US20070216860A1 - Molds for producing contact lenses - Google Patents
Molds for producing contact lenses Download PDFInfo
- Publication number
- US20070216860A1 US20070216860A1 US11/522,230 US52223006A US2007216860A1 US 20070216860 A1 US20070216860 A1 US 20070216860A1 US 52223006 A US52223006 A US 52223006A US 2007216860 A1 US2007216860 A1 US 2007216860A1
- Authority
- US
- United States
- Prior art keywords
- alicyclic
- lens
- polymer
- minutes
- grams
- 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.)
- Abandoned
Links
- 0 *C1([3*])C2CC(C3C=CC32)C1([1*])[2*].*C1([4*])C2C=CC(C2)C1([1*])[2*].*C1([4*])C2CC(C3C4C=CC(C4)C32)C1([1*])[2*].*C1([5*])C2C3C=CC(C3)C2C([1*])([2*])C1([3*])[4*].*C1([5*])C2C3CC(C4C=CC43)C2C([1*])([2*])C1([3*])[4*].C.C.[1*]C1([2*])C2CC(C3C4CC(C5C=CC54)C32)C1([3*])[4*].[1*]C1([2*])C2CCCCC2C2C3C=CC(C3)C21 Chemical compound *C1([3*])C2CC(C3C=CC32)C1([1*])[2*].*C1([4*])C2C=CC(C2)C1([1*])[2*].*C1([4*])C2CC(C3C4C=CC(C4)C32)C1([1*])[2*].*C1([5*])C2C3C=CC(C3)C2C([1*])([2*])C1([3*])[4*].*C1([5*])C2C3CC(C4C=CC43)C2C([1*])([2*])C1([3*])[4*].C.C.[1*]C1([2*])C2CC(C3C4CC(C5C=CC54)C32)C1([3*])[4*].[1*]C1([2*])C2CCCCC2C2C3C=CC(C3)C21 0.000 description 7
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
-
- 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
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
- C08G61/04—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms
- C08G61/06—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds
- C08G61/08—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds of carbocyclic compounds containing one or more carbon-to-carbon double bonds in the ring
-
- 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
-
- 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
- B29D11/00432—Auxiliary operations, e.g. machines for filling the moulds
-
- 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
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F232/00—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
- C08F232/08—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having condensed rings
-
- 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
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
-
- 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
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
- C08G61/04—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions 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; Compositions of derivatives of such polymers
- C08L33/24—Homopolymers or copolymers of amides or imides
- C08L33/26—Homopolymers or copolymers of acrylamide or methacrylamide
-
- 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
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C33/00—Moulds or cores; Details thereof or accessories therefor
- B29C33/38—Moulds or cores; Details thereof or accessories therefor characterised by the material or the manufacturing process
- B29C33/40—Plastics, e.g. foam or rubber
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2823/00—Use of polyalkenes or derivatives thereof as mould material
- B29K2823/38—Polymers of cycloalkenes, e.g. norbornene or cyclopentene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L39/00—Compositions of 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 a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions of derivatives of such polymers
- C08L39/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
- C08L39/06—Homopolymers or copolymers of N-vinyl-pyrrolidones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L45/00—Compositions of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Compositions of derivatives of such polymers
Definitions
- These two part molds contain a male member whose convex surface corresponds to the back curve of a finished lens and a female member whose concave surface corresponds to the front curve of a finished lens.
- an uncured lens formulation is placed between the concave and convex surfaces of the mold halves and subsequently cured.
- the cured lens and the mold are subsequently treated with a liquid medium in order to release the cured lens from the surface of the mold.
- the mold material must be able to withstand the curing conditions and be compatible with such conditions.
- lenses may be cured by either or both heat and light. If a lens is cured by transmitting light to the uncured polymer, it is important that the lens mold permit the transmission of light at the appropriate wavelength.
- the mold material must not stick to the cured lens to a degree that prevents release of the cured lens. Often the lenses are produced in a manufacturing environment where it is important for the lenses to removably adhere to the same said of the lens mold upon separation in a repeatable and predictable fashion. Therefore, the selection of appropriate materials to make the molds continues to be a subject of concern to those who produce soft contact lenses.
- This invention includes a mold for making a lens comprising, consisting essentially of, or consisting of an alicyclic co-polymer wherein said alicyclic co-polymer comprises, consists essentially of, or consists of at least two alicyclic monomers of different chemical structures.
- lens refers to any ophthalmic device that resides in or on the eye. These devices can provide optical correction or may be cosmetic.
- the term lens includes but is not limited to soft contact lenses, intraocular lenses, overlay lenses, ocular inserts, and optical inserts.
- the preferred lenses of the invention are soft contact lenses are made from silicone elastomers or hydrogels, which include but are not limited to silicone hydrogels, and fluorohydrogels.
- Soft contact lens formulations are disclosed in U.S. Pat. No. 5,710,302, WO 9421698, EP 406161, JP 2000016905, U.S. Pat. No. 5,998,498, U.S. patent application Ser. No. 09/957,299 filed on Sep. 20, 2001, U.S. patent application Ser. No. 09/532,943, U.S. Pat. No. 6,087,415, U.S. Pat. No. 5,760,100, U.S. Pat. No. 5,776, 999, U.S. Pat. No. 5,789,461, U.S. Pat. No. 5,849,811, and U.S. Pat. No. 5,965,631.
- alicyclic monomers refers to polymerizable compounds having at least one saturated carbocyclic ring therein.
- the saturated carbocyclic rings may be substituted with one or more members of the group consisting of hydrogen, C 1-10 alkyl, halogen, hydroxyl, C 1-10 alkoxycarbonyl, C 1-10 alkoxy, cyano, amido, imido, silyl, and substituted C 1-10 alkyl where the substituents are selected from one or more members of the group consisting of halogen, hydroxyl, C 1-10 alkoxycarbonyl, C 1-10 alkoxy, cyano, amido, imido, and silyl.
- alicyclic monomers include but are not limited to polymerizable cyclobutanes, cyclopentanes, cyclohexanes, cycloheptanes, cyclooctanes, biscyclobutanes, biscyclopentanes, biscyclohexanes, biscycloheptanes, biscyclooctanes, and norbornanes. It is preferred that the at least two alicyclic monomers be polymerized by ring opening metathesis followed by hydrogenation. Since co-polymers are costly, it is preferable that the molds made from these co-polymers may be used several times to prepare lenses instead of once which is typical. For the preferred molds of the invention, they may be used more than once to produce lenses.
- examples of alicyclic monomer containing saturated carbocyclic rings include but are not limited to the following structures wherein R 1 — 6 are independently selected from one or more members of the group consisting of hydrogen, C 1-10 alkyl, halogen, hydroxyl, C 1-10 alkoxycarbonyl, C 1-10 alkoxy, cyano, amido, imido, silyl, and substituted C 1-10 alkyl where the substituents selected from one or more members of the group consisting of halogen, hydroxyl, C 1-10 alkoxycarbonyl, C 1-10 alkoxy, cyano, amido, imido and silyl.
- R 1-6 may be taken together to form an unsaturated bond, a carbocyclic ring, a carbocyclic ring containing one or more unsaturated bonds, or an aromatic ring.
- the preferred R 1-6 is selected from the group consisting of C 1-10 alkyl and substituted C 1-10 alkyl where the substituents are selected from the group consisting of halogen, hydroxyl, C 1-10 alkoxycarbonyl, C 1-10 alkoxy, cyano, amido, imido and silyl.
- the alicyclic co-polymers consist of at least two different alicyclic monomers.
- the preferred alicyclic co-polymers contain two or three different alicyclic monomers, selected from the group consisting of
- the particularly preferred alicyclic co-polymer contains two different alicyclic momoners where the generic structure of the saturated carbocyclic rings of the alicyclic monomers are of the formula and R 1 -R 4 are C 1-10 alkyl.
- the surface energy of the alicyclic co-polymer is between 30 and 45 dynes/cm at 25° C.
- the more particularly preferred alicyclic co-polymer contains two different alicyclic monomers and is sold by Zeon Chemicals L.P. under the tradename ZEONOR. There are several different grades of ZEONOR, having of glass transition temperatures form 105-160° C.
- the particularly preferred ZEONOR is ZEONOR 1060R, which according the to the manufacturer, ZEON Chemicals L.P.
