force microscopy
  • the surface moduli of a cross section can be characterized (imaged) with AFM (e.g., Force-Volume mode) in order to visualize any changes in surface modulus from the posterior surface side to the anterior surface side across the cross section.
  • the average thickness of each outer hydrogel layer can be determined from the AFM image as well known to a person skilled in the art.
  • the two outer hydrogel layers of a SiHy contact lens of the invention are substantially uniform in thickness. They merge at the peripheral edge of the contact lens to completely enclose the inner layer of the silicone hydrogel material.
  • the thickness of each outer hydrogel layer is from about 0.1 ⁇ to about 20 ⁇ , preferably from about 0.25 ⁇ to about 15 ⁇ , even more preferably from about 0.5 ⁇ to about 12.5 ⁇ , most preferably from about 1 ⁇ to about 10 ⁇ .
  • the thickness of the outer hydrogel layers (or crosslinked coating) of a SiHy contact lens of the invention is determined by AFM analysis of a cross section of the SiHy contact lens in fully hydrated state as described above.
  • each outer hydrogel layer is preferably at most about 30% (i.e., 30% or less), preferably at most about 20% (20% or less), more preferably at most about 10% (10% or less) of the center thickness of the SiHy contact lens in fully hydrated state.
  • the layered structure configuration of a SiHy contact lens of the invention can also be established qualitatively by analysis with scanning electron microscopy (SEM) of a cross section of the freeze-dried SiHy contact lens as shown in Examples. SEM can show the different compositions and/or structures of each layers of a cross section of the SiHy contact lens in freeze-dried state.
  • SEM scanning electron microscopy
  • a significant change e.g., about 20% or greater, preferably about 30% or greater
  • a significant (visually noticeable) changes in structures indicates a transition from one layer to a different layer.
  • the thickness value based on SEM analysis of a cross section of a SiHy lens in freeze-dried state is typically lower than actual value because of collapse of the outer hydrogel layers, transition layer if applicable, and the inner layer after being freeze-dried.
  • the two outer hydrogel layers (the anterior and posterior outer hydrogel layers) of a SiHy contact lens of the invention comprise a (second) water content that must be higher than the (first) water content (WC S iH y ) of the inner layer of the silicone hydrogel material and more specifically must be at least about 1.2 folds (i.e., 120%) of the (first) water content (WC S iH y ) of the inner layer of the silicone hydrogel material. It is believed that the water-swelling ratio of each outer hydrogel layer correlates with its water content and as a good approximation can represent reasonably the water content of the outer hydrogel layer.
  • the water-swelling ratio of each outer hydrogel layer is at least about 150%; where the water content (WC S iH y ) of the inner layer of the silicone hydrogel material is about 60% or less, the water-swelling ratio of each outer hydrogel layer is at least about 200%; where the water content (WC S iH y ) of the inner layer of the silicone hydrogel material is about 65% or less, the water-swelling ratio of each outer hydrogel layer is at least about 250%; where the water content (WC S iH y ) of the inner layer of the silicone hydrogel material is about 70% or less, the water-swelling ratio of each outer hydrogel layer is at least about 300%.
  • the water content of the anterior and posterior outer hydrogel layers can be determined more accurately according to the procedures described in Example 23.
  • the water content of the two outer hydrogel layers can be determined with an article comprising a non-water-absorbent thin substrate and a crosslinked coating thereon, wherein the crosslinked coating is applied onto the non-water-absorbent thin substrate according to the identical coating process for the SiHy contact lens under substantial identical conditions.
  • the water content of each outer hydrogel layer then can be determined based on the difference between dry and hydrated weights of the article with the crosslinked coating.
  • each of the two outer hydrogel layers is substantially free of silicone, preferably totally free of silicone.
  • XPS X-ray photoelectron spectroscopy
  • the term "substantially free of silicon” is used in this application to mean that a surface silicon atomic percentage measured by XPS on a SiHy contact lens is less than about 200%, preferably less than about 175%, more preferably less than about 150%, even more preferably less than about 125% of the silicon atomic percentage of a control sample known to be inherently
  • silicon e.g., a polyethylene sheet, a DAILIES® AquaComfortPlusTM contact lens from CIBA VISION Corporation or an ACUVUE® Moist from Johnson & Johnson.
  • each outer hydrogel layer of a SiHy contact lens of the invention is substantially free of silicon, as characterized by having a silicon atomic percentage of about 5% or less, preferably about 4% or less, even more preferably about 3% or less, of total elemental percentage, as measured by XPS analysis of the contact lens in dried state. It is understood that a small percentage of silicone may be optionally (but preferably not) incorporated into the polymer network of the outer hydrogel layer so long as it would not significantly deteriorate the surface properties (hydrophilicity, wettability, and/or lubricity) of a SiHy contact lens.
  • the anterior and posterior outer hydrogel layers have a crosslinking density (or crosslink density) sufficient low to provide the crosslinked coating or the outer hydrogel layers (i.e., the SiHy contact lens) with a high digital-rubbing resistance as characterized by having no surface cracking lines visible under dark field after the SiHy contact lens is rubbed between fingers. It is believed that digital-rubbing- induced surface cracking may reduce the surface lubricity and/or may not be able prevent silicone from migrating onto the surface (exposure). Surface cracking may also indicate excessive crosslinking density in the surface layers which may affect the surface elastic modulus.
  • the non-silicone hydrogel material in the outer hydrogel layers (the crosslinked coating) comprises crosslinkages derived from azetidinium groups in a thermally-induced coupling reaction.
  • the anterior and posterior surfaces have a low surface concentration of negatively-charged groups including carboxylic acid groups as characterized by attracting at most about 200, preferably at most about 160, more preferably at most about 120, even more preferably at most about 90, most preferably at most about 60 positively-charged particles in positively-charged-particles-adhesion test.
  • the anterior and posterior outer hydrogel layers should have a relatively low carboxylic acid content.
  • the anterior and posterior outer hydrogel layers have a carboxylic acid content of about 20% by weight or less, preferably about 15% by weight or less, even more preferably about 10% by weight or less, most preferably about 5% by weight or less.
  • a SiHy contact lens of the invention has a good surface lubricity characterized by having a critical coefficient of friction (designated as CCOF) of about 0.046 or less, preferably about 0.043 or less, more preferably about 0.040 or less.
  • CCOF critical coefficient of friction
  • a SiHy contact lens of the invention preferably has a lubricity better than ACUVUE OASYS or ACUVUE TruEye as measured in a blind test according to the lubricity evaluation procedures described in Example 1.
  • a SiHy contact lens of the invention further comprises, in its layered structural configuration, two transition layers of polymeric material(s), as schematically illustrated in Figure 2. Each of the two transition layers 115 is located between the inner layer 110 and one of the two outer hydrogel layers 120. Each transition layer is
  • each transition layer is at least about 0.05 ⁇ , preferably from about 0.05 ⁇ to about 10 ⁇ , more preferably from about 0.1 ⁇ to about 7.5 ⁇ , even more preferably from about 0.15 ⁇ to about 5 ⁇ .
  • the transition layers merge at the peripheral edge of the contact lens to completely enclose the inner layer of the silicone hydrogel material.
  • the presence and thickness of the transition layers can be determined preferably by AFM analysis of a cross section of the SiHy contact lens in fully hydrated state as described above for the outer hydrogel layers and inner layers.
  • the two transition layers of a SiHy contact lens of the invention essentially are a base (or primer) coating which is applied onto a preformed SiHy contact lens having a desired Dk, water content, and bulk elastic modulus, before the crosslinked coating (the outer hydrogel layers) is applied thereon.
  • the transition layers (base coating) function to anchor/attach the outer hydrogel layers.
  • the transition layers comprise a carboxyl (COOH)-containing polymer, preferably a homo or copolymer of acrylic acid or methacrylic acid or C 2 -Ci 2 alkylacrylic acid. It is understood that the carboxyl-containing polymer may penetrate into the bulk material and extend into the outer hydrogel layers.
  • each transition layer When such penetration into the inner layer of the silicone hydrogel material occurs, each transition layer would comprise the carboxyl-containing polymer and the silicone hydrogel which are intertwined together. It is also believed that the presence of the transition layers, especially when comprising a carboxyl-containing polymer, may provide a relatively-high water content over a thicker layer and/or a water reservoir for the outer hydrogel layers, because of the high water-binding properties of carboxyl groups.
  • the transition layer may contain high carboxylic acid groups, it would have a minimal adverse impact upon the surface concentration of carboxylic acid groups of the SiHy contact lens, because the surface concentration of carboxylic acid groups is predominantly determined by the outer hydrogel layers which fully cover the transition layer.
  • the outer hydrogel layers with a low surface concentration of carboxylic acid groups can prevent the deposition of positively-charged proteins from the tears of a patient wearing the lens.
  • anterior and posterior outer hydrogel layers independent of each other have a reduced surface modulus of at least about 20%, preferably at least about 25%, more preferably at least about 30%, even more preferably at least about 35%, most preferably at least about 40%, relative to the inner layer.
  • the anterior and posterior outer hydrogel layers are preferably made of the same or substantially identical material(s) (preferably totally free of silicone) and can be formed by applying and crosslinking a water-soluble and crosslinkable hydrophilic polymeric material onto a preformed SiHy contact lens that comprises amino and/or carboxyl groups on and/or near the surface of the contact lens, or a base coating comprising amino and/or carboxyl groups, wherein the preformed SiHy contact lens becomes the inner layer after crosslinking.
  • a preformed SiHy contact lens can either inherently comprise or be modified to comprise amino groups and/or carboxyl groups on and/or near its surface.
  • a preformed SiHy contact lens inherently comprises amino groups and/or carboxyl groups on and/or near its surface, it is obtained by polymerizing a silicone hydrogel lens formulation comprising a reactive vinylic monomer.
  • Examples of preferred reactive vinylic monomers include without limitation amino-C 2 -C 6 alkyl (meth)acrylate, C C 6 alkylamino-C 2 -C 6 alkyl (meth)acrylate, allylamine, vinylamine, amino-C 2 -C 6 alkyl (meth)acrylamide, C C 6 alkylamino-C 2 -C 6 alkyl (meth)acrylamide, acrylic acid, C Ci 2 alkylacrylic acid (e.g., methacrylic acid, ethylacrylic acid, propylacrylic acid, butylacrylic acid, pentylacrylic acid, etc.), ⁇ , ⁇ -2-acrylamidoglycolic acid, beta methyl-acrylic acid (crotonic acid), alpha-phenyl acrylic acid, beta-acryloxy propionic acid, sorbic acid, angelic acid, cinnamic acid, 1-carobxy-4-phenyl butadiene-1 ,3, itaconic acid, citraconic acid,
  • (meth)acrylate C C 6 alkylamino-C 2 -C 6 alkyl (meth)acrylate, allylamine, vinylamine, amino-Cr C 6 alkyl (meth)acrylamide, C C 6 alkylamino-C 2 -C 6 alkyl (meth)acrylamide, acrylic acid, C Ci 2 alkylacrylic acid, ⁇ , ⁇ -2-acrylamidoglycolic acid, and combinations thereof.
  • the lens formulation comprises preferably from about 0.1 % to about 10%, more preferably from about 0.25% to about 7%, even more preferably from about 0.5% to about 5%, most preferably from about 0.75% to about 3%, by weight of a reactive vinylic monomer described above.
  • a preformed SiHy contact lens can also be subjected either to a surface treatment to form a reactive base coating having amino groups and/or carboxyl groups on the surface of the contact lens.
  • surface treatments include without limitation a surface treatment by energy (e.g., a plasma, a static electrical charge, irradiation, or other energy source), chemical treatments, chemical vapor deposition, the grafting of hydrophilic vinylic monomers or macromers onto the surface of an article, layer-by-layer coating ("LbL coating”) obtained according to methods described in US Patent Ser. No. 6,451 ,871 , 6,719,929, 6,793,973, 6,81 1 ,805, and 6,896,926 and in U.S. Patent Application Publication Nos.
  • LbL coating refers to a coating that is not covalently attached to the polymer matrix of a contact lens and is obtained through a layer-by-layer (“LbL") deposition of charged or chargeable (by protonation or deprotonation) and/or non-charged materials on the lens.
  • An LbL coating can be composed of one or more layers.
  • the surface treatment is an LbL coating process.
  • LbL coating process is an LbL coating process.
  • a resultant silicone hydrogel contact lens comprises a reactive LbL base coating (i.e., the two transition layers) including at least one layer of a reactive polymer (i.e., a polymer having pendant amino groups and/or carboxyl groups), wherein the reactive LbL base coating is obtained by contacting the contact lens with a solution of a reactive polymer.
  • a reactive LbL base coating i.e., the two transition layers
  • a reactive polymer i.e., a polymer having pendant amino groups and/or carboxyl groups
  • One contacting process involves solely dipping the contact lens in a bath of a coating solution for a period of time or alternatively dipping the contact lens sequentially in a series of baths of coating solutions for a fixed shorter time period for each bath.
  • Another contacting process involves solely spray a coating solution.
  • the contacting time of a contact lens with a coating solution of a reactive polymer may last up to about 10 minutes, preferably from about 5 to about 360 seconds, more preferably from about 5 to about 250 seconds, even more preferably from about 5 to about 200 seconds.
  • the reactive polymer can be a linear or branched polymer having pendant amino groups and/or carboxyl groups. Any polymers having pendant amino groups and/or carboxyl groups can be used as a reactive polymer for forming base coatings on silicone hydrogel contact lenses.
  • Examples of such reactive polymers include without limitation: a homopolymer of a reactive vinylic monomer; a copolymer of two or more reactive vinylic monomers; a copolymer of a reactive vinylic monomer with one or more non-reactive hydrophilic vinylic monomers (i.e., hydrophilic vinylic monomers free of any carboxyl or (primary or secondary) amino group); polyethyleneimine (PEI);
  • polyvinylalcohol with pendant amino groups e.g., polyvinylalcohol with pendant amino groups
  • a carboxyl-containing cellulose e.g.,
  • non-reactive hydrophilic vinylic monomers free of carboxyl or amino group include without limitation acrylamide (AAm), methacrylamide N,N- dimethylacrylamide (DMA), ⁇ , ⁇ -dimethylmethacrylamide (DMMA), N-vinylpyrrolidone (NVP), ⁇ , ⁇ ,-dimethylaminoethylmethacrylate (DMAEM), ⁇ , ⁇ -dimethylaminoethylacrylate (DMAEA), ⁇ , ⁇ -dimethylaminopropylmethacrylamide (DMAPMAm), N,N-dimethylaminopropylacrylamide (DMAPAAm), glycerol methacrylate, 3-acryloylamino-1-propanol, N-hydroxyethyl acrylamide, N- [tris(hydroxymethyl)methyl]-acrylamide, N-methyl-3-methylene-2-pyrrolidone, 1 -ethyl-3- methylene-2-pyrrolidone,
  • the reactive polymers for forming a reactive LbL base coating are polyacrylic acid, polymethacrylic acid, poly(C 2 -Ci 2 alkylacrylic acid), poly(acrylic acid-co-methacrylic acid), poly[C 2 -Ci2 alkylacrylic acid-co-(meth)acrylic acid], poly(N,N-2-acrylamidoglycolic acid), poly[(meth)acrylic acid-co-acrylamide], poly[(meth)acrylic acid-co-vinylpyrrolidone], poly[C 2 -Ci 2 alkylacrylic acid-co-acrylamide], poly[C 2 -Ci 2 alkylacrylic acid-co-vinylpyrrolidone], hydrolyzed poly[(meth)acrylic acid-co-vinylacetate], hydrolyzed poly[C 2 -Ci 2 alkylacrylic acid-co-vinylacetate], polyethyleneimine (PEI), polyallylamine hydrochloride (PAH)
  • polyvinylamine homo- or copolymer or combinations thereof.
  • the weight average molecular weight M w of a reactive polymer for forming a reactive LbL base coating is at least about 10,000 Daltons, preferably at least about 50,000 Daltons, more preferably from about 100,000 Daltons to 5,000,000 Daltons.
  • a solution of a reactive polymer for forming a reactive LbL base coating on contact lenses can be prepared by dissolving one or more reactive polymers in water, a mixture of water and one or more organic solvents miscible with water, an organic solvent, or a mixture of one or more organic solvent.
  • the reactive polymer is dissolved in a mixture of water and one or more organic solvents, an organic solvent, or a mixture of one or more organic solvent. It is believed that a solvent system containing at least one organic solvent can swell a preformed SiHy contact lens so that a portion of the reactive polymer may penetrate into the preformed SiHy contact lens and increase the durability of the reactive base coating.
  • Any organic solvents described above can be used in preparation of a solution of the reactive polymer, so long as it can dissolve the reactive polymer.
  • a preformed SiHy contact lens comprises inherently amino groups and/or carboxyl groups on and/or near its surface and is further subjected to a surface treatment to form a reactive LbL base coating having amino groups and/or carboxyl groups therein.
  • a preformed SiHy contact lens is subjected to a plasma treatment to form a covalently-attached reactive plasma base coating on the contact lens, i.e., polymerizing one or more reactive vinylic monomers (any one of those described previously) under the effect of plasma generated by electric discharge (so-called plasma-induced polymerization).
  • plasma denotes an ionized gas, e.g. created by electric glow discharge which may be composed of electrons, ions of either polarity, gas atoms and molecules in the ground or any higher state of any form of excitation, as well as of photons. It is often called "low temperature plasma".
  • the plasma-induced polymerization is an "afterglow” plasma-induced polymerization as described in WO98028026 (herein incorporated by reference in its entirety).
  • a non-polymerizable plasma gas e.g. H2, He or Ar
  • the surface thus activated is exposed to a vinylic monomer having an amino group or carboxyl group (any reactive vinylic monomer described above), while the plasma power having been switched off.
  • the activation results in the plasma-induced formation of radicals on the surface which in the subsequent step initiate the polymerization of the vinylic monomer thereon.
  • the water-soluble and crosslinkable hydrophilic polymeric material for forming the outer hydrogel layers (or crosslinked coating) comprises crosslinkable groups, preferably thermally-crosslinkable groups, more preferably azetidinium groups.
  • the water-soluble and crosslinkable hydrophilic polymeric material for forming the outer hydrogel layers (or crosslinked coating) is a partially-crosslinked polymeric material that comprises a three-dimensional network and crosslinkable (preferably thermally- crosslinkable) groups, more preferably azetidinium groups within the network.
  • crosslinkable groups include without limitation azetidinium groups, epoxy groups, isocyanate groups, aziridine groups, aziactone groups, and combinations thereof.
  • the water-soluble and crosslinkable hydrophilic polymeric material for forming the outer hydrogel layers (or crosslinked coating) comprises (i) from about 20% to about 95% by weight of first polymer chains derived from an epichlorohydrin- functionalized polyamine or polyamidoamine, (ii) from about 5% to about 80% by weight of hydrophilic moieties or second polymer chains derived from at least one hydrophilicity-enhancing agent having at least one reactive functional group selected from the group consisting of amino group, carboxyl group, thiol group, and combination thereof, wherein the hydrophilic moieties or second polymer chains are covalently attached to the first polymer chains through one or more covalent linkages each formed between one azetitdinium group of the epichlorohydrin- functionalized polyamine or polyamidoamine and one amino, carboxyl or thiol group of the hydrophilicity-enhancing agent, and (iii) azetidinium groups which are parts of the first polymer chains
  • the outer hydrogel layers can be formed by simply heating a preformed SiHy contact lens (having amino and/or carboxyl groups on and/or near the surface of the contact lens, or a base coating comprising amino and/or carboxyl groups) in an aqueous solution in the presence of the hydrophilic polymeric material to and at a temperature from about 40°C to about 140°C for a period of time sufficient to covalently attach the hydrophilic polymeric material onto the surface of the contact lens through covalent linkages each formed between one azetidinium group of the hydrophilic polymeric material and one of the amino and/or carboxyl groups on and/or near the surface of the contact lens, thereby forming a crosslinked hydrophilic coating on the contact lens.
  • any water-soluble and crosslinkable hydrophilic polymeric material containing crosslinkable groups can be used in the invention to form the anterior and posterior
  • a water-soluble and thermally-crosslinkable hydrophilic polymeric material containing azetidinium groups comprises (i.e., has a composition including) from about 20% to about 95%, preferably from about 35% to about 90%, more preferably from about 50% to about 85%, by weight of first polymer chains derived from an epichlorohydrin-functionalized polyamine or polyamidoamine and from about 5% to about 80%, preferably from about 10% to about 65%, even more preferably from about 15% to about 50%, by weight of hydrophilic moieties or second polymer chains derived from at least one hydrophilicity-enhancing agent having at least one reactive functional group selected from the group consisting of amino group, carboxyl group, thiol group, and combination thereof.
  • the composition of the hydrophilic polymeric material is determined by the composition (based on the total weight of the reactants) of a reactants mixture used for preparing the thermally-crosslinkable hydrophilic polymeric material according to the crosslinking reactions shown in Scheme I above. For example, if a reactant mixture comprises about 75% by weight of an epichlorohydrin-functionalized polyamine or polyamidoamine and about 25% by weight of at least one hydrophilicity-enhancing agent based on the total weight of the reactants, then the resultant hydrophilic polymeric material comprise about 75% by weight of first polymer chains derived from the epichlorohydrin-functionalized polyamine or
  • the azetidinium groups of the thermally-crosslinkable hydrophilic polymeric material are those azetidinium groups (of the epichlorohydrin-functionalized polyamine or polyamidoamine) which do not participate in crosslinking reactions for preparing the thermally-crosslinkable hydrophilic polymeric material.
  • An epichlorohydrin-functionalized polyamine or polyamidoamine can be obtained by reacting epichlorohydrin with a polyamine polymer or a polymer containing primary or secondary amino groups.
  • a poly(alkylene imines) or a poly(amidoamine) which is a polycondensate derived from a polyamine and a dicarboxylic acid (e.g., adipic acid- diethylenetriamine copolymers) can react with epichlorohydrin to form an epichlorohydrin- functionalized polymer.
  • a homopolymer or copolymer of aminoalkyl(meth)acrylate, mono-alkylaminoalkyl (meth)acrylate, aminoalkyl(meth)acrylamide, or mono-alkylaminoalkyl (meth)acrylamide can also react with epichlorohydrin to form an epichlorohydrin-functionalized polyamine.
  • the reaction conditions for epichlorohydrin-functionalization of a polyamine or polyamidoamine polymer are taught in EP1465931 (herein incorporated by reference in its entirety).
  • a preferred epichlorohydrin-functionalized polymer is polyaminoamide-epichlorohydrin (PAE) (or polyamide-polyamine-epichlorohydrin or polyamide-epichlorohydrin), such as, for example, Kymene® or Polycup ® resins (epichlorohydrin-functionalized adipic acid- diethylenetriamine copolymers) from Hercules or Polycup ® or Servamine® resins from
  • hydrophilicity-enhancing agents can be used in the invention so long as they contain at least one amino group, at least one carboxyl group, and/or at least one thiol group.
  • hydrophilicity-enhancing agents include without limitation: amino-, carboxyl- or thiol-containing monosaccharides (e.g., 3-amino-1 ,2-propanediol, 1 -thiolglycerol, 5- keto-D-gluconic acid, galactosamine, glucosamine, galacturonic acid, gluconic acid, glucosaminic acid, mannosamine, saccharic acid 1 ,4-lactone, saccharide acid, Ketodeoxynonulosonic acid, N- methyl-D-glucamine, 1 -amino-1 -deoxy-3-D-galactose, 1 -amino-1 -deoxysorbitol, 1 -methylamino- 1 -deoxysorbitol, N-aminoethyl gluconamide); amino-, carboxyl- or thiol-containing disaccharides (e.g., chondroitin disaccharide sodium salt
  • hydrophilicity-enhancing agents is hydrophilic polymers having one or more amino, carboxyl and/or thiol groups. More preferably, the content of monomeric units having an amino (-NHR' with R' as defined above), carboxyl (-COOH) and/or thiol (-SH) group in a hydrophilic polymer as a hydrophilicity-enhancing agent is less than about 40%, preferably less than about 30%, more preferably less than about 20%, even more preferably less than about 10%, by weight based on the total weight of the hydrophilic polymer.
  • hydrophilic polymers as hydrophilicity-enhancing agents are amino- or carboxyl-containing polysaccharides, for example, such as, carboxymethylcellulose (having a carboxyl content of about 40% or less, which is estimated based on the composition of repeating units,— [C6Hio-m0 5 (CH 2 CC>2H) m ]— in which m is 1 to 3), carboxyethylcellulose (having a carboxyl content of about 36% or less, which is estimated based on the composition of repeating units,— [C6Hio-m0 5 (C2H 4 CC>2H) m ]— in which m is 1 to 3) carboxypropylcellulose (having a carboxyl content of about 32% or less, which is estimated based on the composition of repeating units,— [C6Hio-m0 5 (C 3 H 6 CC>2H) m ]— , in which m is 1 to 3), hyaluronic acid (having a
  • hydrophilic polymers as hydrophilicity-enhancing agents include without limitation: poly(ethylene glycol) (PEG) with mono-amino, carboxyl or thiol group (e.g., PEG-NH 2 , PEG-SH, PEG-COOH); H 2 N-PEG-NH 2 ; HOOC-PEG-COOH; HS-PEG-SH; H 2 N- PEG-COOH; HOOC-PEG-SH; H 2 N-PEG-SH; multi-arm PEG with one or more amino, carboxyl or thiol groups; PEG dendrimers with one or more amino, carboxyl or thiol groups; a diamino- or dicarboxyl-terminated homo- or co-polymer of a non-reactive hydrophilic vinylic monomer; a monoamino- or monocarboxyl-terminated homo- or co-polymer of a non-reactive hydrophilic vinylic monomer; a copolymer
  • a hydrophilic polymer as a hydrophilicity-enhancing agent is PEG-NH 2 ; PEG-SH; PEG-COOH; H 2 N-PEG-NH 2 ; HOOC-PEG-COOH; HS-PEG-SH; H 2 N-PEG-COOH; HOOC-PEG-SH; H 2 N-PEG-SH; multi-arm PEG with one or more amino, carboxyl or thiol groups; PEG dendrimers with one or more amino, carboxyl or thiol groups; a monoamino-,
  • a non-reactive hydrophilic vinylic monomer selected from the group consisting of acrylamide (AAm), N,N- dimethylacrylamide (DMA), N-vinylpyrrolidone (NVP), N-vinyl-N-methyl acetamide, glycerol (meth)acrylate, hydroxyethyl (meth)acrylate, N-hydroxyethyl (meth)acrylamide, C C 4 -alkoxy polyethylene glycol (meth)acrylate having a weight average molecular weight of up to 400 Daltons, vinyl alcohol, N-methyl-3-methylene-2-pyrrolidone, 1-methyl-5-methylene-2-pyrrolidone, 5-methyl-3-methylene-2-pyrrolidone, ⁇ , ⁇ -dimethylaminoethyl (meth)acrylate, N,N- dimethylaminopropyl (metha)cryl
  • the hydrophilicity-enhancing agent as a hydrophilicity-enhancing agent is PEG-NH 2 ; PEG-SH; PEG-COOH; monoamino-, monocarboxyl-, diamino- or dicarboxyl- terminated polyvinylpyrrolidone; monoamino-, monocarboxyl-, diamino- or dicarboxyl-terminated polyacrylamide; monoamino-, monocarboxyl-, diamino- or dicarboxyl-terminated poly(DMA); monoamino- or monocarboxyl-, diamino- or dicarboxyl-terminated poly(DMA-co-NVP);
  • (meth)acryloyloxyethyl phosphorylcholine and (2) from about 0.1 % to about 30%, preferably from about 0.5% to about 20%, more preferably from about 1 % to about 15%, by weight of a carboxylic acid containing vinylic monomer and/or an amino-containing vinylic monomer, and combination thereof.
  • PEGs with functional groups and multi-arm PEGs with functional groups can be obtained from various commercial suppliers, e.g., Polyscience, and Shearwater Polymers, inc., etc.
  • Monoamino-, monocarboxyl-, diamino- or dicarboxyl-terminated homo- or copolymers of one or more non-reactive hydrophilic vinylic monomers or of a phosphorylcholine-containing vinylic monomer can be prepared according to procedures described in U.S. Patent No. 6,218,508, herein incorporated by reference in its entirety.
  • a diamino- or dicarboxyl-terminated homo- or co-polymer of a non-reactive hydrophilic vinylic monomer the non-reactive vinylic monomer, a chain transfer agent with an amino or carboxyl group (e.g., 2- aminoethanethiol, 2-mercaptopropinic acid, thioglycolic acid, thiolactic acid, or other
  • hydroxymercaptanes, aminomercaptans, or carboxyl-containing mercaptanes) and optionally other vinylic monomer are copolymerized (thermally or actinically) with a reactive vinylic monomer (having an amino or carboxyl group), in the presence of an free-radical initiator.
  • the molar ratio of chain transfer agent to that of all of vinylic monomers other than the reactive vinylic monomer is from about 1 :5 to about 1 : 100, whereas the molar ratio of chain transfer agent to the reactive vinylic monomer is 1 :1.
  • the chain transfer agent with amino or carboxyl group is used to control the molecular weight of the resultant hydrophilic polymer and forms a terminal end of the resultant hydrophilic polymer so as to provide the resultant hydrophilic polymer with one terminal amino or carboxyl group, while the reactive vinylic monomer provides the other terminal carboxyl or amino group to the resultant hydrophilic polymer.
  • a monoamino- or monocarboxyl-terminated homo- or co-polymer of a non-reactive hydrophilic vinylic monomer the non-reactive vinylic monomer, a chain transfer agent with an amino or carboxyl group (e.g., 2-aminoethanethiol, 2- mercaptopropinic acid, thioglycolic acid, thiolactic acid, or other hydroxymercaptanes, aminomercaptans, or carboxyl-containing mercaptanes) and optionally other vinylic monomers are copolymerized (thermally or actinically) in the absence of any reactive vinylic monomer.
  • an amino or carboxyl group e.g., 2-aminoethanethiol, 2- mercaptopropinic acid, thioglycolic acid, thiolactic acid, or other hydroxymercaptanes, aminomercaptans, or carboxyl-containing mercaptanes
  • a copolymer of a non-reactive hydrophilic vinylic monomer refers to a polymerization product of a non-reactive hydrophilic vinylic monomer with one or more additional vinylic monomers.
  • Copolymers comprising a non-reactive hydrophilic vinylic monomer and a reactive vinylic monomer can be prepared according to any well-known radical polymerization methods or obtained from commercial suppliers.
  • Copolymers containing methacryloyloxyethyl phosphorylcholine and carboxyl-containing vinylic monomer can be obtained from NOP Corporation (e.g., LIPIDURE® - A and -AF).
  • the weight average molecular weight M w of the hydrophilic polymer having at least one amino, carboxyl or thiol group is preferably from about 500 to about 1 ,000,000, more preferably from about 1 ,000 to about 500,000.
  • the reaction between a hydrophilicity-enhancing agent and an epichlorohydrin-functionalized polyamine or polyamidoamine is carried out at a temperature of from about 40°C to about 100°C for a period of time sufficient (from about 0.3 hour to about 24 hours, preferably from about 1 hour to about 12 hours, even more preferably from about 2 hours to about 8 hours) to form a water-soluble and thermally-crosslinkable hydrophilic polymeric material containing azetidinium groups.
  • the concentration of a hydrophilicity-enhancing agent relative to an epichlorohydrin-functionalized polyamine or polyamidoamine must be selected not to render a resultant hydrophilic polymeric material water-insoluble (i.e., a solubility of less than 0.005 g per 100 ml of water at room temperature) and not to consume more than about 99%, preferably about 98%, more preferably about 97%, even more preferably about 96% of the azetidinium groups of the epichlorohydrin-functionalized polyamine or polyamidoamine.
  • heating is performed preferably by autoclaving a preformed SiHy contact lens that comprises amino and/or carboxyl groups on and/or near the surface of the contact lens, or a base coating comprising amino and/or carboxyl groups and is immersed in a packaging solution (i.e., a buffered aqueous solution) including a water-soluble thermally crosslinkable hydrophilic polymeric material in a sealed lens package at a temperature of from about 1 18°C to about 125°C for approximately 20-90 minutes.
  • the packaging solution is a buffered aqueous solution which is ophthalmically safe after autoclave.
  • a preformed SiHy contact lens which comprises a base coating and a layer of a water-soluble thermally crosslinkabe hydrophilic polymeric material on top of the base coating, immersed in a packaging solution (i.e., a buffered aqueous solution) in a sealed lens package at a temperature of from about 1 18°C to about 125°C for approximately 20-90 minutes.
  • a packaging solution i.e., a buffered aqueous solution
  • Lens packages are well known to a person skilled in the art for autoclaving and storing a soft contact lens. Any lens packages can be used in the invention.
  • a lens package is a blister package which comprises a base and a cover, wherein the cover is detachably sealed to the base, wherein the base includes a cavity for receiving a sterile packaging solution and the contact lens.
  • Lenses are packaged in individual packages, sealed, and sterilized (e.g., by autoclave at about 120°C or higher for at least 30 minutes) prior to dispensing to users.
  • autoclave at about 120°C or higher for at least 30 minutes
  • a person skilled in the art will understand well how to seal and sterilize lens packages.
  • a packaging solution contains at least one buffering agent and one or more other ingredients known to a person skilled in the art.
  • other ingredients include without limitation, tonicity agents, surfactants, antibacterial agents, preservatives, and lubricants (or water-soluble viscosity builders) (e.g., cellulose derivatives, polyvinyl alcohol, polyvinylpyrrolidone).
  • the packaging solution contains a buffering agent in an amount sufficient to maintain a pH of the packaging solution in the desired range, for example, preferably in a physiologically acceptable range of about 6 to about 8.5.
  • a buffering agent in an amount sufficient to maintain a pH of the packaging solution in the desired range, for example, preferably in a physiologically acceptable range of about 6 to about 8.5.
  • Any known, physiologically compatible buffering agents can be used.
  • Suitable buffering agents as a constituent of the contact lens care composition according to the invention are known to the person skilled in the art. Examples are boric acid, borates, e.g. sodium borate, citric acid, citrates, e.g. potassium citrate, bicarbonates, e.g.
  • TRIS (2-amino-2-hydroxymethyl-1 ,3-propanediol), Bis-Tris (Bis-(2- hydroxyethyl)-imino-tris-(hydroxymethyl)-methane), bis-aminopolyols, triethanolamine, ACES (N- (2-hydroxyethyl)-2-aminoethanesulfonic acid), BES (N,N-Bis(2-hydroxyethyl)-2- aminoethanesulfonic acid), HEPES (4-(2-hydroxyethyl)-1-piperazineethanesulfonic acid), MES (2-(N-morpholino)ethanesulfonic acid), MOPS (3-[N-morpholino]-propanesulfonic acid), PIPES (piperazine-N,N'-bis(2-ethanesulfonic acid), TES (N-[Tris(hydroxymethyl)methyl]-2- aminoethanesulfonic acid), salts thereof
  • a preferred bis-aminopolyol is 1 ,3-bis(tris[hydroxymethyl]- methylamino)propane (bis-TRIS-propane).
  • the amount of each buffer agent in a packaging solution is preferably from 0.001 % to 2%, preferably from 0.01 % to 1 %; most preferably from about 0.05% to about 0.30% by weight.
  • the packaging solution has a tonicity of from about 200 to about 450 milliosmol (mOsm), preferably from about 250 to about 350 mOsm.
  • the tonicity of a packaging solution can be adjusted by adding organic or inorganic substances which affect the tonicity.
  • Suitable ocularly acceptable tonicity agents include, but are not limited to sodium chloride, potassium chloride, glycerol, propylene glycol, polyols, mannitols, sorbitol, xylitol and mixtures thereof.
  • a packaging solution of the invention has a viscosity of from about 1 centipoise to about 20 centipoises, preferably from about 1.2 centipoises to about 10 centipoises, more preferably from about 1.5 centipoises to about 5 centipoises, at 25°C.
  • the packaging solution comprises preferably from about 0.01 % to about 2%, more preferably from about 0.05% to about 1.5%, even more preferably from about 0.1 % to about 1 %, most preferably from about 0.2% to about 0.5%, by weight of a water-soluble and thermally-crosslinkable hydrophilic polymeric material of the invention.
  • a packaging solution of the invention can contain a viscosity-enhancing polymer.
  • the viscosity-enhancing polymer preferably is nonionic. Increasing the solution viscosity provides a film on the lens which may facilitate comfortable wearing of the contact lens.
  • the viscosity- enhancing component may also act to cushion the impact on the eye surface during insertion and serves also to alleviate eye irritation.
  • Preferred viscosity-enhancing polymers include, but are not limited to, water soluble cellulose ethers (e.g., methyl cellulose (MC), ethyl cellulose, hydroxymethylcellulose, hydroxyethyl cellulose (HEC), hydroxypropylcellulose (HPC), hydroxypropylmethyl cellulose (HPMC), or a mixture thereof), water-soluble polyvinylalcohols (PVAs), high molecular weight poly(ethylene oxide) having a molecular weight greater than about 2000 (up to 10,000,000 Daltons), polyvinylpyrrolidone with a molecular weight of from about 30,000 daltons to about 1 ,000,000 daltons, a copolymer of N-vinylpyrrolidone and at least one dialkylaminoalkyl (meth)acrylate having 7-20 carbon atoms, and combinations thereof.
  • water soluble cellulose ethers e.g., methyl cellulose (MC), ethyl cellulose, hydroxymethylcellulose,
  • Copolymers of vinylpyrrolidone and dimethylaminoethylmethacrylate are most preferred viscosity-enhancing polymers.
  • Copolymers of N-vinylpyrrolidone and dimethylaminoethylmethacrylate are commercially available, e.g., Copolymer 845 and
  • Copolymer 937 from ISP is Copolymer 937 from ISP.
  • the viscosity-enhancing polymer is present in the packaging solution in an amount of from about 0.01 % to about 5% by weight, preferably from about 0.05% to about 3% by weight, even more preferably from about 0.1 % to about 1 % by weight, based on the total amount of the packaging solution.
  • a packaging solution can further comprises a polyethylene glycol having a molecular weight of about 1200 or less, more preferably 600 or less, most preferably from about 100 to about 500 Daltons.
  • the packaging solution preferably comprises an a-oxo-multi-acid or salt thereof in an amount sufficient to have a reduced susceptibility to oxidation degradation of the polyethylene glycol segments.
  • a commonly-owned co-pending patent application discloses that oxo-multi-acid or salt thereof can reduce the susceptibility to oxidative degradation of a PEG-containing polymeric material.
  • Exemplary a-oxo-multi-acids or biocompatible salts thereof include without limitation citric acid, 2-ketoglutaric acid, or malic acid or biocompatible (preferably ophthalmically compatible) salts thereof. More preferably, a a-oxo-multi-acid is citric or malic acid or biocompatible
  • salts thereof e.g., sodium, potassium, or the like.
  • the packaging solution can further comprises mucin-like materials, ophthalmically beneficial materials, and/or surfactants.
  • mucin-like materials described above, exemplary ophthalmically beneficial materials described above, exemplary surfactants described above can be used in this embodiment.
  • a SiHy contact lens of the invention has a relatively long water break up time (WBUT).
  • WBUT is the time needed for the water film to break (de-wet) exposing the underlying lens material under visual examination.
  • a SiHy contact lens having a longer WBUT can hold water (tears) film on its surface for a relatively longer period time when worn on the eye. It would be less likely to develop dry spots between blinks of the eyelids and could provide enhanced wearing comfort.
  • WBUT can be measured according to the procedures described in Example hereinafter.
  • a SiHy contact lens of the invention has a surface hydrophilicity characterized by having a water breakup time of at least about 10 seconds.
  • a SiHy contact lens of the invention has a surface wettability characterized by having an averaged water contact angle of about 90 degrees or less, preferably about 80 degrees or less, more preferably about 70 degrees or less, even more preferably about 60 degrees or less, most preferably about 50 degrees or less.
  • a SiHy contact lens has an oxygen transmissibility of at least about 40, preferably at least about 60, more preferably at least about 80, even more preferably at least about 100, most preferably at least about 120, barrers/mm.
  • a hydrated silicone hydrogel contact lens of the invention comprises: a silicone hydrogel material as bulk material, an anterior surface and an opposite posterior surface; wherein the contact lens has an oxygen transmissibility of at least about 40, preferably at least about 60, more preferably at least about 80, even more preferably at least about 1 10 barrers/mm, and a cross-sectional surface-modulus profile which comprises, along a shortest line between the anterior and posterior surfaces on the surface of a cross section of the contact lens, an anterior outer zone including and near the anterior surface, an inner zone including and around the center of the shortest line, and a posterior outer zone including and near the posterior surface, wherein the anterior outer zone has an average anterior surface modulus (designated as SM ⁇ ) while the posterior outer zone has an average posterior surface modulus (designated as SM Post ), wherein the inner zone has an average inner surface modulus (designated as SM Inner ), wherein at least
  • one of xl00% and Inner Ant xl00% is at least about 20%, preferably at
  • the anterior and posterior outer zones covers a span of at least about 0.1 ⁇ , preferably from about 0.1 ⁇ to about 20 ⁇ , more preferably from about 0.25 ⁇ to about 15 ⁇ , even more preferably from about 0.5 ⁇ to about 12.5 ⁇ , most preferably from about 1 ⁇ to about 10 ⁇ .
  • the hydrated silicone hydrogel contact lens can have an elastic modulus (or Young's Modulus) of from about 0.3 MPa to about 1.8 MPa, preferably from about 0.4 MPa to about 1.5 MPa, more preferably from about 0.5 MPa to about 1.2 MPa; a water content of from about 10% to about 75%, preferably from about 10% to about 70%, more preferably from about 15% to about 65%; even more preferably from about 20% to about 60%, most preferably from about 25% to about 55% by weight; a surface wettability characterized by having an averaged water contact angle of about 90 degrees or less, preferably about 80 degrees or less, more preferably about 70 degrees or less, even more preferably about 60 degrees or less, most preferably about 50 degrees or less; a surface hydrophilicity characterized by having a WBUT of at least about 10 seconds; or combinations thereof.
  • an elastic modulus or Young's Modulus
  • the anterior and posterior surfaces have a low surface concentration of negatively-charged groups (e.g., carboxylic acid groups) as characterized by attracting at most about 200, preferably at most about 160, more preferably at most about 120, even more preferably at most about 90, most preferably at most about 60 positively-charged particles in positively-charged-particles-adhesion test.
  • the anterior and posterior outer hydrogel layers should have a relatively low carboxylic acid content.
  • the anterior and posterior outer hydrogel layers have a carboxylic acid content of about 20% by weight or less, preferably about 15% by weight or less, even more preferably about 10% by weight or less, most preferably about 5% by weight or less.
  • a SiHy contact lens of the invention has a good surface lubricity characterized by having a critical coefficient of friction (designated as CCOF) of about 0.046 or less, preferably about 0.043 or less, more preferably about 0.040 or less.
  • CCOF critical coefficient of friction
  • a SiHy contact lens of the invention preferably has a lubricity better than ACUVUE OASYS or ACUVUE TruEye as measured in a blind test according to the lubricity evaluation procedures described in Example 1.
  • the hydrated SiHy contact lens preferably has a high digital-rubbing resistance as characterized by having no surface cracking lines visible under dark field after the SiHy contact lens is rubbed between fingers. It is believed that digital-rubbing- induced surface cracking may reduce the surface lubricity and/or may not be able prevent silicone from migrating onto the surface (exposure).
  • a hydrated SiHy contact lens of the invention comprises an inner layer of the silicone hydrogel material, an anterior outer hydrogel layer, and a posterior outer hydrogel layer, wherein the anterior and posterior outer hydrogel layers are substantially uniform in thickness and merge at the peripheral edge of the contact lens to completely enclose the inner layer of the silicone hydrogel material.
  • the first and second outer zones in the cross-sectional surface modulus profile correspond to the two outer hydrogel layers while the inner zone corresponds to the inner layer of the silicone hydrogel material. All of the various embodiments of the outer hydrogel layers (crosslinked coating) as described above for the other aspect of the invention can be used, alone or in any combination, in this aspect of the invention as the outer hydrogel layers.
  • the outer hydrogel layers are substantially uniform in thickness and have a thickness of at least about 0.1 ⁇ , preferably from about 0.1 ⁇ to about 20 ⁇ , more preferably from about 0.25 ⁇ to about 15 ⁇ , even more preferably from about 0.5 ⁇ to about 12.5 ⁇ , most preferably from about 1 ⁇ to about 10 ⁇ .
  • each outer hydrogel layer of a SiHy contact lens of the invention is determined by AFM analysis of a cross section of the SiHy contact lens in fully hydrated state as described above.
  • the thickness of each outer hydrogel layer is at most about 30% (i.e., 30% or less), preferably at most about 20% (20% or less), more preferably at most about 10% (10% or less) of the center thickness of the SiHy contact lens in fully hydrated state.
  • each of the two outer hydrogel layers is substantially free of silicone (as characterized by having a silicon atomic percentage of about 5% or less, preferably about 4% or less, even more preferably about 3% or less, of total elemental percentage, as measured by XPS analysis of the contact lens in dried state), preferably totally free of silicone. It is understood that a small percentage of silicone may be optionally (but preferably not) incorporated into the polymer network of the outer hydrogel layer so long as it would not significantly deteriorate the surface properties (hydrophilicity, wettability, and/or lubricity) of a SiHy contact lens.
  • the two outer hydrogel layers of a hydrated SiHy contact lens of the invention comprise a water content higher than the water content (designated WC L ens) of the hydrated silicone hydrogel contact lens and more specifically must be at least about 1.2 folds (i.e., 120%) of WC Le ns- It is believed that the water-swelling ratio of each outer hydrogel layer can represent approximately the water content of the outer hydrogel layer as discussed above. Where WC Le ns is about 45% or less, the water-swelling ratio of each outer hydrogel layer is preferably at least at least about 150%, more preferably at least about 200%, more preferably at least about 250%, even more preferably at least about 300%.
  • the water-swelling ratio of each outer hydrogel layer is at least about 120 » WC Lens % ferab
  • WC L ens is about 55% or less, the water-swelling ratio of each outer hydrogel layer is at least about 150%; where WC Len s is about 60% or less, the water-swelling ratio of each outer hydrogel layer is at least about 200%; where WC Len s is about 65% or less, the water-swelling ratio of each outer hydrogel layer is at least about 250%; where WC Len s WC Len s is about 70% or less, the water-swelling ratio of each outer hydrogel layer is at least about 300%.
  • the SiHy contact lens further comprises a transition layer located between the silicone hydrogel material and the outer hydrogel layer.
  • a transition layer located between the silicone hydrogel material and the outer hydrogel layer. All of the various embodiments of the transition layer as described for the previous aspect of the invention can be used, alone or in any combination, in this aspect of the invention.
  • a hydrated SiHy contact lens of the invention can be prepared according to the methods described above. All of the various embodiments of the inner layer (i.e., silicone hydrogel material) described above can be used, alone or in any combination, in this aspect of the invention as the silicone hydrogel core. All of the various embodiments as described above for the previous aspect of the invention can be used, alone or in any combination, in this aspect of the invention.
  • silicone hydrogel material i.e., silicone hydrogel material
  • a hydrated silicone hydrogel contact lens of the invention comprises: a silicone hydrogel material as bulk material, an anterior surface and an opposite posterior surface; wherein the contact lens has (1 ) an oxygen transmissibility of at least about 40, preferably at least about 60, more preferably at least about 80, even more preferably at least about 1 10 barrers/mm, and (2) a surface lubricity characterized by having a critical coefficient of friction (designated as CCOF) of about 0.046 or less, preferably about 0.043 or less, more preferably about 0.040 or less, wherein the anterior and posterior surfaces have a low surface concentration of negatively-charged groups including carboxylic acid groups as characterized by attracting at most about 200, preferably at most about 160, more preferably at most about 120, even more preferably at most about 90, most preferably at most about 60 positively-charged particles in positively-charged- particles-adhesion test.
  • CCOF critical coefficient of friction
  • the hydrated silicone hydrogel contact lens has an elastic modulus (or Young's Modulus) of from about 0.3 MPa to about 1.8 MPa, preferably from about 0.4 MPa to about 1.5 MPa, more preferably from about 0.5 MPa to about 1.2 MPa; a water content of from about 10% to about 75%, preferably from about 10% to about 70%, more preferably from about 15% to about 65%; even more preferably from about 20% to about 60%, most preferably from about 25% to about 55% by weight; a surface wettability characterized by having an averaged water contact angle of about 90 degrees or less, preferably about 80 degrees or less, more preferably about 70 degrees or less, even more preferably about 60 degrees or less, most preferably about 50 degrees or less; a surface hydrophilicity characterized by having a WBUT of at least about 10 seconds; or combinations thereof.
  • an elastic modulus or Young's Modulus
  • the hydrated SiHy contact lens preferably has a high digital-rubbing resistance as characterized by having no surface cracking lines visible under dark field after the SiHy contact lens is rubbed between fingers. It is believed that digital-rubbing- induced surface cracking may reduce the surface lubricity and/or may not be able prevent silicone from migrating onto the surface (exposure).
  • a hydrated SiHy contact lens of the invention comprises an inner layer of the silicone hydrogel material, an anterior outer hydrogel layer, and a posterior outer hydrogel layer, wherein the anterior and posterior outer hydrogel layers are substantially uniform in thickness and merge at the peripheral edge of the contact lens to completely enclose the inner layer of the silicone hydrogel material.
  • the first and second outer zones in the cross-sectional surface modulus profile correspond to the two outer hydrogel layers while the inner zone corresponds to the inner layer of the silicone hydrogel material.
  • All of the various embodiments of the outer hydrogel layers (crosslinked coating) as described above for the other aspect of the invention can be used, alone or in any combination, in this aspect of the invention as the outer hydrogel layers.
  • All of the various embodiments of the inner layer of a silicone hydrogel material as described above for the other aspect of the invention can be used, alone or in any combination, in this aspect of the invention as the inner layer of the silicone hydrogel material.
  • the outer hydrogel layers are
  • each outer hydrogel layer of a SiHy contact lens of the invention is determined by AFM analysis of a cross section of the SiHy contact lens in fully hydrated state as described above.
  • each outer hydrogel layer is preferably at most about 30% (i.e., 30% or less), preferably at most about 20% (20% or less), more preferably at most about 10% (10% or less) of the center thickness of the SiHy contact lens in fully hydrated state.
  • each of the two outer hydrogel layers is substantially free of silicone (as characterized by having a silicon atomic percentage of about 5% or less, preferably about 4% or less, even more preferably about 3% or less, of total elemental percentage, as measured by XPS analysis of the contact lens in dried state), preferably totally free of silicone.
  • the anterior and posterior outer hydrogel layers should have a relatively low carboxylic acid content.
  • the anterior and posterior outer hydrogel layers have a carboxylic acid content of about 20% by weight or less, preferably about 15% by weight or less, even more preferably about 10% by weight or less, most preferably about 5% by weight or less.
  • the two outer hydrogel layers of a hydrated SiHy contact lens of the invention comprise a water content higher than the water content (designated WC L ens) of the hydrated silicone hydrogel contact lens and more specifically must be at least about 1.2 folds (i.e., 120%) of the water content (WC Le ns) of the hydrated silicone hydrogel contact lens. It is believed that the water-swelling ratio of each outer hydrogel layer can represent approximately the water content of the outer hydrogel layer as discussed above.
  • the water-swelling ratio of each outer hydrogel layer is preferably at least at least about 150%, more preferably at least about 200%, more preferably at least about 250%, even more preferably at least about 300%. Where WC Len s is higher than 45%, the water-swelling ratio of each outer hydrogel layer is at least about — ⁇ "/o , preferably
  • water-swelling ratio of each outer hydrogel layer is at least about 150%; where WC Len s is about 60% or less, the water-swelling ratio of each outer hydrogel layer is at least about 200%; where WC L ens is about 65% or less, the water-swelling ratio of each outer hydrogel layer is at least about 250%; where WC Len s is about 70% or less, the water-swelling ratio of each outer hydrogel layer is at least about 300%.
  • anterior and posterior outer hydrogel layers independent of each other have a reduced surface modulus of at least about 20%, preferably at least about 25%, more preferably at least about 30%, even more preferably at least about 35%, most preferably at least about 40%, relative to the inner layer.
  • the SiHy contact lens further comprises a transition layer located between the silicone hydrogel material and the outer hydrogel layer.
  • a transition layer located between the silicone hydrogel material and the outer hydrogel layer. All of the various embodiments of the transition layer as described for the previous aspect of the invention can be used, alone or in any combination, in this aspect of the invention.
  • a hydrated SiHy contact lens of the invention can be prepared according to the methods described above. All of the various embodiments of the inner layer (i.e., silicone hydrogel material) described above can be used, alone or in any combination, in this aspect of the invention as the silicone hydrogel core. All of the various embodiments as described above for the previous aspect of the invention can be used, alone or in any combination, in this aspect of the invention. It should be understood that although in this aspect of the invention various embodiments including preferred embodiments of the invention may be separately described above, they can be combined and/or used together in any desirable fashion to arrive at different embodiments of a silicone hydrogel contact lenses of the invention. All of the various embodiments described above for the previous aspect of the invention can be used alone or in combination in any desirable fashion in this aspect of the invention.
  • the apparent oxygen permeability of a lens and oxygen transmissibility of a lens material is determined according to a technique similar to the one described in U.S. Patent No. 5,760,100 and in an article by Winterton et al., (The Cornea: Transactions of the World Congress on the Cornea 1 1 1 , H.D. Cavanagh Ed., Raven Press: New York 1988, pp273-280), both of which are herein incorporated by reference in their entireties.
  • Oxygen fluxes (J) are measured at 34°C in a wet cell (i.e., gas streams are maintained at about 100% relative humidity) using a Dk1000 instrument (available from Applied Design and Development Co., Norcross, GA), or similar analytical instrument.
  • An air stream having a known percentage of oxygen (e.g., 21 %), is passed across one side of the lens at a rate of about 10 to 20 cm 3 /min., while a nitrogen stream is passed on the opposite side of the lens at a rate of about 10 to 20 cm 3 /min.
  • a sample is equilibrated in a test media (i.e., saline or distilled water) at the prescribed test temperature for at least 30 minutes prior to measurement but not more than 45 minutes. Any test media used as the overlayer is equilibrated at the prescribed test temperature for at least 30 minutes prior to measurement but not more than 45 minutes.
  • the stir motor's speed is set to 1200 ⁇ 50 rpm, corresponding to an indicated setting of 400 ⁇ 15 on the stepper motor controller.
  • the barometric pressure surrounding the system, Pmeasured, is measured.
  • the thickness (t) of the lens in the area being exposed for testing is determined by measuring about 10 locations with a Mitotoya micrometer VL-50, or similar instrument, and averaging the measurements.
  • the oxygen concentration in the nitrogen stream i.e., oxygen which diffuses through the lens
  • the apparent oxygen permeability of the lens material, Dk app is determined from the following formula:
  • Dkgpp is expressed in units of barrers.
  • the apparent oxygen transmissibility (Dk It) of the material may be calculated by dividing the apparent oxygen permeability (Dk app ) by the average thickness (t) of the lens.
  • the above described measurements are not corrected for the so-called boundary layer effect which is attributable to the use of a water or saline bath on top of the contact lens during the oxygen flux measurement.
  • the boundary layer effect causes the reported value for the apparent Dk of a silicone hydrogel material to be lower than the actual intrinsic Dk value. Further, the relative impact of the boundary layer effect is greater for thinner lenses than with thicker lenses. The net effect is that the reported Dk appear to change as a function of lens thickness when it should remain constant.
  • the intrinsic Dk value of a lens can be estimated based on a Dk value corrected for the surface resistance to oxygen flux caused by the boundary layer effect as follows.
  • a thickness series should cover a thickness range of approximately 100 ⁇ or more.
  • the range of reference lens thicknesses will bracket the test lens thicknesses.
  • the Dk app of these reference lenses must be measured on the same equipment as the test lenses and should ideally be measured contemporaneously with the test lenses.
  • the equipment setup and measurement parameters should be held constant throughout the experiment. The individual samples may be measured multiple times if desired.
  • the estimated intrinsic Dk of the test lens can be used to calculate what the apparent Dk (Dk a s td) would have been for a standard thickness lens in the same test environment based on Equation 3.
  • the standard thickness (t st d) for lotrafilcon A 85 ⁇ .
  • the standard thickness for lotrafilcon B 60 ⁇ .
  • the ion permeability of a lens is measured according to procedures described in U.S. Patent No. 5,760, 100 (herein incorporated by reference in its entirety.
  • the values of ion permeability reported in the following examples are relative ionoflux diffusion coefficients (D/D ref ) in reference to a lens material, Alsacon, as reference material.
  • Alsacon has an ionoflux diffusion coefficient of 0.314X10 3 mm 2 /minute.
  • the lubricity rating is a qualitative ranking scheme where 0 is assigned to control lenses coated with polyacrylic acid, 1 is assigned to OasysTM/TruEyeTM commercial lenses and 4 is assigned to commercial Air OptixTM lenses.
  • the samples are rinsed with excess Dl water for at least three times and then transferred to PBS before the evaluation. Before the evaluation, hands are rinsed with a soap solution, extensively rinsed with Dl water and then dried with KimWipe® towels.
  • the samples are handled between the fingers and a numerical number is assigned for each sample relative to the above standard lenses described above. For example, if lenses are determined to be only slightly better than Air OptixTM lenses, then they are assigned a number 3. For consistency, all ratings are independently collected by the same two operators in order to avoid bias and the data reveal good qualitative agreement and consistency in the evaluation.
  • Water contact angle on a contact lens is a general measure of the surface wettability of the contact lens. In particular, a low water contact angle corresponds to more wettable surface.
  • Average contact angles (Sessile Drop) of contact lenses are measured using a VCA 2500 XE contact angle measurement device from AST, Inc., located in Boston, Massachusetts. This equipment is capable of measuring advancing or receding contact angles or sessile (static) contact angles. The measurements are performed on fully hydrated contact lenses and immediately after blot-drying as follows. A contact lens is removed from the vial and washed 3 times in ⁇ 200ml of fresh Dl water in order to remove loosely bound packaging additives from the lens surface. The lens is then placed on top of a lint-free clean cloth (Alpha Wipe TX1009), dabbed well to remove surface water, mounted on the contact angle
  • the Dl water used for measuring the contact angle has a resistivity > 18MQcm and the droplet volume used is 2 ⁇ .
  • uncoated silicone hydrogel lenses after autoclave have a sessile drop contact angle around 120 degrees. The tweezers and the pedestal are washed well with Isopropanol and rinsed with Dl water before coming in contact with the contact lenses.
  • WBUT Water Break-up Time Tests.
  • the surface hydrophilicity of the lenses (after autoclave) is assessed by determining the time required for the water film to start breaking on the lens surface. Briefly, lenses are removed from the vial and washed 3 times in ⁇ 200ml of fresh Dl water in order to remove loosely bound packaging additives from the lens surface. The lens is removed from the solution and held with tweezers against a bright light source. The time that is needed for the water film to break (de-wet) exposing the underlying lens material is noted visually. Uncoated lenses typically instantly break upon removal from Dl water and are assigned a WBUT of 0 seconds. Lenses exhibiting WBUT ⁇ 5 seconds are considered good hydrophilicity and are expected to exhibit adequate ability to support the tear film on-eye.
  • the intactness of a coating on the surface of a contact lens can be tested according to Sudan Black stain test as follow.
  • Contact lenses with a coating are dipped into a Sudan Black dye solution (Sudan Black in vitamin E oil) and then rinsed extensively in water.
  • Sudan Black dye is hydrophobic and has a great tendency to be absorbed by a hydrophobic material or onto a hydrophobic lens surface or hydrophobic spots on a partially coated surface of a hydrophobic lens (e.g., silicone hydrogel contact lens). If the coating on a hydrophobic lens is intact, no staining spots should be observed on or in the lens. All of the lenses under test are fully hydrated.
  • the lenses are digitally rubbed with Solo-care® multi-purpose lens care solution for 30 times and then rinsed with saline. The above procedure is repeated for a given times, e.g., from 1 to 30 times, (i.e., number of consecutive digital rubbing tests which imitate cleaning and soaking cycles).
  • the lenses are then subjected to Sudan Black test (i.e., coating intactness test described above) to examine whether the coating is still intact.
  • Sudan Black test i.e., coating intactness test described above
  • staining spots e.g., staining spots covering no more than about 5% of the total lens surface. Water contact angles are measured to determine the coating durability.
  • azetidinium content in PAE can be determined according to one of the following assays.
  • PAE charge density i.e., azetidinium content
  • PAE charge density can be determined according to PPVS assay, a colorimetric titration assay where the titrant is potassium vinyl sulfate (PPVS) and Toluidine Blue is the indicator.
  • PPVS a colorimetric titration assay where the titrant is potassium vinyl sulfate (PPVS) and Toluidine Blue is the indicator.
  • PPVS binds positively-charged species, e.g., Toluidine Blue and the azetidinium groups of PAE. Decreases in Toluidine Blue absorbance intensities are indicative of proportionate PAE charge density (azetidinium content).
  • PES-Na assay is another colorimetric titration assay for determining PAE charge density (azetidinium content).
  • the titrant is Sodium- polyethylensulphonate (PES-Na) instead of PPVS.
  • PES-Na Sodium- polyethylensulphonate
  • PCD assays are a potentiometric titration assay for determining PAE charge density (azetidinium content).
  • the titrant is Sodium-polyethylensulphonate (PES-Na), PPVS or other titrant.
  • the active positively charged moiety in PAE is the azetidinium group (AZR).
  • the NMR ratio method is a ratio of the number of AZR group-specific protons versus the number of non-AZR related protons. This ratio is an indicator of the charge or AZR density for PAE.
  • Debris Adhesion Test Contact lenses with a highly charged surface can be susceptible to increased debris adhesion during patient handling. A paper towel is rubbed against gloved hands and then both sides of the lens are rubbed with the fingers to transfer any debris to the lens surface. The lens is briefly rinsed and then observed under a microscope. A qualitative rating scale from 0 (no debris adhesion) to 4 (debris adhesion equivalent to a PAA coated control lens) is used to rate each lens. Lenses with a score of "0" or "1 " are deemed to be acceptable.
  • Example 2 Example 2
  • IPDI isophorone diisocyanate
  • the reactor is held for 4.5 h at about 40° C, forming HO-PDMS- IPDI-PDMS-IPDI-PDMS-OH.
  • MEK is then removed under reduced pressure.
  • the terminal hydroxyl-groups are capped with methacryloyloxyethyl groups in a third step by addition of 7.77 g of isocyanatoethylmethacrylate (IEM) and an additional 0.063 g of DBTDL, forming IEM-PDMS-IPDI-PDMS-IPDI-PDMS-IEM (i.e., CE-PDMS terminated with methacrylate groups).
  • IEM isocyanatoethylmethacrylate
  • 240.43 g of KF-6001 is added into a 1-L reactor equipped with stirring, thermometer, cryostat, dropping funnel, and nitrogen/vacuum inlet adapter, and then dried by application of high vacuum (2x10 "2 mBar). Then, under an atmosphere of dry nitrogen, 320 g of distilled MEK is then added into the reactor and the mixture is stirred thoroughly. 0.235 g of DBTDL is added to the reactor. After the reactor is warmed to 45°C, 45.86 g of IPDI are added through an addition funnel over 10 minutes to the reactor under moderate stirring. The reaction is kept for 2 hours at 60°C.
  • a lens formulation is prepared by dissolving components in 1-propanol to have the following composition: 33% by weight of CE-PDMS macromer prepared in Example 2, 17% by weight of N-[tris(trimethylsiloxy)-silylpropyl]acrylamide (TRIS-Am), 24% by weight of N,N- dimethylacrylamide (DMA), 0.5% by weight of N-(carbonyl-methoxypolyethylene glycol-2000)- 1 ,2-disteaoyl-sn-glycero-3-phosphoethanolamin, sodium salt) (L-PEG), 1.0% by weight Darocur 1173 (DC1 173), 0.1 % by weight of visitint (5% copper phthalocyanine blue pigment dispersion in tris(trimethylsiloxy)silylpropylmethacrylate, TRIS), and 24.5% by weight of 1-propanol.
  • TRIS tris(trimethylsiloxy)silylpropylmethacrylate
  • Lenses are prepared by cast-molding from the lens formulation prepared above in a reusable mold, similar to the mold shown in Figs. 1-6 in U.S. patent Nos.7,384,590 and
  • the mold comprises a female mold half made of CaF 2 and a male mold half made of PMMA.
  • the UV irradiation source is a Hamamatsu lamp with the WG335 +TM297 cut off filter at an intensity of about 4 mW /cm 2 .
  • the lens formulation in the mold is irradiated with UV irradiation for about 25 seconds. Cast-molded lenses are extracted with isopropanol (or methyl ethyl ketone, MEK), rinsed in water, coated with polyacrylic acid (PAA) by dipping lenses in a propanol solution of PAA (0.1 % by weight, acidified with formic acid to about pH 2.5), and hydrated in water.
  • PAA polyacrylic acid
  • Resultant lenses having a reactive PAA-LbL base coating thereon are determined to have the following properties: ion permeability of about 8.0 to about 9.0 relative to Alsacon lens material; apparent Dk (single point) of about 90 to 100; a water content of about 30% to about 33%; and a bulk elastic modulus of about 0.60 MPa to about 0.65 MPa.
  • IPC in-package coating
  • PBS phosphate buffer saline
  • Lenses from Example 3 are placed in a polypropylene lens packaging shell with 0.6 mL of the IPC saline (half of the IPC saline is added prior to inserting the lens). The blister is then sealed with foil and autoclaved for about 30 minutes at 121°C, forming crosslinked coatings (PAA-x-PAE coating) on the lenses.
  • IPC saline half of the IPC saline is added prior to inserting the lens.
  • the blister is then sealed with foil and autoclaved for about 30 minutes at 121°C, forming crosslinked coatings (PAA-x-PAE coating) on the lenses.
  • the test lenses (packaged/autoclaved in the IPC saline, i.e., lenses having PAA-x-PAE coating thereon) show no debris adhesion after being rubbed against a paper towel while control lenses (packaged/autoclaved in PBS, i.e., lenses having a PAA-LbL base coating thereon) show severe debris adhesion.
  • the water contact angle (WCA) of the test lenses is low (-20 degrees) but the WBUT is less than 2 seconds. When observed under dark field microscope, severe cracking lines are visible after handling the lens (lens inversion and rubbing between the fingers). The test lenses are much less lubricous than the control lenses as judged by a qualitative finger-rubbing test.
  • Example 5 Example 5
  • Poly(acrylamide-co-acrylic acid) (or PAAm-PAA or poly(AAm-co-AA) or p(AAm-co-AA)) partial sodium salt ( -80% solid content, Poly(AAm-co-AA)( 80/20), Mw. 520,000, Mn 150,000) is purchased from Aldrich and used as received.
  • IPC saline is prepared by dissolving 0.02% of Poly(AAm-co-AA)(80/20) and 0.2% of PAE (Kymene from Ashland as an aqueous solution and used as received, azetidinium content of 0.46 assayed with NMR) in PBS. The pH is adjusted to 7.2-7.4. PBS is prepared by dissolving 0.76% NaCI, 0.044% NaH 2 P0 4 H 2 0 and 0.388% Na 2 HPCy2H 2 0 in water.
  • Lenses having a PAA-LbL base coating thereon prepared in Example 3 are placed in a polypropylene lens packaging shell with 0.6 mL of the IPC saline (half of the saline is added prior to inserting the lens). The blister is then sealed with foil and autoclaved for about 30 minutes at about 121 °C. It is believed that a crosslinked coating composed of three layers PAA-x-PAE-x- poly(AAm-co-AA) is formed on the lenses during autoclave.
  • test lenses (packaged/autoclaved in the IPC saline, i.e., lenses having PAA-x-PAE- x-poly(AAm-co-AA) crosslinked coating thereon) have no debris adhesion after being rubbed against a paper towel.
  • the test lenses have a WBUT of longer than 10 seconds. When observed under dark field microscope, cracking lines are visible after rubbing the test lenses.
  • the test lenses are much more lubricous than the test lenses from Example 4 but still not as lubricous as the control lenses packaged in PBS.
  • IPC saline is prepared by dissolving 0.02% of poly(AAm-co-AA) (80/20) and 0.2% of PAE (Kymene from Ashland as an aqueous solution and used as received, azetidinium content of 0.46 assayed with NMR) in PBS and adjusting the pH to 7.2-7.4. Then the saline is then treated by heating to and at about 70°C for 4 hours (heat pre-treatment).
  • poly(AAm-co-AA) and PAE are partially crosslinked between each other (i.e., not consuming all azetidinium groups of PAE) to form a water-soluble and thermally-crosslinkable hydrophilic polymeric material containing azetidinium groups within the branched polymer network in the IPC saline.
  • the final IPC saline is filtered using a 0.22micron polyether sulphone (PES) membrane filter and cooled down back to room
  • Lenses having a PAA-LbL base coating thereon prepared in Example 3 are placed in a polypropylene lens packaging shell with 0.6 mL of the IPC saline (half of the saline is added prior to inserting the lens). The blister is then sealed with foil and autoclaved for about 30 minutes at about 121 °C, forming a crosslinked coating (PAA-x-hydrophilic polymeric material) on the lenses.
  • test lenses (packaged in the heat-pretreated IPC saline, i.e., lenses having PAA-x- hydrophilic polymeric material coating thereon) show no debris adhesion after being rubbed against paper towel while the control lenses (packaged in PBS, i.e., lenses having a non- covalently attached layer of PAA thereon) show severe debris adhesion.
  • the test lenses have a WBUT of longer than 10 seconds. When observed under dark field microscope, no cracking lines are visible after rubbing the test lens. The test lenses are very lubricious in a finger rubbing test and equivalent to the control lenses.
  • Poly(acrylamide-co-acrylic acid) partial sodium salt ( -90% solid content, poly(AAm-co- AA) 90/10, Mw 200,000) is purchased from Polysciences, Inc. and used as received.
  • IPC saline is prepared by dissolving 0.07% of PAAm-PAA (90/10) and 0.2% of PAE (Kymene from Ashland as an aqueous solution and used as received, azetidinium content of 0.46 assayed with NMR) in PBS and adjusting the pH to 7.2-7.4. Then the saline is heat pre- treated for about 4 hours at about 70°C (heat pre-treatment).
  • poly(AAm-co-AA) and PAE are partially crosslinked to each other (i.e., not consuming all azetidinium groups of PAE) to form a water-soluble and thermally-crosslinkable hydrophilic polymeric material containing azetidinium groups within the branched polymer network in the IPC saline.
  • the IPC saline is filtered using a 0.22micron polyether sulphone [PES] membrane filter and cooled down back to room temperature.
  • Lenses having a PAA-LbL base coating thereon prepared in Example 3 and uncoated Lotrafilcon B lenses (from CIBA VISION CORPORATION) that are dipped into an acidic propanol solution of PAA (ca. 0.1 %, pH - 2.5) are placed in a polypropylene lens packaging shells with 0.6 ml_ of the heat-pretreated IPC saline (half of the IPC saline is added prior to inserting the lens).
  • the blister is then sealed with foil and autoclaved for about 30 minutes at 121 °C, forming a crosslinked coating (PAA-x-hydrophilic polymeric material) on the lenses.
  • test lenses both Lotrafilcon B and Example 3 lenses having a PAA-x-hydrophilic polymer thereon
  • the test lenses have no debris adhesion after being rubbed against paper towel.
  • the test lenses have a WBUT of longer than 10 seconds. When observed under dark field microscope, cracking lines are not visible after rubbing the lenses between the fingers.
  • the lenses are extremely lubricous in qualitative finger rubbing tests.
  • IPC salines are produced to contain from between about 0.05% and about 0.09% PAAm-PAA and from about 0.075% to about 0.19% PAE (Kymene from Ashland as an aqueous solution and used as received, azetidinium content of 0.46 assayed with NMR) in PBS.
  • the IPC salines are heat-treated for 8 hours at 60°C and lenses from Example 3 are packaged in the heat-pretreated IPC salines. No differences in the final lens surface properties are observed and all lenses showed excellent lubricity, resistance to debris adhesion, excellent wettability, and no evidence of surface cracking.
  • IPC salines are produced to contain about 0.07% PAAm-PAA and sufficient PAE to provide an initial azetidinium content of approximately 8.8 millimole equivalents / Liter (-0.15% PAE).
  • the heat pre-treatment conditions are varied in a central composite design from 50°C to 70°C and the pre-reaction time is varied from about 4 to about 12 hours. A 24 hour pre-treatment time at 60°C is also tested. 10 ppm hydrogen peroxide is then added to the salines to prevent bioburden growth and the IPC salines are filtered using a 0.22micron polyether sulphone [PES] membrane filter.
  • Lenses from Example 3 are packaged in the heat-pretreated IPC salines and the blisters are then autoclaved for 45 minutes at 121 °C. All lenses have excellent lubricity, wettability, and resistance to surface cracking. Some of the lenses show debris adhesion from paper towels as indicated in Table 1.
  • MPC methacryloyloxyethyl phosphorylcholine
  • MS carboxyl- containing vinylic monomer
  • MA methacrylic acid
  • BMA butylmethacrylate
  • Na 2 HP0 4 -2H 2 0 (0.3576% by weight) and Dl water (97.59 % by weight) is prepared and 0.2% PAE (polycup 3160) is added. The pH is adjusted to about 7.3.
  • 0.25% of one of several MPC copolymers is then added to form an IPC saline and the IPC saline is heat pre-treated at 70°C for 4 hours (heat pre-treatment).
  • MPC and PAE are partially crosslinked to each other (i.e., not consuming all azetidinium groups of PAE) to form a water-soluble and thermally-crosslinkable hydrophilic polymeric material containing azetidinium groups within the branched polymer network in the IPC saline.
  • Lenses having a PAA-LbL base coating thereon prepared in Example 3 are packaged in the heat-pretreated IPC saline and autoclaved for about 30 minutes at 121°C. Table 2 shows that all lenses possess excellent surface properties.
  • WBUT is longer than 10 seconds.
  • PAA-coated lenses Lenses cast-molded from a lens formulation prepared in Example 3 according to the molding process described in Example 3 are extracted and coated by dipping in the following series of baths: 3 MEK baths (22, 78 and 224 seconds); Dl water bath (56 seconds); 2 baths of PAA coating solution (prepared by dissolving 3.6g of PAA (M.W.: 450kDa, from Lubrizol) in 975ml of 1-propanol and 25 ml of formic acid) for 44 and 56 seconds separately; and 3 Dl water baths each for 56 seconds.
  • 3 MEK baths 22, 78 and 224 seconds
  • Dl water bath 56 seconds
  • PAA coating solution prepared by dissolving 3.6g of PAA (M.W.: 450kDa, from Lubrizol) in 975ml of 1-propanol and 25 ml of formic acid) for 44 and 56 seconds separately
  • 3 Dl water baths each for 56 seconds.
  • PAE/PAA-coated lenses The above-prepared lenses with a PAA base coating thereon are dipped successively into the following baths: 2 baths of PAE coating solution, which is prepared by dissolving 0.25 wt% of PAE (Polycup 172, from Hercules) in Dl water and adjusting the pH to about 5.0 using sodium hydroxide and finally filtering the resultant solution using a 5um filter, for 44 and 56 seconds respectively; and 3 baths of Dl water each for 56 seconds. After this treatment, the lenses have one layer of PAA and one layer of PAE.
  • 2 baths of PAE coating solution which is prepared by dissolving 0.25 wt% of PAE (Polycup 172, from Hercules) in Dl water and adjusting the pH to about 5.0 using sodium hydroxide and finally filtering the resultant solution using a 5um filter, for 44 and 56 seconds respectively; and 3 baths of Dl water each for 56 seconds.
  • the lenses After this treatment, the lenses have one layer of PAA and
  • Lenses with PAA-x-PAE-x-CMC coatings thereon One batch of lenses with one layer of PAA and one layer of PAE thereon are packaged in a 0.2% Sodium carboxymethylcellulose (CMC, Product# 7H 3SF PH, Ashland Aqualon) in phosphate buffer saline (PBS) and the pH is then adjusted to 7.2 - 7.4. The blisters are then sealed and autoclaved for about 30 minutes at 121 C, forming crosslinked coatings (PAA-x-PAE-x-CMC) on the lenses.
  • CMC Sodium carboxymethylcellulose
  • PBS phosphate buffer saline
  • Lenses with PAA-x-PAE-x-HA coatings thereon Another batch of lenses with one layer of PAA and one layer of PAE thereon are packaged in 0.2% Hyaluronic acid (HA, Products 6915004, Novozymes) in phosphate buffer saline (PBS) and the pH is then adjusted to 7.2 - 7.4. The blisters are then sealed and autoclaved for about 30 minutes at 121 C, forming crosslinked coatings (PAA-x-PAE-x-HA) on the lenses.
  • HA Hyaluronic acid
  • PBS phosphate buffer saline
  • the resultants lenses either with PAA-x-PAE-x-CMC coating or with PAA-x-PAE-x-HA coating thereon show no Sudan black staining, no debris adhesion, and no cracking under microscopy examination.
  • the lenses with PAA-x-PAE-x-CMC coating thereon have an average contact angle of 30 ⁇ 3 degrees, while the lenses PAA-x-PAE-x-HA coating thereon have an average contact angle of 20 ⁇ 3 degrees.
  • IPC solution preparation A reaction mixture is prepared by dissolving 2.86% by weight of mPEG-SH 2000 (Methoxy-Poly(Ethylene Glycol)-Thiol, Avg MW 2000, Product #MPEG-SH- 2000, Laysan Bio Inc.) along with 2% by weight of PAE (Kymene from Ashland as an aqueous solution and used as received, azetidinium content of 0.46 assayed with NMR) in PBS and the final pH adjusted to 7.5.
  • PAE Korean from Ashland as an aqueous solution and used as received, azetidinium content of 0.46 assayed with NMR
  • the solution is heat-treated for about 4 hours at 45 °C (heat pretreatment).
  • mPEG-SH 2000 and PAE are reacted with each other to form a water-soluble and thermally-crosslinkable hydrophilic polymeric material containing azetidinium groups and chemically-grafted polyethyleneglycol polymer chains.
  • the solution is diluted with 10-fold PBS containing 0.25% sodium citrate, pH adjusted to 7.2-7.4, and then filtered using 0.22micron polyether sulphone (PES) membrane filter.
  • the final IPC saline contains 0.286% by weight of hydrophilic polymeric material (consisting of about 59% by weight of MPEG-SH-2000 chains and about 41 % by weight of PAE chains) and 0.25% Sodium citrate dihydrate.
  • the PBS is prepared by dissolving 0.74% NaCI, 0.053% NaH 2 P0 4 .H 2 0 and 0.353% Na 2 HP0 4 .2H 2 0 in water.
  • PAA-coated lenses from Example 1 1 are packaged in the above IPC saline in polypropylene lens packaging shells and then autoclaved for about 30 minutes at about 121 ° C, forming a crosslinked coating on the lenses.
  • the final lenses show no debris adhesion, no cracking lines after rubbing the lens.
  • the lenses are very lubricious in a finger rubbing test comparable to control PAA-coated lenses.
  • the lens lubricity increases accordingly. It is believed that the increase in the contact angle of the surface may be due to the increasing density of terminal methyl groups on the surface with increasing grafting density. At high grafting densities, corresponding to a solution concentration of 0.6%, the contact angle approaches measurements obtained on Polyethylene glycol (PEG) monolayer grafted flat substrates (Reference: Langmuir 2008, 24, 10646-10653).
  • PEG Polyethylene glycol
  • the IPC saline is prepared similar to the procedure described in Example 12.
  • mPEG-SH 1000 mPEG-SH 1000
  • mPEG-SH 2000 mPEG-SH 5000
  • mPEG-SH 20000 All the salines are subjected to heat treatment at 45 °C for 4 hours and 10-fold dilution. The results and the reaction conditions are shown below:
  • a reaction mixture is prepared by dissolving 2.5% of mPEG-SH 2000, 10% of PAE (Kymene from Ashland as an aqueous solution and used as received, azetidinium content of 0.46 assayed with NMR) in PBS and 0.25% of sodium citrate dihydrate. The pH of this solution is then adjusted to 7.5 and also degassed by bubbling nitrogen gas through the container for 2 hours. This solution is later heat treated for about 6 hours at 45 °C forming a thermally crosslinkable hydrophilic polymeric material containing mPEG-SH-2000 groups chemically grafted onto the polymer by reaction with the Azetidinium groups in PAE.
  • the solution is diluted 50-fold using PBS containing 0.25% sodium citrate, pH adjusted to 7.2-7.4, and then filtered using 0.22micron polyether sulphone (PES) membrane filter.
  • PBS polyether sulphone
  • the final IPC saline contains about 0.30% by weight of the polymeric material (consisting of about 17% wt.mPEG-SH-2000 and about 83% wt. PAE) and 0.25% Sodium citrate dihydrate.
  • PAA-coated lenses from Example 1 1 are packaged in the above IPC saline in
  • the final lenses show no debris adhesion, no cracking lines after rubbing the lens.
  • the test lenses are very lubricious in a finger rubbing test comparable to control PAA-coated lenses.
  • a reaction mixture is prepared by dissolving 3.62% of mPEG-NH 2 550 (methoxy- poly(ethyleneglycol)-amine, M.W. ⁇ 550 (Product #MPEG-NH 2 -550, Laysan Bio Inc.) along with 2% of PAE (Kymene from Ashland as an aqueous solution and used as received, azetidinium ratio of 0.46 assayed with NMR) in PBS and the final pH adjusted to 10.
  • the solution is heat- treated for about 4 hours at 45 °C forming a thermally crosslinkable hydrophilic polymeric material containing MPEG-NH 2 -550 groups chemically grafted onto the polymer by reaction with the azetidinium groups in PAE.
  • the solution is diluted with 10-fold PBS containing 0.25% sodium citrate, pH adjusted to 7.2-7.4, and then filtered using 0.22micron polyether sulphone (PES) membrane filter.
  • the final IPC saline contains about 0.562% wt. of polymeric material (consisting of 64% wt. MPEG-SH-2000 and about 36% wt. PAE) and 0.25% Sodium citrate dihydrate.
  • PBS is prepared by dissolving 0.74% NaCI, 0.053% NaH 2 P0 4 .H 2 0 and 0.353% Na 2 HP0 4 .2H 2 0 in water.
  • PAA-coated lenses from Example 1 1 are packaged in the above IPC saline in
  • Nelfilcon A is a polymerizable polyvinyl alcohol obtained by modifying a polyvinyl alcohol (e.g., Gohsenol KL-03 from Nippon Gohsei or the like) with N-(2,2-Dimethoxyethyl)acrylamide under cyclic- acetal formation reaction conditions (Bijhler et al., CHIMIA, 53 (1999), 269-274, herein incorporated by reference in its entirety). About 2.5% of vinyl alcohol units in nelfilcon A is modified by N-(2,2-Dimethoxyethyl)acrylamide.
  • a polyvinyl alcohol e.g., Gohsenol KL-03 from Nippon Gohsei or the like
  • N-(2,2-Dimethoxyethyl)acrylamide under cyclic- acetal formation reaction conditions
  • IPC saline is prepared by dissolving 0.004% poloxamer 108, 0.8% nelfilcon A, 0.2% PAE (Kymene, Polycup 3160), 0.45% NaCI, and 1.1 % disodium hydrogen phosphate (dihydrate) in Dl water.
  • the saline is heat pre-treated by stirring for 2 hrs at about 65 - 70°C. After heated pre- treatment, the saline is allowed to cool to room temperature and then filtered using a 0.2 ⁇ PES filter.
  • Lenses prepared in Example 3 are placed in a polypropylene lens packaging shell with 0.6 ml_ of the IPC saline (half of the saline is added prior to inserting the lens). The blister is then sealed with foil and autoclaved for about 30 minutes at 121°C.
  • test lenses show no debris adhesion after being rubbed against paper towel.
  • the lenses had a WBUT of above 10 seconds. When observed under dark foiled microscope, cracking lines are not visible after rubbing the lenses between the fingers.
  • the lens is much more lubricous than the lenses from Example 4 but still not as lubricous as PAA-coated control lenses packaged in PBS.
  • the OH molar equivalent weights of KF-6001 A and KF-6002A are determined by titration of hydroxyl groups and are used to calculate the millimolar equivalent to be used in the synthesis.
  • a one-liter reaction vessel is evacuated overnight to remove moisture, and the vacuum broken with dry nitrogen.
  • 75.00 g (75 meq) of dried KF6001 A is charged to the reactor, and then 16.68 g (150 meq) of freshly distilled IPDI is added into the reactor.
  • the reactor is purged with nitrogen and heated to 45°C with stirring and then 0.30 g of DBTDL is added.
  • the reactor is sealed, and a positive flow of nitrogen is maintained. An exotherm occurs, after which the reaction mixture is allowed to cool and stir at 55°C for 2 hours.
  • 248.00 g (150 meq) of dried KF6002A is added to the reactor at 55°C and then 100 ⁇ _ of DBTDL is added.
  • the reactor is stirred for four hours.
  • a 1-L jacketed reactor is equipped with 500-mL addition funnel, overhead stirring, reflux condenser with nitrogen/vacuum inlet adapter, thermometer, and sampling adapter.
  • the reactor is charged with 45.6 g of 80% IEM-capped CE-PDMS prepared above and sealed.
  • a solution of 0.65 g of hydroxyethyl methacrylate (HEMA), 25.80 g of DMA, 27.80 g of (tris(trimethylsilyl))- siloxypropyl)methacrylate (TRIS), in 279 g of ethyl acetate is charged to the addition funnel.
  • the reactor is degassed at ⁇ 1 mbar for 30 minutes at RT with a high-vacuum pump.
  • the monomer solution is degassed at 100 mbar and RT for 10 minutes for three cycles, breaking vacuum with nitrogen between degas cycles.
  • the monomer solution is then charged to the reactor, and then the reaction mixture is stirred and heated to 67°C. While heating, a solution of 1.50 g of mercaptoethanol (chain transfer agent, CTA) and 0.26 g of azoisobutyronitrile dissolved in 39 g of ethyl acetate is charged to the addition funnel and deoxygenated three times at 100 mbar, RT for 10 minutes.
  • CTA chain transfer agent
  • azoisobutyronitrile azoisobutyronitrile
  • the resultant reaction mixture then is siphoned to a dry single-neck flask with airtight lid, and 4.452 g of IEM is added with 0.21 g of DBTDL.
  • the mixture is stirred 24 hs at room temperature, forming non-UV-absorbing amphiphilic branched polysiloxane prepolymer.
  • 100 uL of hydroxy-tetramethylene piperonyloxy solution in ethyl acetate (2 g/20 mL) is added.
  • the solution is then concentrated to 200 g (-50%) using rota-vap at 30 ° C and filtered through 1 um pore size filter paper. After solvent exchange to 1-propanol, the solution is further concentrated to the desired concentration.
  • a 1-L jacketed reactor is equipped with 500-mL addition funnel, overhead stirring, reflux condenser with nitrogen/vacuum inlet adapter, thermometer, and sampling adapter. The reactor is then charged with 45.98 g of 80% IEM-capped CE- PDMS prepared above and the reactor is sealed.
  • a solution of 0.512 g of HEMA, 25.354 g of DMA, 1.38 g of Norbloc methacrylate, 26.034 g of TRIS, in 263 g of ethyl acetate is charged to the addition funnel.
  • the reactor is degassed at ⁇ 1 mbar for 30 minutes at RT with a high-vacuum pump.
  • the monomer solution is degassed at 100 mbar and RT for 10 minutes for three cycles, breaking vacuum with nitrogen between degas cycles.
  • the monomer solution is then charged to the reactor, and then the reaction mixture is stirred and heated to 67°C. While heating, a solution of 1.480 g of mercaptoethanol (chain transfer agent, CTA) and 0.260 g of azoisobutyronitrile dissolved in 38 g of ethyl acetate is charged to the addition funnel and deoxygenated three times at 100 mbar, room temperature for 10 minutes.
  • CTA chain transfer agent
  • azoisobutyronitrile dissolved in 38 g of ethyl acetate
  • the resultant reaction mixture then is siphoned to a dry single-neck flask with airtight lid, and 3.841 g of isocyanatoethyl acrylate is added with 0.15 g of DBTDL.
  • the mixture is stirred 24 hs at room temperature, forming a UV-absorbing amphiphilic branched polysiloxane prepolymer.
  • 100 uL of hydroxy-tetramethylene piperonyloxy solution in ethyl acetate (2 g/20 mL) is added.
  • the solution is then concentrated to 200 g (-50%) using rota-vap at 30 °C and filtered through 1 um pore size filter paper.
  • D-2 Lens formulation with UV-absorbing polysiloxane prepolymer (4% DMA)
  • D-3 Lens formulation with UV-absorbing polysiloxane prepolymer (2% DMA / 2% HEA)
  • Monomers containing amine groups N-(3-Aminopropyl)methacrylamide hydrochloride (APMAA-HCI) or N-(2-aminoethyl) methacrylamide hydrochloride (AEMAA-HCI) are purchased from Polysciences and used as received.
  • Poly(amidoamine epichlorohydrine) (PAE) is received from Ashland as an aqueous solution and used as received.
  • Poly(acrylamide-co-acrylic acid) (poly(AAm-co-AA) (90/10) from Polysciences, mPEG-SH from Laysan Bio, and poly(MPC-co- AeMA) (i.e., a copolymer of methacryloyloxyethyl phosphorylcholine (MPC) and
  • APMAA-HCI monomer is dissolved in methanol and added to the lens formulations D-1 , D-2 and D-3 (prepared in Example 17) to achieve a 1 wt% concentration.
  • Reactive packaging saline is prepared by dissolving the components listed in Table 4 along with appropriate buffer salts in Dl water.
  • the saline is heat pre-treated by stirring for 8 hrs at about 60°C. After heated pre-treatment, the saline is allowed to cool to room temperature and then filtered using a 0.2 ⁇ PES filter.
  • Lens formulation D-1 prepared in Example 17 is modified by addition of the APMAA-HCI monomer (stock solution of APMMA-HCL in 1 :1 methanokpropanol) and cured at 16mW/cm 2 with 330nm filter.
  • Lens Formulations D-2 and D-3 prepared in Example 17 are modified by addition of the APMAA-HCI monomer and cured at 4.6mW/cm 2 with 380nm filter.
  • DSM lenses Female portions of polypropylene lens molds are filled with about 75 microliters of a lens formulation prepared as above, and the molds are closed with the male portion of the polypropylene lens molds (base curve molds). Contact lenses are obtained by curing the closed molds for about 5 minutes with an UV irradiation source (Hamamatsu lamp with a 330 nm-cut-off filter at an intensity of about 16 mW /cm 2 .
  • an UV irradiation source Haamatsu lamp with a 330 nm-cut-off filter at an intensity of about 16 mW /cm 2 .
  • LS lenses are prepared by cast-molding from a lens formulation prepared as above in a reusable mold, similar to the mold shown in Figs. 1-6 in U.S. patent Nos.7,384,590 and 7,387,759 (Figs. 1-6).
  • the mold comprises a female mold half made of CaF 2 and a male mold half made of PMMA.
  • the UV irradiation source is a Hamamatsu lamp with a 380 nm-cut-off filter at an intensity of about 4.6 mW /cm 2 .
  • the lens formulation in the mold is irradiated with UV irradiation for about 30 seconds.
  • Lens formulation D-1 modified with APMAA-HCI is cured according to DSM and LS methods described above, while with lens formulation D-2 or D-3 is cured according to the LS method described above.
  • Molded lenses are extracted in methyl ethyl ketone, hydrated, and packaged in one of the salines described in Table 4. Lenses are placed in a polypropylene lens packaging shell with 0.6 mL of the IPC saline (half of the saline is added prior to inserting the lens). The blister is then sealed with foil and autoclaved for 30 min at 121 °C.
  • the lens surface wettability (WBUT), lubricity, and contact angle are measured and results are summarized in Table 5.
  • the lenses are made according DSM method unless specified otherwise. Lubricity is rated against a qualitative scale from 0 to 5 where lower numbers indicate greater lubricity. In general, all properties are shown to improve after application of the in-package coating.