- MFR melt flow rate
- the term “mold” refers to a rigid object that may be used to form lenses from uncured formulations.
- the preferred molds are two part molds as described above, where either the front curve or the back curve of the mold is made of the alicyclic co-polymers of the invention and the other curve is made of polypropylene.
- the preferred polypropylenes are those that have a melt flow of less that 21 g/10 min. Examples of polypropylene include but are not limited to metallocene catalyzed polypropylene that is nucleated and clarified, such as but not limited to Achieve 1615, or Achieve 1654 from Exxon and ATOFINA EOD 00-11.
- polypropylene examples include Ziegler-Natta catalyst based polypropylenes, such as but not limited to Exxon 9544 MED, Exxon 49486-002, Atofina 3620Wz, Atofina NO 3105, having a melt flow of 12 g/10 min, ⁇ 21 g/10 min; 12 g/10 min; and 18 g/10 min respectively.
- the preferred method of making the molds of the invention is by injection molding using known techniques, but the molds could be made by other techniques lathing, diamond turning, or laser cutting.
- lenses are formed on at least one surface of both mold parts.
- one surface of the lenses may be formed from a mold and the other surface could be formed using a lathing method, or other methods.
- the molds of the invention may contain additives that facilitate the separation of the lens forming surfaces, reduce the adhesion of the cured lens to the molding surface, or both.
- additives such as metal or ammonium salts of stearic acid, amide waxes, polyethylene or polypropylene waxes, organic phosphate esters, glycerol esters or alcohol esters may be added to alicyclic co-polymers prior to curing said polymers to form a mold.
- additives include but are not limited to Dow Siloxane MB50-321 (a silicone dispersion), Nurcrel 535 & 932 (ethylene-methacrylic acid co-polymer resin Registry No.
- Zeospheres anti-block (slip/anti blocking agent); Ampacet 40604 (fatty acid amide), Kemamide (fatty acid amide), Licowax fatty acid amide, Hypermer B246SF, XNAP, polyethylene glycol monolaurate (anti-stat) epoxidized soy bean oil, talc (hydrated Magnsium silicate), calcium carbonate, behenic acid, pentaerythritol tetrastearate, succinic acid, epolene E43-Wax, methyl cellulose, cocamide (anti-blocking agent Registry No. 61789-19-3), poly vinyl pyrrolidinone (360,000 MW) and the additives disclosed in U.S. Pat.
- the preferred additives are polyvinyl pyrrolidinone, zinc stearate and glycerol mono stearate, where a weight percentage of additives based upon the total weight of the polymers is about 0.05 to about 10.0 weight percent, preferably about 0.05 to about 3.0, most preferably about 2.0 weight percent.
- the separation of the lens forming surfaces may be facilitated by applying surfactants to the lens forming surfaces.
- suitable surfactants include Tween surfactants, particularly Tween 80 as described in U.S. Pat. No. 5,837,314 which is hereby incorporated by reference in its entirety.
- Other examples of surfactants are disclosed in U.S. Pat. No. 5,264,161 which is hereby incorporated by reference in its entirety.
- the molds of the invention may contain other polymers such as polypropylene, polyethylene, polystyrene, polymethyl methacrylate, and modified polyolefins containing an alicyclic moiety in the main chain.
- a blend of the alicyclic co-polymers and polypropylene may be used, where the ratio by weight percentage of alicyclic co-polymer to polypropylene ranges from about 99:1, to about 20:80 respectively.
- This blend can be used on either or both mold halves, where it is preferred that this blend is used on the back curve and the front curve consists of the alicyclic co-polymers.
- this invention includes a method of making a lens comprising, consisting essentially of, or consisting of 1) dispensing an uncured lens formulation onto a mold surface comprising, consisting essentially of, or consisting of, an alicyclic co-polymer wherein said alicyclic co-polymer comprises, consists essentially of, or consists of at least two alicyclic monomers of different chemical structures, and 2) curing said lens formulation under suitable conditions.
- the terms lenses, alicyclic monomers, and molds have their aforementioned meaning and preferred ranges.
- the term “uncured” refers to the physical state of a lens formulation prior to final curing to form a lens.
- Some lens formulations contain mixtures of monomers which are cured only once.
- Other lens formulations contain monomers, partially cured monomers, macromers and other components.
- partially cured formulations are disclosed in U.S. Pat. Nos. 6,419,858; 6,308,314; and 6,416,690. This invention will be useful these formulations among others.
- curing under suitable conditions refers to any of the known methods of curing lens formulations, such as using light, heat, and the appropriate catalysts to produce a cured lens. Examples of such curing conditions may be found in the soft lens formulation references listed herein.
- the invention includes a lens produced by a method comprising, consisting essentially of, or consisting of 1) dispensing an uncured lens formulation onto a surface of a mold comprising, consisting essentially of, or consisting of, an alicyclic co-polymer wherein said alicyclic co-polymer comprises, consists essentially of, or consists of at least two alicyclic monomers of different chemical structures and 2) curing said lens formulation under suitable conditions.
- lens, alicyclic monomers, uncured, and molds have their aforementioned meaning and preferred ranges.
- the invention includes a mold comprising, consisting essentially of, or consisting of, an alicyclic co-polymer and at least one lens forming surface
- lens forming surface means the surface that is used to mold the lens. Such surface has an optical quality surface finish, meaning that it is sufficiently smooth so that a lens surface formed by the polymerization of a lens forming material in contact with the molding surface is optically acceptable. Further said surface has a geometry that is necessary to impart to the lens surface the desired optical characteristics, including without limitation, spherical aspherical and cylinder power, wave front aberration correction, corneal topography correction and the like as well as combinations thereof.
- high molecular weight means an average molecular weight (“MW”) sufficiently high so as to avoid dissolution of the coating into the lens formulation or the mold material.
- MW average molecular weight
- the molecular weight is determined using gel permeation chromatography (“GPC”) with a light scattering detector and a high sensitivity refractive index detector, for example model PL-RI available from Polymer Labs.
- GPC gel permeation chromatography
- the GPC is performed using a phenogel 5 ⁇ m linear column equipped with a guard column of the same components and a solution of 0.5 weight percent lithium bromide in dimethyl formamide as the eluent. Flow rates are 0.5 mL per minute with injection volumes from about 10 to about 20 ⁇ L.
- the precise MW used will depend upon the coating selected and the monomer mixture used. In a preferred embodiment, the MW of the coating is greater than about 300 kD.
- Coating compositions useful in this invention include a wide variety of known monomers and polymers. Preferred are poly(vinyl alcohol), polyethylene oxide, poly(2-hydroxyethyl methacrylate), poly(methyl methacrylate), poly(acrylic acid), poly(methacrylic acid), poly(maleic acid), poly(itaconic acid), poly(acrylamide), poly(methacrylamide), poly(dimethylacrylamide), poly(glycerol methacrylate), polystyrene sulfonic acid, polysulfonate polymers, poly(vinyl pyrrolidone), carboxymethylated polymers, such as carboxymethylcellulose, polysaccharides, glucose amino glycans, polylactic acid, polyglycolic acid, block or random copolymers of the aforementioned, and the like, and mixtures thereof.
- poly(2-hydroxyethyl methacrylate), poly(vinyl pyrrolidone), poly(acrylic acid), poly(methacrylic acid), poly(meth)acrylamide, or poly(acrylamide) is used. More preferably, poly(2-hydroxyethyl methacrylate) is used.
- the coating composition may include a low boiling point (less than about 100° C.) solvent and a high boiling point, (greater than about 100° C.) solvent.
- Suitable low boiling solvents include, without limitation, acetone, chloroform, and alcohols such as methanol, ethanol, isopropanol, tert-butanol, and the like.
- Useful high boiling solvents include, without limitation, methyl-, ethyl-, and isopropyl lactate, ethylene and (poly)ethylene glycol, propylene glycol, n-methyl pyrrolidone, dimethyl formamide, tetrahydrogeraniol, 1-butanol, 1-pentanol, 1-hexanol, 1-octanol, 3-methyl-3-pentanol, dimethyl-3-octanol, 3-methoxy-1-butanol, 1,2 and 1,4-butanediol, 1,3-hexanediol, water, and the like.
- the ratio of the low to high boiling solvent will be about 10:90 to 90:10 when coating between 15 and 45 degrees C.