  • the number is the packaging saline number shown in Table 4.
  • a lens formulation is prepared by dissolving components in 1-propanol to have the following composition: about 32% by weight of CE-PDMS macromer prepared in Example 2, about 21 % by weight of TRIS-Am, about 23% by weight of DMA, about 0.6% by weight of L-PEG, about 1 % by weight of DC1 173, about 0.1 % by weight of visitint (5% copper phthalocyanine blue pigment dispersion in TRIS), about 0.8% by weight of DMPC, about 200 ppm H-tempo, and about 22% by weight of 1-propanol.
  • Preparation of Lenses Preparation of Lenses.
  • Lenses are prepared by cast-molding from the lens formulation prepared above in a reusable mold (quartz female mold half and glass male mold half), similar to the mold shown in Figs. 1-6 in U.S. patent Nos.7,384,590 and 7,387,759 (Figs. 1-6).
  • the lens formulation in the molds is irradiated with UV irradiation (13.0 mW/cm 2 ) for about 24 seconds.
  • PAA-coating solution A PAA coating solution is prepared by dissolving an amount of PAA (M.W.: 450kDa, from Lubrizol) in a given volume of 1-propanol to have a concentration of about 0.36% by weight and the pH is adjusted with formic acid to about 2.0.
  • PAA-coated lenses Cast-molded contact lenses as above are extracted and coated by dipping in the following series of baths: Dl water bath (about 56 seconds); 6 MEK baths (about 44, 56, 56, 56, 56, and 56 second respectively); Dl water bath (about 56 seconds); one bath of PAA coating solution (about 0.36% by weight, acidified with formic acid to about pH 2.0) in 100% 1- propanol (about 44 seconds); one bath of a water/1 -propanol 50%/50% mixture (about 56 seconds); 4 Dl water baths each for about 56 seconds; one PBS bath for about 56 seconds; and one Dl water bath for about 56 seconds.
  • IPC saline Poly(AAm-co-AA)(90/10) partial sodium salt ( -90% solid content, poly(AAm-co-AA) 90/10, Mw 200,000) is purchased from Polysciences, Inc. and used as received.
  • PAE Korean, an azetidinium content of 0.46 assayed with NMR is purchased from Ashland as an aqueous solution and used as received.
  • IPC saline is prepared by dissolving about 0.07% w/w of poly(AAm-co-AA)(90/10) and about 0.15% of PAE (an initial azetidinium millimolar equivalents of about 8.8 millimole) in PBS (about 0.044 w/w% NaH 2 P0 4 H 2 0, about 0.388 w/w/%
  • the IPC saline is heat pre-treated for about 4 hours at about 70°C (heat pretreatment) During this heat pretreatment, poly(AAm-co-AA) and PAE are partially crosslinked to each other (i.e., not consuming all azetidinium groups of PAE) to form a water-soluble and thermally-crosslinkable hydrophilic polymeric material containing azetidinium groups within the branched polymer network in the IPC saline. After the heat pre-treatment, the IPC saline is filtered using a
  • Lenses having a PAA-LbL base coating thereon prepared above are placed in polypropylene lens packaging shells (one lens per shell) with 0.6 mL of the IPC saline (half of the saline is added prior to inserting the lens).
  • the blisters are then sealed with foil and autoclaved for about 30 minutes at about 121°C, forming SiHy contact lenses with crosslinked coatings (PAA-x-hydrophilic polymeric material) thereon.
  • the resultant SiHy contact lenses with crosslinked coatings (PAA-x-hydrophilic polymeric material) thereon show no debris adhesion after being rubbed against paper towel while the control lenses (packaged in PBS, i.e., lenses having a non- covalently attached layer of PAA thereon) show severe debris adhesion.
  • the lenses have an oxygen permeability (Dk c or estimated intrinsic Dk) of 146 barrers, a bulk elastic modulus of 0.76 MPa, a water content of about 32% by weight, a relative ion permeability of about 6 (relative to Alsacon lens), a contact angle of from about 34 to 47 degrees, a WBUT of longer than 10 seconds.
  • Dk c or estimated intrinsic Dk oxygen permeability
  • SiHy lenses and IPC salines in lens packages after autoclave which are prepared in Examples 6, 14 and 19, are subjected to following biocompatibility studies.
  • SiHy lenses are evaluated by the USP Direct Contact Material Assay.
  • Lens extracts are evaluated by the USP MEM Elution and ISO CEN Cell Growth
  • ISO Sensitization Study (Guinea Pig Maximization Testing of Packaging Solutions) shows that the IPC saline after autoclave do not cause any delayed dermal contact sensitization in the guinea pig.
  • ISO Sensitization Study (Guinea Pig Maximization Testing of Lens Extracts) shows that Sodium chloride and sesame oil extracts of the lenses do not cause delayed dermal contact sensitization in the guinea pig.
  • IPC salines from the lens packages are tested according to Chromosome Aberration Test in Chinese Hamster Ovary
  • the IPC salines are negative for the induction of structural and numerical chromosome aberrations assays using CHO cells in both non-activated and S9-activated test systems.
  • SiHy lens extracts are tested according to Cell Gene Mutation Test (Mouse Lymphoma Mutagenesis Assay)
  • the lens extracts are shown to be negative in the Mouse Lymphoma Mutagenesis Assay.
  • the surface compositions of preformed SiHy contact lenses i.e., SiHy contact lens without any coating and prior to applying the PAA base coating
  • SiHy contact lenses with PAA coating i.e., those lenses before being sealed and autoclaved in lens packages with the IPC saline
  • SiHy contact lenses with a crosslinked coating thereon are determined by characterizing vacuum dried contact lenses with X-ray photoelectron spectroscopy (XPS).
  • XPS is a method for measuring the surface composition of lenses with a sampling depth of about 10nm.
  • Table 6 The surface compositions of three types of lenses are reported in Table 6.
  • Table 6 shows that when a PAA coating is applied onto a SiHy lens (preformed without coating), the silicon atomic composition is substantially reduced (from 12.1 % to 4.5%) and the nitrogen atomic composition is also reduced (from 6.2% to 1.6%).
  • a crosslinked coating is further applied onto the PAA coating, the surface composition is predominated by carbon, nitrogen and oxygen, which are the three atomic composition (excluding hydrogen because XPS does not count hydrogen in the surface composition).
  • the outmost layer of the SiHy contact lens with crosslinked coating is likely to be essentially consisting of the hydrophilic polymeric material which is the reaction product of poly(AAm-co-AA)(90/10) (60% C, 22% O and 18% N) and PAE.
  • a SiHy contact lens of the invention has a nominal silicon content, about 1.4%, in the surface layer, much lower than those of commercial SiHy lenses without plasma coatings (Acuvue® Advance®, Acuvue® Oasys®, TruEyeTM, Biofinity®, AvairaTM) and
  • SiHy contact lenses of the invention prepared according to the procedures described in Example 19
  • commercial SiHy contact lenses CLARITITM 1 Day, ACUVUE® TruEyeTM (narafilcon A and narafilcon B)
  • polyhydroxyethylmethacrylate hydrogel lenses i.e., non-silicone hydrogel lenses
  • All lenses are vacuum-dried.
  • Polyethylene sheets, DAILIES® and ACUVUE® Moist are used as control because they do not contain silicon.
  • the silicon atomic compositions in the surface layers of the test samples are as following: 1.3 ⁇ 0.2 (polyethylene sheet); 1.7 ⁇ 0.9 (DAILIES®); 2.8 ⁇ 0.9 (ACUVUE® Moist); 3.7 ⁇ 1.2 (three SiHy lenses prepared according to the procedures described in Example 19); 5.8 ⁇ 1.5 (CLARITITM 1 Day); 7.8 ⁇ 0.1 (ACUVUE®
  • PAA-F Fluorescein tagged PAA
  • PAA-F is synthesized in-house by covalently attaching 5-aminofluorescein to PAA (Mw 450k).
  • Lenses are prepared by cast-molding from the lens formulation prepared above in Example 19 in a reusable mold (quartz female mold half and glass male mold half), similar to the mold shown in Figs. 1-6 in U.S. patent Nos.7,384,590 and 7,387,759 (Figs. 1-6).
  • the lens formulation in the molds is irradiated with UV irradiation (13.0 mW/cm 2 ) for about 24 seconds.
  • PAA-F coating solution is prepared by cast-molding from the lens formulation prepared above in Example 19 in a reusable mold (quartz female mold half and glass male mold half), similar to the mold shown in Figs. 1-6 in U.S. patent Nos.7,384,590 and 7,387,759 (Figs. 1-6).
  • the lens formulation in the molds is irradiated with UV irradiation (13.0 mW/cm 2 ) for about 24 seconds.
  • PAA-F coating solution is prepared by cast-
  • a PAA-F coating solution is prepared by dissolving an amount of PAA-F prepared above in a given volume of 1-PrOH/water (95/5) solvent mixture to have a concentration of about 0.36% by weight and the pH is adjusted with formic acid to about 2.0. About 5% water is used in order to dissolve PAA-F.
  • Cast-molded contact lenses are extracted and coated by dipping in the following series of baths: Dl water bath (about 56 seconds); 6 MEK baths (about 44, 56, 56, 56, 56, and 56 second respectively); Dl water bath (about 56 seconds); one bath of PAA-F coating solution (about 0.36% by weight, acidified with formic acid to about pH 2.0) in 1-PrOH/water (95/5) solvent mixture (about 44 seconds); one bath of a water/1 -propanol 50%/50% mixture (about 56 seconds); 4 Dl water baths each for about 56 seconds; one PBS bath for about 56 seconds; and one Dl water bath for about 56 seconds.
  • polypropylene lens packaging shells (one lens per shell) with 0.6 mL of the IPC saline prepared according to the procedures described in Example 19 (half of the saline is added prior to inserting the lens).
  • the blisters are then sealed with foil and autoclaved for about 30 minutes at about 121 °C, forming SiHy contact lenses with crosslinked coatings (PAA-x-hydrophilic polymeric material) thereon.
  • a cross section of a hydrated SiHy lens with crosslinked coating (prepared above) is cut and placed between two glass cover slips and the image is collected on a con-focal laser fluorescent microscope (model # Zeiss LSM 510 Vis). It is scanned from the front curve side of the lens to the base curve side of the lens, or vice versa.
  • the presence of PAA-F is shown by the green fluorescence and con-focal laser fluorescence microscopic images can be obtained.
  • the examination of the con-focal laser fluorescence microscopic images reveals that the PAA-F rich layer is present on both lens surfaces (anterior and posterior surfaces) and at the peripheral edge, while no PAA-F is observed in the bulk material of the hydrated lens.
  • FIG. 3 shows two representative the fluorescence intensity profiles along two lines across the lens cross section, one at the point where the lens thickness is about 100 ⁇ (panel A) and the other at the point where the lens thickness is about 200 ⁇ (panel B).
  • the original points in Figure 3 are the center points between the anterior and posterior surfaces along the lines. It can be noticed in Figure 3 that there is a PAA-F-rich layer near the outermost surfaces of the SiHy lens with crosslinked coating, no PAA-F is present at the bulk of the lens, and the coating thickness is similar on these two cross-sections regardless the thickness of the cross-sections.
  • the thickness of the PAA-F rich layer i.e., the sum of the infusion depth into the outer hydrogel layer and the penetration depth of PAA-F into the bulk material (i.e., the inner layer)), or the transition layer (for schematic illustration see Figure 2, the transition layer 1 15), can be estimated from the fluorescence intensity profile shown in Figure 3.
  • the possible thickness of the transition layer (PAA-F-rich layer) is estimated by the distance from zero intensity, after crossing the peak intensity, to zero intensity again. Considering that there are possible contribution from unknown factors (such as scattering) to the fluorescence intensity, the minimum layer thickness is the thickness for which a florescent intensity of at least 10% of the maximum peak intensity is retained.
  • the minimum PAA-F-rich layer thickness could be at least about 5 microns. Note that the thickness for the SiHy lenses with PAA coating of the previous Examples could be higher, considering the PAA concentration used is 10 times higher than the PAA-F concentration used in the experiments here.
  • a lens with thicker coating can also be prepared by using a dip coating time that is more than 44 seconds, 44 seconds were the dip coating time for PAA-F used in this experiment.
  • a lens with thicker coating may also be prepared by using PAA of different molecular weight.
  • This example illustrates how to determine the water content of the crosslinked coating (the two outer hydrogel layers) on a SiHy of the invention).
  • samples of polymer consisting of the coating components are prepared for evaluation.
  • the resulting gels are then hydrated and tested to determine water content.
  • Solutions are prepared using the two polymeric components of a crosslinked coating formed in Example 19: poly(AAm-co-AA)(90/10) and PAE, to have the following composition: 12.55% w/w of PAE, 6.45% w/w of poly(AAm-co-AA)(90/10), and 81 % w/w of water.
  • the ratio of PAE/poly(AAm-co-AA) is identical to that in the IPC saline of Example 19, but the individual concentrations of the components are higher to ensure a gel is formed during autoclave.
  • the solution is then autoclaved about 45 minutes at 121 °C after which the sample gels.
  • Hydrated samples are blotted dry and the mass at hydrated state is recorded via mass balance. Following the recording of the mass at hydrated state, the samples are all placed in a vacuum oven set at approximately 50°C and dried under a vacuum of ⁇ 1 inch Hg overnight.
  • Water content is calculated using the following relationship:
  • Water content (wet mass - dry mass) / wet mass x 100% The water content of the samples is determined to be 84.6 ⁇ 0.4 w/w%.
  • this water content of this PAE/poly(AAm-co-AA) hydrogel represents the outer hydrogel layer (crosslinked coating) of the SiHy contact lenses of Example 19 for the following reasons.
  • hydrophobic bulk lens polymers silicon hydrogel
  • there is no or very low silicon content at the surface of the SiHy lens with the crosslinked coating indicating that the outer surface layer is composed almost entirely of the coating polymers (PAE and PAAm-PAA).
  • the polyacrylic acid (PAA) base coating (the transition layer) presumably has a minimal impact on the water content of the surface layer. This assumption may not be valid. But, if any charged PAA would be present in the outer surface layer, it would further increase the water content beyond 84.6%.
  • PAE and PAAm-PAA a much higher concentration of PAE and PAAm-PAA is needed to produce PAE/poly(AAm-co-AA) hydrogel than is used in the IPC saline of Example 19. This could result in a higher crosslinking density for the PAE/poly(AAm-co-AA) hydrogel which may give an artificially low water content result.
  • Example 19 both the presence of PAA in the outer hydrogel layer and lower crosslinking density due to the lower concentration of polymeric materials during crosslinking (in Example 19) may result in an surface layer (outer hydrogel layer) having a water content that is even higher than that measured in the tests in this example. It can be assumed that the outer coating layer of the SiHy contact lenses of Example 19 comprises at least 80% water and may be even higher when fully hydrated.
  • An Abbe refractometer is typically used to measure the refractive index of contact lenses.
  • the refractive index difference between a testing lens and the instrument prism creates a unique angle of total internal reflectance which results in a dark visible shadow line.
  • the angle at which this shadow line appears is directly related to the refractive index of the testing lens.
  • Most contact lenses (including SiHy contact lenses without coating prepared in Example 19) produce a distinct shadow line in the Abbe refractometer, but SiHy with crosslinked coating (i.e., the outer hydrogel layers) of Example 19 do not produce a distinct shadow line. It is believed that this phenomenon is due to a decrease in the refractive index of the lens at the surface compared to the bulk and the fact that the transition from bulk to surface is not abrupt. It is further believed that near the surface of the lens the water content begins to increase which results in a localized decrease in the refractive index of the lens. This in effect would create simultaneous shadow lines at multiple angles resulting in a blurred image of the shadow line.
  • the Abbe data demonstrates that the outer surface layer is characterized by an increase in the water content near the surface of the lens, consistent with the results described in Example 23.
  • SiHy contact lenses with crosslinked coating i.e., the outer hydrogel layers prepared in Example 19 desalinated in ultrapure water, placed individually in a 50ml_ disposable beaker with 50 ml_ of ultra-pure water and frozen by placing the beaker in a bath with dry ice and isopropyl alcohol.
  • Lens samples are cut in half and two strips are then cut from the middle of each half and mounted on their edges for imaging of cross sections. Samples are then sputter coated with Au/Pd for ⁇ 1 min and exampled by SEM using a Bruker Quantax Microanalysis System (JEOLJSM-800LV SEM). The sample stage is tilted -0-60° at the discretion of the analyst to obtain the desired sample orientation.
  • JEOLJSM-800LV SEM Bruker Quantax Microanalysis System
  • FIG 4 shows the top view of a SEM image of a surface of a freeze-dried SiHy contact lens prepared in Example 19. It can be seen from Figure 4 that the freeze-dried SiHy contact lens has a sponge- like surface structure which would be expected for a high water content hydrogel. This result further confirms that a SiHy contact lens of the invention comprises the two outer hydrogel layers of a high water content hydrogel.
  • panels B and C show the side views at two different angles of a cross section of the freeze-dried SiHy contact lens shown in panel A.
  • the panels B and C show the thick inner layer having a smooth surface, a transition layer (PAA layer) with a brighter color on top of the inner layer, and an outer hydrogel layer with sponge-like structures on top of the transition layer. Based on the data shown in the panels B and C, the thickness of the freeze-dried outer hydrogel layer is estimated to be between about 2 ⁇ and 2.5 ⁇ .
  • PAAm-PAA-F Fluorescein tagged Poly(AAm-co-AA)(90/10)
  • PAAm-PAA-F is synthesized in-house by covalently attaching 5-aminofluorescein to PAAm-PAA (90/10), by a procedure similar to the preparation of PAA-F.
  • Poly(AAm-co- AA)(90/10) partial sodium salt ( -90% solid content, poly(AAm-co-AA) 90/10, Mw 200,000) is purchased from Polysciences, Inc. and used as received.
  • the labeling degree of fluorescein is about 0.04 mole%.
  • This saline is prepared by the same procedure of IPC preparation, as described in Example 19, except where PAAm-PAA is replaced with PAAm-PAA-F.
  • Lenses are prepared by cast-molding from the lens formulation prepared above in Example 19 in a reusable mold (quartz female mold half and glass male mold half), similar to the mold shown in Figs. 1-6 in U.S. patent Nos.7,384,590 and 7,387,759 (Figs. 1-6).
  • the lens formulation in the molds is irradiated with UV irradiation (13.0 mW/cm 2 ) for about 24 seconds.
  • Cast-molded contact lenses are extracted and coated by dipping in the following series of baths: Dl water bath (about 56 seconds); 6 MEK baths (about 44, 56, 56, 56, 56, and 56 second respectively); Dl water bath (about 56 seconds); one bath of PAA coating solution (about 0.36% by weight, acidified with formic acid to about pH 2.0) in 1-PrOH solvent (about 44 seconds); one bath of a water/1 -propanol 50%/50% mixture (about 56 seconds); 4 Dl water baths each for about 56 seconds; one PBS bath for about 56 seconds; and one Dl water bath for about 56 seconds.
  • Lenses having a PAA- base coating thereon prepared above are placed in polypropylene lens packaging shells (one lens per shell) with 0.6 mL of the modified IPC saline prepared above using PAAm-PAA-F (half of the saline is added prior to inserting the lens).
  • the blisters are then sealed with foil and autoclaved for about 30 minutes at about 121 °C, forming SiHy contact lenses with crosslinked coatings (PAA-x-hydrophilic polymeric material) thereon.
  • a piece of a hydrated SiHy lens with crosslinked coating (prepared above) is placed between two glass cover slips and the image is collected on a con-focal laser fluorescent microscope (model # Zeiss LSM 510 Vis). It is scanned from the front curve side of the lens to the base curve side of the lens, or vice versa. The presence of PAAm-PAA-F is shown by the green fluorescence and con-focal laser fluorescence microscopic images can be obtained.
  • the examination of the con-focal laser fluorescence microscopic images reveals that the PAAm- PAA-F rich layer (i.e., the outer hydrogel layers) is present on both lens surfaces (anterior and posterior surfaces) and at the peripheral edge, while no PAAm-PAA-F is observed in the bulk material of the lens.
  • the PAAm- PAA-F rich layer i.e., the outer hydrogel layers
  • the fluorescence intensity profiles are examined across the lens cross section along a line passing through both the posterior and anterior surfaces and normal to the posterior surface.
  • the thickness of the PAAm-PAA-F rich layer can be estimated from the fluorescence intensity profile across the lens.
  • the possible thickness of the outer hydrogel layer (PAAm-PAA-F-rich layer) is estimated by the distance from zero intensity, after crossing the peak intensity, to zero intensity again. Considering that there are possible contribution from unknown factors (such as scattering) to the fluorescence intensity, the minimum layer thickness is the thickness for which a florescent intensity of at least 10% of the maximum peak intensity is retained. Based on such estimation, the minimum PAAm-PAA-F-rich layer (hydrated outer hydrogel layer) thickness could be at least about 5 microns.
  • Lenses are fabricated using lens formulation D-2 (Example 17) to which APMAA monomer has been added to a concentration of 1 %.
  • LS lenses are prepared by cast-molding from a lens formulation prepared as above in a reusable mold, similar to the mold shown in Figs. 1-6 in U.S. patent Nos.7,384,590 and 7,387,759 (Figs. 1-6).
  • the mold comprises a female mold half made of glass and a male mold half made of quartz.
  • the UV irradiation source is a
  • the lens formulation in the mold is irradiated with UV irradiation for about 30 seconds.
  • Cast-molded lenses are extracted with methyl ethyl ketone (MEK), rinsed in water, coated with polyacrylic acid (PAA) by dipping lenses in a propanol solution of PAA (0.0044% by weight, acidified with formic acid to about pH 2.5), and hydrated in water.
  • MEK methyl ethyl ketone
  • PAA polyacrylic acid
  • IPC Saline is prepared according to the composition described in Example 9 with pre- reaction conditions of 8 hrs at approximately 60°C. Lenses are placed in a polypropylene lens packaging shell with 0.6 mL of the IPC saline (half of the saline is added prior to inserting the lens). The blister is then sealed with foil and autoclaved for 30 min at 121°C.
  • the lens surface wettability (WBUT) is greater than 10 seconds, lubricity is rated as “1 ", and contact angle is approximately 20°.
  • the lens water content for the coated lens can be estimated to be -96% according to the following calculation
  • estimated here for the crosslinked coating on a contact lens may be not accurate because the difference in dry wet weight between the first and second groups of contact lens is too small and even smaller than the standard deviation.
  • the inclined plate method is a simple test to setup as shown in Figure 5.
  • the set up for inclined plate method is composed of a plastic reservoir or tank 501 which is filled with a phosphate buffered saline (PBS, pH ⁇ 7.3) 502, a 503 borosilicate glass plate 503 and a shim 506 with an adjustable height between 5 mm and 20 mm height. Both the borosilicate glass plate 503 and the shim 506 are submerged in the phosphate- buffered saline 502 in the plastic reservoir or tank 501.
  • PBS phosphate buffered saline
  • a contact lens 504 is placed on the borosilicate glass plate and then a stainless steel ferrule 505 (to provide physiologically relevant pressure).
  • the critical angle ⁇ is the tangent of the critical angle ⁇ .
  • a lens which does not move will be below the CCOF, while a lens which does not stop during the travel distance will be above the CCOF. Angles above or below the CCOF are removed from analysis. Derby friction test can provide a direct way of measuring the kinematic coefficient of friction.
  • all lenses are stored in PBS solution at least overnight (>6 hours) before testing, in order to remove any residual packaging solution.
  • the glass plate (6" x 4" borosilicate glass) is scrubbed with a soap solution (1 % Micro-90) and wiped (AlphaWipe TX1009). Each plate is rinsed thoroughly in Dl water, about 2 minutes. A section of the plate friction is tested by finger rubbing to ensure all soap solution is removed. The water is wiped with paper towels (KimTech Kimwipe #34705) and inspected under light to ensure no foreign particles remain on the glass.
  • the glass plate is placed on shims of various heights in a plastic reservoir or tank, and the height of this plane is measured with a micrometer and recorded.
  • the reservoir is filled with phosphate buffered saline (PBS) to ensure the lens is completely submerged (28 mm depth).
  • PBS phosphate buffered saline
  • Each lens is placed on the "starting line” and a 0.79 g ferrule (1/4" stainless steel to provide physiologically relevant pressure) is dropped onto the lens surface. The lens is allowed to slide down the plate, and the time the lens took to travel the 96 mm is recorded.
  • the lens is moved to the starting position with the weight removed prior to retesting. This "pre-loading" effect should be minimized for best repeatability.
  • the lens may be tested at multiple angles to obtain the ideal CCOF.
  • This Example illustrates how to characterize the negatively-charged surface of a SiHy contact lens according to the Positively Charged Particles Adhesion test.
  • the surface charge of a lens surface can be detected indirectly via its interaction with charged particles or beads.
  • a negatively charged surface will attract positively charged particles.
  • a surface free of negative charge or substantially free of negative charge will not attract positively charged particles or will attract few positively charged particles.
  • Uncoated SiHy contact lenses i.e., cast-molded and extracted with MEK as described in Example 19
  • PAA-coated SiHy contact lenses (as prepared in Example 19)
  • SiHy contact lenses with a crosslinked coating thereon (as prepared in Examples 14 and 19) are tested as follows.
  • the PAA coating of PAA-coated contact lenses has a surface concentration of
  • DOWEX 1x4 20-50 Mesh resins are purchased from Sigma-Aldrich and used as received.
  • DOWEXTM 1x4 20-50 Mesh resins are spherical, Type I strong base anion resins and are styrene/divinylbenzene copolymer containing N + (CH 3 ) 3 Cr functional groups and 4% divinylbenzene.
  • a 5% of 1x4 20-50 Mesh resins are dispersed in PBS and mixed well by stirring or vortexing at approximately 1000 rpm for 10 seconds.
  • Lenses are immersed into this dispersion and vortexd between rpm 1000-1 100 for 1 min, followed by rinsing with Dl water and vortex for 1 min.
  • the lenses are then placed in water in glass Petri dishes and images of lenses are taken with Nikon optical microscope, using bottom lighting.
  • adhered positively charged particles Figure 6a
  • Figure 6B a total of about 50 positively charged particles are adhered onto lenses with crosslinked coating prepared in Example 19
  • Figure 6C no positively charged particles are adhered onto lenses with crosslinked coating prepared in Example 14
  • Some loosely adhered particles may fall off the lens surface and can also be found in the water surrounding the lenses.
  • DOWEXTM monosphere ion exchange resins cross-linked polystyrene beads, chloride form, -590 microns in size, from Sigma-Aldrich
  • the number of particles adhered onto the particles can be decreased.
  • About 30% of these DOWEX monosphere resins are dispersed in PBS. Lenses are immersed into this dispersion for ⁇ 1 min, followed by rinsing with Dl water. The lenses are then placed in water in glass Petri dishes and images of lenses are taken with Nikon optical microscope, using bottom lighting.
  • Negatively charge resins (Amberlite CG50) are purchased from Sigma and used as received. A 5% of this Amberlite CG50 beads is dispersed in PBS and vortexed at about 1000 rpm for 10 seconds. PAA-coated lenses are immersed into this dispersion and vortexed between rpm 1000-1 100 for 1 min, followed by rinsing with Dl water and vortexed for 1 min. The lenses are then placed in water in glass Petri dishes and images of lenses are taken with Nikon optical microscope, using bottom lighting. No Amberlite particles (negatively charged) are found on PAA-coated lenses.
  • Negatively charged beads (Amberlite CG50), which are coated with polyethylenimine (PEI, a positively charged electrolytes), are used in this experiment.
  • the PEI coating procedure is performed as follows. PEI (Lupasol SK, 24% in water, Mw of -2000000) is purchased from BASF and used as received. Prepare an aqueous dispersion of 1 % Amberlite particles and 5% PEI. Adjust the pH to 7 and make sure solution is well-mixed (e.g. by stirring for 30min).
  • PEI-coated Amberlite A 5% of PEI-coated Amberlite CG50 particles are dispersed in PBS and vortexed at about 1000 rpm for 10 seconds. Lenses are immersed into this dispersion and vortexed between rpm 1000-1 100 for 1 min, followed by rinsing with Dl water and vortex for 1 min. The lenses are then placed in water in glass Petri dishes and images of lenses are taken with Nikon optical microscope, using bottom lighting.
  • AFM studies have been conducted on SiHy contact lenses (prepared in Example 19) in hydrated state and in dry state.
  • a lens is removed from its blister pack (sealed and autoclaved) and a cross-section is cut (for example by using a razor blade).
  • the cross-section piece of the lens is mounted vertically in a metal clamp, as shown in Figure 7.
  • a small piece of lens is sticking out of the top of the holder to allow the AFM tip (above the lens cross section in Figure 7) to scan it.
  • AFM phosphate buffer solution
  • the first AFM instrument is Veeco BioScope AFM with a Nanoscope IV controller. Data is collected utilizing triangular silicon cantilevers with a spring constant of 0.58 N/m and a nominal tip radius of curvature of 20-60 nm. Scans are done in constant contact (force-volume) mode with a probe velocity of 30 microns/second and a force-volume scan rate of 0.19 Hz. The topographic data and force-volume data are collected simultaneously. Each force curve consisted of about 30 data points. The lens is fully immersed in PBS during the AFM scan.
  • FIG 9 shows a cross sectional surface modulus profile of a SiHy contact lens with a crosslinked coating (prepared in Example 19) in fully hydrated state. Because the surface modulus of a material is proportional to the cantilever deflection, a cross-sectional surface modulus profile of a contact lens can be obtained approximately by plotting the values of cantilevers deflection (as a measure for the surface modulus of a material at a specific location on the lens cross section) as a functional of the distance from the side (anterior or posterior surface) of the cross section along two lines across the cross section shown in Figure 8.
  • the crosslinked coating (the anterior and posterior outer layers of the contact lens of Example 19) is softer than the bulk (inner layer of) silicone hydrogel lens material.
  • the surface modulus first remains almost constant with an average cantilever deflection of about 52 nm (i.e., average surface modulus) over the zone between 0 and about 5.9 microns and then gradually increases at locations further inside lens until reaching a maximum and remains approximately constant thereafter (plateau) with an average cantilever deflection of about 91 (i.e., average surface modulus) over the zone above about 7 microns.
  • SM ⁇ is the average surface modulus of the posterior or anterior hydrogel layer
  • SM Inner is the average surface modulus of the inner layer
  • the SiHy contact lenses (prepared in Example 19) are studied with the second AFM instrument.
  • the scanning is done using a Bruker Icon AFM in Quantitative Nanomechanical Measurements (PeakForce QNM) mode using lenses in either fully-hydrated (PBS without NaCI but with glycerol to reach at the similar osmolarity) or dry state.
  • the lens cross section is mounted in a metal clamp as described above.
  • Test conditions include, a Spring Constant of 1.3 N/m, Tip Radius of 33.3 nm, Sensitivity of 31 nm V, Scan Rate of 0.4 Hz, and a scan Resolution of 512x512.
  • AFM image of a cross section of the SiHy contact lens (Example 19) in fully hydrated state and in dry state are obtained according to the PeakForce QNM method.
  • the thickness of the crosslinked coating in fully hydrated state is determined to be about 4.4 microns
  • the thickness of the crosslinked coating in dry state is determined to be about 1.2 microns for vacuum dried sample, about 1.6 microns for oven dried sample.
  • the water-swelling ratio ( ⁇ Wet xl00% in which L We t is the average thickness of the outer hydrogel
  • L Dry is the average thickness of that outer hydrogel layer of the SiHy contact lens in dry state) of the crosslinked coating of the SiHy contact lenses (prepared in Example 19) is calculated to be about 277% (oven dried sample) or about 369% (vacuum dried sample).
  • Formulation I is prepared by dissolving components in 1-propanol to have the following composition: 33% by weight of CE-PDMS macromer prepared in Example 2, 17% by weight of N-[tris(trimethylsiloxy)-silylpropyl]acrylamide (TRIS-Am), 24% by weight of N,N- dimethylacrylamide (DMA), 0.5% by weight of N-(carbonyl-methoxypolyethylene glycol-2000)- 1 ,2-disteaoyl-sn-glycero-3-phosphoethanolamin, sodium salt) (L-PEG), 1.0% by weight Darocur 1173 (DC1 173), 0.1 % by weight of visitint (5% copper phthalocyanine blue pigment dispersion in tris(trimethylsiloxy)silylpropylmethacrylate, TRIS), and 24.5% by weight of 1-propanol.
  • TRIS tris(trimethylsiloxy)silylpropylmethacrylate
  • Formulation II is prepared by dissolving components in 1-propanol to have the following composition: about 32% by weight of CE-PDMS macromer prepared in Example 2, about 21 % by weight of TRIS-Am, about 23% by weight of DMA, about 0.6% by weight of L-PEG, about 1 % by weight of DC1 173, about 0.1 % by weight of visitint (5% copper phthalocyanine blue pigment dispersion in TRIS), about 0.8% by weight of DMPC, about 200 ppm H-tempo, and about 22% by weight of 1-propanol.
  • Lenses are prepared by cast-molding from a lens formulation prepared above in a reusable mold (quartz female mold half and glass male mold half), similar to the mold shown in Figs. 1-6 in U.S. patent Nos.7,384,590 and 7,387,759 (Figs. 1-6).
  • the UV irradiation source is a Hamamatsu lamp with the WG335 +TM297 cut off filter at an intensity of about 4 mW /cm 2 .
  • the lens formulation in the mold is irradiated with UV irradiation for about 25 seconds. Cast-molded lenses are extracted with methyl ethyl ketone (MEK) (or propanol or isopropanol).
  • MEK methyl ethyl ketone
  • a polyacrylic acid coating solution (PAA-1 ) is prepared by dissolving an amount of PAA (M.W.: 450kDa, from Lubrizol) in a given volume of 1-propanol to have a concentration of about 0.36% by weight and the pH is adjusted with formic acid to about 2.0.
  • PAA-2 Another PAA coating solution (PAA-2) is prepared by dissolving an amount of PAA (M.W.: 450kDa, from Lubrizol) in a given volume of an organic-based solvent (50/50 1-propanol /H 2 0) to have a concentration of about 0.39% by weight and the pH is adjusted with formic acid to about 2.0.
  • PAA PAA coating solution
  • SiHy contact lenses are subjected to one of dipping processes shown in Tables 10 and 1 1.
  • PrOH represents 100% 1 -propanol
  • PBS stands for phosphate-buffered saline
  • MEK stands for methyl ethyl ketone
  • 50/50 stands a solvent mixture of 50/50 1 -PrOH/H 2 0.
  • PrOH represents 100% 1-propanol
  • PBS stands for phosphate-buffered saline
  • MEK stands for methyl ethyl ketone
  • 50/50 stands a solvent mixture of 50/50 1 -PrOH/H 2 0.
  • Poly(acrylamide-co-acrylic acid) partial sodium salt Poly(AAm-co-AA)(90/10) ( -90% solid content, poly(AAm-co-AA) 90/10, Mw 200,000) is purchased from Polysciences, Inc. and used as received.
  • PAE Korean, an azetidinium content of 0.46 assayed with NMR is purchased from Ashland as an aqueous solution and used as received.
  • IPC in-package- crosslinking
  • PBS phosphate buffered saline
  • PAE an initial azetidinium millimolar equivalents of about 8.8 millimole
  • PBS phosphate buffered saline
  • the IPC saline is heat pre-treated for about 4 hours at about 70°C (heat pretreatment).
  • poly(AAm-co-AA) and PAE are partially crosslinked to each other (i.e., not consuming all azetidinium groups of PAE) to form a water-soluble and thermally-crosslinkable hydrophilic polymeric material containing azetidinium groups within the branched polymer network in the IPC saline.
  • the IPC saline is filtered using a 0.22micron polyether sulphone [PES] membrane filter and cooled down back to room temperature. 10 ppm hydrogen peroxide is then added to the final IPC saline to prevent bioburden growth and the IPC saline is filtered using a 0.22micron polyether sulphone [PES] membrane filter.
  • Lenses having a PAA prime coating thereon prepared above are placed in polypropylene lens packaging shells (one lens per shell) with 0.6 ml_ of the IPC saline (half of the saline is added prior to inserting the lens).
  • the blisters are then sealed with foil and autoclaved for about 30 minutes at about 121°C, forming SiHy contact lenses with crosslinked hydrophilic coatings thereon.
  • the resultant SiHy contact lenses with crosslinked hydrophilic coatings thereon and a center thickness of about 0.95 microns have an oxygen permeability (Dk c or estimated intrinsic Dk) of about 142 to about 150 barrers, a bulk elastic modulus of about 0.72 to about 0.79 MPa, a water content of about 30% to about 33% by weight, a relative ion permeability of about 6 (relative to Alsacon lens), and a contact angle of from about 34 to about 47 degrees.
  • Dk c or estimated intrinsic Dk oxygen permeability
  • TDIC Transmission-Differential-lnterference-Contrast
  • Reflection-Differential-lnterference-Contrast (RDIC) Method Lenses are placed on a glass slide and flattened by making 4 radial cuts every -90 degrees. Excess saline is blown off the surface using compressed air. Lens surface is then examined using Nikon Optiphot-2 with reflection differential interference contrast optics for the presence of winkled surface patterns on the surfaces of a contact lens using 10x, 20x and 50x objective lenses. A representative image of each side is acquired using 50x objective lens. The contact lens is then flipped over, excess saline removed and the other side of the contact lens and is inspected in the same way. The obtained RDIC images are then evaluated to determine the presence of winkled surface patterns (e.g., random and/or ordered worm-like patterns, or the likes).
  • winkled surface patterns e.g., random and/or ordered worm-like patterns, or the likes.
  • DFLM Dark Field Light Microscopy
  • This technique consists of a light source outside or blocked from the observer's field of view in order to illuminate a sample at an angle relative to normal transmitted light. Since the un-scattered light from the source is not gathered by the objective lens, it is not part of the image and the background of the image appears dark. Since the light source is illuminating the sample at an angle, the light observed in the sample image is that which is scatted by the sample toward the observer, contrast is then created between this scattered light from the sample and the dark background of the image. This contrast mechanism makes dark illumination especially useful for the observation of scattered phenomena such as haze.
  • DFLM is used to evaluate the haziness of contact lenses as follows. It is believed that since the dark-field setup involves scattered light, dark-field data could provide the worst-case estimate of haziness.
  • GSI grey scale intensity
  • each image pixel is assigned a grey scale intensity (GSI) value in the range from 0-255. Zero represents a pixel that is perfectly black and 255 represents a pixel that is perfectly white. An increase in the scattered light captured in the image will produce pixels with higher GSI values. This GSI value can then be used as a mechanism to quantify the amount of scattered light observed in a dark field image.
  • the haziness is expressed by averaging the GSI values of all pixels in an area of interest (AOI) (e.g., a whole lens or the lenticular zone or optical zone of a lens).
  • AOI area of interest
  • the experimental set-up consists of a microscope or equivalent optics, an attached digital camera and a dark field stand with ring light and variable intensity light source. Optics is designed/arranged so that the entirety of the contact lens to be observed fills the field of view (typically ⁇ 15mmx20mm field of view).
  • Illumination is set to a level appropriate to observe the desired changes in the relevant samples.
  • Light intensity is adjusted /calibrated to the same level for each set of samples using a density/light scattering standard as known to a person skilled in the art.
  • a density/light scattering standard is composed of two overlapping plastic cover slips (identical and slight or moderately frosted).
  • Such standard consists of areas with three different averaged GSI that include two areas with intermediate grey scale levels and saturated white (edges).
  • the black areas represent the empty dark field.
  • the black and saturated white areas can be used to verify gain and offset (contrast and brightness) settings of camera.
  • the intermediate grey levels can provide three points to verify the linear response of the camera.
  • Light intensity is adjusted so that the average GSI of the empty dark field approaches 0 and that of a defined AOI in a digital image of the standard is the same each time within ⁇ 5 GSI units.
  • a contact lens is immersed in 0.2 ⁇ -filtered phosphate buffer saline in a quartz Petri dish or a dish or similar clarity which is placed on the DFLM stand.
  • An 8-bit grey scale digital image of the lens is then acquired as viewed using the calibrated illumination and the average GSI of a defined AOI within the portion of the image containing the lens is determined. This is repeated for a sample set of contact lenses.
  • Light intensity calibration is re-evaluated periodically over the course of a test to ensure consistency.
  • the level of haziness under DFLM examination refers to a DFLM haziness ⁇ xl00% .
  • SiHy contact lenses the PAA prime coating of which is obtained according to either of the dipping processes 20-0 and 80-0, are determined to have an averaged DFLM haziness of about 73% and show wrinkle surface patterns (random worm-like patterns) that can be visually observed by examining the contact lens in hydrated state, according to the method of either RDIC or TDIC as described above. But, the winkled surface patterns have practically no adverse effects upon the light transmissibility of the contact lenses.
  • SiHy contact lenses the PAA prime coating of which is obtained according to either of the dipping processes 20-1 to 20-4, are determined to have a low averaged DFLM haziness of about 26% (probably due to the presence of visitint pigment particles) and show no noticeable wrinkle surface patterns (random worm-like patterns) when examined under either RDIC or TDIC as described above.
  • a high percentage of SiHy contact lenses are determined to have a moderate averaged DFLM haziness of about 45% and show slightly noticeable wrinkle surface patterns when examined under either RDIC or TDIC as described above. But, the winkled surface patterns have practically no adverse effects upon the light transmissibility of the contact lenses.
  • a 1-L jacketed reactor is equipped with 500-mL addition funnel, overhead stirring, reflux condenser with nitrogen/vacuum inlet adapter, thermometer, and sampling adapter. 89.95 g of 80%partially ethylenically functionalized polysiloxane prepared in Example 17, A, is charged to the reactor and then degassed under vacuum less than 1 mbar at room temperature for about 30 minutes.
  • the monomer solution prepared by mixing 1.03 g of HEMA, 50.73 g of DMA, 2.76 g of Norbloc methacrylate, 52.07 g of TRIS, and 526.05 g of ethyl acetate is charged to the 500- mL addition funnel followed with a degas under vacuum 100 mbar at room temperature for 10 minutes and then refilled with nitrogen gas.
  • the monomer solution is degassed with same conditions for additional two cycles.
  • the monomer solution is then charged to the reactor.
  • the reaction mixture is heated to 67°C with adequate stirring.
  • the copolymer solution prepared above is ethylenically functionalized to form an amphiphilic branched prepolymer by adding 8.44 g of IEM (or 2-isocyanatoethyl methacrylate in a desired molar equivalent amount) in the presence of 0.50 g of DBTDL. The mixture is stirred at room temperature under a sealed condition for 24 hours. The prepared prepolymer is then stabilized with 100 ppm of hydroxy-tetramethylene piperonyloxy before the solution is concentrated to 200 g (-50%) and filtered through 1 um pore size filter paper. After the reaction solvent is exchanged to 1-propanol through repeated cycles of evaporation and dilution, the solution is ready to be used for formulation. The solid content is measured via removing the solvent at vacuum oven at 80 ° C .
  • a lens formulation is prepared to have the following composition: 71 % by weight of prepolymer prepared above; 4% by weight of DMA; 1 % by weight of TPO; 1 % by weight of DMPC; 1 % by weight of Brij 52 (from Sigma-Aldrich), and 22% by weight of 1-PrOH.
  • Lenses are fabricated by cast-molding of the lens formulation prepared above using reusable mold, similar to the mold shown in Figs. 1-6 in U.S. patent Nos.7,384,590 and
  • the mold comprises a female mold half made of glass and a male mold half made of quartz.
  • the UV irradiation source is a Hamamatsu lamp with a 380 nm-cut-off filter at an intensity of about 4.6 mW /cm 2 .
  • the lens formulation in the mold is irradiated with UV irradiation for about 30 seconds.
  • Cast-molded lenses are extracted with methyl ethyl ketone (MEK), rinsed in water, coated with polyacrylic acid (PAA) by dipping lenses in a propanol solution of PAA (0.004% by weight, acidified with formic acid to about pH 2.0), and hydrated in water.
  • MEK methyl ethyl ketone
  • PAA polyacrylic acid
  • IPC Saline is prepared from a composition containing about 0.07% PAAm-PAA and sufficient PAE to provide an initial azetidinium content of approximately 8.8 millimole equivalents / Liter (-0.15% PAE) under pre-reaction conditions of 6 hrs at approximately 60°C. 5 ppm hydrogen peroxide is then added to the IPC salines to prevent bioburden growth and the IPC salines are filtered using a 0.22micron polyether sulphone [PES] membrane filter Lenses are placed in a polypropylene lens packaging shell with 0.6 mL of the IPC saline (half of the saline is added prior to inserting the lens). The blister is then sealed with foil and autoclaved for 30 min at 121 °C.
  • PES polyether sulphone
  • the obtained lenses have the following properties: E' ⁇ 0.82 MPa; DK C ⁇ 159.4 (using lotrafilcon B as reference lenses, an average center thickness of 80 ⁇ and an intrinsic Dk 1 10); IP-2.3; water% ⁇ 26.9; and UVA/UVB %T ⁇ 4.6/0.1. When observed under dark field microscope, no cracking lines are visible after rubbing the test lens. The lenses are very lubricious in a finger rubbing test and equivalent to the control lenses.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ophthalmology & Optometry (AREA)
  • Organic Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • General Health & Medical Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Eyeglasses (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Materials For Medical Uses (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Silicon Polymers (AREA)
  • Laminated Bodies (AREA)
  • Paints Or Removers (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
  • Polyethers (AREA)
PCT/US2011/045808 2010-07-30 2011-07-29 Silicone hydrogel lenses with water-rich surfaces Ceased WO2012016096A1 (en)

Priority Applications (33)

Application Number Priority Date Filing Date Title
KR1020197016694A KR102104222B1 (ko) 2010-07-30 2011-07-29 수분이 풍부한 표면을 갖는 실리콘 히드로겔 렌즈
AU2011282602A AU2011282602C1 (en) 2010-07-30 2011-07-29 Silicone hydrogel lenses with water-rich surfaces
BR122013012250-8A BR122013012250B1 (pt) 2010-07-30 2011-07-29 lentes de contato de silicone hidrogel apresentando uma configuração estrutural em camadas e um gradiente de teor de água do interior para o exterior da lente de contato de silicone hidrogel
EP25209874.4A EP4657145A2 (en) 2010-07-30 2011-07-29 Silicone hydrogel lenses with water-rich surfaces
KR1020217003655A KR102266815B1 (ko) 2010-07-30 2011-07-29 수분이 풍부한 표면을 갖는 실리콘 히드로겔 렌즈
KR1020137005040A KR101413390B1 (ko) 2010-07-30 2011-07-29 수분이 풍부한 표면을 갖는 실리콘 히드로겔 렌즈
KR1020207026811A KR102215955B1 (ko) 2010-07-30 2011-07-29 수분이 풍부한 표면을 갖는 실리콘 히드로겔 렌즈
SI201130045T SI2461767T1 (sl) 2010-07-30 2011-07-29 Silikonske hidrogelne leče s površinami, bogatimi z vodo
EP11813220.8A EP2461767B1 (en) 2010-07-30 2011-07-29 Silicone hydrogel lenses with water-rich surfaces
CN201180037423.5A CN103052364B (zh) 2010-07-30 2011-07-29 具有富水表面的硅水凝胶透镜
RS20130337A RS52882B (sr) 2010-07-30 2011-07-29 Silikonska hidrogel sočiva sa površinama bogatim vodom
BR112013002179-9A BR112013002179B1 (pt) 2010-07-30 2011-07-29 Lentes de silicone hidrogel com superfícies ricas em água
JP2013521992A JP5882322B2 (ja) 2010-07-30 2011-07-29 水分含量の多い表面を有するシリコーンヒドロゲルレンズ
BR122020017231-2A BR122020017231B1 (pt) 2010-07-30 2011-07-29 lentes de silicone hidrogel hidratadas
CA2802793A CA2802793C (en) 2010-07-30 2011-07-29 Silicone hydrogel lenses with water-rich surfaces
KR1020217017970A KR102411923B1 (ko) 2010-07-30 2011-07-29 수분이 풍부한 표면을 갖는 실리콘 히드로겔 렌즈
DK11813220.8T DK2461767T3 (da) 2010-07-30 2011-07-29 Silikonehydrogellinser med vandrige overflader
RU2013108693/05A RU2540655C2 (ru) 2010-07-30 2011-07-29 Силиконовые гидрогелевые линзы с обогащенными водой поверхностями
KR1020187022807A KR101990757B1 (ko) 2010-07-30 2011-07-29 수분이 풍부한 표면을 갖는 실리콘 히드로겔 렌즈
MX2013001189A MX382876B (es) 2010-07-30 2011-07-29 Lentes de hidrogel de silicona con superficies ricas en agua.
KR1020207011019A KR102159909B1 (ko) 2010-07-30 2011-07-29 수분이 풍부한 표면을 갖는 실리콘 히드로겔 렌즈
EP25209870.2A EP4657144A2 (en) 2010-07-30 2011-07-29 Silicone hydrogel lenses with water-rich surfaces
KR1020137016191A KR101800059B1 (ko) 2010-07-30 2011-07-29 수분이 풍부한 표면을 갖는 실리콘 히드로겔 렌즈
KR1020177031719A KR101889246B1 (ko) 2010-07-30 2011-07-29 수분이 풍부한 표면을 갖는 실리콘 히드로겔 렌즈
EP13160647.7A EP2705808B1 (en) 2010-07-30 2011-07-29 Silicone hydrogel lenses with water-rich surfaces
HK12106456.0A HK1165690B (en) 2010-07-30 2011-07-29 Silicone hydrogel lenses with water-rich surfaces
PL11813220T PL2461767T3 (pl) 2010-07-30 2011-07-29 Soczewki silikonowo-hydrożelowe z powierzchniami bogatymi w wodę
BR122020017237-1A BR122020017237B1 (pt) 2010-07-30 2011-07-29 lentes de silicone hidrogel hidratadas
SG2013006887A SG187237A1 (en) 2010-07-30 2011-07-29 Silicone hydrogel lenses with water-rich surfaces
MYPI2018001205A MY186340A (en) 2010-07-30 2011-07-29 Silicone hydrogel lenses with water-rich surfaces
KR1020167030352A KR101795983B1 (ko) 2010-07-30 2011-07-29 수분이 풍부한 표면을 갖는 실리콘 히드로겔 렌즈
EP13160886.1A EP2638878B1 (en) 2010-07-30 2011-07-29 Silicone hydrogel lenses with water-rich surfaces
ES11813220T ES2423914T3 (es) 2010-07-30 2011-07-29 Lentes de hidrogel de silicona con superficies ricas en agua