- the coating composition contains either or both low boiling and high boiling solvents.
- the coating composition may include at least one surfactant.
- Suitable surfactants include, without limitation, anionic surfactants, such as carboxylic acid salts, sulfonic acid salts, sulfuric acid salts, phosphoric and polyphosphoric acid esters, cationic surfactants, such as long chain amines and their salts, diamines and polyamines and their salts, quarternary ammonium salts, amine oxides, nonionic surfactants, such as polyoxyethylenated alkylphenols, alkyl phenol ethoxylates, polyoxyethylenated straight chain alcohols, polyethoxylated polyoxypropylene glycols, polyethoxylated polydimethylsiloxane copolymers, fluorinated alkane ethoxylate copolymers, and long chain carboxylic acid esters, zwitterionic surfactants, such as pH-sensitive and pH insensitive surfactants, and the like, and combinations thereof.
- the specific type and amount of surfactants used will depend upon the other components of the coating composition and the molding surface used. Typically, greater than or equal to about 0.001 weight percent and less than or equal to about 5 weight percent based on the total weight of the coating composition will be used.
- the coating composition may be applied to the molding surface by any suitable method including, but not limited to, compression, swabbing, spray coating, ink jet printing, aerosolization, nebulization, dip coating, spin coating, and the like and combinations thereof.
- spin coating is used.
- the coating is dried, or rendered non-tacky, prior to its use for forming lenses. Drying may be carried out using any suitable method, but preferably is carried out at temperatures up to about the glass transition temperature (“Tg”) of the mold material in air or under vacuum followed by equilibration under a blanket of nitrogen at any temperature up to about the Tg of the mold material.
- Tg glass transition temperature
- cold traps or other filters preferably are used to prevent contamination of the mold.
- the coating composition preferably has a lower surface tension than that of the molding surface's surface energy. More preferably, the surface tension of the coating composition is greater than about 3 dynes/cm below that of the surface energy of the molding surface to which it is applied when measured at the coating application temperature. Most preferably, the surface tension of the coating composition is more than 8 dynes/cm below that of the surface energy of the molding surface.
- spin coating is used to deposit a coating of a dry thickness of about 5 to about 70 nm onto a molding surface of a mold. If the surface tension of the coating differs from the surface energy of the mold by greater than about 8 dynes/cm when measured at the coating application temperature, a suitable spin profile of at least about 6,000 and no more than about 8,000 RPM using at least about 2 and no more than about 20 ⁇ l of coating composition and spinning for at least about 3 sec.
- the mold is spun up to at least about 3,000 and no more than about 5,000 RPM using at least about 2 and no more than about 10 ⁇ l of coating composition and then the mold is spun up to at least about 7,000 and more than about 10,000 RPM for at least about 3 seconds prior to stopping.
- Any excess coating accumulating at the mold edges must be removed and removal may be carried out by any convenient method including, without limitation, swabbing the excess, removing the excess using vacuum, solvent, washing or pressurized air jet.
- the excess is removed using an air jet.
- coating effective amount refers to the thickness and the roughness of the coating composition on the lens forming surface.
- a peak-to-peak surface roughness of the hydrated lens is less than about 500 nm is preferable.
- coating effective amount is meant an amount of the coating composition sufficient to provide a dry film thickness of the coating composition on the lens forming surface that will result in a hydrated article with an acceptable surface roughness and for contact lenses preferably a hydrated lens peak-to-peak surface roughness of less than about 500 nm.
- the amount of coating composition used is an amount sufficient to produce a dry film thickness of at least about 5 nm and no more than about 70 nm, preferably at least about 5 nm and no more than about 50 nm, more preferably at least about 20 nm and no more than about 40 nm. Still more preferably said coating effective amount covers the entire or substantially the entire lens forming surface.
- Coating additives may be added to the high molecular weight coating compositions of the invention.
- Coating additives may include but are not limited to tints, pigments, and antimicrobial compositions. Examples of antimicrobial compositions that may be used in this manner are disclosed in the following U.S. Patents and applications which are hereby incorporated by reference in their entirety, U.S. Pat. Nos. 6,218,492; 6,248,811; 6,160,056 and U.S. patent application Ser. No. 10/028,400 filed on Dec. 20, 2001, entitled Antimicrobial Contact Lenses and Methods for Their Production; and Ser. No. 10/029,526, filed on Dec. 21, 2001, entitled Antimicrobial Contact Lenses and Methods of Use.
- the invention includes a method for making a coated lenses comprising, consisting essentially of, or consisting of
- Pellets of the alicyclic co-polymer ZEONOR® 1060R were placed in a de-humidifying dryer at 90° C. for approximately one to four (1-4) hours. The material was subsequently heated and purged through an injection molding machine using the techniques generally described in I NJECTION M OLDING H ANDBOOK , edited by Dominick & Donald Rosato, Published by Nan Nostrand Reinhold Company, 1986. Approximately three (3) pounds of material was purged and molded within 10-15 minutes to give front curves and back curves for lenses having a power of ⁇ 1.00 D. Normal usable lens molds were recovered and used to make lenses following the procedure of Example 2.
- the front and back curve molds prepared by the method of Example 1 were coated with a high MW poly-HEMA coating.
- Approximately 6 microliters of a 1.3% wt percent solution of poly-HEMA in 70:30 ethanol:ethyl lactate was applied onto the front curve mold surface (concave) by spin coating at 8000 rpm for 8 sec.
- a jet of air was applied to the edge of the spinning part during the last two seconds of the spin cycle to remove the excess coating.
- Approximately 8.5 microliters of a 1.1% solution of poly-HEMA in 70:30 ethanol:ethyl lactate was applied to the back curve mold surface (convex) by spin coating at 6000 rpm for 2 sec followed by 6 sec at 8000 rpm.
- a jet of air was applied to the edge of the spinning part during the last two seconds of the spin cycle to remove the excess coating.
- Lenses were made by dispensing the above lens formulation into the lens molds, closing the parts, precuring under visible lights for 45 sec at 45° C. followed by approximately 7 minutes of cure under visible lights at 70° C. In all cases the precure was begun within 30 sec of lens monomer dose into the mold.
- the lenses were tested clinically and were found to be equivalent in on-eye wettability, or tear break-up time, and deposition resistance to ACUVUE® etafilcon A lenses demonstrating that application of the coating to the lens results in a physiological compatible lens.
- FC and BC of lens molds were prepared using the method of Example 1 and substituting polypropylene (manufactured by Atofina EOD 00-11) for the alicyclic co-polymer of Example 1.
- Example 2 Lenses were made using the formulation and method of Example 2, but substituting the molds of Example 3, for the molds of Example 1.
- the finished lenses were examined for defects in the coating using a visual inspection apparatus. Defects were discrete areas on the surface of the finished lens where the coating was not applied. The percentage of defects was calculated and recorded in Table B, below.
- This example demonstrates that molds made from alicyclic co-polymers may be used to produce coated lenses with significantly reduced coating defects. TABLE B Mold Material Number of for the FC Lenses Coating Defect and BC Examined Rate Example 3 1200 39.1% Example 3 1200 45.5% Example 3 1200 50.0% Example 1 1600 2.0% Example 1 1600 6.3% Example 1 4800 4.4% Example 1 400 0.3%
- FC and BC molds made by the method of Examples 1 and 3 were used to prepare lenses by the method of Example 2. Dissimilar mold materials were used to make some lenses as per Table C.
- the coating defect rate was measured as well as the haze The haze values indicated were measured by placing test lenses in saline in a clear cell above a black background, illuminating from below with a fiber optic lamp at an angle 66° normal to the lens cell, and capturing an image of the lens from above with a video camera.
- the background-subtracted scattered light image was quantitatively analyzed, by integrating over the central 10 mm of the lens, and then compared to a ⁇ 1.00 diopter CSI Thin lens (commercial lens made by Wesley Jessen 33 East Tower A, Des Planes, Ill.), which is arbitrarily set at a haze value of 100, with no lens set as a haze value of zero.
- This data shows that the lowest number of defects are produced when the FC and the BC molds were made from an alicyclic co-polymer.