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US36910210P 2010-07-30 2010-07-30
US61/369,102 2010-07-30
US201161448478P 2011-03-02 2011-03-02
US61/448,478 2011-03-02

Publications (1)

Publication Number Publication Date
WO2012016096A1 true WO2012016096A1 (en) 2012-02-02

Family

ID=45526406

Family Applications (2)

Application Number Title Priority Date Filing Date
PCT/US2011/045808 Ceased WO2012016096A1 (en) 2010-07-30 2011-07-29 Silicone hydrogel lenses with water-rich surfaces
PCT/US2011/045810 Ceased WO2012016098A1 (en) 2010-07-30 2011-07-29 A silicone hydrogel lens with a crosslinked hydrophilic coating

Family Applications After (1)

Application Number Title Priority Date Filing Date
PCT/US2011/045810 Ceased WO2012016098A1 (en) 2010-07-30 2011-07-29 A silicone hydrogel lens with a crosslinked hydrophilic coating

Country Status (21)

Country Link
US (20) US8529057B2 (enExample)
EP (9) EP2638879A3 (enExample)
JP (17) JP5882322B2 (enExample)
KR (21) KR101795983B1 (enExample)
CN (5) CN105334640B (enExample)
AU (2) AU2011282604B2 (enExample)
BR (5) BR112013002150B1 (enExample)
CA (2) CA2802793C (enExample)
DK (1) DK2461767T3 (enExample)
ES (4) ES3015692T3 (enExample)
MX (5) MX382876B (enExample)
MY (4) MY154750A (enExample)
NZ (2) NZ610544A (enExample)
PL (1) PL2461767T3 (enExample)
PT (2) PT2461767E (enExample)
RS (1) RS52882B (enExample)
RU (13) RU2644349C1 (enExample)
SG (4) SG187237A1 (enExample)
SI (1) SI2461767T1 (enExample)
TW (17) TWI599813B (enExample)
WO (2) WO2012016096A1 (enExample)

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013074535A1 (en) * 2011-11-15 2013-05-23 Novartis Ag A silicone hydrogel lens with a crosslinked hydrophilic coating
CN104956256A (zh) * 2012-08-27 2015-09-30 视觉力学有限责任公司 具有亲水层的接触透镜
KR20150140851A (ko) * 2013-04-30 2015-12-16 쿠퍼비젼 인터내셔날 홀딩 캄파니, 엘피 1급 아민-함유 실리콘 히드로겔 콘택트 렌즈, 및 관련 조성물 및 방법
EP2855546B1 (en) 2012-05-25 2016-07-13 Johnson & Johnson Vision Care Inc. Contact lenses comprising water soluble n-(2 hydroxyalkyl) (meth)acrylamide polymers or copolymers
JP2017515171A (ja) * 2014-05-09 2017-06-08 インテロジョ インコーポレーテッドＩｎｔｅｒｏｊｏ Ｉｎｃ． 湿潤性表面を有するハイドロゲルコンタクトレンズ及びその製造方法
US9726906B2 (en) 2012-05-25 2017-08-08 Johnson & Johnson Vision Care, Inc. Polymers and nanogel materials and methods for making and using the same
US9815979B2 (en) 2010-05-06 2017-11-14 Johnson & Johnson Vision Care, Inc. Non-reactive, hydrophilic polymers having terminal siloxanes and methods for making and using the same
US10073192B2 (en) 2012-05-25 2018-09-11 Johnson & Johnson Vision Care, Inc. Polymers and nanogel materials and methods for making and using the same
US10386545B2 (en) 2011-05-04 2019-08-20 Johnson & Johnson Vision Care, Inc. Medical devices having homogeneous charge density and methods for making same
US10441676B2 (en) 2013-01-15 2019-10-15 Medicem Institute s.r.o. Light-adjustable hydrogel and bioanalogic intraocular lens
US10667903B2 (en) 2013-01-15 2020-06-02 Medicem Institute s.r.o. Bioanalogic intraocular lens
US11256003B2 (en) 2017-12-13 2022-02-22 Alcon Inc. Weekly and monthly disposable water gradient contact lenses
RU2798842C1 (ru) * 2019-06-28 2023-06-28 Алькон Инк. Офтальмологические композиции
US12072556B2 (en) 2019-11-04 2024-08-27 Alcon Inc. Contact lenses with surfaces having different softness

Families Citing this family (298)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9322958B2 (en) * 2004-08-27 2016-04-26 Coopervision International Holding Company, Lp Silicone hydrogel contact lenses
KR101389300B1 (ko) 2005-02-14 2014-04-25 존슨 앤드 존슨 비젼 케어, 인코포레이티드 안과용 렌즈의 제조방법, 안과용 장치 및 콘택트 렌즈
US20150219928A1 (en) * 2006-02-10 2015-08-06 Johnson & Johnson Vision Care, Inc. Comfortable ophthalmic device and methods of its production
TWI506333B (zh) 2008-12-05 2015-11-01 Novartis Ag 用以傳遞疏水性舒適劑之眼用裝置及其製造方法
TWI599813B (zh) 2010-07-30 2017-09-21 諾華公司 水合隱形鏡片
US8524215B2 (en) * 2010-08-02 2013-09-03 Janssen Biotech, Inc. Absorbable PEG-based hydrogels
ES2693275T3 (es) * 2011-02-28 2018-12-10 Coopervision International Holding Company, Lp Lentes de contacto de hidrogel de silicona
US20130203813A1 (en) 2011-05-04 2013-08-08 Johnson & Johnson Vision Care, Inc. Medical devices having homogeneous charge density and methods for making same
US8798332B2 (en) 2012-05-15 2014-08-05 Google Inc. Contact lenses
US20130313733A1 (en) * 2012-05-25 2013-11-28 Ivan Nunez Method of making a fully polymerized uv blocking silicone hydrogel lens
JP6163543B2 (ja) * 2012-05-25 2017-07-12 ボシュ・アンド・ロム・インコーポレイテッドＢａｕｓｃｈ ＆ Ｌｏｍｂ Ｉｎｃｏｒｐｏｒａｔｅｄ 完全に重合したｕｖブロック性シリコーンハイドロゲルレンズ
US9075187B2 (en) * 2012-05-25 2015-07-07 Bausch & Lomb Incorporated Fully polymerized UV blocking silicone hydrogel lens
US9297929B2 (en) 2012-05-25 2016-03-29 Johnson & Johnson Vision Care, Inc. Contact lenses comprising water soluble N-(2 hydroxyalkyl) (meth)acrylamide polymers or copolymers
US8807745B2 (en) * 2012-05-25 2014-08-19 Bausch & Lomb Incorporated Fully polymerized UV blocking silicone hydrogel lens
US20130323291A1 (en) * 2012-05-31 2013-12-05 Biocoat Incorporated Hydrophilic and non-thrombogenic polymer for coating of medical devices
WO2013188274A2 (en) * 2012-06-14 2013-12-19 Novartis Ag Azetidinium-containing copolymers and uses thereof
US9298020B1 (en) 2012-07-26 2016-03-29 Verily Life Sciences Llc Input system
US8857981B2 (en) 2012-07-26 2014-10-14 Google Inc. Facilitation of contact lenses with capacitive sensors
US9523865B2 (en) 2012-07-26 2016-12-20 Verily Life Sciences Llc Contact lenses with hybrid power sources
US9158133B1 (en) 2012-07-26 2015-10-13 Google Inc. Contact lens employing optical signals for power and/or communication
US8919953B1 (en) 2012-08-02 2014-12-30 Google Inc. Actuatable contact lenses
US8971978B2 (en) 2012-08-21 2015-03-03 Google Inc. Contact lens with integrated pulse oximeter
US9696564B1 (en) 2012-08-21 2017-07-04 Verily Life Sciences Llc Contact lens with metal portion and polymer layer having indentations
US9111473B1 (en) 2012-08-24 2015-08-18 Google Inc. Input system
US8820934B1 (en) 2012-09-05 2014-09-02 Google Inc. Passive surface acoustic wave communication
US20140192315A1 (en) 2012-09-07 2014-07-10 Google Inc. In-situ tear sample collection and testing using a contact lens
US9398868B1 (en) 2012-09-11 2016-07-26 Verily Life Sciences Llc Cancellation of a baseline current signal via current subtraction within a linear relaxation oscillator-based current-to-frequency converter circuit
US10010270B2 (en) 2012-09-17 2018-07-03 Verily Life Sciences Llc Sensing system
US9326710B1 (en) 2012-09-20 2016-05-03 Verily Life Sciences Llc Contact lenses having sensors with adjustable sensitivity
US8960898B1 (en) 2012-09-24 2015-02-24 Google Inc. Contact lens that restricts incoming light to the eye
US8870370B1 (en) 2012-09-24 2014-10-28 Google Inc. Contact lens that facilitates antenna communication via sensor impedance modulation
US8979271B2 (en) 2012-09-25 2015-03-17 Google Inc. Facilitation of temperature compensation for contact lens sensors and temperature sensing
US20140088372A1 (en) 2012-09-25 2014-03-27 Google Inc. Information processing method
US8989834B2 (en) 2012-09-25 2015-03-24 Google Inc. Wearable device
US9884180B1 (en) 2012-09-26 2018-02-06 Verily Life Sciences Llc Power transducer for a retinal implant using a contact lens
US8821811B2 (en) 2012-09-26 2014-09-02 Google Inc. In-vitro contact lens testing
US8985763B1 (en) 2012-09-26 2015-03-24 Google Inc. Contact lens having an uneven embedded substrate and method of manufacture
US8960899B2 (en) 2012-09-26 2015-02-24 Google Inc. Assembling thin silicon chips on a contact lens
US9063351B1 (en) 2012-09-28 2015-06-23 Google Inc. Input detection system
US8965478B2 (en) 2012-10-12 2015-02-24 Google Inc. Microelectrodes in an ophthalmic electrochemical sensor
US9176332B1 (en) 2012-10-24 2015-11-03 Google Inc. Contact lens and method of manufacture to improve sensor sensitivity
US9757056B1 (en) 2012-10-26 2017-09-12 Verily Life Sciences Llc Over-molding of sensor apparatus in eye-mountable device
SG11201504592YA (en) 2012-12-11 2015-07-30 Novartis Ag Method for applying a coating onto a silicone hydrogel lens
MY172901A (en) 2012-12-17 2019-12-13 Alcon Inc Method for making improved uv-absorbing ophthalmic lenses
US20140178327A1 (en) * 2012-12-21 2014-06-26 Coopervision International Holding Company, Lp Antimicrobial Ophthalmic Devices
US9161598B2 (en) * 2012-12-21 2015-10-20 Coopervision International Holding Company, Lp Ophthalmic devices for delivery of beneficial agents
US8874182B2 (en) 2013-01-15 2014-10-28 Google Inc. Encapsulated electronics
US9289954B2 (en) 2013-01-17 2016-03-22 Verily Life Sciences Llc Method of ring-shaped structure placement in an eye-mountable device
US9636016B1 (en) 2013-01-25 2017-05-02 Verily Life Sciences Llc Eye-mountable devices and methods for accurately placing a flexible ring containing electronics in eye-mountable devices
US20140209481A1 (en) 2013-01-25 2014-07-31 Google Inc. Standby Biasing Of Electrochemical Sensor To Reduce Sensor Stabilization Time During Measurement
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
US9161712B2 (en) 2013-03-26 2015-10-20 Google Inc. Systems and methods for encapsulating electronics in a mountable device
US9113829B2 (en) 2013-03-27 2015-08-25 Google Inc. Systems and methods for encapsulating electronics in a mountable device
SG2013035662A (en) * 2013-05-08 2014-12-30 Menicon Singapore Pte Ltd Systems and methods for printing on a contact lens
US9950483B2 (en) * 2013-05-29 2018-04-24 Novartis Ag Method for determining the surface concentration of carboxyl groups on a lens
US20140371560A1 (en) 2013-06-14 2014-12-18 Google Inc. Body-Mountable Devices and Methods for Embedding a Structure in a Body-Mountable Device
US9084561B2 (en) 2013-06-17 2015-07-21 Google Inc. Symmetrically arranged sensor electrodes in an ophthalmic electrochemical sensor
US9948895B1 (en) 2013-06-18 2018-04-17 Verily Life Sciences Llc Fully integrated pinhole camera for eye-mountable imaging system
US9685689B1 (en) 2013-06-27 2017-06-20 Verily Life Sciences Llc Fabrication methods for bio-compatible devices
US9492118B1 (en) 2013-06-28 2016-11-15 Life Sciences Llc Pre-treatment process for electrochemical amperometric sensor
US9028772B2 (en) 2013-06-28 2015-05-12 Google Inc. Methods for forming a channel through a polymer layer using one or more photoresist layers
US9307901B1 (en) 2013-06-28 2016-04-12 Verily Life Sciences Llc Methods for leaving a channel in a polymer layer using a cross-linked polymer plug
US9814387B2 (en) 2013-06-28 2017-11-14 Verily Life Sciences, LLC Device identification
JP5452756B1 (ja) * 2013-07-02 2014-03-26 Ｈｏｙａ株式会社 親水性表面を有するシリコーン含有共重合体成形品を作製する方法及び親水性表面を有するシリコーンハイドロゲルコンタクトレンズ
US9315669B2 (en) 2013-09-30 2016-04-19 Novartis Ag Method for making UV-absorbing ophthalmic lenses
US9568645B2 (en) 2013-09-30 2017-02-14 Novartis Ag Silicone hydrogel lenses with relatively-long thermal stability
SG11201602210WA (en) 2013-10-31 2016-05-30 Novartis Ag Method for producing ophthalmic lenses
US9668916B2 (en) 2013-11-04 2017-06-06 Vance M. Thompson Conjunctival cover and methods therefor
CA2930552C (en) 2013-11-15 2022-12-13 Ocular Dynamics, Llc Contact lens with a hydrophilic layer
CN104628943B (zh) * 2013-11-15 2016-09-21 中国石油化工股份有限公司 一种丙烯酰胺系共聚物及其制备方法和应用
WO2015082232A1 (en) 2013-12-02 2015-06-11 Novartis Ag Novel process for making molded devices
MY183117A (en) 2013-12-13 2021-02-15 Alcon Inc Method for making contact lenses
US9708087B2 (en) 2013-12-17 2017-07-18 Novartis Ag Silicone hydrogel lens with a crosslinked hydrophilic coating
US9572522B2 (en) 2013-12-20 2017-02-21 Verily Life Sciences Llc Tear fluid conductivity sensor
US9654674B1 (en) 2013-12-20 2017-05-16 Verily Life Sciences Llc Image sensor with a plurality of light channels
US9366570B1 (en) 2014-03-10 2016-06-14 Verily Life Sciences Llc Photodiode operable in photoconductive mode and photovoltaic mode
US9184698B1 (en) 2014-03-11 2015-11-10 Google Inc. Reference frequency from ambient light signal
US9789655B1 (en) 2014-03-14 2017-10-17 Verily Life Sciences Llc Methods for mold release of body-mountable devices including microelectronics
CN106104365B (zh) 2014-04-08 2019-08-02 诺华股份有限公司 其中具有产生氧的元件的眼科镜片
EP3134461B1 (en) 2014-04-25 2018-02-14 Novartis AG Hydrophilized carbosiloxane vinylic monomers
TW201617692A (zh) * 2014-07-21 2016-05-16 視覺動力公司 隱形眼鏡及製造隱形眼鏡之方法
US11002884B2 (en) 2014-08-26 2021-05-11 Alcon Inc. Method for applying stable coating on silicone hydrogel contact lenses
BR112017003447B1 (pt) 2014-08-26 2021-10-26 Alcon Inc Copolímero de poli(oxazolina-co-etilenoimina)-epicloridrina, material polimérico hidrofílico reticulável termicamente e solúvel em água, e métodos para produzir lentes de contato revestidas
WO2016046178A1 (en) * 2014-09-23 2016-03-31 Momentive Performance Materials Gmbh Silicone compounds and compositions thereof for the treatment of amino acid based substrates
MY179853A (en) 2014-09-26 2020-11-18 Alcon Inc Polymerizable polysiloxanes with hydrophilic substituents
US9408684B2 (en) 2014-10-03 2016-08-09 Soft Health Technologies, Llc Systems and methods for incontinence control
US10261342B2 (en) * 2014-10-08 2019-04-16 Innovega, Inc. Contact lens and method and systems for constructing a contact lens
US9869884B2 (en) 2014-11-22 2018-01-16 Innovega, Inc. Contact lens
CN104406927B (zh) * 2014-11-28 2017-09-29 华南理工大学 一种基于光学的水合物生成监测方法和系统
CA2970010A1 (en) 2014-12-09 2016-06-16 Karen Havenstrite Medical device coating with a biocompatible layer
EP3233450B1 (en) 2014-12-17 2019-01-30 Novartis AG Reusable lens molds and methods of use thereof
WO2016100457A1 (en) 2014-12-17 2016-06-23 Novartis Ag Reusable lens molds and methods of use thereof
CN204758942U (zh) * 2015-01-29 2015-11-11 广州琦安琦视觉科技有限公司 一种具有防紫外线、衍射光及蓝光多功能隐形眼镜
US10723842B2 (en) 2015-03-11 2020-07-28 University Of Florida Research Foundation, Inc. Mesh size control of lubrication in gemini hydrogels
US9869883B2 (en) 2015-03-11 2018-01-16 Vance M. Thompson Tear shaping for refractive correction
CN106033150B (zh) * 2015-03-17 2019-04-05 专力国际开发股份有限公司 复合隐形眼镜
CN107532038B (zh) * 2015-05-07 2020-08-11 爱尔康公司 用于生产在其上具有耐用润滑涂层的接触镜片的方法
DK3300482T3 (da) 2015-05-19 2021-10-18 Lubris Llc Brug af prg4 til at forbedre dynamisk synsstyrke og højere ordens aberrationer
WO2016208640A1 (ja) * 2015-06-24 2016-12-29 住友大阪セメント株式会社 硬化性シリコーン樹脂組成物、シリコーン樹脂複合体、光半導体発光装置、照明器具及び液晶画像装置
JP6791143B2 (ja) * 2015-07-31 2020-11-25 日産化学株式会社 液晶配向剤、液晶配向膜及び液晶表示素子
US9810812B2 (en) 2015-09-04 2017-11-07 Novartis Ag Method for producing contact lenses with durable lubricious coatings thereon
CA2992173C (en) * 2015-09-04 2020-07-14 Novartis Ag Soft silicone medical devices with durable lubricious coatings thereon
EP3374143B1 (en) * 2015-11-11 2020-10-28 Onefocus Vision, Inc. Accommodating lens with cavity
MY186090A (en) 2015-12-03 2021-06-21 Alcon Inc Contact lens packaging solutions
EP3390497B1 (en) 2015-12-15 2021-01-20 Alcon Inc. Polymerizable polysiloxanes with hydrophilic substituents
JP6616512B2 (ja) 2015-12-15 2019-12-04 ノバルティス アーゲー 親水化ポリジオルガノシロキサンビニル架橋剤およびその使用
EP3390026A1 (en) 2015-12-15 2018-10-24 Novartis AG Method for producing contact lenses with a lubricious surface
EP3391101B1 (en) * 2015-12-15 2020-07-08 Alcon Inc. Method for applying stable coating on silicone hydrogel contact lenses
US10138316B2 (en) 2015-12-15 2018-11-27 Novartis Ag Amphiphilic branched polydiorganosiloxane macromers
HUE063934T2 (hu) 2015-12-17 2024-02-28 Alcon Inc Újrahasználható lencseszerszámok, valamint eljárások azok használatára
RU2612121C1 (ru) * 2016-01-27 2017-03-02 Федеральное государственное бюджетное научное учреждение "Научно-исследовательский институт глазных болезней" Лечебная силикон-гидрогелевая мягкая контактная линза
JP6807011B2 (ja) * 2016-02-15 2021-01-06 日油株式会社 表面にホスホリルコリン基含有親水性ポリマーを有するコンタクトレンズ
WO2017146102A1 (ja) * 2016-02-22 2017-08-31 東レ株式会社 デバイスおよびその製造方法
WO2017146101A1 (ja) * 2016-02-22 2017-08-31 東レ株式会社 デバイスおよびその製造方法
CA3010574C (en) 2016-02-22 2020-10-13 Novartis Ag Soft silicone medical devices
CN109154724B (zh) * 2016-03-11 2020-12-25 印诺维嘉有限公司 接触镜
TWI716586B (zh) * 2016-04-28 2021-01-21 日商日油股份有限公司 隱形眼鏡用表面處理劑及隱形眼鏡
JP6961587B2 (ja) * 2016-06-29 2021-11-05 日油株式会社 滑り性付与剤および滑り性付与方法
KR20230108354A (ko) * 2016-08-01 2023-07-18 유니버시티 오브 워싱턴 근시를 치료하기 위한 안과 렌즈들
HUE053707T2 (hu) 2016-09-20 2021-07-28 Alcon Inc Színezett hidrogél kontaktlencsék rajtuk síkosító bevonattal
HUE056815T2 (hu) * 2016-09-20 2022-03-28 Alcon Inc Eljárás vízoldható, hõkezeléssel térhálósítható polimer anyag elõállítására
MY189895A (en) 2016-09-20 2022-03-18 Novartis Ag Process for producing contact lenses with durable lubricious coatings thereon
CA3032588C (en) * 2016-09-20 2021-03-23 Novartis Ag Hydrogel contact lenses with lubricious coating thereon
US10850461B2 (en) * 2016-09-27 2020-12-01 Coopervision International Holding Company, Lp Method of manufacturing contact lenses
JP6859432B2 (ja) 2016-10-11 2021-04-14 アルコン インク． 鎖延長ポリジメチルシロキサンビニル架橋剤およびその使用
CA3033596C (en) 2016-10-11 2021-02-09 Novartis Ag Polymerizable polydimethylsiloxane-polyoxyalkylene block copolymers
US10353220B2 (en) 2016-10-17 2019-07-16 Vance M. Thompson Tear shaping for refractive correction
CA3034604C (en) 2016-10-19 2021-03-09 Novartis Ag Hydrophilic copolymer with pendant thiol groups
JP6777814B2 (ja) * 2016-10-19 2020-10-28 アルコン インク． １個のチオール含有末端基を有する親水性コポリマー
WO2018078542A1 (en) 2016-10-26 2018-05-03 Novartis Ag Soft contact lenses with a lubricious coating covalently-attached thereon
US10527757B2 (en) 2016-10-26 2020-01-07 Novartis Ag Amphiphilic branched polydiorganosiloxane macromers
KR101910842B1 (ko) * 2016-10-27 2018-10-23 연세대학교 산학협력단 표면이 친수화된 안과용 재료 및 이의 제조방법
US10718960B2 (en) 2016-10-31 2020-07-21 Alcon Inc. Method for producing contact lenses with wearing comfort
WO2018089699A1 (en) 2016-11-11 2018-05-17 Onefocus Vision, Inc. Accommodating cavity lens shaped with photocleavable insert
KR101872120B1 (ko) * 2016-11-21 2018-06-27 대구가톨릭대학교산학협력단 고 함수율 표면층을 갖는 하이드로겔 콘택트렌즈 및 그 제조방법
JP6961624B2 (ja) * 2017-01-13 2021-11-05 富士フイルム株式会社 医療用潤滑性部材に用いる積層材料、医療用潤滑性部材、および医療機器
WO2018155475A1 (ja) * 2017-02-21 2018-08-30 三井化学株式会社 光学材料用重合性組成物、当該組成物から得られる光学材料およびプラスチックレンズ
TWI610802B (zh) * 2017-04-10 2018-01-11 明基材料股份有限公司 眼用鏡片及其製造方法
US10509238B2 (en) * 2017-04-14 2019-12-17 Verily Life Sciences Llc Electrowetting opthalmic optics including gas-permeable components
US11358352B2 (en) 2017-05-11 2022-06-14 Toray Industries, Inc. Method for producing medical device
US11378570B2 (en) 2017-05-24 2022-07-05 Alcon Inc. Cytotoxicity test method for medical devices
EP4481478A3 (en) 2017-06-07 2025-03-26 Alcon Inc. Silicone hydrogel contact lenses
AU2018279285B2 (en) 2017-06-07 2020-12-17 Alcon Inc. Silicone hydrogel contact lenses
US10843422B2 (en) 2017-06-07 2020-11-24 Alcon, Inc. Method for producing silicone hydrogel contact lenses
CN107796674B (zh) * 2017-07-04 2021-03-16 程树军 一种动物角膜长期培养评价眼刺激性损伤及修复的方法
TWI640557B (zh) 2017-07-05 2018-11-11 晶碩光學股份有限公司 具表面修飾的隱形眼鏡及其製備方法
US10920099B2 (en) 2017-07-18 2021-02-16 Alcon Inc. Poly(meth)acrylamide-based copolymers with carboxyl-terminated pendant chains
US10676608B2 (en) 2017-07-18 2020-06-09 Alcon Inc. Phosphorylcholine-containing poly(meth)acrylamide-based copolymers
EP3662809B1 (en) * 2017-08-01 2023-05-03 Seed Co., Ltd. Hood for endoscope
EP3666300B1 (en) 2017-08-09 2023-02-15 Toray Industries, Inc. Medical device and method for manufacturing same
US11795431B2 (en) 2017-08-17 2023-10-24 The Trustees Of Princeton University Ultrathin interfacial layer on a hydrogel to direct its surface properties and cell adhesion
JP6678959B2 (ja) * 2017-08-22 2020-04-15 芳人 川瀬 樹脂成形物の表面へのコーティング層形成方法。
US10809181B2 (en) 2017-08-24 2020-10-20 Alcon Inc. Method and apparatus for determining a coefficient of friction at a test site on a surface of a contact lens
US10906258B2 (en) 2017-08-29 2021-02-02 Alcon Inc. Cast-molding process for producing contact lenses
KR101944008B1 (ko) 2017-09-18 2019-01-30 (주) 제이씨바이오 히알루론산을 포함하는 투명 하이드로겔 막 및 이를 이용한 콘택트렌즈
JP7501908B2 (ja) * 2017-09-19 2024-06-18 香港科技大学 生体適合性材料、並びにそれを作製及び使用する方法
US11029538B2 (en) 2017-10-25 2021-06-08 Coopervision International Limited Contact lenses having an ion-impermeable portion and related methods
US11067831B2 (en) 2017-10-30 2021-07-20 Coopervision International Limited Methods of manufacturing coated contact lenses
JP7228119B2 (ja) * 2017-12-04 2023-02-24 日油株式会社 ソフトコンタクトレンズ用処理液
MY199542A (en) 2018-01-22 2023-11-06 Alcon Inc Cast-molding process for producing uv-absorbing contact lenses
US10884264B2 (en) 2018-01-30 2021-01-05 Sightglass Vision, Inc. Ophthalmic lenses with light scattering for treating myopia
CN111919141B (zh) 2018-02-26 2023-11-14 爱尔康公司 硅氧烷水凝胶隐形眼镜
US12486403B2 (en) 2018-03-02 2025-12-02 Johnson & Johnson Vision Care, Inc. Polymerizable absorbers of UV and high energy visible light
US10935695B2 (en) 2018-03-02 2021-03-02 Johnson & Johnson Vision Care, Inc. Polymerizable absorbers of UV and high energy visible light
US11543683B2 (en) 2019-08-30 2023-01-03 Johnson & Johnson Vision Care, Inc. Multifocal contact lens displaying improved vision attributes
US12486348B2 (en) 2019-08-30 2025-12-02 Johnson & Johnson Vision Care, Inc. Contact lens displaying improved vision attributes
US11993037B1 (en) 2018-03-02 2024-05-28 Johnson & Johnson Vision Care, Inc. Contact lens displaying improved vision attributes
EP3774310B1 (en) 2018-03-28 2022-07-06 Alcon Inc. Method for making silicone hydrogel contact lenses
US10678067B2 (en) 2018-04-06 2020-06-09 Vance M. Thompson Tear shaping for refractive correction
WO2019198034A1 (en) 2018-04-13 2019-10-17 Alcon Inc. Evaluation method for the coverage of a coating on a contact lens surface
HUE063073T2 (hu) 2018-06-04 2023-12-28 Alcon Inc Eljárás szilikon-hidrogél kontaktlencsék elõállítására
SG11202009915VA (en) 2018-06-04 2020-12-30 Alcon Inc Method for producing silicone hydrogel contact lenses
US11254075B2 (en) 2018-06-04 2022-02-22 Alcon Inc. Method for producing silicone hydrogel contact lenses
US11046636B2 (en) 2018-06-29 2021-06-29 Johnson & Johnson Vision Care, Inc. Polymerizable absorbers of UV and high energy visible light
AU2019302757B2 (en) 2018-07-12 2022-09-01 Sightglass Vision, Inc. Methods and devices for reducing myopia in children
EP3824917B1 (en) 2018-07-17 2025-10-29 FUJIFILM Corporation Use of a composition for a laminated material used for a medical lubricating member, use of a laminated material used for a medical lubricating member, medical lubricating member, and medical device
US20200085564A1 (en) 2018-09-18 2020-03-19 Vance M. Thompson Structures and methods for tear shaping for refractive correction
US12178512B2 (en) * 2018-10-17 2024-12-31 Qura, Inc. Implantable devices with embedded pressure sensors
TWI690424B (zh) * 2018-10-29 2020-04-11 優你康光學股份有限公司 具有聚合物多層膜的隱形眼鏡之製備方法
US11061169B2 (en) 2018-11-15 2021-07-13 Alcon Inc. Contact lens with phosphorylcholine-modified polyvinylalcohols therein
US11520167B2 (en) 2018-11-30 2022-12-06 Alcon Inc. Environmental scanning electron microscopy analysis for contact lens coating selection and manufacturing
SG11202104402PA (en) 2018-12-03 2021-06-29 Alcon Inc Method for coated silicone hydrogel contact lenses
SG11202104403VA (en) 2018-12-03 2021-06-29 Alcon Inc Method for making coated silicone hydrogel contact lenses
KR102757119B1 (ko) 2018-12-12 2025-01-22 도레이 카부시키가이샤 의료 디바이스 및 그 제조 방법
SG11202105233QA (en) 2018-12-14 2021-06-29 Alcon Inc Method for making silicone hydrogel contact lenses
WO2020131787A1 (en) * 2018-12-18 2020-06-25 Hewlett-Packard Development Company, L.P. Pre-treatment composition and printable medium
MY203595A (en) 2019-01-28 2024-07-05 Alcon Inc High molecular weight poly(methacrylic acid)
KR102176460B1 (ko) * 2019-04-03 2020-11-09 연세대학교 산학협력단 염증성 질환 진단용 조성물 및 이를 포함하는 안내렌즈형 센서
US11678975B2 (en) 2019-04-05 2023-06-20 Amo Groningen B.V. Systems and methods for treating ocular disease with an intraocular lens and refractive index writing
US12357509B2 (en) 2019-04-05 2025-07-15 Amo Groningen B.V. Systems and methods for improving vision from an intraocular lens in an incorrect position and using refractive index writing
US11583389B2 (en) 2019-04-05 2023-02-21 Amo Groningen B.V. Systems and methods for correcting photic phenomenon from an intraocular lens and using refractive index writing
US11564839B2 (en) 2019-04-05 2023-01-31 Amo Groningen B.V. Systems and methods for vergence matching of an intraocular lens with refractive index writing
US11944574B2 (en) 2019-04-05 2024-04-02 Amo Groningen B.V. Systems and methods for multiple layer intraocular lens and using refractive index writing
US11529230B2 (en) 2019-04-05 2022-12-20 Amo Groningen B.V. Systems and methods for correcting power of an intraocular lens using refractive index writing
US12377622B2 (en) 2019-04-05 2025-08-05 Amo Groningen B.V. Systems and methods for vergence matching with an optical profile and using refractive index writing
US11583388B2 (en) 2019-04-05 2023-02-21 Amo Groningen B.V. Systems and methods for spectacle independence using refractive index writing with an intraocular lens
WO2020208576A1 (en) 2019-04-10 2020-10-15 Alcon Inc. Method for producing coated contact lenses
US11708440B2 (en) 2019-05-03 2023-07-25 Johnson & Johnson Surgical Vision, Inc. High refractive index, high Abbe compositions
AU2020270003A1 (en) 2019-05-03 2020-12-03 Johnson & Johnson Surgical Vision, Inc. High reactive index, high abbe compositions
WO2020230016A1 (en) 2019-05-13 2020-11-19 Alcon Inc. Method for producing photochromic contact lenses
MY206069A (en) 2019-05-28 2024-11-27 Alcon Inc Pad transfer printing method for making colored contact lenses
WO2020240440A1 (en) 2019-05-28 2020-12-03 Alcon Inc. Method for making opaque colored silicone hydrogel contact lenses
US20200385532A1 (en) * 2019-06-06 2020-12-10 Apexlens Co., Ltd. Hydrophilic and oxygen permeable polymer material
TWI798452B (zh) * 2019-06-17 2023-04-11 晶碩光學股份有限公司 隱形眼鏡產品
WO2020256995A1 (en) * 2019-06-19 2020-12-24 Board Of Regents, The University Of Texas System A semiliquid surface with liquid and solid repellence
TWI757773B (zh) * 2019-06-28 2022-03-11 瑞士商愛爾康公司 眼用組成物
US11958824B2 (en) 2019-06-28 2024-04-16 Johnson & Johnson Vision Care, Inc. Photostable mimics of macular pigment
US12433970B2 (en) * 2019-08-27 2025-10-07 Toray Industries, Inc. Method for manufacturing medical device
WO2021070862A1 (ja) * 2019-10-09 2021-04-15 日油株式会社 ソフトコンタクトレンズ用表面処理剤
US11927512B2 (en) 2019-11-05 2024-03-12 Alcon Inc. Method for determining coating thickness on coated contact lenses
EP4369081B1 (en) 2019-12-16 2025-06-25 Alcon Inc. Method for producing an ophthalmic product
KR102334955B1 (ko) * 2019-12-19 2021-12-06 주식회사 더원 폴리(2-메타크릴로일옥시에틸 포스포릴콜린)로 개질된 하이드로겔 및 상기 하이드로겔로 이루어진 렌즈.
CN111013553B (zh) * 2019-12-26 2022-02-11 西南石油大学 一种亚甲基蓝和罗丹明b吸附剂及其制备方法
CN115039021B (zh) * 2020-02-03 2024-07-19 尹景泰 一种隐形眼镜及其制造方法
KR102387402B1 (ko) * 2020-03-03 2022-04-14 건양대학교 산학협력단 반짝임 변성이 감소된 소수성 아크릴 인공수정체의 제조방법
KR102149837B1 (ko) * 2020-03-09 2020-08-31 김대곤 착용감이 개선된 콘택트 렌즈 제조방법
KR102149838B1 (ko) * 2020-03-09 2020-08-31 김대곤 블루라이트 차단 콘택트 렌즈 제조방법
KR102149839B1 (ko) * 2020-03-09 2020-08-31 김대곤 착색 콘택트 렌즈 제조방법
US20210284778A1 (en) 2020-03-11 2021-09-16 Alcon Inc. Photochromic polydiorganosiloxane vinylic crosslinkers
KR102790644B1 (ko) 2020-03-19 2025-04-04 알콘 인코포레이티드 내장형 실리콘 히드로겔 콘택트 렌즈
TWI767616B (zh) 2020-03-19 2022-06-11 瑞士商愛爾康公司 用於生產嵌入或混合水凝膠接觸鏡片之方法
WO2021187394A1 (ja) * 2020-03-19 2021-09-23 日油株式会社 コンタクトレンズ用モノマー組成物およびコンタクトレンズ用重合体
TWI788804B (zh) 2020-03-19 2023-01-01 瑞士商愛爾康公司 用於嵌入式接觸鏡片之高折射率矽氧烷插入物材料
KR102828785B1 (ko) 2020-03-19 2025-07-04 알콘 인코포레이티드 높은 산소 투과율 및 높은 굴절률을 갖는 삽입물 재료
HUE066269T2 (hu) 2020-05-07 2024-07-28 Alcon Inc Eljárás szilikonhidrogél kontaktlencsék elõállítására
TWI785630B (zh) 2020-06-02 2022-12-01 瑞士商愛爾康公司 光致變色矽酮水凝膠接觸鏡片及可聚合組合物及製造彼等之方法
JP6943318B1 (ja) 2020-06-05 2021-09-29 ダイキン工業株式会社 プログラム、情報処理方法、及び情報処理装置
US20220026601A1 (en) * 2020-07-22 2022-01-27 National Yang Ming Chiao Tung University Surface-modified contact lens, method of preparing the same, and method of modifying surface of polymeric material
US12358247B2 (en) 2020-07-28 2025-07-15 Alcon Inc. Contact lenses with softer lens surfaces
JP7226492B2 (ja) * 2020-09-03 2023-02-21 荒川化学工業株式会社 化合物、活性エネルギー線硬化型コーティング剤組成物、離型コーティング剤組成物、積層体、及び積層体の製造方法
EP4177669A4 (en) * 2020-09-14 2024-08-14 Toray Industries, Inc. Coated silicone member manufacturing method
EP4237232B1 (en) 2020-10-28 2024-11-27 Alcon Inc. Method for making photochromic contact lenses
US11795252B2 (en) 2020-10-29 2023-10-24 Johnson & Johnson Surgical Vision, Inc. Compositions with high refractive index and Abbe number
WO2022097049A1 (en) 2020-11-04 2022-05-12 Alcon Inc. Method for making photochromic contact lenses
WO2022097048A1 (en) 2020-11-04 2022-05-12 Alcon Inc. Method for making photochromic contact lenses
US12393057B2 (en) 2020-12-15 2025-08-19 Coopervision International Limited Oleic acid-releasing contact lens
US20220183433A1 (en) * 2020-12-15 2022-06-16 Coopervision International Limited Cationic contact lens
CN112932786B (zh) * 2021-02-02 2024-01-23 陈振林 一种全密封的护目镜
WO2022172154A1 (en) 2021-02-09 2022-08-18 Alcon Inc. Hydrophilized polydiorganosiloxane vinylic crosslinkers
WO2022189940A1 (en) 2021-03-08 2022-09-15 Alcon Inc. Method for making photofunctional contact lenses
WO2022201013A1 (en) 2021-03-23 2022-09-29 Alcon Inc. Polysiloxane vinylic crosslinkers with high refractive index
US12194698B2 (en) 2021-03-24 2025-01-14 Alcon Inc. Method for making embedded hydrogel contact lenses
US11833771B2 (en) 2021-04-01 2023-12-05 Alcon Inc. Method for making photochromic contact lenses
KR20230144635A (ko) 2021-04-01 2023-10-16 알콘 인코포레이티드 내장형 히드로겔 콘택트 렌즈의 제조 방법
HUE071684T2 (hu) 2021-04-01 2025-09-28 Alcon Inc Beágyazott hidrogél kontaktlencsék
JP7541543B2 (ja) * 2021-04-16 2024-08-28 ペガヴィジョン コーポレーション コンタクトレンズ及びその製造方法
CN115220245B (zh) * 2021-04-16 2025-11-18 晶硕光学股份有限公司 隐形眼镜及其制造方法
US20240288711A1 (en) 2021-04-19 2024-08-29 National Institute For Materials Science Soft ocular lens and method for manufacturing same
WO2022224169A1 (en) 2021-04-22 2022-10-27 Alcon Inc. Method for applying a coating onto a non-silicone hydrogel lens
US12379611B2 (en) 2021-06-14 2025-08-05 Alcon Inc. Diffractive contact lenses
CN113248765B (zh) * 2021-06-15 2022-08-05 哈尔滨工程大学 一种改性硅橡胶及其制备方法和应用
US12054499B2 (en) 2021-06-30 2024-08-06 Johnson & Johnson Vision Care, Inc. Transition metal complexes as visible light absorbers
CN113717334A (zh) * 2021-07-06 2021-11-30 吉林爱惠瞳医用科技有限公司 一种高氧气透过率角膜接触镜及其制备方法
JP7692112B2 (ja) * 2021-09-01 2025-06-12 アルコン インク． 湿潤性シリコーンハイドロゲルコンタクトレンズを製造するための方法
CN113952518B (zh) * 2021-09-18 2022-11-29 暨南大学 一种抗细菌粘附的医用材料表面改性方法及应用
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
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
US20230176251A1 (en) 2021-09-29 2023-06-08 Johnson & Johnson Vision Care, Inc. Ophthalmic lenses and their manufacture by in-mold modification
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
JPWO2023068316A1 (enExample) * 2021-10-20 2023-04-27
TWI854369B (zh) * 2021-11-22 2024-09-01 美商蓋列斯特股份有限公司 用於在模製期間誘發隱形眼鏡組成物之較大濕潤性的方法
TWI806404B (zh) * 2022-02-08 2023-06-21 視陽光學股份有限公司 隱形眼鏡的吸水裝置及隱形眼鏡含水率量測系統
US12129602B2 (en) * 2022-03-07 2024-10-29 Appvion, Llc Multi-functional barrier coating for molded fiber containers
TW202408774A (zh) 2022-04-26 2024-03-01 瑞士商愛爾康公司 用於製造嵌入式水凝膠接觸鏡片之方法
WO2023209570A1 (en) 2022-04-26 2023-11-02 Alcon Inc. Method for making embedded hydrogel contact lenses
TW202406726A (zh) 2022-04-28 2024-02-16 瑞士商愛爾康公司 用於製造ｕｖ吸收性和ｈｅｖｌ吸收性眼科鏡片之方法
TW202402513A (zh) 2022-04-29 2024-01-16 瑞士商愛爾康公司 用於製造矽酮水凝膠接觸鏡片之方法
US20230357478A1 (en) 2022-05-09 2023-11-09 Alcon Inc. Method for making embedded hydrogel contact lenses
US12448516B2 (en) * 2022-05-20 2025-10-21 Interojo Inc. Silicone hydrogel contact lenses
JP2025517724A (ja) 2022-05-23 2025-06-10 アルコン インク． Ｕｖ／ｈｅｖｌフィルタリングコンタクトレンズ
WO2023228054A1 (en) 2022-05-23 2023-11-30 Alcon Inc. Method for making hevl-filtering contact lenses
US12391014B2 (en) 2022-05-25 2025-08-19 Alcon Inc. Method for making embedded hydrogel contact lenses
GB2619780B (en) * 2022-06-13 2025-04-09 Coopervision Int Ltd Cationic lens having improved stability
KR102693464B1 (ko) * 2022-07-06 2024-08-07 포항공과대학교 산학협력단 습도 변화에 영향을 받지 않는 이온 젤 시스템 및 그의 제조방법
US20240092043A1 (en) 2022-08-17 2024-03-21 Alcon Inc. Contact lens with a hydrogel coating thereon
US12153287B2 (en) 2022-09-27 2024-11-26 Coopervision International Limited Sustained fatty acid release from contact lens
GB2622890A (en) * 2022-09-27 2024-04-03 Coopervision Int Ltd Sustained fatty acid release from contact lens
CN115490754B (zh) * 2022-10-13 2024-04-26 河南科技大学 一种抗肿瘤活性多肽衍生物及其制备方法与应用
US20240228466A1 (en) 2022-12-15 2024-07-11 Johnson & Johnson Vision Care, Inc. Transition metal complexes as visible light absorbers
CN116239948B (zh) * 2022-12-27 2024-01-02 江苏汇鼎光学眼镜有限公司 一种超抗水型镜片及其制备方法
EP4658491A1 (en) 2023-02-02 2025-12-10 Alcon Inc. Water gradient silicone hydrogel contact lenses
US20240293985A1 (en) 2023-02-27 2024-09-05 Alcon Inc. Method for producing wettable silicone hydrogel contact lenses
CN119173379A (zh) 2023-03-20 2024-12-20 强生视力健公司 眼科镜片及其通过模内修改的制造
KR20250136869A (ko) 2023-03-22 2025-09-16 알콘 인코포레이티드 내장형 히드로겔 콘택트 렌즈의 제조 방법
WO2024215972A1 (en) * 2023-04-14 2024-10-17 Twenty Twenty Therapeutics Llc Under lens device incorporating hyaluronic acid
WO2024220971A1 (en) * 2023-04-21 2024-10-24 Azul 3D, Inc. Optical lenses, optical components, and methods of manufacturing optical components
US20240352170A1 (en) * 2023-04-21 2024-10-24 Bausch + Lomb Ireland Limited Rigid gas permeable prepolymer and rigid gas permeable contact lens formed therefrom
CN119547005A (zh) * 2023-05-15 2025-02-28 阿戈斯视觉股份有限公司 包括水凝胶涂层的接触透镜和形成具有水凝胶涂层的接触透镜的方法
TWI857612B (zh) * 2023-05-16 2024-10-01 望隼科技股份有限公司 隱形眼鏡及矽水膠隱形眼鏡
CN121039534A (zh) 2023-05-18 2025-11-28 爱尔康公司 Uv/hevl过滤性硅氧烷水凝胶隐形眼镜
US20240383865A1 (en) 2023-05-18 2024-11-21 Alcon Inc. High-energy-violet-absorbing vinylic monomers
WO2024241239A1 (en) 2023-05-25 2024-11-28 Alcon Inc. Coated silicone hydrogel contact lenses and method for making the same
US20240399686A1 (en) 2023-06-01 2024-12-05 Alcon Inc. Method for making embedded hydrogel contact lenses
WO2025032504A2 (en) 2023-08-07 2025-02-13 Alcon Inc. Uv/hevl-filtering silicone hydrogel contact lenses
US20250164823A1 (en) 2023-11-20 2025-05-22 Alcon Inc. Embedded contact lens with a high refractive index insert therein
US20250361400A1 (en) 2024-05-22 2025-11-27 Alcon Inc. Reactive hevl-absorbing dyes
WO2025243219A1 (en) 2024-05-22 2025-11-27 Alcon Inc. Reactive dyes and their use in contact lenses
WO2025243218A1 (en) 2024-05-22 2025-11-27 Alcon Inc. Method for making centrally colored contact lenses

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020149742A1 (en) * 2000-03-31 2002-10-17 Ocular Sciences, Inc. Contact lens having a uniform horizontal thickness profile
US20060063852A1 (en) * 2004-08-27 2006-03-23 Asahikasei Aime Co. Ltd. Silicone hydrogel contact lens
US20090200692A1 (en) 2008-02-07 2009-08-13 Jame Chang Method for manufacturing a silicone contact lens having a hydrophilic surface
US20100149482A1 (en) * 2008-12-12 2010-06-17 Ammon Jr Daniel M Contact lens

Family Cites Families (559)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2296891A (en) 1940-11-09 1942-09-29 Celanese Corp Cement
US2926154A (en) 1957-09-05 1960-02-23 Hercules Powder Co Ltd Cationic thermosetting polyamide-epichlorohydrin resins and process of making same
US3161935A (en) 1959-04-28 1964-12-22 Carl W Chanlund Tamping mechanism
US3224986A (en) 1962-04-18 1965-12-21 Hercules Powder Co Ltd Cationic epichlorohydrin modified polyamide reacted with water-soluble polymers
US3171502A (en) 1962-07-26 1965-03-02 Jean K Kamphere Expansible rotary drill bits
NL128305C (enExample) 1963-09-11
SE306597B (enExample) 1964-12-17 1968-12-02 Incentive Ab
US3434984A (en) 1966-04-25 1969-03-25 Owens Illinois Inc Thermosetting cationic resin and method of making same
US3488327A (en) 1967-06-30 1970-01-06 Roehm & Haas Gmbh Preparation of coating materials
DE1745348A1 (de) 1967-12-01 1971-09-09 Roehm Gmbh Azlactongruppen enthaltende Mischpolymerisate
US3598790A (en) 1966-07-01 1971-08-10 Roehm & Haas Gmbh Azlactone copolymers
US3617344A (en) 1966-08-05 1971-11-02 Us Health Education & Welfare Nonthrombogenic plastic surfaces and preparation thereof
GB1218394A (en) 1967-03-08 1971-01-06 Toho Kagaku Kogyo Kabushiki Ka Process for producing water-soluble thermosetting polymer
US3566874A (en) 1968-08-13 1971-03-02 Nat Patent Dev Corp Catheter
US3639141A (en) 1968-09-16 1972-02-01 Cordis Corp Heparinization of plastic
JPS4813341B1 (enExample) 1969-06-13 1973-04-26
US3663288A (en) 1969-09-04 1972-05-16 American Cyanamid Co Physiologically acceptible elastomeric article
US3772076A (en) 1970-01-26 1973-11-13 Hercules Inc Reaction products of epihalohydrin and polymers of diallylamine and their use in paper
US3616935A (en) 1970-02-05 1971-11-02 Dow Chemical Co Preparation of antithrombogenic surfaces
US3925178A (en) 1970-04-17 1975-12-09 Hymie D Gesser Contact lenses
US3700623A (en) 1970-04-22 1972-10-24 Hercules Inc Reaction products of epihalohydrin and polymers of diallylamine and their use in paper
US3695921A (en) 1970-09-09 1972-10-03 Nat Patent Dev Corp Method of coating a catheter
US3844989A (en) 1971-12-23 1974-10-29 Toray Industries Shampooer with rotary foam generating means anti-thrombogenic polymer compositions with internally bound heparin
US3892696A (en) 1972-05-12 1975-07-01 Grace W R & Co Polyureas and preparation thereof
US3975350A (en) 1972-08-02 1976-08-17 Princeton Polymer Laboratories, Incorporated Hydrophilic or hydrogel carrier systems such as coatings, body implants and other articles
US3813695A (en) 1973-02-21 1974-06-04 D Podell Surgical glove
US3900672A (en) 1973-04-04 1975-08-19 Hoya Lens Co Ltd Process for coating an optical material and the resulting product
US3861396A (en) 1973-08-08 1975-01-21 Hydro Med Sciences Inc Drainage tube
US4099859A (en) * 1974-12-02 1978-07-11 High Voltage Engineering Corporation Contact lens having a smooth surface layer of a hydrophilic polymer
SE400173B (sv) 1975-03-20 1978-03-20 Aminkemi Ab Forfarande vid stabilisering av en hepariniserad yta innehallande vid blodkontakt utlosbart heparin
FR2306243A1 (fr) 1975-04-03 1976-10-29 Asahi Dow Ltd Composition de revetement hydrophyle
DE2614662A1 (de) 1975-04-07 1977-01-27 Dow Chemical Co Zusammensetzung zur herstellung von in wasser quellbaren gegenstaenden
US4154898A (en) 1976-09-27 1979-05-15 The Dow Chemical Company Absorbent articles and methods for their preparation
US4143949A (en) 1976-10-28 1979-03-13 Bausch & Lomb Incorporated Process for putting a hydrophilic coating on a hydrophobic contact lens
US4182822A (en) 1976-11-08 1980-01-08 Chang Sing Hsiung Hydrophilic, soft and oxygen permeable copolymer composition
US4343927A (en) 1976-11-08 1982-08-10 Chang Sing Hsiung Hydrophilic, soft and oxygen permeable copolymer compositions
JPS5413694A (en) 1977-07-01 1979-02-01 Sumitomo Electric Industries Composite blood vessel prosthesis and method of producing same
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
DE2839249A1 (de) 1977-09-12 1979-03-22 Toray Industries Verfahren zur herstellung einer weichen kontaktlinse und ausgangsloesung zur durchfuehrung des verfahrens
US4168112A (en) 1978-01-05 1979-09-18 Polymer Technology Corporation Contact lens with a hydrophilic, polyelectrolyte complex coating and method for forming same
US4298715A (en) 1978-03-01 1981-11-03 Monsanto Company Polyamine/epihalohydrin reaction products
US4217038A (en) 1978-06-05 1980-08-12 Bausch & Lomb Incorporated Glass coated polysiloxane contact lens
US4191596A (en) 1978-09-06 1980-03-04 Union Carbide Corporation Method and compositions for coating aluminum
US4280970A (en) 1979-01-19 1981-07-28 Puropore Inc. Polyoxyethylene grafted membrane materials with grafting links derived from a diisocyanate
US4261875A (en) 1979-01-31 1981-04-14 American Optical Corporation Contact lenses containing hydrophilic silicone polymers
US4298639A (en) 1979-03-19 1981-11-03 Monsanto Company Wet strength polymers
JPS5836604B2 (ja) 1979-04-18 1983-08-10 株式会社日立製作所 高温電気透析方法と装置
US4209289A (en) 1979-05-14 1980-06-24 American Optical Corporation Contact lens mold
US4263188A (en) 1979-05-23 1981-04-21 Verbatim Corporation Aqueous coating composition and method
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
US4276402A (en) 1979-09-13 1981-06-30 Bausch & Lomb Incorporated Polysiloxane/acrylic acid/polcyclic esters of methacrylic acid polymer contact lens
US4312575A (en) 1979-09-18 1982-01-26 Peyman Gholam A Soft corneal contact lens with tightly cross-linked polymer coating and method of making same
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
US4259467A (en) 1979-12-10 1981-03-31 Bausch & Lomb Incorporated Hydrophilic contact lens made from polysiloxanes containing hydrophilic sidechains
US4293642A (en) 1980-05-13 1981-10-06 Gaf Corporation In photographic emulsion adhesion to a polyester film base
US4423099A (en) 1980-07-28 1983-12-27 Ciba-Geigy Corporation Membrane modified hydrogels
JPS5774369A (en) 1980-10-28 1982-05-10 Mitsui Petrochem Ind Ltd Coating composition
US4462665A (en) 1981-01-29 1984-07-31 The Kendall Company Composite hydrogel-forming lens and method of making same
US4355147A (en) 1981-02-26 1982-10-19 Bausch & Lomb Incorporated Polysiloxane with polycyclic modifier composition and biomedical devices
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
US4416729A (en) * 1982-01-04 1983-11-22 The Dow Chemical Company Ammonium polyamidoamines
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
US4373009A (en) 1981-05-18 1983-02-08 International Silicone Corporation Method of forming a hydrophilic coating on a substrate
US4379893A (en) 1981-08-26 1983-04-12 Diamond Shamrock Corporation Surface-treated soft contact lenses
DE3135830A1 (de) 1981-09-10 1983-03-24 Basf Ag, 6700 Ludwigshafen Verfahren zur herstellung von wasserloeslichen, stickstoffhaltigen kondensationsprodukten und deren verwendung bei der papierherstellung
US4444711A (en) 1981-12-21 1984-04-24 Husky Injection Molding Systems Ltd. Method of operating a two-shot injection-molding machine
US4661575A (en) 1982-01-25 1987-04-28 Hercules Incorporated Dicyclopentadiene polymer product
SE456347B (sv) 1982-02-09 1988-09-26 Ird Biomaterial Ab Ytmodifierat fast substrat samt forfarande for framstellning derav
SE8200751L (sv) 1982-02-09 1983-08-10 Olle Larm Forfarande for kovalent koppling for framstellning av konjugat och hervid erhallna produkter
US4487808A (en) 1982-04-22 1984-12-11 Astra Meditec Aktiebolag Medical article having a hydrophilic coating
US4499154A (en) 1982-09-03 1985-02-12 Howard L. Podell Dipped rubber article
US4460534A (en) 1982-09-07 1984-07-17 International Business Machines Corporation Two-shot injection molding
US5217492A (en) 1982-09-29 1993-06-08 Bio-Metric Systems, Inc. Biomolecule attachment to hydrophobic surfaces
US4973493A (en) 1982-09-29 1990-11-27 Bio-Metric Systems, Inc. Method of improving the biocompatibility of solid surfaces
US5002582A (en) 1982-09-29 1991-03-26 Bio-Metric Systems, Inc. Preparation of polymeric surfaces via covalently attaching polymers
US4486577A (en) 1982-10-12 1984-12-04 Ciba-Geigy Corporation Strong, silicone containing polymers with high oxygen permeability
US4479312A (en) * 1983-04-11 1984-10-30 Valley Engineering, Inc. Foldable snow compactor with side wings pivotable behind central blade
US4543398A (en) 1983-04-28 1985-09-24 Minnesota Mining And Manufacturing Company Ophthalmic devices fabricated from urethane acrylates of polysiloxane alcohols
US4527293A (en) 1983-05-18 1985-07-09 University Of Miami Hydrogel surface of urological prosthesis
US4689374A (en) 1983-06-09 1987-08-25 W. R. Grace & Co. Water soluble polyamidoaminepolyamine having weight average molecular weight of at least 5×105
US4521564A (en) 1984-02-10 1985-06-04 Warner-Lambert Company Covalent bonded antithrombogenic polyurethane material
US4695608A (en) 1984-03-29 1987-09-22 Minnesota Mining And Manufacturing Company Continuous process for making polymers having pendant azlactone or macromolecular moieties
EP0166998B1 (en) 1984-06-04 1991-05-08 TERUMO KABUSHIKI KAISHA trading as TERUMO CORPORATION Medical instrument and method for making
US4959074A (en) 1984-08-23 1990-09-25 Gergory Halpern Method of hydrophilic coating of plastics
US4605712A (en) 1984-09-24 1986-08-12 Ciba-Geigy Corporation Unsaturated polysiloxanes and polymers thereof
AT380897B (de) 1984-12-10 1986-07-25 Koller Anton Mischung zur pflege und reinigung von kontaktlinsen
US4833218A (en) 1984-12-18 1989-05-23 Dow Corning Corporation Hydrophilic silicone-organic copolymer elastomers containing bioactine agent
US4546123A (en) 1984-12-28 1985-10-08 Alcon Laboratories, Inc. Polymer hydrogels adapted for use as soft contact lenses, and method of preparing same
JPH0674369B2 (ja) 1985-03-14 1994-09-21 大日本インキ化学工業株式会社 ビニル共重合体樹脂水分散液の製法
DE3517615C2 (de) 1985-05-15 1987-04-09 Titmus Eurocon Kontaktlinsen GmbH, 8750 Aschaffenburg Verfahren zur Hydrophilierung eines Siliconkautschukformkörpers an seiner Oberfläche
US4684538A (en) 1986-02-21 1987-08-04 Loctite Corporation Polysiloxane urethane compounds and adhesive compositions, and method of making and using the same
US4786556A (en) 1986-03-24 1988-11-22 Becton, Dickinson And Company Polymeric articles having enhanced antithrombogenic activity
US4720512A (en) 1986-03-24 1988-01-19 Becton, Dickinson And Company Polymeric articles having enhanced antithrombogenic activity
DE3708308A1 (de) 1986-04-10 1987-10-22 Bayer Ag Kontaktoptische gegenstaende
US4791175A (en) 1986-08-04 1988-12-13 Ciba-Geigy Corporation Particulate hydroperoxidized poly-n-vinyl lactam, its preparation and use thereof
DE3778446D1 (de) 1986-08-18 1992-05-27 Mueller Lierheim Wolfgang G K Kontaktlinse.
US5263992A (en) 1986-10-17 1993-11-23 Bio-Metric Systems, Inc. Biocompatible device with covalently bonded biocompatible agent
US4979959A (en) 1986-10-17 1990-12-25 Bio-Metric Systems, Inc. Biocompatible coating for solid surfaces
US4734475A (en) 1986-12-15 1988-03-29 Ciba-Geigy Corporation Wettable surface modified contact lens fabricated from an oxirane containing hydrophobic polymer
US5712327A (en) 1987-01-07 1998-01-27 Chang; Sing-Hsiung Soft gas permeable contact lens having improved clinical performance
US5108776A (en) 1987-04-10 1992-04-28 University Of Florida Ocular implants and methods for their manufacture
US5290548A (en) 1987-04-10 1994-03-01 University Of Florida Surface modified ocular implants, surgical instruments, devices, prostheses, contact lenses and the like
JP2551580B2 (ja) 1987-04-30 1996-11-06 ホ−ヤ株式会社 コンタクトレンズの親水化方法
US4837289A (en) 1987-04-30 1989-06-06 Ciba-Geigy Corporation UV- and heat curable terminal polyvinyl functional macromers and polymers thereof
US5059659A (en) 1987-05-29 1991-10-22 Harry P. Gregor Surface treatments to impart hydrophilicity
US4978713A (en) 1987-12-16 1990-12-18 Ciba-Geigy Corporation Polyvinyl alcohol derivatives containing pendant vinylic monomer reaction product units bound through ether groups and hydrogel contact lenses made therefrom
US4943460A (en) 1988-02-19 1990-07-24 Snyder Laboratories, Inc. Process for coating polymer surfaces and coated products produced using such process
US5070170A (en) 1988-02-26 1991-12-03 Ciba-Geigy Corporation Wettable, rigid gas permeable, substantially non-swellable contact lens containing block copolymer polysiloxane-polyoxyalkylene backbone units, and use thereof
AU629203B2 (en) 1988-03-23 1992-10-01 E.I. Du Pont De Nemours And Company Low coefficient of friction surface
JP2561309B2 (ja) 1988-03-28 1996-12-04 テルモ株式会社 医療用材料およびその製造方法
DE68911181T2 (de) * 1988-03-31 1994-04-07 Grace W R & Co Mit Protein nichtabsorbierend polyureum-urethan-polymerbeschichtete Gegenstände.
US5061738A (en) 1988-04-18 1991-10-29 Becton, Dickinson And Company Blood compatible, lubricious article and composition and method therefor
US4954587A (en) 1988-07-05 1990-09-04 Ciba-Geigy Corporation Dimethylacrylamide-copolymer hydrogels with high oxygen permeability
US5019393A (en) 1988-08-03 1991-05-28 New England Deaconess Hospital Corporation Biocompatible substance with thromboresistance
WO1990001344A1 (fr) 1988-08-09 1990-02-22 Toray Industries, Inc. Materiau medical glissant et son procede de production
JPH0651795B2 (ja) 1988-09-16 1994-07-06 信越化学工業株式会社 メタクリル官能性ジメチルポリシロキサン
US5053048A (en) 1988-09-22 1991-10-01 Cordis Corporation Thromboresistant coating
US5270046A (en) 1988-09-27 1993-12-14 Ube Industries, Ltd. Heparin bound anti-thrombotic material
EP0362137A3 (en) 1988-09-28 1991-09-04 Ciba-Geigy Ag Molded polymers with hydrophilic surfaces, and process for making them
US4983702A (en) 1988-09-28 1991-01-08 Ciba-Geigy Corporation Crosslinked siloxane-urethane polymer contact lens
US5510418A (en) 1988-11-21 1996-04-23 Collagen Corporation Glycosaminoglycan-synthetic polymer conjugates
US5039459A (en) 1988-11-25 1991-08-13 Johnson & Johnson Vision Products, Inc. Method of forming shaped hydrogel articles including contact lenses
US5214452A (en) 1988-12-19 1993-05-25 Ciba-Geigy Corporation Hydrogels based on fluorine-containing and saccharide monomers
ATE117699T1 (de) 1988-12-19 1995-02-15 Ciba Geigy Ag Hydrogele auf der basis von fluorhaltigen und saccharid-monomeren.
US4973359A (en) 1989-01-04 1990-11-27 Nippon Paint Co., Ltd. Surface treatment chemical and bath for forming hydrophilic coatings and method of surface-treating aluminum members
US4978481A (en) * 1989-01-13 1990-12-18 Ciba-Geigy Corporation Process for the encapsulation of preformed substrates by graft copolymerization
US4968532A (en) 1989-01-13 1990-11-06 Ciba-Geigy Corporation Process for graft copolymerization on surfaces of preformed substrates to modify surface properties
US4954586A (en) 1989-01-17 1990-09-04 Menicon Co., Ltd Soft ocular lens material
US5091205A (en) 1989-01-17 1992-02-25 Union Carbide Chemicals & Plastics Technology Corporation Hydrophilic lubricious coatings
US5262484A (en) 1989-04-10 1993-11-16 Minnesota Mining And Manufacturing Company Azlactone graft copolymers
ATE139549T1 (de) 1989-04-14 1996-07-15 Jessen Wesley Corp Verfahren zum färben von kontaktlinsen
US5080924A (en) 1989-04-24 1992-01-14 Drexel University Method of making biocompatible, surface modified materials
US4990357A (en) 1989-05-04 1991-02-05 Becton, Dickinson And Company Elastomeric segmented hydrophilic polyetherurethane based lubricious coatings
US5034461A (en) 1989-06-07 1991-07-23 Bausch & Lomb Incorporated Novel prepolymers useful in biomedical devices
US5272012A (en) 1989-06-23 1993-12-21 C. R. Bard, Inc. Medical apparatus having protective, lubricious coating
KR920701271A (ko) 1989-09-14 1992-08-11 메이-자이 창 개선된 임상성능을 갖는 기체 투과성 소프트 콘택트렌즈
JPH03102313A (ja) * 1989-09-18 1991-04-26 Seiko Epson Corp コンタクトレンズ
US5049403A (en) 1989-10-12 1991-09-17 Horsk Hydro A.S. Process for the preparation of surface modified solid substrates
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
US5135516A (en) 1989-12-15 1992-08-04 Boston Scientific Corporation Lubricious antithrombogenic catheters, guidewires and coatings
GB9004881D0 (en) 1990-03-05 1990-05-02 Biocompatibles Ltd Method of improving the ocular of synthetic polymers haemo and biocompatibility
GB9009097D0 (en) 1990-04-23 1990-06-20 Lrc Products Method of making dipped rubber articles
DE4026978A1 (de) 1990-08-25 1992-02-27 Bayer Ag Auf traegern angebrachte ein- oder mehrlagige schichtelemente und ihre herstellung
JPH0783761B2 (ja) 1990-10-04 1995-09-13 テルモ株式会社 医療用具
US5160790A (en) 1990-11-01 1992-11-03 C. R. Bard, Inc. Lubricious hydrogel coatings
US5132108A (en) 1990-11-08 1992-07-21 Cordis Corporation Radiofrequency plasma treated polymeric surfaces having immobilized anti-thrombogenic agents
US5135297A (en) 1990-11-27 1992-08-04 Bausch & Lomb Incorporated Surface coating of polymer objects
ES2093245T3 (es) 1990-11-27 1996-12-16 Bausch & Lomb Macromonomeros tensioactivos.
US5112900A (en) 1990-11-28 1992-05-12 Tactyl Technologies, Inc. Elastomeric triblock copolymer compositions and articles made therewith
US5407715A (en) 1990-11-28 1995-04-18 Tactyl Technologies, Inc. Elastomeric triblock copolymer compositions and articles made therewith
AU649287B2 (en) 1990-12-19 1994-05-19 Novartis Ag Process for rendering contact lenses hydrophilic
US5270415A (en) 1990-12-21 1993-12-14 Allergan Inc. Balanced charge polymer and hydrophilic contact lens manufactured therefrom
JPH04316013A (ja) * 1991-04-16 1992-11-06 Seiko Epson Corp コンタクトレンズの製造方法
US5739236A (en) 1991-04-24 1998-04-14 Biocompatibles Limited Biocompatible zwitterion polymers
US5397848A (en) 1991-04-25 1995-03-14 Allergan, Inc. Enhancing the hydrophilicity of silicone polymers
US5443907A (en) 1991-06-18 1995-08-22 Scimed Life Systems, Inc. Coating for medical insertion guides
GB9113875D0 (en) 1991-06-27 1991-08-14 Biointeractions Ltd Polymer coatings
US6743878B2 (en) 1991-07-05 2004-06-01 Biocompatibles Uk Limited Polymeric surface coatings
US6284854B1 (en) 1991-07-05 2001-09-04 Biccompatibles Limited Polymeric surface coatings
ATE190988T1 (de) 1991-07-05 2000-04-15 Biocompatibles Ltd Polymere oberflächenbeschichtungszusammensetzungen
US6090901A (en) 1991-07-05 2000-07-18 Biocompatibles Limited Polymeric surface coatings
US6225431B1 (en) 1991-07-05 2001-05-01 Biocompatibles Limited Biocompatibilizing process
US5705583A (en) 1991-07-05 1998-01-06 Biocompatibles Limited Polymeric surface coatings
US5210111A (en) 1991-08-22 1993-05-11 Ciba-Geigy Corporation Crosslinked hydrogels derived from hydrophilic polymer backbones
EP0603268B1 (en) 1991-09-12 1996-12-18 BAUSCH & LOMB INCORPORATED Wettable silicone hydrogel compositions and methods
WO1993005825A1 (en) 1991-09-20 1993-04-01 Baxter International Inc. Processes for reducing the thrombogenicity of biomaterials
DE69212102T2 (de) 1991-10-14 1996-11-21 Nobuo Nakabayashi Behandlungslotion für Kontaktlinsen
JP3093375B2 (ja) 1991-11-01 2000-10-03 株式会社東海メディカルプロダクツ 抗血栓性物質の固定化方法
US5352714A (en) 1991-11-05 1994-10-04 Bausch & Lomb Incorporated Wettable silicone hydrogel compositions and methods for their manufacture
EP0611379B1 (en) 1991-11-05 1996-05-29 BAUSCH & LOMB INCORPORATED Wettable silicone hydrogel compositions and methods for their manufacture
GB9124353D0 (en) 1991-11-15 1992-01-08 Albright & Wilson Immobilisation of metal contaminants from a liquid to a solid metal
WO1993011751A1 (en) 1991-12-18 1993-06-24 Scimed Life Systems, Inc. Lubricous polymer network
US6314199B1 (en) 1991-12-18 2001-11-06 Novartis Ag Process and apparatus for examining optical components, especially optical components for the eye and device for illuminating clear-transparent
IL100443A (en) 1991-12-20 1995-03-30 Dotan Gideon Inspection system for detecting surface flaws
CA2107683C (en) 1992-02-13 2004-07-20 Dale G. Swan Immobilization of chemical species in crosslinked matrices
US5470944A (en) 1992-02-13 1995-11-28 Arch Development Corporation Production of high molecular weight polylactic acid
JPH05285164A (ja) 1992-04-03 1993-11-02 Unitika Ltd 抗血栓性眼内レンズ
US5358995A (en) 1992-05-15 1994-10-25 Bausch & Lomb Incorporated Surface wettable silicone hydrogels
US5805264A (en) 1992-06-09 1998-09-08 Ciba Vision Corporation Process for graft polymerization on surfaces of preformed substates to modify surface properties
JPH0649251A (ja) 1992-06-09 1994-02-22 Ciba Geigy Ag 表面特性を改質するための、予め成形した基材表面へのグラフト重合法
DK172393B1 (da) 1992-06-10 1998-05-18 Maersk Medical As Fremgangsmåde til fremstilling af en genstand med friktionsnedsættende overfladebelægning, belægningsmateriale til anvendelse ved fremstilling af en sådan genstand samt anvendelse af en osmolalitetsforøgende forbindelse i opslæmmet eller emulgeret form i belægningsmaterialet
US5292514A (en) 1992-06-24 1994-03-08 Minnesota Mining And Manufacturing Company Azlactone-functional substrates, corneal prostheses, and manufacture and use thereof
JP3195662B2 (ja) 1992-08-24 2001-08-06 株式会社メニコン 眼用レンズ材料
JP2774233B2 (ja) 1992-08-26 1998-07-09 株式会社メニコン 眼用レンズ材料
US5310571A (en) 1992-09-01 1994-05-10 Allergan, Inc. Chemical treatment to improve oxygen permeability through and protein deposition on hydrophilic (soft) and rigid gas permeable (RGP) contact lenses
IL106922A (en) 1992-09-14 1998-08-16 Novartis Ag Composite materials with one or more wettable surfaces and process for their preparation
KR0122741B1 (ko) 1992-09-23 1997-11-17 배순훈 병렬 구조를 갖는 기억 장치
US5316704B1 (en) 1992-09-28 1996-05-21 Kabi Pharmacia Ophthalmics Inc Process for fabricating full sized expansible hydrogel intraocular lenses
US5480950A (en) 1992-09-28 1996-01-02 Kabi Pharmacia Ophthalmics, Inc. High refractive index hydrogels and uses thereof
US5409731A (en) 1992-10-08 1995-04-25 Tomei Sangyo Kabushiki Kaisha Method for imparting a hydrophilic nature to a contact lens
EP0672084B2 (en) 1992-11-30 2007-03-07 Bulk Chemicals, Inc. A method and composition for treating metal surfaces
IL107603A (en) 1992-12-21 1997-01-10 Johnson & Johnson Vision Prod Ophthalmic lens inspection method and apparatus
IL107602A0 (en) 1992-12-21 1994-02-27 Johnson & Johnson Vision Prod Method of inspecting ophthalmic lenses
NZ250042A (en) 1992-12-21 1997-01-29 Johnson & Johnson Vision Prod Robotic inspection of ophthalmic lenses
IL107605A (en) 1992-12-21 1998-01-04 Johnson & Johnson Vision Prod Lens inspection system
IL107601A (en) 1992-12-21 1997-09-30 Johnson & Johnson Vision Prod Illumination and imaging subsystems for a lens inspection system
GB9226791D0 (en) 1992-12-23 1993-02-17 Biocompatibles Ltd New materials
US5350800A (en) 1993-01-19 1994-09-27 Medtronic, Inc. Method for improving the biocompatibility of solid surfaces
US5308641A (en) 1993-01-19 1994-05-03 Medtronic, Inc. Biocompatibility of solid surfaces
EP0681507B1 (en) 1993-01-29 1997-05-28 Minnesota Mining And Manufacturing Company Thermally induced phase separated azlactone membrane
CA2114697C (en) 1993-02-08 2006-06-13 Kenichi Shimura Medical tool having lubricious surface in a wetted state and method for production thereof
EP0689465A1 (en) 1993-03-18 1996-01-03 Cedars-Sinai Medical Center Drug incorporating and releasing polymeric coating for bioprosthesis
US5531715A (en) 1993-05-12 1996-07-02 Target Therapeutics, Inc. Lubricious catheters
TW328535B (en) 1993-07-02 1998-03-21 Novartis Ag Functional photoinitiators and their manufacture
US6800225B1 (en) 1994-07-14 2004-10-05 Novartis Ag Process and device for the manufacture of mouldings and mouldings manufactured in accordance with that process
US5578675A (en) 1993-07-21 1996-11-26 Basf Corporation Non-isocyanate basecoat/clearcoat coating compositions which may be ambient cured
TW325744U (en) 1993-07-21 1998-01-21 Ciba Geigy Ag Two-sided contact lens mold
AU7473894A (en) 1993-07-29 1995-02-28 Wesley-Jessen Corporation Inspection system for optical components
TW272976B (enExample) 1993-08-06 1996-03-21 Ciba Geigy Ag
TW253849B (enExample) 1993-08-09 1995-08-11 Ciba Geigy
US5408002A (en) 1993-09-09 1995-04-18 Minnesota Mining And Manufacturing Company Azlactone-functional polymer blends, articles produced therefrom and methods for preparing both
FR2709756B1 (fr) 1993-09-10 1995-10-20 Essilor Int Matériau hydrophile, transparent à haute perméabilité à l'oxygène, à base d'un polymère à réseaux interpénétrés, son mode de préparation et fabrication de lentilles de contact souples à haute perméabilité à l'oxygène.
US5514478A (en) 1993-09-29 1996-05-07 Alcan International Limited Nonabrasive, corrosion resistant, hydrophilic coatings for aluminum surfaces, methods of application, and articles coated therewith
US5723145A (en) 1993-09-30 1998-03-03 Takiron Co., Ltd. Transdermal absorption preparation
US5936703A (en) 1993-10-13 1999-08-10 Nof Corporation Alkoxysilane compound, surface processing solution and contact lens
GB9321714D0 (en) 1993-10-21 1993-12-15 Sandoz Ltd Improvements in or relating to organic compounds
US5446090A (en) 1993-11-12 1995-08-29 Shearwater Polymers, Inc. Isolatable, water soluble, and hydrolytically stable active sulfones of poly(ethylene glycol) and related polymers for modification of surfaces and molecules
US5712356A (en) 1993-11-26 1998-01-27 Ciba Vision Corporation Cross-linkable copolymers and hydrogels
US5894002A (en) 1993-12-13 1999-04-13 Ciba Vision Corporation Process and apparatus for the manufacture of a contact lens
JP3734512B2 (ja) 1993-12-27 2006-01-11 株式会社メニコン コンタクトレンズ外観検査方法および外観検査装置
US6075066A (en) * 1994-03-14 2000-06-13 Seikagaku Kogyo Kabushiki Kaisha Material to be worn on the eyeball
JPH10500712A (ja) 1994-04-11 1998-01-20 ヘキスト セラニーズ コーポレーション 超吸収性ポリマー及びそれから得られる生成物
US5476665A (en) 1994-04-13 1995-12-19 Minnesota Mining And Manufacturing Company Azlactone functional particles incorporated in a membrane formed by solvent phase inversion
ES2145910T3 (es) * 1994-05-19 2000-07-16 Minnesota Mining & Mfg Articulo polimerico con hidrofilia mejorada y un metodo para su fabricacion.
US5500732A (en) 1994-06-10 1996-03-19 Johnson & Johnson Vision Products, Inc. Lens inspection system and method
US5626000A (en) 1994-06-10 1997-05-06 Johnson & Johnson Vision Products, Inc. Packaging arrangement
US5843346A (en) 1994-06-30 1998-12-01 Polymer Technology Corporation Method of cast molding contact lenses
US5670558A (en) 1994-07-07 1997-09-23 Terumo Kabushiki Kaisha Medical instruments that exhibit surface lubricity when wetted
US5760100B1 (en) 1994-09-06 2000-11-14 Ciba Vision Corp Extended wear ophthalmic lens
US7468398B2 (en) 1994-09-06 2008-12-23 Ciba Vision Corporation Extended wear ophthalmic lens
US5509899A (en) 1994-09-22 1996-04-23 Boston Scientific Corp. Medical device with lubricious coating
IT1270125B (it) 1994-10-05 1997-04-28 Spherilene Srl Processo per la ( co) polimerizzazione di olefine
US5681510A (en) 1994-10-13 1997-10-28 Bausch & Lomb Incorporated Method for treating plastic mold pieces
US6342570B1 (en) 1994-11-14 2002-01-29 Novartis Ag Cross-linkable copolymers and hydrogels
US5507804A (en) 1994-11-16 1996-04-16 Alcon Laboratories, Inc. Cross-linked polyethylene oxide coatings to improve the biocompatibility of implantable medical devices
JP3647093B2 (ja) 1994-11-17 2005-05-11 株式会社メニコン 親水性化酸素透過性コンタクトレンズ及びその製造法
US5665840A (en) 1994-11-18 1997-09-09 Novartis Corporation Polymeric networks from water-soluble prepolymers
US5510004A (en) 1994-12-01 1996-04-23 Hercules Incorporated Azetidinium polymers for improving wet strength of paper
SE503711C2 (sv) 1994-12-14 1996-08-12 Medicarb Ab Flerstegsförfarande för beläggning av en intraokulär lins
US5700559A (en) 1994-12-16 1997-12-23 Advanced Surface Technology Durable hydrophilic surface coatings
TW353086B (en) 1994-12-30 1999-02-21 Novartis Ag Method for multistep coating of a surface
US5995213A (en) 1995-01-17 1999-11-30 Johnson & Johnson Vision Products, Inc. Lens inspection system
US5532311A (en) 1995-02-01 1996-07-02 Minnesota Mining And Manufacturing Company Process for modifying surfaces
WO1996024075A1 (en) 1995-02-03 1996-08-08 Novartis Ag Crosslinked polymers containing ester or amide groups
TW349967B (en) 1995-02-03 1999-01-11 Novartis Ag Process for producing contact lenses and a cross-linkable polyvinylalcohol used therefor
US5599576A (en) 1995-02-06 1997-02-04 Surface Solutions Laboratories, Inc. Medical apparatus with scratch-resistant coating and method of making same
JPH10513378A (ja) 1995-02-07 1998-12-22 フィディア・アドバンスト・バイオポリマーズ・ソシエタ・ア・レスポンサビリタ・リミタータ ヒアルロン酸、その誘導体、および半合成ポリマーで物体を被覆する方法
US6179817B1 (en) 1995-02-22 2001-01-30 Boston Scientific Corporation Hybrid coating for medical devices
US5869127A (en) 1995-02-22 1999-02-09 Boston Scientific Corporation Method of providing a substrate with a bio-active/biocompatible coating
US5702754A (en) 1995-02-22 1997-12-30 Meadox Medicals, Inc. Method of providing a substrate with a hydrophilic coating and substrates, particularly medical devices, provided with such coatings
JPH08239639A (ja) 1995-03-02 1996-09-17 Sekisui Chem Co Ltd 粘着剤組成物及びそれを用いた粘着加工品
US5633504A (en) 1995-03-30 1997-05-27 Wesley-Jessen Corporation Inspection of optical components
US5674942A (en) 1995-03-31 1997-10-07 Johnson & Johnson Vision Products, Inc. Interpenetrating polymer networks for contact lens production
DE29624309U1 (de) 1995-04-04 2002-01-03 Commonwealth Scientific And Industrial Research Organisation, Campbell Dauertraglinsen
TW585882B (en) 1995-04-04 2004-05-01 Novartis Ag A method of using a contact lens as an extended wear lens and a method of screening an ophthalmic lens for utility as an extended-wear lens
TW393498B (en) 1995-04-04 2000-06-11 Novartis Ag The preparation and use of Polysiloxane-comprising perfluoroalkyl ethers
US5688855A (en) 1995-05-01 1997-11-18 S.K.Y. Polymers, Inc. Thin film hydrophilic coatings
WO1996037241A1 (en) 1995-05-25 1996-11-28 Minnesota Mining And Manufacturing Company Process for producing biocompatible surfaces
US5583463A (en) 1995-05-30 1996-12-10 Micron Technology, Inc. Redundant row fuse bank circuit
US5620738A (en) 1995-06-07 1997-04-15 Union Carbide Chemicals & Plastics Technology Corporation Non-reactive lubicious coating process
US5731087A (en) 1995-06-07 1998-03-24 Union Carbide Chemicals & Plastics Technology Corporation Lubricious coatings containing polymers with vinyl and carboxylic acid moieties
US6087462A (en) 1995-06-07 2000-07-11 Biocompatibles Limited Polymeric surface coatings
AUPN354595A0 (en) 1995-06-14 1995-07-06 Ciba-Geigy Ag Novel materials
TW428018B (en) 1995-06-29 2001-04-01 Ciba Sc Holding Ag Aminosilane salts and silanamides of carboxylic acids as corrosion inhibitors
RU2163246C2 (ru) 1995-06-30 2001-02-20 Коммонвелт Сайентифик Энд Индастриал Рисерч Организейшн Способ модификации, по меньшей мере, части поверхности полимера