- An amount of polypropylene (ATOFINA EOD-0011, 50%) was blended with Zeonor 1060 R (50%) in a mixing tumbler and processed for 15 minutes. This mixture was processed in a extrusion or palletizing process to generate a uniform material. The blended material was placed into an injection molding machine and extruded into male and female halves of a lens mold and subsequently cured. The cured molds were placed into a nitrogen environment of 30 minutes before use.
- reaction components and diluent (D30) listed in Table D were mixed together with stirring or rolling for at least about 3 hours at about 23° C., until all components were dissolved.
- the reactive components are reported as weight percent of all reactive components and the diluent is weight percent of final reaction mixture.
- the reaction mixture was placed into the lens molds of Example 7 and irradiated using Philips TL 20W/03T fluorescent bulbs at 45° C. under N2.
- the cure conditions in a glove box are at approx 0.2 mW/c2 for about 6.5 minutes, followed by 2.5 mWw/c2 for about 12 min.
- the oxygen level was ⁇ 1.5% 02.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Ophthalmology & Optometry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Eyeglasses (AREA)
- Moulds For Moulding Plastics Or The Like (AREA)
- Casting Or Compression Moulding Of Plastics Or The Like (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
This invention describes molds made from alicyclic co-polymers that are useful in the production of contact lenses and methods for their use.
Description
- This application is a continuation-in-part of U.S. patent application Ser. No. 10/639,823, which is a continuation-in-part of U.S. patent application Ser. No. 10/395,755, which is a continuation-in-part of U.S. patent application Ser. No. 10/222,373.
- Contact lenses have been used commercially to improve vision since the 1950s. The first contact lenses were made of hard materials. Although these lenses are currently used, they are not suitable for all patients due to their poor initial comfort and their relatively low permeability to oxygen. Later developments in the field gave rise to soft contact lenses, based upon hydrogels, which are extremely popular today. These lenses have higher oxygen permeability and are often more comfortable to wear than contact lenses made of hard materials. Unlike hard lenses that are manufactured by lathing hard pieces of plastic, malleable soft contact lenses are often manufactured by forming the lens using a two part mold where each half has topography consistent with the desired final lens. Examples of such molds and their methods of production may be found in U.S. Pat. Nos. 4,565,348, 4,640,489, 4,495,313, JP 08025378, and JP 0726644 which are hereby incorporated by reference in their entirety.
- These two part molds contain a male member whose convex surface corresponds to the back curve of a finished lens and a female member whose concave surface corresponds to the front curve of a finished lens. To prepare lenses using these molds, an uncured lens formulation is placed between the concave and convex surfaces of the mold halves and subsequently cured. The cured lens and the mold are subsequently treated with a liquid medium in order to release the cured lens from the surface of the mold. Although this is a process is straightforward, there are a number requirements that must be satisfied in order to produce a useable lens. First the material from which the mold is made must have properties that are chemically compatible with the uncured lens formulation. Second, the mold material must be able to withstand the curing conditions and be compatible with such conditions. For example, lenses may be cured by either or both heat and light. If a lens is cured by transmitting light to the uncured polymer, it is important that the lens mold permit the transmission of light at the appropriate wavelength. Third, the mold material must not stick to the cured lens to a degree that prevents release of the cured lens. Often the lenses are produced in a manufacturing environment where it is important for the lenses to removably adhere to the same said of the lens mold upon separation in a repeatable and predictable fashion. Therefore, the selection of appropriate materials to make the molds continues to be a subject of concern to those who produce soft contact lenses.
- Others have used materials such as polypropylene, polystryene, polyethylene, polymethyl methacrylates, and modified polyolefins containing an alicyclic moiety in the main chain to prepare two part lens molds. Although these materials are useful, with discovery of different lens formulations, particularly silicone hydrogel lens formulations, other useful mold materials are needed.
- Further, new developments in the field have led to contact lenses made from hydrogels and silicone hydrogels that are coated with polymers to improve the comfort of the lenses. Often lenses are coated by treating the cured lenses with a polymer. Recently polymer coated lenses have been produced by coating the surfaces of a two part mold with a polymer, adding an uncured formulation to the coated lens mold, curing the lens, and subsequently releasing the cured lens from the mold where the surface of said cured lens is coated with the polymer that was originally adhered to the surface of the mold. This process is described in further detail in U.S. patent application Ser. No. 09/921,192, filed on Aug. 8, 2001 and entitled “Method for Correcting Articles by Mold Transfer,” which is hereby incorporated by reference in its entirety. When using this method of coating a lens, the choice of mold material is even more critical than when one is producing an uncoated lens.
- Therefore, there remains an unmet need to produce lens molds that may be used to produce many different types of soft contact lenses. It is this need that the following invention fills.
- This invention includes a mold for making a lens comprising, consisting essentially of, or consisting of an alicyclic co-polymer wherein said alicyclic co-polymer comprises, consists essentially of, or consists of at least two alicyclic monomers of different chemical structures. As used herein “lens” refers to any ophthalmic device that resides in or on the eye. These devices can provide optical correction or may be cosmetic. The term lens includes but is not limited to soft contact lenses, intraocular lenses, overlay lenses, ocular inserts, and optical inserts. The preferred lenses of the invention are soft contact lenses are made from silicone elastomers or hydrogels, which include but are not limited to silicone hydrogels, and fluorohydrogels. Soft contact lens formulations are disclosed in U.S. Pat. No. 5,710,302, WO 9421698, EP 406161, JP 2000016905, U.S. Pat. No. 5,998,498, U.S. patent application Ser. No. 09/957,299 filed on Sep. 20, 2001, U.S. patent application Ser. No. 09/532,943, U.S. Pat. No. 6,087,415, U.S. Pat. No. 5,760,100, U.S. Pat. No. 5,776, 999, U.S. Pat. No. 5,789,461, U.S. Pat. No. 5,849,811, and U.S. Pat. No. 5,965,631. Further polymers that may be used to form soft contact lenses are disclosed in the following U.S. Pat. Nos. 6,419,858; 6,308,314; and 6,416,690. The foregoing references are hereby incorporated by reference in their entirety. The particularly preferred lenses of the inventions are etafilcon A, genfilcon A, lenefilcon A, polymacon, acquafilcon A, balafilcon A, lotrafilcon A, galyfilcon A, senofilcon A, silicone hydrogels as prepared in U.S. Pat. No. 5,998,498, U.S. patent application Ser. No. 09/532,943, a continuation-in-part of U.S. patent application Ser. No. 09/532,943, filed on Aug. 30, 2000, U.S. patent application Ser. No. 09/957,299 filed on Sep. 20, 2001, soft contact lenses as prepared in U.S. Pat. App. No. 60/318,536, entitled Biomedical Devices Containing Internal Wetting Agents,” filed on Sep. 10, 2001 and its non-provisional counterpart of the same title, filed on Sep. 6, 2002, U.S. Pat. No. 6,087,415, U.S. Pat. No. 5,760,100, U.S. Pat. No.5,776,999, U.S. Pat. No. 5,789,461, U.S. Pat. No. 5,849,811, and U.S. Pat. No. 5,965,631. These patents (and applications) as well as all other patent disclosed in this application are hereby incorporated by reference in their entirety.
- As used herein, the term “alicyclic monomers” refers to polymerizable compounds having at least one saturated carbocyclic ring therein. The saturated carbocyclic rings may be substituted with one or more members of the group consisting of hydrogen, C1-10alkyl, halogen, hydroxyl, C1-10alkoxycarbonyl, C1-10alkoxy, cyano, amido, imido, silyl, and substituted C1-10alkyl where the substituents are selected from one or more members of the group consisting of halogen, hydroxyl, C1-10alkoxycarbonyl, C1-10alkoxy, cyano, amido, imido, and silyl. Examples of alicyclic monomers include but are not limited to polymerizable cyclobutanes, cyclopentanes, cyclohexanes, cycloheptanes, cyclooctanes, biscyclobutanes, biscyclopentanes, biscyclohexanes, biscycloheptanes, biscyclooctanes, and norbornanes. It is preferred that the at least two alicyclic monomers be polymerized by ring opening metathesis followed by hydrogenation. Since co-polymers are costly, it is preferable that the molds made from these co-polymers may be used several times to prepare lenses instead of once which is typical. For the preferred molds of the invention, they may be used more than once to produce lenses.
- More particularly, examples of alicyclic monomer containing saturated carbocyclic rings include but are not limited to the following structures
wherein R1— 6 are independently selected from one or more members of the group consisting of hydrogen, C1-10alkyl, halogen, hydroxyl, C1-10alkoxycarbonyl, C1-10alkoxy, cyano, amido, imido, silyl, and substituted C1-10alkyl where the substituents selected from one or more members of the group consisting of halogen, hydroxyl, C1-10alkoxycarbonyl, C1-10alkoxy, cyano, amido, imido and silyl. Further two or more of R1-6 may be taken together to form an unsaturated bond, a carbocyclic ring, a carbocyclic ring containing one or more unsaturated bonds, or an aromatic ring. The preferred R1-6 is selected from the group consisting of C1-10alkyl and substituted C1-10alkyl where the substituents are selected from the group consisting of halogen, hydroxyl, C1-10alkoxycarbonyl, C1-10alkoxy, cyano, amido, imido and silyl. -
-
- Typically the surface energy of the alicyclic co-polymer is between 30 and 45 dynes/cm at 25° C. The more particularly preferred alicyclic co-polymer contains two different alicyclic monomers and is sold by Zeon Chemicals L.P. under the tradename ZEONOR. There are several different grades of ZEONOR, having of glass transition temperatures form 105-160° C. The particularly preferred ZEONOR, is ZEONOR 1060R, which according the to the manufacturer, ZEON Chemicals L.P. has an melt flow rate (“MFR”) range of 11.0 grams/10 minutes to 18.0 grams/10 minutes (as tested JISK 6719 (230° C.)), a specific gravity (H2O=1) of 1.01 and a glass transition temperature of 105° C.
- As used here, the term “mold” refers to a rigid object that may be used to form lenses from uncured formulations. The preferred molds are two part molds as described above, where either the front curve or the back curve of the mold is made of the alicyclic co-polymers of the invention and the other curve is made of polypropylene. The preferred polypropylenes are those that have a melt flow of less that 21 g/10 min. Examples of polypropylene include but are not limited to metallocene catalyzed polypropylene that is nucleated and clarified, such as but not limited to Achieve 1615, or Achieve 1654 from Exxon and ATOFINA EOD 00-11. Further examples of polypropylene include Ziegler-Natta catalyst based polypropylenes, such as but not limited to Exxon 9544 MED, Exxon 49486-002, Atofina 3620Wz, Atofina NO 3105, having a melt flow of 12 g/10 min, <21 g/10 min; 12 g/10 min; and 18 g/10 min respectively. The preferred method of making the molds of the invention is by injection molding using known techniques, but the molds could be made by other techniques lathing, diamond turning, or laser cutting.
- Typically lenses are formed on at least one surface of both mold parts. However, if need be one surface of the lenses may be formed from a mold and the other surface could be formed using a lathing method, or other methods.
- Aside from the alicyclic co-polymers, the molds of the invention may contain additives that facilitate the separation of the lens forming surfaces, reduce the adhesion of the cured lens to the molding surface, or both. For example additives such as metal or ammonium salts of stearic acid, amide waxes, polyethylene or polypropylene waxes, organic phosphate esters, glycerol esters or alcohol esters may be added to alicyclic co-polymers prior to curing said polymers to form a mold. Examples of such additives include but are not limited to Dow Siloxane MB50-321 (a silicone dispersion), Nurcrel 535 & 932 (ethylene-methacrylic acid co-polymer resin Registry No. 25053-53-6), Erucamide (fatty acid amide Registry No. 112-84-5), Oleamide (fatty acid amide Registry No. 301-02-0), Mica (Registry No. 12001-26-2), Atmer 163 (fatty alkyl diethanolamine Registry No. 107043-84-5), Pluronic (polyoxypropylene-polyoxyethylene block co-polymer Registry No. 106392-12-5), Tetronic (alkyoxylated amine 110617-70-4), Flura (Registry No. 7681-49-4), calcium stearate, zinc stearate, Super-Floss anti block (slip/anti blocking agent, Registry No. 61790-53-2), Zeospheres anti-block (slip/anti blocking agent); Ampacet 40604 (fatty acid amide), Kemamide (fatty acid amide), Licowax fatty acid amide, Hypermer B246SF, XNAP, polyethylene glycol monolaurate (anti-stat) epoxidized soy bean oil, talc (hydrated Magnsium silicate), calcium carbonate, behenic acid, pentaerythritol tetrastearate, succinic acid, epolene E43-Wax, methyl cellulose, cocamide (anti-blocking agent Registry No. 61789-19-3), poly vinyl pyrrolidinone (360,000 MW) and the additives disclosed in U.S. Pat. No. 5,690,865 which is hereby incorporated by reference in its entirety. The preferred additives are polyvinyl pyrrolidinone, zinc stearate and glycerol mono stearate, where a weight percentage of additives based upon the total weight of the polymers is about 0.05 to about 10.0 weight percent, preferably about 0.05 to about 3.0, most preferably about 2.0 weight percent.
- In addition to additives, the separation of the lens forming surfaces may be facilitated by applying surfactants to the lens forming surfaces. Examples of suitable surfactants include Tween surfactants, particularly Tween 80 as described in U.S. Pat. No. 5,837,314 which is hereby incorporated by reference in its entirety. Other examples of surfactants are disclosed in U.S. Pat. No. 5,264,161 which is hereby incorporated by reference in its entirety.
- Still further, in addition to the alicyclic co-polymers, the molds of the invention may contain other polymers such as polypropylene, polyethylene, polystyrene, polymethyl methacrylate, and modified polyolefins containing an alicyclic moiety in the main chain. For example, a blend of the alicyclic co-polymers and polypropylene (metallocene catalyst process with nucleation, where ATOFINA EOD 00-11) may be used, where the ratio by weight percentage of alicyclic co-polymer to polypropylene ranges from about 99:1, to about 20:80 respectively. This blend can be used on either or both mold halves, where it is preferred that this blend is used on the back curve and the front curve consists of the alicyclic co-polymers.
- Further this invention includes a method of making a lens comprising, consisting essentially of, or consisting of 1) dispensing an uncured lens formulation onto a mold surface comprising, consisting essentially of, or consisting of, an alicyclic co-polymer wherein said alicyclic co-polymer comprises, consists essentially of, or consists of at least two alicyclic monomers of different chemical structures, and 2) curing said lens formulation under suitable conditions. The terms lenses, alicyclic monomers, and molds have their aforementioned meaning and preferred ranges.
- As used herein, the term “uncured” refers to the physical state of a lens formulation prior to final curing to form a lens. Some lens formulations contain mixtures of monomers which are cured only once. Other lens formulations contain monomers, partially cured monomers, macromers and other components. For examples of such partially cured formulations are disclosed in U.S. Pat. Nos. 6,419,858; 6,308,314; and 6,416,690. This invention will be useful these formulations among others.
- As used herein, the phrase “curing under suitable conditions” refers to any of the known methods of curing lens formulations, such as using light, heat, and the appropriate catalysts to produce a cured lens. Examples of such curing conditions may be found in the soft lens formulation references listed herein.
- Still further, the invention includes a lens produced by a method comprising, consisting essentially of, or consisting of 1) dispensing an uncured lens formulation onto a surface of a mold comprising, consisting essentially of, or consisting of, an alicyclic co-polymer wherein said alicyclic co-polymer comprises, consists essentially of, or consists of at least two alicyclic monomers of different chemical structures and 2) curing said lens formulation under suitable conditions. The terms lens, alicyclic monomers, uncured, and molds have their aforementioned meaning and preferred ranges.
- Yet still further, the invention includes a mold comprising, consisting essentially of, or consisting of, an alicyclic co-polymer and at least one lens forming surface
-
- wherein said alicyclic co-polymer comprises, consists essentially of, or consists of at least two alicyclic monomers of different chemical structures, and
- wherein said at least one lens forming surface comprises, consists essentially of, or consists of a coating effective amount of a high molecular weight coating composition.
The terms lens, alicyclic monomers, uncured, and molds have their aforementioned meaning and preferred ranges.
- As used herein “lens forming surface” means the surface that is used to mold the lens. Such surface has an optical quality surface finish, meaning that it is sufficiently smooth so that a lens surface formed by the polymerization of a lens forming material in contact with the molding surface is optically acceptable. Further said surface has a geometry that is necessary to impart to the lens surface the desired optical characteristics, including without limitation, spherical aspherical and cylinder power, wave front aberration correction, corneal topography correction and the like as well as combinations thereof.