CN1189774A (zh) * 1995-07-03 1998-08-05 伊兰公司Plc 难溶药物的控释制剂
US5874127A (en) 1995-08-16 1999-02-23 Ciba Vision Corporation Method and apparatus for gaseous treatment
US5672638A (en) 1995-08-22 1997-09-30 Medtronic, Inc. Biocompatability for solid surfaces
US5855825A (en) 1995-09-06 1999-01-05 Menicon Co., Ltd. Process for producing ocular lens and ocular lens produced by the process
DE69625658T2 (de) 1995-09-13 2003-07-17 Seikagaku Kogyo K.K.(Seikagaku Corp.), Tokio/Tokyo Kontaktlinse auf Basis photogehärteter Hyaluronsäure
US5849222A (en) 1995-09-29 1998-12-15 Johnson & Johnson Vision Products, Inc. Method for reducing lens hole defects in production of contact lens blanks
US5674557A (en) * 1995-09-29 1997-10-07 Johnson & Johnson Vision Products, Inc. Method for transiently wetting lens molds in production of contact lens blanks to reduce lens hole defects
AU698522B2 (en) 1995-09-29 1998-10-29 Johnson & Johnson Vision Products, Inc. Lens parameter measurement using optical sectioning
AU6556196A (en) * 1995-09-29 1997-04-10 Johnson & Johnson Vision Products, Inc. Laminated barrier materials for the packaging of contact lenses
US6007526A (en) 1995-10-12 1999-12-28 Hollister Incorporated Male external catheter with short annular sealing flap
US5804318A (en) 1995-10-26 1998-09-08 Corvita Corporation Lubricious hydrogel surface modification
US6509098B1 (en) 1995-11-17 2003-01-21 Massachusetts Institute Of Technology Poly(ethylene oxide) coated surfaces
KR100468803B1 (ko) 1995-12-07 2005-04-19 바슈 앤드 롬 인코포레이티드 실리콘히드로겔의모듈러스를감소시키는데유용한단량체단위
AU709598B2 (en) 1995-12-08 1999-09-02 Biocure, Inc. Plasma-induced polymer coatings
US5922249A (en) 1995-12-08 1999-07-13 Novartis Ag Ophthalmic lens production process
EP1704878B1 (en) 1995-12-18 2013-04-10 AngioDevice International GmbH Crosslinked polymer compositions and methods for their use
JP2000506554A (ja) 1995-12-22 2000-05-30 ノバルティス アクチエンゲゼルシャフト ポリシロキサン／ポリオールマクロマーから製造されるポリウレタン
EP0780419A1 (en) 1995-12-22 1997-06-25 Holland Biomaterials Group B.V. Multi-functional site containing polymers, and applications thereof
US6238799B1 (en) 1996-02-09 2001-05-29 Surface Solutions Laboratories, Inc. Articles prepared from water-based hydrophilic coating compositions
US5792531A (en) 1996-02-20 1998-08-11 Tactyl Technologies, Inc. Readily donned, powder free elastomeric article
US5779943A (en) 1996-03-19 1998-07-14 Johnson & Johnson Vision Products, Inc. Molded polymeric object with wettable surface made from latent-hydrophilic monomers
US5786429A (en) * 1996-04-18 1998-07-28 Hercules Incorporated Highly branched polyamidoamines and their preparation
US6096138A (en) 1997-04-30 2000-08-01 Bausch & Lomb Incorporated Method for inhibiting the deposition of protein on contact lens
US5811151A (en) 1996-05-31 1998-09-22 Medtronic, Inc. Method of modifying the surface of a medical device
EP0814116A1 (de) 1996-06-19 1997-12-29 Hüls Aktiengesellschaft Hydrophile Beschichtung von Oberflächen polymerer Substrate
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
US6174326B1 (en) 1996-09-25 2001-01-16 Terumo Kabushiki Kaisha Radiopaque, antithrombogenic stent and method for its production
US6169127B1 (en) 1996-08-30 2001-01-02 Novartis Ag Plasma-induced polymer coatings
US5800412A (en) 1996-10-10 1998-09-01 Sts Biopolymers, Inc. Hydrophilic coatings with hydrating agents
WO1998017704A1 (en) 1996-10-21 1998-04-30 Novartis Ag Crosslinkable polymers
US6639007B2 (en) 1996-11-15 2003-10-28 Tactyl Technologies, Inc. Elastomeric copolymer compositions and articles made therewith
AR009439A1 (es) 1996-12-23 2000-04-12 Novartis Ag Un articulo que comprende un sustrato con un recubrimiento polimerico primario que porta grupos reactivos predominantemente en su superficie, unmetodo para preparar dicho articulo, un articulo que posee un recubrimiento de tipo hibrido y una lente de contacto
US6306514B1 (en) 1996-12-31 2001-10-23 Ansell Healthcare Products Inc. Slip-coated elastomeric flexible articles and their method of manufacture
US5882687A (en) 1997-01-10 1999-03-16 Allergan Compositions and methods for storing contact lenses
EP0892297A4 (en) 1997-01-23 2001-08-29 Menicon Co Ltd PROCESS FOR PRODUCING CONTACT LENSES WITH HYDROPHILIC SURFACE AND CONTACT LENS THUS OBTAINED
US5997517A (en) 1997-01-27 1999-12-07 Sts Biopolymers, Inc. Bonding layers for medical device surface coatings
EP0867456A1 (de) 1997-02-04 1998-09-30 Novartis AG Ophthalmischer Formkörper
US5801822A (en) 1997-02-06 1998-09-01 Pbh, Inc. Ophthalmic lens inspection system
US5818573A (en) 1997-02-06 1998-10-06 Pbh, Inc. Opthalmic lens inspection system
ES2175698T3 (es) 1997-02-21 2002-11-16 Novartis Ag Articulos de moldeo oftalmicos.
US5879697A (en) 1997-04-30 1999-03-09 Schneider Usa Inc Drug-releasing coatings for medical devices
US6221467B1 (en) 1997-06-03 2001-04-24 Scimed Life Systems, Inc. Coating gradient for lubricious coatings on balloon catheters
GB9711818D0 (en) 1997-06-06 1997-08-06 Bausch & Lomb Contact lens packing solutions and methods for improving the comfort of disposable contact lenses
US6866938B2 (en) 1997-07-22 2005-03-15 Nissha Printing Co., Ltd. Foil-detecting sheet and method of producing a foil-decorated resin article using the same
DE19732587A1 (de) 1997-07-29 1999-02-04 Huels Chemische Werke Ag Bioaktive Beschichtung mit Reibungsarmer Oberfläche
US6165322A (en) 1997-07-29 2000-12-26 Hercules Incorporated Polyamidoamine/epichlorohydrin resins bearing polyol sidechains as dry strength agents
WO1999015917A1 (en) 1997-09-23 1999-04-01 Novartis Ag Method for hydrogel surface treatment and article formed therefrom
US5858653A (en) 1997-09-30 1999-01-12 Surmodics, Inc. Reagent and method for attaching target molecules to a surface
TW429327B (en) 1997-10-21 2001-04-11 Novartis Ag Single mould alignment
US6054504A (en) 1997-12-31 2000-04-25 Hydromer, Inc. Biostatic coatings for the reduction and prevention of bacterial adhesion
PL341346A1 (en) * 1998-01-09 2001-04-09 Novartis Ag Polymeric coatings
US6451871B1 (en) 1998-11-25 2002-09-17 Novartis Ag Methods of modifying surface characteristics
JPH11223901A (ja) 1998-02-06 1999-08-17 Fuji Photo Film Co Ltd 熱現像記録材料
US6943203B2 (en) * 1998-03-02 2005-09-13 Johnson & Johnson Vision Care, Inc. Soft contact lenses
US5962548A (en) 1998-03-02 1999-10-05 Johnson & Johnson Vision Products, Inc. Silicone hydrogel polymers
US6367929B1 (en) 1998-03-02 2002-04-09 Johnson & Johnson Vision Care, Inc. Hydrogel with internal wetting agent
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
US7461937B2 (en) 2001-09-10 2008-12-09 Johnson & Johnson Vision Care, Inc. Soft contact lenses displaying superior on-eye comfort
US5998498A (en) 1998-03-02 1999-12-07 Johnson & Johnson Vision Products, Inc. Soft contact lenses
US6096726A (en) 1998-03-11 2000-08-01 Surface Solutions Laboratories Incorporated Multicomponent complex for use with substrate
DE69934536T2 (de) 1998-04-09 2007-10-04 Nippon Shokubai Co. Ltd. Vernetzes Polymerteilchen und Verfahren zu seiner Herstellung und Verwendung
US6686054B2 (en) 1998-04-22 2004-02-03 Sri International Method and composition for the sizing of paper using azetidinium and/or guanidine polymers
TW473488B (en) * 1998-04-30 2002-01-21 Novartis Ag Composite materials, biomedical articles formed thereof and process for their manufacture
CA2328897A1 (en) 1998-05-05 1999-11-11 Bausch & Lomb Incorporated Plasma surface treatment of silicone hydrogel contact lenses
AU3786699A (en) 1998-05-05 1999-11-23 Bausch & Lomb Incorporated Surface treatment of silicone hydrogel contact lenses
US6106889A (en) 1998-06-11 2000-08-22 Biocoat Incorporated Method of selective coating of articles
US6500481B1 (en) 1998-06-11 2002-12-31 Johnson & Johnson Vision Care, Inc. Biomedical devices with amid-containing coatings
US6087415A (en) 1998-06-11 2000-07-11 Johnson & Johnson Vision Care, Inc. Biomedical devices with hydrophilic coatings
JP2000010055A (ja) * 1998-06-19 2000-01-14 Seed Co Ltd 親水性眼用レンズ及びその製造方法
US6039913A (en) 1998-08-27 2000-03-21 Novartis Ag Process for the manufacture of an ophthalmic molding
US6099852A (en) 1998-09-23 2000-08-08 Johnson & Johnson Vision Products, Inc. Wettable silicone-based lenses
JP3105871B2 (ja) 1998-09-25 2000-11-06 埼玉日本電気株式会社 無線装置とその無線受信方法
US6149842A (en) 1998-11-12 2000-11-21 Novartis Ag Methods and compositions for manufacturing tinted ophthalmic lenses
US6207796B1 (en) * 1998-11-18 2001-03-27 Nippon Shokubai Co., Ltd. Production process for hydrophilic polymer
EP1002807A1 (en) 1998-11-20 2000-05-24 Novartis AG Functionalized resin derived from polyallylamine
US5981675A (en) 1998-12-07 1999-11-09 Bausch & Lomb Incorporated Silicone-containing macromonomers and low water materials
TW480246B (en) 1998-12-18 2002-03-21 Kimberly Clark Co Cationically charged coating on glass fibers and method for making the same
US6537614B1 (en) 1998-12-18 2003-03-25 Kimberly-Clark Worldwide, Inc. Cationically charged coating on hydrophobic polymer fibers with poly (vinyl alcohol) assist
US6550915B1 (en) 1998-12-21 2003-04-22 Bausch & Lomb Incorporated Surface treatment of fluorinated contact lens materials
US6896769B2 (en) 1999-01-25 2005-05-24 Kimberly-Clark Worldwide, Inc. Modified condensation polymers containing azetidinium groups in conjunction with amphiphilic hydrocarbon moieties
US6517678B1 (en) 2000-01-20 2003-02-11 Kimberly-Clark Worldwide, Inc. Modified polysaccharides containing amphiphillic hydrocarbon moieties
US6340465B1 (en) 1999-04-12 2002-01-22 Edwards Lifesciences Corp. Lubricious coatings for medical devices
JP2000351862A (ja) * 1999-04-30 2000-12-19 Novartis Ag 中性塗膜
US6630243B2 (en) * 1999-05-20 2003-10-07 Bausch & Lomb Incorporated Surface treatment of silicone hydrogel contact lenses comprising hydrophilic polymer chains attached to an intermediate carbon coating
US6440571B1 (en) * 1999-05-20 2002-08-27 Bausch & Lomb Incorporated Surface treatment of silicone medical devices with reactive hydrophilic polymers
CN100412149C (zh) 1999-07-08 2008-08-20 赫尔克里士公司 赋予材料期望性质的组合物
US7344607B2 (en) 1999-07-08 2008-03-18 Ge Betz, Inc. Non-chromate conversion coating treatment for metals
EP1196499B1 (en) 1999-07-27 2003-08-27 Bausch & Lomb Incorporated Contact lens material
US6632905B2 (en) 1999-09-02 2003-10-14 Alcon Universal Ltd. Covalently-bound, hydrophilic coating compositions for surgical implants
PT1208393E (pt) 1999-09-02 2008-10-24 Alcon Inc Composições de revestimento hidrofílicas, ligadas covalentemente, para implantes
US6723815B2 (en) 1999-09-02 2004-04-20 Alcon, Inc. Covalently-bound, hydrophilic coating compositions for surgical implants
JP2001075060A (ja) * 1999-09-03 2001-03-23 Seiko Epson Corp コンタクトレンズおよびその製造方法
JP4295939B2 (ja) 1999-09-20 2009-07-15 株式会社メニコン コンタクトレンズ用液剤
CN1313842C (zh) * 1999-10-12 2007-05-02 庄臣及庄臣视力保护公司 接触透镜涂层选择及其制造工艺
US6478423B1 (en) 1999-10-12 2002-11-12 Johnson & Johnson Vison Care, Inc. Contact lens coating selection and manufacturing process
JP2001117054A (ja) * 1999-10-19 2001-04-27 Nof Corp 表面処理コンタクトレンズおよび製造方法
AU1387401A (en) 1999-10-27 2001-05-08 Commonwealth Scientific And Industrial Research Organisation Coating process
JP2001163933A (ja) 1999-10-27 2001-06-19 Novartis Ag 材料表面を改質する方法
JP2001163932A (ja) 1999-10-27 2001-06-19 Novartis Ag 材料表面を改質する方法
JP2001158813A (ja) 1999-10-27 2001-06-12 Novartis Ag 材料表面を被覆する方法
KR100492652B1 (ko) * 1999-11-09 2005-05-31 닛폰 유시 가부시키가이샤 하이드로겔용 조성물, 하이드로겔 및 그 용도
JP4657550B2 (ja) 1999-11-24 2011-03-23 ハーキュリーズ・インコーポレーテッド クレーピング接着剤
CN100374881C (zh) 1999-12-16 2008-03-12 旭化成爱美株式会社 可长期配戴的软性隐形镜片
US6465602B2 (en) 2000-01-20 2002-10-15 Kimberly-Clark Worldwide, Inc. Modified condensation polymers having azetidinium groups and containing polysiloxane moieties
US6719929B2 (en) 2000-02-04 2004-04-13 Novartis Ag Method for modifying a surface
AR027348A1 (es) 2000-02-04 2003-03-26 Novartis Ag Proceso para recubrir una superficie
JP3929014B2 (ja) 2000-02-24 2007-06-13 Ｈｏｙａヘルスケア株式会社 側鎖にポリシロキサン構造を有するマクロマーからなるコンタクトレンズ材料
US7521519B1 (en) 2000-03-14 2009-04-21 Novartis Ag Organic compounds
GB0006891D0 (en) 2000-03-23 2000-05-10 Arjobex Ltd Coating composition
JP5242876B2 (ja) 2000-03-24 2013-07-24 ノバルティス アーゲー 架橋結合性または重合性プレポリマー
CN100510847C (zh) * 2000-03-31 2009-07-08 库柏维景国际控股公司 贴目镜片
US6923538B2 (en) 2000-07-06 2005-08-02 Coopervision, Inc. Method for cast moulding contact lenses with a rounded edge form
US6599559B1 (en) 2000-04-03 2003-07-29 Bausch & Lomb Incorporated Renewable surface treatment of silicone medical devices with reactive hydrophilic polymers
AU2001255210B2 (en) 2000-05-02 2005-08-18 Bausch & Lomb Incorporated Low ionic strength ophthalmic compositions
JP4834916B2 (ja) 2000-05-10 2011-12-14 東レ株式会社 表面処理プラスチック成形品
US6689480B2 (en) 2000-05-10 2004-02-10 Toray Industries, Inc. Surface-treated plastic article and method of surface treatment
US6589665B2 (en) 2000-05-30 2003-07-08 Novartis Ag Coated articles
MXPA02011857A (es) * 2000-05-30 2003-04-10 Novartis Ag Articulos recubiertos.
US6428839B1 (en) * 2000-06-02 2002-08-06 Bausch & Lomb Incorporated Surface treatment of medical device
US6364934B1 (en) 2000-07-31 2002-04-02 Bausch & Lomb Incorporated Method of making ocular devices
US6482221B1 (en) 2000-08-21 2002-11-19 Counter Clockwise, Inc. Manipulatable delivery catheter for occlusive devices (II)
WO2002015911A1 (fr) 2000-08-22 2002-02-28 Nof Corporation Agent lubrifiant et solution permettant de faciliter l'insertion de verres de contact
US6852353B2 (en) * 2000-08-24 2005-02-08 Novartis Ag Process for surface modifying substrates and modified substrates resulting therefrom
MXPA03002322A (es) 2000-09-19 2003-06-24 Bausch & Lomb Metodo para aplicar un recubrimiento a lentes polimericas.
US6551267B1 (en) 2000-10-18 2003-04-22 Becton, Dickinson And Company Medical article having blood-contacting surface
US20020182315A1 (en) 2000-11-01 2002-12-05 Heiler David J. Surface treatment of non-plasma treated silicone hydrogel contact lenses
DE10055762A1 (de) 2000-11-10 2002-06-06 Woehlk Contact Linsen Gmbh Hydrogelkontaktlinsen mit hoher Biokompatibilität
US6861123B2 (en) * 2000-12-01 2005-03-01 Johnson & Johnson Vision Care, Inc. Silicone hydrogel contact lens
US6531432B2 (en) * 2000-12-07 2003-03-11 Johnson & Johnson Vision Care, Inc. Contact lens packaging solutions
GB0030177D0 (en) * 2000-12-11 2001-01-24 Unilever Plc Textile care composition
JP4043789B2 (ja) 2001-01-24 2008-02-06 ノバルティス アクチエンゲゼルシャフト 表面を修飾するための方法
RU2196784C2 (ru) * 2001-03-30 2003-01-20 Кемеровский государственный университет Способ модификации полидиметилсилоксанового каучука
US6835410B2 (en) 2001-05-21 2004-12-28 Novartis Ag Bottle-brush type coatings with entangled hydrophilic polymer
JP2003066381A (ja) 2001-05-23 2003-03-05 Novartis Ag 流体で物品を処理するためのシステム及び方法
US6811805B2 (en) 2001-05-30 2004-11-02 Novatis Ag Method for applying a coating
US6815074B2 (en) 2001-05-30 2004-11-09 Novartis Ag Polymeric materials for making contact lenses
US7879267B2 (en) 2001-08-02 2011-02-01 J&J Vision Care, Inc. Method for coating articles by mold transfer
US6891010B2 (en) 2001-10-29 2005-05-10 Bausch & Lomb Incorporated Silicone hydrogels based on vinyl carbonate endcapped fluorinated side chain polysiloxanes
TW200407367A (en) 2001-11-13 2004-05-16 Novartis Ag Method for modifying the surface of biomedical articles
US7402318B2 (en) * 2001-11-14 2008-07-22 Novartis Ag Medical devices having antimicrobial coatings thereon
US20030165015A1 (en) 2001-12-05 2003-09-04 Ocular Sciences, Inc. Coated contact lenses and methods for making same
TWI255224B (en) 2002-01-09 2006-05-21 Novartis Ag Polymeric articles having a lubricious coating and method for making the same
GB0201165D0 (en) 2002-01-18 2002-03-06 Unilever Plc Azetidinium modidfied poymers and fabric treatment composition
US6936641B2 (en) 2002-06-25 2005-08-30 Johnson & Johnson Vision Care, Inc. Macromer forming catalysts
US7270678B2 (en) 2002-06-28 2007-09-18 Bausch & Lomb Incorporated Surface modification of functional group-containing medical devices with catalyst-containing reactive polymer system
AU2002950469A0 (en) 2002-07-30 2002-09-12 Commonwealth Scientific And Industrial Research Organisation Improved biomedical compositions
KR100618368B1 (ko) 2002-07-30 2006-08-30 닛토덴코 가부시키가이샤 광학 필름 및 그 제조방법
WO2004016671A1 (en) 2002-08-14 2004-02-26 Novartis Ag Radiation-curable prepolymers
US20070138692A1 (en) * 2002-09-06 2007-06-21 Ford James D Process for forming clear, wettable silicone hydrogel articles
US20080299179A1 (en) 2002-09-06 2008-12-04 Osman Rathore Solutions for ophthalmic lenses containing at least one silicone containing component
US6896926B2 (en) 2002-09-11 2005-05-24 Novartis Ag Method for applying an LbL coating onto a medical device
US6926965B2 (en) 2002-09-11 2005-08-09 Novartis Ag LbL-coated medical device and method for making the same
US6740336B2 (en) 2002-10-04 2004-05-25 Mirus Corporation Process for generating multilayered particles
US20040116564A1 (en) 2002-11-27 2004-06-17 Devlin Brian Gerrard Stabilization of poly(oxyalkylene) containing polymeric materials
US8172395B2 (en) 2002-12-03 2012-05-08 Novartis Ag Medical devices having antimicrobial coatings thereon
US7032251B2 (en) 2002-12-10 2006-04-25 Kimberly-Clark Worldwide, Inc. Crosslinking agent for coated elastomeric articles
US7384590B2 (en) 2002-12-17 2008-06-10 Novartis Ag System and method for curing polymeric moldings
US7387759B2 (en) 2002-12-17 2008-06-17 Novartis Ag System and method for curing polymeric moldings having a masking collar
US6958169B2 (en) 2002-12-17 2005-10-25 Bausch & Lomb Incorporated Surface treatment of medical device
WO2004063795A1 (ja) * 2003-01-10 2004-07-29 Menicon Co., Ltd. 安全性の高いシリコーン含有眼用レンズ材料およびその製造方法
PL1603603T3 (pl) 2003-02-28 2015-07-31 Biointeractions Ltd System sieci polimerowych dla urządzeń medycznych oraz sposoby zastosowania
US20040214914A1 (en) 2003-04-24 2004-10-28 Ocular Sciences, Inc. Hydrogel contact lenses and package systems and production methods for same
CN1207326C (zh) * 2003-07-18 2005-06-22 清华大学 一种表面负载功能基团的天然高分子微球的制备方法
GB0322640D0 (en) 2003-09-26 2003-10-29 1800 Contacts Process
US20050070688A1 (en) 2003-09-26 2005-03-31 3M Innovative Properties Company Reactive hydrophilic oligomers
JP4369194B2 (ja) * 2003-09-30 2009-11-18 Ｈｏｙａ株式会社 プラスチックレンズ及びその製造方法
US7977430B2 (en) 2003-11-25 2011-07-12 Novartis Ag Crosslinkable polyurea prepolymers
US7084188B2 (en) 2003-12-05 2006-08-01 Bausch & Lomb Incorporated Surface modification of contact lenses
JP4572072B2 (ja) * 2003-12-26 2010-10-27 Ｈｏｙａ株式会社 眼内レンズ
US7214809B2 (en) 2004-02-11 2007-05-08 Johnson & Johnson Vision Care, Inc. (Meth)acrylamide monomers containing hydroxy and silicone functionalities
US8147728B2 (en) 2004-04-01 2012-04-03 Novartis Ag Pad transfer printing of silicone hydrogel lenses using colored ink
CA2561788C (en) 2004-04-21 2013-05-21 Novartis Ag Curable colored inks for making colored silicone hydrogel lenses
US20060052306A1 (en) * 2004-05-10 2006-03-09 Nastech Pharmaceutical Company Inc. GRAS composition for enhanced mucosal delivery of parathyroid hormone
ES2351396T3 (es) 2004-05-28 2011-02-04 Menicon Co., Ltd. Lente de contacto.
CN101163991A (zh) * 2004-08-27 2008-04-16 旭化成爱目股份有限公司 硅水凝胶隐形眼镜
US20060065138A1 (en) 2004-09-30 2006-03-30 Tucker Robert C Pad printing method for making colored contact lenses
US7249848B2 (en) 2004-09-30 2007-07-31 Johnson & Johnson Vision Care, Inc. Wettable hydrogels comprising reactive, hydrophilic, polymeric internal wetting agents
US7556858B2 (en) 2004-09-30 2009-07-07 3M Innovative Properties Company Substrate with attached dendrimers
US7247692B2 (en) 2004-09-30 2007-07-24 Johnson & Johnson Vision Care, Inc. Biomedical devices containing amphiphilic block copolymers
JP4782508B2 (ja) 2004-09-30 2011-09-28 株式会社シード 高酸素透過含水性眼用レンズ
EP2147686A1 (en) 2004-10-01 2010-01-27 Menicon Co., Ltd. Method for packaging contact lenses
US7857447B2 (en) 2004-10-05 2010-12-28 The Board Of Trustees Of The Leland Stanford Junior University Interpenetrating polymer network hydrogel contact lenses
US20060100113A1 (en) 2004-11-05 2006-05-11 Pegram Stephen C Methods of inhabiting the adherence of lenses to surfaces during their manufacture
JP5324100B2 (ja) 2004-11-29 2013-10-23 ディーエスエム アイピー アセッツ ビー．ブイ． ポリマーコーティングに含まれる移行性物質の量を減少させる方法
WO2006063836A1 (en) * 2004-12-17 2006-06-22 Novartis Ag Colored contact lenses for enhancing a wearer’s natural eye color
SE0403092D0 (sv) 2004-12-20 2004-12-20 Amo Groningen Bv Amphiphilic block copolymers and their use
RU2269552C1 (ru) * 2004-12-23 2006-02-10 Институт Катализа Им. Г.К. Борескова Сибирского Отделения Российской Академии Наук Полимерная композиция для мягких контактных линз продленного ношения и способ ее получения
ATE425198T1 (de) 2004-12-29 2009-03-15 Bausch & Lomb Polysiloxanprepolymere für biomedizinische vorrichtungen
WO2006071388A1 (en) 2004-12-29 2006-07-06 Bausch & Lomb Incorporated Polysiloxane prepolymers for biomedical devices
DE602006006424D1 (de) 2005-02-09 2009-06-04 Safilens S R L Ackung zur aufbewahrung und pflege einer kontaktlinse
KR101389300B1 (ko) 2005-02-14 2014-04-25 존슨 앤드 존슨 비젼 케어, 인코포레이티드 안과용 렌즈의 제조방법, 안과용 장치 및 콘택트 렌즈
US20060193894A1 (en) * 2005-02-28 2006-08-31 Jen James S Methods for providing biomedical devices with hydrophilic antimicrobial coatings
US7426993B2 (en) 2005-08-09 2008-09-23 Coopervision International Holding Company, Lp Contact lens package
WO2007017243A1 (en) 2005-08-10 2007-02-15 Novartis Ag Silicone hydrogels
TWI385429B (zh) * 2005-08-11 2013-02-11 Coopervision Int Holding Co Lp 隱形眼鏡及減少隱形眼鏡配戴者之結膜壓力之方法
US20070037897A1 (en) * 2005-08-12 2007-02-15 Guigui Wang Method for making contact lenses
EP1754731A1 (en) 2005-08-16 2007-02-21 Nederlandse Organisatie voor Toegepast-Natuuurwetenschappelijk Onderzoek TNO Method of modifying materials surfaces
US20070087113A1 (en) 2005-10-19 2007-04-19 Bausch & Lomb Incorporated Surface-modified medical devices and method of making
WO2007054468A2 (en) 2005-11-14 2007-05-18 Ciba Holding Inc. Preparation of functionalized cationic polymers and their preparation and application in personal care
JP2007130386A (ja) * 2005-11-14 2007-05-31 Univ Of Tokyo 眼用装置
WO2007064594A2 (en) 2005-11-29 2007-06-07 Bausch & Lomb Incorporated New coatings on ophthalmic lenses
US20070149428A1 (en) 2005-12-14 2007-06-28 Bausch & Lomb Incorporated Method of Packaging a Lens
CN101378892A (zh) * 2005-12-20 2009-03-04 庄臣及庄臣视力保护公司 以醇溶液浸提硅氧烷水凝胶眼镜片并使其脱模的方法和系统
US7825273B2 (en) 2006-01-06 2010-11-02 Bausch & Lomb Incorporated Process for making cationic hydrophilic siloxanyl monomers
WO2007103775A2 (en) 2006-03-03 2007-09-13 Washington University In St. Louis Biomaterials having nanoscale layers and coatings
US8044112B2 (en) * 2006-03-30 2011-10-25 Novartis Ag Method for applying a coating onto a silicone hydrogel lens
JP2009533190A (ja) 2006-04-20 2009-09-17 エイオーテク バイオマテリアルズ プロプライアタリー リミティド ゲル
US7789509B2 (en) 2006-06-01 2010-09-07 Advanced Vision Science, Inc. Non- or reduced glistenings intraocular lens and method of manufacturing same
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
CN101467094B (zh) * 2006-06-15 2011-02-23 库柏维景国际控股公司 可湿性硅氧水凝胶隐形眼镜以及相关组合物和方法
US7540609B2 (en) 2006-06-15 2009-06-02 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
TWI512017B (zh) * 2006-06-15 2015-12-11 Coopervision Int Holding Co Lp 可溼性矽氧水凝膠隱形眼鏡及相關組合物及方法
US20080002146A1 (en) * 2006-06-28 2008-01-03 Stachowski Mark J Biocompatible, surface modified materials
US7960465B2 (en) 2006-06-30 2011-06-14 Johnson & Johnson Vision Care, Inc. Antimicrobial lenses, processes to prepare them and methods of their use
US20080003259A1 (en) 2006-06-30 2008-01-03 Salamone Joseph C Modification of surfaces of polymeric articles by Michael addition reaction
ATE470681T1 (de) * 2006-07-12 2010-06-15 Novartis Ag Aktinisch vernetzbare copolymere zur herstellung von kontaktlinsen
US8459445B2 (en) 2006-07-21 2013-06-11 Menicon, Co., Ltd. Colored contact lens primary packaging
WO2008038719A1 (en) * 2006-09-29 2008-04-03 Toray Industries, Inc. Silicone polymer, ocular lenses, and contact lens
EP2089069B1 (en) * 2006-10-30 2016-01-27 Novartis AG Method for applying a coating onto a silicone hydrogel lens
BRPI0718543A2 (pt) 2006-11-06 2013-11-12 Novartis Ag Dispositivos oculares e métodos de fabricação e uso dos mesmos
US20080110770A1 (en) * 2006-11-10 2008-05-15 Bausch & Lomb Incorporated Packaging solutions
GB0623299D0 (en) 2006-11-22 2007-01-03 Sauflon Cl Ltd Contact lens
CN101595419B (zh) * 2006-11-29 2012-01-25 普罗康涅控股公司 包含含羧基甜菜碱酯单体的聚合物的水凝胶接触透镜
TWI434926B (zh) 2006-12-11 2014-04-21 Alcon Res Ltd 眼用組成物中聚氧化乙烯-聚氧化丁烯（ｐｅｏ-ｐｂｏ）嵌段共聚物之使用
AR064286A1 (es) 2006-12-13 2009-03-25 Quiceno Gomez Alexandra Lorena Produccion de dispositivos oftalmicos basados en la polimerizacion por crecimiento escalonado fotoinducida
JP5669396B2 (ja) 2006-12-13 2015-02-12 ノバルティス アーゲー 化学線硬化性シリコーンヒドロゲルコポリマーおよびその使用
US20080142038A1 (en) 2006-12-15 2008-06-19 Bausch & Lomb Incorporated Surface treatment of medical devices
US20080141628A1 (en) 2006-12-15 2008-06-19 Bausch & Lomb Incorporated Packaging Solutions
EP2091585B1 (en) 2006-12-15 2010-12-15 Bausch & Lomb Incorporated Surface treatment of biomedical devices
US7832856B2 (en) 2006-12-20 2010-11-16 Bausch & Lomb Incorporated Coatings and solutions for contact lenses
US20080148689A1 (en) 2006-12-20 2008-06-26 Bausch & Lomb Incorporated Packaging solutions
EP2101838B1 (en) 2006-12-21 2010-12-01 Novartis AG Process for the coating of contact lenses
US20080152540A1 (en) 2006-12-22 2008-06-26 Bausch & Lomb Incorporated Packaging solutions
DE602008002555D1 (de) 2007-01-12 2010-10-28 Dow Corning Silikonhaltige zusammensetzung
ATE532089T1 (de) * 2007-02-09 2011-11-15 Novartis Ag Vernetzbare polyionische beschichtungen für kontaktlinsen
CA2680524C (en) * 2007-03-22 2016-05-17 Novartis Ag Silicone-containing prepolymers with dangling hydrophilic polymer chains
RU2462361C2 (ru) 2007-03-22 2012-09-27 Новартис Аг Форполимеры с подвешенными полисилоксансодержащими полимерными цепями
JP5217240B2 (ja) 2007-05-21 2013-06-19 星光Ｐｍｃ株式会社 紙用添加剤およびそれを使用した製紙方法
US7691917B2 (en) 2007-06-14 2010-04-06 Bausch & Lomb Incorporated Silcone-containing prepolymers
US20080314767A1 (en) 2007-06-22 2008-12-25 Bausch & Lomb Incorporated Ophthalmic Solutions
KR101231181B1 (ko) * 2007-06-25 2013-02-07 남택인 연질 콘텍트렌즈용 실리콘 하이드로겔 조성물 및 그 조성에의해 제조된 연질 콘텍트렌즈
US7868071B2 (en) 2007-07-30 2011-01-11 Georgia-Pacific Chemicals Llc Method of stabilizing aqueous cationic polymers
US20090033864A1 (en) * 2007-07-30 2009-02-05 Shone Thomas R Multifocal contact lenses and methods for improving vision and for producing multifocal contact lenses
TWI551305B (zh) * 2007-08-31 2016-10-01 諾華公司 相對黏稠封裝溶液之用途
JP5643092B2 (ja) 2007-08-31 2014-12-17 ノバルティス アーゲー コンタクトレンズのパッケージング溶液
TW200918983A (en) 2007-10-22 2009-05-01 mo-wei Hong Forming method of a silicone gel contact lens and its structure
US8490782B2 (en) 2007-10-23 2013-07-23 Bausch & Lomb Incorporated Packaging solutions
US20090111942A1 (en) 2007-10-25 2009-04-30 Bausch & Lomb Incorporated Method for Making Surface Modified Biomedical Devices
WO2009070429A1 (en) 2007-11-29 2009-06-04 Bausch & Lomb Incorporated Process for making biomedical devices
WO2009070443A1 (en) 2007-11-29 2009-06-04 Bausch & Lomb Incorporated Process for making biomedical devices
US8044111B2 (en) * 2007-11-30 2011-10-25 Novartis Ag Actinically-crosslinkable silicone-containing block copolymers
US7934830B2 (en) 2007-12-03 2011-05-03 Bausch & Lomb Incorporated High water content silicone hydrogels
US20090145091A1 (en) 2007-12-11 2009-06-11 Richard Connolly Method for treating ophthalmic lenses
US20090145086A1 (en) 2007-12-11 2009-06-11 Reynolds Ger M Method for treating ophthalmic lenses
WO2009079224A2 (en) * 2007-12-14 2009-06-25 Bausch & Lomb Incorporated Surface modified biomedical devices
RU2488863C2 (ru) 2007-12-20 2013-07-27 Новартис Аг Способ изготовления контактных линз
US20090171049A1 (en) 2007-12-27 2009-07-02 Linhardt Jeffrey G Segmented reactive block copolymers
US20090173045A1 (en) 2008-01-09 2009-07-09 Yu-Chin Lai Packaging Solutions
US20090173643A1 (en) 2008-01-09 2009-07-09 Yu-Chin Lai Packaging Solutions
US7837934B2 (en) 2008-01-09 2010-11-23 Bausch & Lomb Incorporated Packaging solutions
US20090182068A1 (en) * 2008-01-14 2009-07-16 Yuwen Liu Polymerizable Contact Lens Formulations and Contact Lenses Obtained Therefrom
EP2234798B1 (en) 2008-01-23 2012-03-28 Novartis AG Method for coating silicone hydrogels
WO2009094368A1 (en) * 2008-01-25 2009-07-30 Bausch & Lomb Incorporated Contact lens
AU2009211623B2 (en) 2008-02-08 2012-04-12 Coopervision International Limited Hydrophilic polysiloxane monomer, and production method and application thereof
US7781554B2 (en) 2008-03-05 2010-08-24 Bausch & Lomb Incorporated Polysiloxanes and polysiloxane prepolymers with vinyl or epoxy functionality
US8460743B2 (en) 2008-03-18 2013-06-11 Novartis Ag Coating process for ophthalmic lenses
US20090244479A1 (en) 2008-03-31 2009-10-01 Diana Zanini Tinted silicone ophthalmic devices, processes and polymers used in the preparation of same
US8470906B2 (en) 2008-09-30 2013-06-25 Johnson & Johnson Vision Care, Inc. Ionic silicone hydrogels having improved hydrolytic stability
US8246168B2 (en) 2008-11-10 2012-08-21 Bausch & Lomb Incorporated Methacrylate-based bulky side-chain siloxane cross linkers for optical medical devices
CA2739102C (en) * 2008-11-13 2016-06-21 Novartis Ag Silicone hydrogel materials with chemically bound wetting agents
TWI506333B (zh) * 2008-12-05 2015-11-01 Novartis Ag 用以傳遞疏水性舒適劑之眼用裝置及其製造方法
NZ592674A (en) 2008-12-18 2012-08-31 Novartis Ag Method for making silicone hydrogel contact lenses
US8534031B2 (en) 2008-12-30 2013-09-17 Bausch & Lomb Incorporated Packaging solutions
WO2010077708A1 (en) 2008-12-30 2010-07-08 Bausch & Lomb Incorporated Packaging solutions
JP5240520B2 (ja) 2009-01-15 2013-07-17 星光Ｐｍｃ株式会社 クレーピング用接着剤をドライヤーに塗布する製紙方法
US8383744B2 (en) 2009-05-22 2013-02-26 Novartis Ag Actinically-crosslinkable siloxane-containing copolymers
US8642712B2 (en) 2009-05-22 2014-02-04 Novartis Ag Actinically-crosslinkable siloxane-containing copolymers
SG176987A1 (en) 2009-07-09 2012-01-30 Bausch & Lomb Mono ethylenically unsaturated polymerizable group containing polycarbosiloxane monomers
US7915323B2 (en) 2009-07-09 2011-03-29 Bausch & Lamb Incorporated Mono ethylenically unsaturated polycarbosiloxane monomers
HUE049309T2 (hu) 2009-11-04 2020-09-28 Alcon Inc Szilikon hidrogél lencse ojtott hidrofil bevonattal
TWI483996B (zh) 2009-12-08 2015-05-11 Novartis Ag 具有共價貼合塗層之聚矽氧水凝膠鏡片
TWI599813B (zh) * 2010-07-30 2017-09-21 諾華公司 水合隱形鏡片
US8557940B2 (en) * 2010-07-30 2013-10-15 Novartis Ag Amphiphilic polysiloxane prepolymers and uses thereof
SG190218A1 (en) 2010-11-10 2013-06-28 Novartis Ag Method for making contact lenses
SG194955A1 (en) 2011-06-09 2013-12-30 Novartis Ag Silicone hydrogel lenses with nano-textured surfaces
JP6434108B2 (ja) * 2017-10-27 2018-12-05 国立大学法人 岡山大学 放射性セシウムの植物移行抑制剤及びその製造方法、並びに植物の生長方法
US10721913B2 (en) 2018-08-24 2020-07-28 David V. Poma Drop feeder