- The term “high molecular weight” means an average molecular weight (“MW”) sufficiently high so as to avoid dissolution of the coating into the lens formulation or the mold material. For purposes of the invention, preferably the molecular weight is determined using gel permeation chromatography (“GPC”) with a light scattering detector and a high sensitivity refractive index detector, for example model PL-RI available from Polymer Labs. The GPC is performed using a phenogel 5 μm linear column equipped with a guard column of the same components and a solution of 0.5 weight percent lithium bromide in dimethyl formamide as the eluent. Flow rates are 0.5 mL per minute with injection volumes from about 10 to about 20 μL. The precise MW used will depend upon the coating selected and the monomer mixture used. In a preferred embodiment, the MW of the coating is greater than about 300 kD.
- “Coating compositions” useful in this invention include a wide variety of known monomers and polymers. Preferred are poly(vinyl alcohol), polyethylene oxide, poly(2-hydroxyethyl methacrylate), poly(methyl methacrylate), poly(acrylic acid), poly(methacrylic acid), poly(maleic acid), poly(itaconic acid), poly(acrylamide), poly(methacrylamide), poly(dimethylacrylamide), poly(glycerol methacrylate), polystyrene sulfonic acid, polysulfonate polymers, poly(vinyl pyrrolidone), carboxymethylated polymers, such as carboxymethylcellulose, polysaccharides, glucose amino glycans, polylactic acid, polyglycolic acid, block or random copolymers of the aforementioned, and the like, and mixtures thereof. Preferably, poly(2-hydroxyethyl methacrylate), poly(vinyl pyrrolidone), poly(acrylic acid), poly(methacrylic acid), poly(meth)acrylamide, or poly(acrylamide) is used. More preferably, poly(2-hydroxyethyl methacrylate) is used.
- Aside from the high molecular weight polymers, the coating composition may include a low boiling point (less than about 100° C.) solvent and a high boiling point, (greater than about 100° C.) solvent. Suitable low boiling solvents include, without limitation, acetone, chloroform, and alcohols such as methanol, ethanol, isopropanol, tert-butanol, and the like. Useful high boiling solvents include, without limitation, methyl-, ethyl-, and isopropyl lactate, ethylene and (poly)ethylene glycol, propylene glycol, n-methyl pyrrolidone, dimethyl formamide, tetrahydrogeraniol, 1-butanol, 1-pentanol, 1-hexanol, 1-octanol, 3-methyl-3-pentanol, dimethyl-3-octanol, 3-methoxy-1-butanol, 1,2 and 1,4-butanediol, 1,3-hexanediol, water, and the like. Typically, the ratio of the low to high boiling solvent will be about 10:90 to 90:10 when coating between 15 and 45 degrees C. When the coating composition is applied using spin coating (discussed below), the coating composition contains either or both low boiling and high boiling solvents.
- Additionally, the coating composition may include at least one surfactant. Suitable surfactants include, without limitation, anionic surfactants, such as carboxylic acid salts, sulfonic acid salts, sulfuric acid salts, phosphoric and polyphosphoric acid esters, cationic surfactants, such as long chain amines and their salts, diamines and polyamines and their salts, quarternary ammonium salts, amine oxides, nonionic surfactants, such as polyoxyethylenated alkylphenols, alkyl phenol ethoxylates, polyoxyethylenated straight chain alcohols, polyethoxylated polyoxypropylene glycols, polyethoxylated polydimethylsiloxane copolymers, fluorinated alkane ethoxylate copolymers, and long chain carboxylic acid esters, zwitterionic surfactants, such as pH-sensitive and pH insensitive surfactants, and the like, and combinations thereof. The specific type and amount of surfactants used will depend upon the other components of the coating composition and the molding surface used. Typically, greater than or equal to about 0.001 weight percent and less than or equal to about 5 weight percent based on the total weight of the coating composition will be used.
- The coating composition may be applied to the molding surface by any suitable method including, but not limited to, compression, swabbing, spray coating, ink jet printing, aerosolization, nebulization, dip coating, spin coating, and the like and combinations thereof. Preferably, spin coating is used. Also, preferably, the coating is dried, or rendered non-tacky, prior to its use for forming lenses. Drying may be carried out using any suitable method, but preferably is carried out at temperatures up to about the glass transition temperature (“Tg”) of the mold material in air or under vacuum followed by equilibration under a blanket of nitrogen at any temperature up to about the Tg of the mold material. During the vacuum exposure process, cold traps or other filters preferably are used to prevent contamination of the mold.
- In a spin coating method, the coating composition preferably has a lower surface tension than that of the molding surface's surface energy. More preferably, the surface tension of the coating composition is greater than about 3 dynes/cm below that of the surface energy of the molding surface to which it is applied when measured at the coating application temperature. Most preferably, the surface tension of the coating composition is more than 8 dynes/cm below that of the surface energy of the molding surface.
- In a preferred spin coating method for use in forming contact lenses, spin coating is used to deposit a coating of a dry thickness of about 5 to about 70 nm onto a molding surface of a mold. If the surface tension of the coating differs from the surface energy of the mold by greater than about 8 dynes/cm when measured at the coating application temperature, a suitable spin profile of at least about 6,000 and no more than about 8,000 RPM using at least about 2 and no more than about 20 μl of coating composition and spinning for at least about 3 sec. If the surface tension difference is less than about 8 dynes/cm, the mold is spun up to at least about 3,000 and no more than about 5,000 RPM using at least about 2 and no more than about 10 μl of coating composition and then the mold is spun up to at least about 7,000 and more than about 10,000 RPM for at least about 3 seconds prior to stopping.
- Any excess coating accumulating at the mold edges must be removed and removal may be carried out by any convenient method including, without limitation, swabbing the excess, removing the excess using vacuum, solvent, washing or pressurized air jet. Preferably, the excess is removed using an air jet. In using the air-jet, it is critical that spinning is started prior to the jet being turned on and, preferably, the air jet pressure is equal to or greater than about 3 psi.
- The term “coating effective amount” refers to the thickness and the roughness of the coating composition on the lens forming surface. For hydrated contact lenses, preferably a peak-to-peak surface roughness of the hydrated lens is less than about 500 nm is preferable. Thus, by coating effective amount is meant an amount of the coating composition sufficient to provide a dry film thickness of the coating composition on the lens forming surface that will result in a hydrated article with an acceptable surface roughness and for contact lenses preferably a hydrated lens peak-to-peak surface roughness of less than about 500 nm. More preferably, the amount of coating composition used is an amount sufficient to produce a dry film thickness of at least about 5 nm and no more than about 70 nm, preferably at least about 5 nm and no more than about 50 nm, more preferably at least about 20 nm and no more than about 40 nm. Still more preferably said coating effective amount covers the entire or substantially the entire lens forming surface.
- Coating additives may be added to the high molecular weight coating compositions of the invention. Coating additives may include but are not limited to tints, pigments, and antimicrobial compositions. Examples of antimicrobial compositions that may be used in this manner are disclosed in the following U.S. Patents and applications which are hereby incorporated by reference in their entirety, U.S. Pat. Nos. 6,218,492; 6,248,811; 6,160,056 and U.S. patent application Ser. No. 10/028,400 filed on Dec. 20, 2001, entitled Antimicrobial Contact Lenses and Methods for Their Production; and Ser. No. 10/029,526, filed on Dec. 21, 2001, entitled Antimicrobial Contact Lenses and Methods of Use.
- Still, yet further, the invention includes a method for making a coated lenses comprising, consisting essentially of, or consisting of
- (1) coating at least one lens forming surface of a lens mold with a coating effective amount of a high molecular weight coating composition wherein said lens mold comprises an alicyclic co-polymer and at least one lens forming surface;
- wherein said alicyclic co-polymer comprises, consists essentially of, or consists of at least two alicyclic monomers of different chemical structures;
- (2) dispensing an uncured lens formulation onto said at least one lens forming surface; and
- (3) curing said lens formulation and said coating composition using a dwell time of less than about 5 minutes and under conditions suitable to form a coated lens.
The terms lens, alicyclic monomers, uncured, molds, high molecular weight, coating composition, and coating effective amount all have their aforementioned meaning and preferred ranges. - In order to illustrate the invention the following examples are included. These examples do not limit the invention. They are meant only to suggest a method of practicing the invention. Those knowledgeable in the production of lenses as well as other specialties may find other methods of practicing the invention. However, those methods are deemed to be within the scope of this invention.
- In the examples, the following abbreviations are used:
- BC back curve
- Blue-HEMA product of the base-promoted displacement of one chloride of Reactive Blue # 4 dye by hydroxyethyl methacrylate.
- CIP Pre-Cure
- CGI 1850 1:1 (wt) blend of 1-hydroxycyclohexyl phenyl ketone and bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentyl phosphine oxide
- CGI 819 Bis(2,4,6-trimethylbenzolyl)phenyl phosphine oxide
- D3O 3,7-dimethyl-3-octanol
- Darocur 1173 UV photo initiator Ciba Speciality Chemicals
- DMA N,N-dimethylacrylamide
- FC front curve
- ATOFINA EOD 00-11 A metallocene and isotactic polypropylene having a melt flow of 14-18 g/10 minutes, ASTM D1238
- HEMA 2-hydroxyethyl methacrylate
- IPA isopropanol
- Macromer 2 the reaction product of described in the examples of U.S. patent application Ser. No. 10/028,400 filed on Dec. 20, 2001 and entitled Antimicrobial Contact Lenses and Methods for Their Production
- mPDMS monomethacryloxypropyl terminated polydimethylsiloxane
- m-PDMS-OH mono-(3-methacryloxy-2-hydroxypropyloxy)propyl terminated, mono-butyl terminated polydimethylsiloxane (MW 1100)
- Norbloc 2-(2′-hydroxy-5-methacrylyloxyethylphenyl)-2H-benzotriazole
- PVP poly(N-vinyl pyrrolidone)
- poly-Hema poly hydroxy ethylmethacylate having a molecular weight of greater than 1 MM Dalton
- SIGMA 2-propenoic acid, 2-methyl-,2-hydroxy-3-[3-[1,3,3,3-tetramethyl-1-[(trimethylsilyl)oxy]disiloxanyl]propoxy]propyl ester
- TEGDMA tetraethyleneglycol dimethacrylate
- TrEGDMA triethyleneglycol dimethacrylate
- TBACB tetrabutyl ammonium-m-chlorobenzoate
- THF tetrahydrofuran
- TMI 3-isopropenyl-α,α-dimethylbenzyl isocyanate
- TRIS 3-methacryloxypropyltris(trimethylsiloxy)silane
- Pellets of the alicyclic co-polymer ZEONOR® 1060R were placed in a de-humidifying dryer at 90° C. for approximately one to four (1-4) hours. The material was subsequently heated and purged through an injection molding machine using the techniques generally described in I
NJECTION MOLDING HANDBOOK , edited by Dominick & Donald Rosato, Published by Nan Nostrand Reinhold Company, 1986. Approximately three (3) pounds of material was purged and molded within 10-15 minutes to give front curves and back curves for lenses having a power of −1.00 D. Normal usable lens molds were recovered and used to make lenses following the procedure of Example 2. - The formulation listed in Table A was used to prepare silicone hydrogel lenses. Further details on the precise mixing procedure is disclosed in U.S. patent application Ser. No. 09/957,299 filed on Sep. 20, 2001.
TABLE A Weight Percent Macromer 2 17.98 TRIS 14.00 DMA 26.00 MPDMS 28.00 TEGDMA 1.00 HEMA 5.00 PVP 5.00 NORBLOC 2.00 Blue HEMA 0.02 CGI 1850 1.00
The remainder of the formulation were additives and diluents. The monomer to diluent ratio was 100:20, the diluent being 3,7-dimethyl-3-octanol. Acetic acid, 1% of the final mix, was used to stabilize the monomer. - The front and back curve molds prepared by the method of Example 1 were coated with a high MW poly-HEMA coating. Approximately 6 microliters of a 1.3% wt percent solution of poly-HEMA in 70:30 ethanol:ethyl lactate was applied onto the front curve mold surface (concave) by spin coating at 8000 rpm for 8 sec. A jet of air was applied to the edge of the spinning part during the last two seconds of the spin cycle to remove the excess coating. Approximately 8.5 microliters of a 1.1% solution of poly-HEMA in 70:30 ethanol:ethyl lactate was applied to the back curve mold surface (convex) by spin coating at 6000 rpm for 2 sec followed by 6 sec at 8000 rpm. A jet of air was applied to the edge of the spinning part during the last two seconds of the spin cycle to remove the excess coating. Lenses were made by dispensing the above lens formulation into the lens molds, closing the parts, precuring under visible lights for 45 sec at 45° C. followed by approximately 7 minutes of cure under visible lights at 70° C. In all cases the precure was begun within 30 sec of lens monomer dose into the mold.
- The lenses were tested clinically and were found to be equivalent in on-eye wettability, or tear break-up time, and deposition resistance to ACUVUE® etafilcon A lenses demonstrating that application of the coating to the lens results in a physiological compatible lens.
- The FC and BC of lens molds were prepared using the method of Example 1 and substituting polypropylene (manufactured by Atofina EOD 00-11) for the alicyclic co-polymer of Example 1.
- Lenses were made using the formulation and method of Example 2, but substituting the molds of Example 3, for the molds of Example 1. The finished lenses were examined for defects in the coating using a visual inspection apparatus. Defects were discrete areas on the surface of the finished lens where the coating was not applied. The percentage of defects was calculated and recorded in Table B, below. This example demonstrates that molds made from alicyclic co-polymers may be used to produce coated lenses with significantly reduced coating defects.
TABLE B Mold Material Number of for the FC Lenses Coating Defect and BC Examined Rate Example 3 1200 39.1% Example 3 1200 45.5% Example 3 1200 50.0% Example 1 1600 2.0% Example 1 1600 6.3% Example 1 4800 4.4% Example 1 400 0.3% - FC and BC molds made by the method of Examples 1 and 3 were used to prepare lenses by the method of Example 2. Dissimilar mold materials were used to make some lenses as per Table C. The coating defect rate was measured as well as the haze The haze values indicated were measured by placing test lenses in saline in a clear cell above a black background, illuminating from below with a fiber optic lamp at an angle 66° normal to the lens cell, and capturing an image of the lens from above with a video camera. The background-subtracted scattered light image was quantitatively analyzed, by integrating over the central 10 mm of the lens, and then compared to a −1.00 diopter CSI Thin lens (commercial lens made by Wesley Jessen 33 East Tower A, Des Planes, Ill.), which is arbitrarily set at a haze value of 100, with no lens set as a haze value of zero. This data shows that the lowest number of defects are produced when the FC and the BC molds were made from an alicyclic co-polymer.
TABLE C CIP Coating Defect Haze FC Mold Material BC Mold Material Time Rate (% CSI) ZEONOR ZEONOR 60 0.7% 24.7 ZEONOR ZEONOR 30 0% 20.5 ZEONOR PP 60 1.4% 31.2 ZEONOR PP 30 8.5% 53.8 - Pellets of the alicyclic polymer Zeonex® 480R were placed in a dehumidifying dryer at 100° C. for approximately four (4) hours. An attempt was made to form molds using the method of Example 1. Usable lens molds could not be formed with this material. Only tabs of cured materials were recovered and the lens mold cavities were not formed. Increasing the temperature of the molding machine (to the machine's maximum safety level) and the temperature of the mold material did not correct this problem. No usable molds were formed. This example demonstrates the distinction between the successful production of molds made from alicyclic co-polymers and the failure of molds made from alicyclic polymers.
- An amount of polypropylene (ATOFINA EOD-0011, 50%) was blended with Zeonor 1060 R (50%) in a mixing tumbler and processed for 15 minutes. This mixture was processed in a extrusion or palletizing process to generate a uniform material. The blended material was placed into an injection molding machine and extruded into male and female halves of a lens mold and subsequently cured. The cured molds were placed into a nitrogen environment of 30 minutes before use.