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020149742A1 (en) * 2000-03-31 2002-10-17 Ocular Sciences, Inc. Contact lens having a uniform horizontal thickness profile
US20060063852A1 (en) * 2004-08-27 2006-03-23 Asahikasei Aime Co. Ltd. Silicone hydrogel contact lens
US20090200692A1 (en) 2008-02-07 2009-08-13 Jame Chang Method for manufacturing a silicone contact lens having a hydrophilic surface
US20100149482A1 (en) * 2008-12-12 2010-06-17 Ammon Jr Daniel M Contact lens

Cited By (31)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10301465B2 (en) 2010-05-06 2019-05-28 Johnson & Johnson Vision Care, Inc. Non-reactive, hydrophilic polymers having terminal siloxanes and methods for making and using the same
US9815979B2 (en) 2010-05-06 2017-11-14 Johnson & Johnson Vision Care, Inc. Non-reactive, hydrophilic polymers having terminal siloxanes and methods for making and using the same
US11067720B2 (en) 2011-05-04 2021-07-20 Johnson & Johnson Vision Care, Inc. Medical devices having homogeneous charge density and methods for making same
US10386545B2 (en) 2011-05-04 2019-08-20 Johnson & Johnson Vision Care, Inc. Medical devices having homogeneous charge density and methods for making same
US9505184B2 (en) 2011-11-15 2016-11-29 Novartis Ag Silicone hydrogel lens with a crosslinked hydrophilic coating
WO2013074535A1 (en) * 2011-11-15 2013-05-23 Novartis Ag A silicone hydrogel lens with a crosslinked hydrophilic coating
US10502978B2 (en) 2012-05-25 2019-12-10 Johnson & Johnson Vision Care, Inc. Polymers and nanogel materials and methods for making and using the same
US10073192B2 (en) 2012-05-25 2018-09-11 Johnson & Johnson Vision Care, Inc. Polymers and nanogel materials and methods for making and using the same
US11782296B2 (en) 2012-05-25 2023-10-10 Johnson & Johnson Vision Care, Inc. Polymers and nanogel materials and methods for making and using the same
US11029539B2 (en) 2012-05-25 2021-06-08 Johnson & Johnson Vision Care, Inc. Polymers and nanogel materials and methods for making and using the same
US10871595B2 (en) 2012-05-25 2020-12-22 Johnson & Johnson Vision Care, Inc. Polymers and nanogel materials and methods for making and using the same
US10502867B2 (en) 2012-05-25 2019-12-10 Johnson & Johnson Vision Care, Inc. Polymers and nanogel materials and methods for making and using the same
US9726906B2 (en) 2012-05-25 2017-08-08 Johnson & Johnson Vision Care, Inc. Polymers and nanogel materials and methods for making and using the same
EP2855545B1 (en) 2012-05-25 2017-11-01 Johnson & Johnson Vision Care Inc. Polymers and nanogel materials and methods for making and using the same
EP2855546B1 (en) 2012-05-25 2016-07-13 Johnson & Johnson Vision Care Inc. Contact lenses comprising water soluble n-(2 hydroxyalkyl) (meth)acrylamide polymers or copolymers
CN104956256A (zh) * 2012-08-27 2015-09-30 视觉力学有限责任公司 具有亲水层的接触透镜
CN104956256B (zh) * 2012-08-27 2017-08-08 实体科学有限责任公司 具有亲水层的接触透镜
JP2018022174A (ja) * 2012-08-27 2018-02-08 タンジブル サイエンス リミテッド ライアビリティ カンパニー 親水性層を有するコンタクトレンズ
JP2015534106A (ja) * 2012-08-27 2015-11-26 オキュラー ダイナミクス リミテッド ライアビリティ カンパニー 親水性層を有するコンタクトレンズ
US10667903B2 (en) 2013-01-15 2020-06-02 Medicem Institute s.r.o. Bioanalogic intraocular lens
US10441676B2 (en) 2013-01-15 2019-10-15 Medicem Institute s.r.o. Light-adjustable hydrogel and bioanalogic intraocular lens
US11793908B2 (en) 2013-01-15 2023-10-24 Medicem Institute s.r.o Light-adjustable hydrogel and bioanalogic intraocular lens
KR20150140851A (ko) * 2013-04-30 2015-12-16 쿠퍼비젼 인터내셔날 홀딩 캄파니, 엘피 1급 아민-함유 실리콘 히드로겔 콘택트 렌즈, 및 관련 조성물 및 방법
US20160054475A1 (en) * 2013-04-30 2016-02-25 CooperVision International Holding Company., LP Primary Amine-Containing Silicone Hydrogel Contact Lenses And Related Compositions And Methods
KR101640725B1 (ko) * 2013-04-30 2016-07-18 쿠퍼비젼 인터내셔날 홀딩 캄파니, 엘피 1급 아민-함유 실리콘 히드로겔 콘택트 렌즈, 및 관련 조성물 및 방법
JP2016524178A (ja) * 2013-04-30 2016-08-12 クーパーヴィジョン インターナショナル ホウルディング カンパニー リミテッド パートナーシップ 一級アミン含有シリコーンヒドロゲルコンタクトレンズ並びに関連する組成物及び方法
US9429684B2 (en) * 2013-04-30 2016-08-30 Coopervision International Holding Company, Lp Primary amine-containing silicone hydrogel contact lenses and related compositions and methods
JP2017515171A (ja) * 2014-05-09 2017-06-08 インテロジョ インコーポレーテッドＩｎｔｅｒｏｊｏ Ｉｎｃ． 湿潤性表面を有するハイドロゲルコンタクトレンズ及びその製造方法
US11256003B2 (en) 2017-12-13 2022-02-22 Alcon Inc. Weekly and monthly disposable water gradient contact lenses
RU2798842C1 (ru) * 2019-06-28 2023-06-28 Алькон Инк. Офтальмологические композиции
US12072556B2 (en) 2019-11-04 2024-08-27 Alcon Inc. Contact lenses with surfaces having different softness

Also Published As

Publication number Publication date
EP2705808A3 (en) 2018-01-24
US12311621B2 (en) 2025-05-27
RU2013108701A (ru) 2014-09-10
KR20170125126A (ko) 2017-11-13
KR20200044132A (ko) 2020-04-28
AU2011282602C1 (en) 2015-01-22
KR102104222B1 (ko) 2020-04-24
CN104678462A (zh) 2015-06-03
RU2675109C1 (ru) 2018-12-17
RU2013125115A (ru) 2014-12-10
MX2013001189A (es) 2013-02-21
TW202521643A (zh) 2025-06-01
PT2638878T (pt) 2019-12-05
TWI519845B (zh) 2016-02-01
MX382876B (es) 2025-03-13
CA2802337A1 (en) 2012-02-02
BR112013002179A2 (pt) 2019-08-06
AU2011282604B2 (en) 2014-06-26
JP2016122203A (ja) 2016-07-07
KR102009137B1 (ko) 2019-08-08
US20150099822A1 (en) 2015-04-09
ES2423914T3 (es) 2013-09-25
RU2714143C1 (ru) 2020-02-12
US20190309188A1 (en) 2019-10-10
KR20150118200A (ko) 2015-10-21
CN104678462B (zh) 2019-11-05
KR20180093097A (ko) 2018-08-20
KR102266813B1 (ko) 2021-06-18
KR20180135104A (ko) 2018-12-19
MX363760B (es) 2019-04-02
JP2018106189A (ja) 2018-07-05
DK2461767T3 (da) 2013-08-05
JP2024010117A (ja) 2024-01-23
JP2025134736A (ja) 2025-09-17
TWI758885B (zh) 2022-03-21
US10308835B2 (en) 2019-06-04
EP2638878A2 (en) 2013-09-18
EP2638879A2 (en) 2013-09-18
US20120026457A1 (en) 2012-02-02
JP2020008873A (ja) 2020-01-16
KR102139022B1 (ko) 2020-07-29
KR102215955B1 (ko) 2021-02-16
KR20130086252A (ko) 2013-07-31
US9239409B2 (en) 2016-01-19
JP6664081B2 (ja) 2020-03-13
EP4657145A2 (en) 2025-12-03
US9244200B2 (en) 2016-01-26
JP6982640B2 (ja) 2021-12-17
TW201535009A (zh) 2015-09-16
TWI616704B (zh) 2018-03-01
KR20130086607A (ko) 2013-08-02
US20160377885A1 (en) 2016-12-29
JP2013533517A (ja) 2013-08-22
TW201612590A (en) 2016-04-01
US20170306178A1 (en) 2017-10-26
TW202434689A (zh) 2024-09-01
KR20210075210A (ko) 2021-06-22
KR101413390B1 (ko) 2014-06-27
KR102411923B1 (ko) 2022-06-22
TW201207465A (en) 2012-02-16
RU2691047C1 (ru) 2019-06-07
US20130250234A1 (en) 2013-09-26
EP2461767A1 (en) 2012-06-13
JP2016118797A (ja) 2016-06-30
TW201335660A (zh) 2013-09-01
TWI524110B (zh) 2016-03-01
TW201706676A (zh) 2017-02-16
TWI875491B (zh) 2025-03-01
US20210130648A1 (en) 2021-05-06
KR20200111273A (ko) 2020-09-28
RU2712195C1 (ru) 2020-01-24
BR122020017237B1 (pt) 2021-02-02
CA2802337C (en) 2014-11-18
US20130308093A1 (en) 2013-11-21
BR122013012250A2 (pt) 2019-10-01
EP2598938B1 (en) 2025-01-29
CN105334640A (zh) 2016-02-17
US20200017713A1 (en) 2020-01-16
TWI648571B (zh) 2019-01-21
US9738813B2 (en) 2017-08-22
RU2583370C2 (ru) 2016-05-10
RU2754524C1 (ru) 2021-09-02
US12420501B2 (en) 2025-09-23
RU2013108693A (ru) 2014-09-10
TWI587032B (zh) 2017-06-11
HK1165690A1 (en) 2012-10-12
EP2461767B1 (en) 2013-05-08
JP6187832B2 (ja) 2017-08-30
TWI836373B (zh) 2024-03-21
EP4657144A2 (en) 2025-12-03
AU2011282602B2 (en) 2014-06-26
KR101889246B1 (ko) 2018-08-16
JP7448512B2 (ja) 2024-03-12
CN103038699A (zh) 2013-04-10
CN103038699B (zh) 2015-03-18
MX2021006023A (es) 2021-07-21
KR20210018960A (ko) 2021-02-18
US20200157378A1 (en) 2020-05-21
US20190055427A1 (en) 2019-02-21
KR101880415B1 (ko) 2018-07-19
KR20190140108A (ko) 2019-12-18
TWI567443B (zh) 2017-01-21
MX2013001188A (es) 2013-02-21
US10781340B2 (en) 2020-09-22
US20230158760A1 (en) 2023-05-25
KR20190026973A (ko) 2019-03-13
US8529057B2 (en) 2013-09-10
KR102159909B1 (ko) 2020-09-25
US10513628B2 (en) 2019-12-24
EP2461767A4 (en) 2012-12-26
BR112013002150B1 (pt) 2020-11-17
US20120026458A1 (en) 2012-02-02
US8480227B2 (en) 2013-07-09
JP7464640B2 (ja) 2024-04-09
ES2758722T3 (es) 2020-05-06
HK1207689A1 (en) 2016-02-05
TW201921040A (zh) 2019-06-01
CN103052364A (zh) 2013-04-17
JP2025029005A (ja) 2025-03-05
EP2638878B1 (en) 2019-10-23
JP2017062489A (ja) 2017-03-30
CN103293707A (zh) 2013-09-11
KR20140017706A (ko) 2014-02-11
KR20190095500A (ko) 2019-08-14
PT2461767E (pt) 2013-08-26
US20150092156A1 (en) 2015-04-02
SG187026A1 (en) 2013-02-28
JP2013190822A (ja) 2013-09-26
RU2645991C1 (ru) 2018-02-28
RU2571747C2 (ru) 2015-12-20
KR20200091498A (ko) 2020-07-30
RU2728781C1 (ru) 2020-07-31
BR122013012250B1 (pt) 2021-01-12
US20180044549A1 (en) 2018-02-15
TW202102622A (zh) 2021-01-16
TW201938712A (zh) 2019-10-01
CA2802793C (en) 2014-10-21
MY186340A (en) 2021-07-13
SG187237A1 (en) 2013-03-28
EP4553545A2 (en) 2025-05-14
JP6076199B2 (ja) 2017-02-08
ES3015692T3 (en) 2025-05-07
US9507173B2 (en) 2016-11-29
RU2540655C2 (ru) 2015-02-10
EP4571370A2 (en) 2025-06-18
KR101717826B1 (ko) 2017-03-17
TWI707926B (zh) 2020-10-21
US10131815B2 (en) 2018-11-20
TW201207466A (en) 2012-02-16
ES2980213T3 (es) 2024-09-30
EP2705808B1 (en) 2024-05-01
MX2021006022A (es) 2021-07-06
MY154750A (en) 2015-07-15
KR20180006487A (ko) 2018-01-17
NZ610544A (en) 2014-08-29
JP6590981B2 (ja) 2019-10-16
TWI708093B (zh) 2020-10-21
KR101819873B1 (ko) 2018-01-17
US8939577B2 (en) 2015-01-27
TW202424596A (zh) 2024-06-16
KR101724984B1 (ko) 2017-04-07
BR122020017231B1 (pt) 2021-02-02
JP6326115B2 (ja) 2018-05-16
TW202244149A (zh) 2022-11-16
US10563090B2 (en) 2020-02-18
US20220281190A1 (en) 2022-09-08
TWI669554B (zh) 2019-08-21
JP7250826B2 (ja) 2023-04-03
US11534994B2 (en) 2022-12-27
KR101958162B1 (ko) 2019-03-13
KR101990757B1 (ko) 2019-06-18
RU2619715C1 (ru) 2017-05-17
TW201812394A (zh) 2018-04-01
EP2638879A3 (en) 2018-05-16
JP6295281B2 (ja) 2018-03-14
EP2598938A1 (en) 2013-06-05
KR20130105610A (ko) 2013-09-25
CN105334640B (zh) 2018-12-28
KR102057814B1 (ko) 2019-12-19
TWI507764B (zh) 2015-11-11
PL2461767T3 (pl) 2013-09-30
JP2018139002A (ja) 2018-09-06
RS52882B (sr) 2014-02-28
EP2638878A3 (en) 2018-01-10
KR101930686B1 (ko) 2018-12-18
KR101386293B1 (ko) 2014-04-24
TW201610508A (zh) 2016-03-16
JP2020098354A (ja) 2020-06-25
JP2022031756A (ja) 2022-02-22
JP2021060623A (ja) 2021-04-15
JP2022071139A (ja) 2022-05-13
US10920102B2 (en) 2021-02-16
NZ617864A (en) 2014-08-29
US8944592B2 (en) 2015-02-03
KR20180083954A (ko) 2018-07-23
EP2598938A4 (en) 2018-01-24
KR101800059B1 (ko) 2017-11-21
SG2014007348A (en) 2014-07-30
US20250222667A1 (en) 2025-07-10
KR20160130521A (ko) 2016-11-11
CN103293707B (zh) 2014-12-31
TW202104988A (zh) 2021-02-01
KR102266815B1 (ko) 2021-06-18
TWI775148B (zh) 2022-08-21
US20170037276A1 (en) 2017-02-09
AU2011282602A1 (en) 2013-02-28
US20160097938A1 (en) 2016-04-07
TW202225788A (zh) 2022-07-01
EP2705808A2 (en) 2014-03-12
CN103052364B (zh) 2015-12-02
US20160091734A1 (en) 2016-03-31
JP7071950B2 (ja) 2022-05-19
JP2024020518A (ja) 2024-02-14
MX2019003771A (es) 2019-09-02
US9816009B2 (en) 2017-11-14
JP5930221B2 (ja) 2016-06-08
JP7597900B2 (ja) 2024-12-10
AU2011282604A1 (en) 2013-02-28
RU2644349C1 (ru) 2018-02-09
TWI599813B (zh) 2017-09-21
KR101795983B1 (ko) 2017-11-08
SG10201505892WA (en) 2015-09-29
RU2015148819A (ru) 2017-05-19
TW201738625A (zh) 2017-11-01
MY156626A (en) 2016-03-15
JP7692978B2 (ja) 2025-06-16
MY174013A (en) 2020-03-04
BR112013002179B1 (pt) 2020-12-15
KR20190069619A (ko) 2019-06-19
JP5882322B2 (ja) 2016-03-09
RU2739355C1 (ru) 2020-12-23
WO2012016098A1 (en) 2012-02-02
US9411171B2 (en) 2016-08-09
KR20170038193A (ko) 2017-04-06
SI2461767T1 (sl) 2013-08-30
BR112013002150A2 (pt) 2016-05-31
JP2013533518A (ja) 2013-08-22
CA2802793A1 (en) 2012-02-02

Similar Documents

Publication Publication Date Title
US12420501B2 (en) Silicone hydrogel lenses with water-rich surfaces
US11364695B2 (en) Silicone hydrogel lenses with water-rich surfaces
AU2014221267B2 (en) Silicone hydrogel lenses with water-rich surfaces
AU2020270462B2 (en) Silicone hydrogel lenses with water-rich surfaces
US20250387989A1 (en) Silicone hydrogel lenses with water-rich surfaces
AU2013204092B2 (en) Silicone hydrogel lenses with water-rich surfaces
HK1192132B (en) Silicone hydrogel lenses with water-rich surfaces
HK1192132A (en) Silicone hydrogel lenses with water-rich surfaces
HK1185530A (en) Silicone hydrogel lenses with water-rich surfaces
HK1185530B (en) Silicone hydrogel lenses with water-rich surfaces
HK1185531A (en) Silicone hydrogel lenses with water-rich surfaces
HK1165690B (en) Silicone hydrogel lenses with water-rich surfaces

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 201180037423.5

Country of ref document: CN

WWE Wipo information: entry into national phase

Ref document number: 2011813220

Country of ref document: EP

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 11813220

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 10847/DELNP/2012

Country of ref document: IN

ENP Entry into the national phase

Ref document number: 2802793

Country of ref document: CA

ENP Entry into the national phase

Ref document number: 2013521992

Country of ref document: JP

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: MX/A/2013/001189

Country of ref document: MX

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 20137005040

Country of ref document: KR

Kind code of ref document: A

ENP Entry into the national phase

Ref document number: 2011282602

Country of ref document: AU

Date of ref document: 20110729

Kind code of ref document: A

Ref document number: 2013108693

Country of ref document: RU

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: P-2013/0337

Country of ref document: RS

REG Reference to national code

Ref country code: BR

Ref legal event code: B01A

Ref document number: 112013002179

Country of ref document: BR

REG Reference to national code

Ref country code: BR

Ref legal event code: B01E

Ref document number: 112013002179

Country of ref document: BR

ENP Entry into the national phase

Ref document number: 112013002179

Country of ref document: BR

Kind code of ref document: A2

Effective date: 20130129

WWW Wipo information: withdrawn in national office

Ref document number: 2011813220

Country of ref document: EP