- The reaction components and diluent (D30) listed in Table D were mixed together with stirring or rolling for at least about 3 hours at about 23° C., until all components were dissolved. The reactive components are reported as weight percent of all reactive components and the diluent is weight percent of final reaction mixture. The reaction mixture was placed into the lens molds of Example 7 and irradiated using Philips TL 20W/03T fluorescent bulbs at 45° C. under N2. The cure conditions in a glove box are at approx 0.2 mW/c2 for about 6.5 minutes, followed by 2.5 mWw/c2 for about 12 min. The oxygen level was <1.5% 02. The molds were opened by hand the lenses were evaluated to determine if the cured lenses remained with the front curve or the back curve of the mold. Table E lists the percentage of Zeonor and polypropylene (pp) in each lens mold half and the number of lenses of Lens Type B which remained with either the front curve or the back curve after they were separated.
TABLE D Lens Type Comp. B C D E F G H I J K SIGMA 28 30 28.6 28 31 32 29 39.4 20 68 PVP (K90) 7 10 7.1 7 7 7 6 6.7 3 7 DMA 24 17 24.5 23.5 20 20 24 16.4 37 22 mPDMS 31 32 0 31 31 34 31 29.8 15 0 TRIS 0 0 0 0 0 0 0 0 15 0 HEMA 6 6 6.1 6 6.5 3 5.5 2.9 8 0 Norbloc 2 2 0 2.0 2 2 2 1.9 0 0 CGI 1850 0.48 1 1.02 1 1 1 1 1 1 0 TEGDMA 1.5 2 1.02 1.5 1.5 1 1.5 1.9 0 2 TrEGDMA 0 0 0 0 0 0 0 0 1 0 Blue HEMA 0.02 0 0 0 0 0 0 0 0 0 mPDMS-OH 0 0 31.6 0 0 0 0 0 0 0 Darocur 0 0 0 0 0 0 0 0 0 1 1173 D30 % 23 26 17 23 23 29 32 28 17 27 -
TABLE E Back Curve Front Curve % lenses in FC Total No. Tested 5% pp 100% Zeonor 29 24 95% Zeonor 25% pp 100% Zeonor 71 24 75% Zeonor 35% pp 100% Zeonor 88 24 65% Zeonor 35% pp 100% Zeonor 91 32 65% Zeonor 40% pp 100% Zeonor 97 32 60% Zeonor 40% pp 100% Zeonor 100 24 60% Zeonor 45% pp 100% Zeonor 100 32 55% Zeonor 50% pp 100% Zeonor 100 32 50% Zeonor 75% pp 100% Zeonor 100 32 25% Zeonor - This example illustrates that as the amount of polypropylene in the blend increases, the lenses
Claims (40)
1. A mold for making a lens comprising an alicyclic co-polymer wherein said alicyclic co-polymer comprises at least two alicyclic monomers of different chemical structures wherein one curve of the mold comprises said alicyclic co-polymer and the other curve of the mold comprises a Ziegler-Natta catalyst based polypropylene.
2. The mold of claim 1 wherein the alicyclic monomers comprise polymerizable cyclobutanes, cyclopentanes, cyclohexanes, cycloheptanes, cycloctanes, biscyclobutanes, biscyclopentanes, biscyclohexanes, biscycloheptanes, biscyclooctanes, or norbornanes.
3. The mold of claim 1 wherein the alicyclic monomers are selected from the group consisting of
wherein R1-6 are independently selected from one or more members of the group consisting of hydrogen, C1-10alkyl, halogen, hydroxyl, C1-10alkoxycarbonyl, C1-10alkoxy, cyano, amido, imido, silyl, and substituted C1-10alkyl where the substituents are selected from the group consisting of halogen, hydroxyl, C1-10alkoxycarbonyl, C1-10alkoxy, cyano, amido, imido and silyl.
5. The mold of claim 1 wherein the alicyclic monomers are selected from the group consisting of
wherein R1-6 are independently selected from one or more members of the group consisting of hydrogen, C1-10alkyl, halogen, hydroxyl, C1-10alkoxycarbonyl, C1-10alkoxy, cyano, amido, imido, silyl, and substituted C1-10alkyl where the substituents are selected from one or more members of the group consisting of halogen, hydroxyl, C1-10alkoxycarbonyl, C1-10alkoxy, cyano, amido, imido and silyl.
7. The mold of claim 1 wherein the alicyclic co-polymer has a MFR of about 11.0 grams/10 minutes to about 18.0 grams/10 minutes, a specific gravity of 1.01 and a glass transition temperature of 105° C.
8. The mold of claim 1 wherein the mold further comprises an additive.
9. The mold of claim 1 wherein the alicyclic co-polymer has a MFR of about 11.0 grams/10 minutes to about 18.0 grams/10 minutes, a specific gravity of 1.01 and a glass transition temperature of 105° C.
10. The mold of claim 1 wherein the front curve comprises an alicyclic co-polymer having a MFR of about 11.0 grams/10 minutes to about 18.0 grams/10 minutes, a specific gravity of 1.01 and a glass transition temperature of 105° C. and the back curve comprises polypropylene having a melt flow of less than about 21 g/10 min.
11. The mold of claim 1 wherein the back curve comprises an alicyclic co-polymer having a MFR of about 11.0 grams/10 minutes to about 18.0 grams/10 minutes, a specific gravity of 1.01 and a glass transition temperature of 105° C. and the front curve comprises polypropylene having a melt flow of less than about 21 g/10 min.
12. The mold of claim 1 wherein the front curve comprises an alicyclic co-polymer having a MFR of about 11.0 grams/10 minutes to about 18.0 grams/10 minutes, a specific gravity of 1.01 and a glass transition temperature of 105° C. and the back curve comprises polypropylene having a melt flow of less than about 21 g/10 min and an alicyclic co-polymer having a melt flow of 14, a share rate of MFR=12.0 g and 17.6 g, a specific gravity of 1.01, and a glass transition temperature of 105°.
13. The mold of claim 1 wherein the back curve comprises an alicyclic co-polymer having a MFR of about 11.0 grams/10 minutes to about 18.0 grams/10 minutes, a specific gravity of 1.01 and a glass transition temperature of 105° C. and the front curve comprises polypropylene having a melt flow of less than about 21 g/10 min and an alicyclic co-polymer having a MFR of about 11.0 grams/10 minutes to about 18.0 grams/10 minutes, a specific gravity of 1.01 and a glass transition temperature of 105° C.
14. The mold of claim 13 wherein the ratio of alicyclic co-polymer to polypropylene is about 5:95 to about 95:5.
15. The mold of claim 13 wherein the ratio of alicyclic co-polymer to polypropylene is about 20:80 to about 80:20.
16. The mold of claim 13 wherein the ratio of alicyclic co-polymer to polypropylene is about 40:60 to about 60:40.
17. A method of making a lens comprising
1) dispensing an uncured lens formulation onto a mold surface of a mold of claim 1 , and
2) curing said lens formulation under suitable conditions.
18. The method of claim 17 wherein the mold surface comprises a front curve and a back curve and the method further comprises the step of
3) separating the front curve of the lens mold and the back curve of the lens mold where the cured lens removably adheres to the front curve.
19. The method of claim 18 wherein the front curve comprises an alicyclic co-polymer having a MFR of about 11.0 grams/10 minutes to about 18.0 grams/10 minutes, a specific gravity of 1.01 and a glass transition temperature of 105° C. and the back curve comprises polypropylene having a melt flow of less than about 21 g/10 min.
20. The method of claim 18 wherein the front curve comprises an alicyclic co-polymer having a MFR of about 11.0 grams/10 minutes to about 18.0 grams/10 minutes, a specific gravity of 1.01 and a glass transition temperature of 105° C. and the back curve comprises polypropylene having a melt flow of less than about 21 g/10 min and an alicyclic co-polymer having a MFR of about 11.0 grams/10 minutes to about 18.0 grams/10 minutes, a specific gravity of 1.01 and a glass transition temperature of 105° C.
21. The method of claim 20 wherein the ratio of alicyclic co-polymer to polyproylene in the back curve is about 20:80 to about 80:20.
22. The method of claims 20 wherein the ratio of alicyclic co-polymer to polyproylene in the back curve is about 55:45.
23. The mold of claim 1 wherein the lens forming surface comprises a coating effective amount of a high molecular weight coating composition.
24. A lens produced by the method of claims 17.
25. The lens of claim 24 wherein the uncured lens formulation comprises silicone hydrogel formulations.
26. The lens of claim 24 wherein the uncured lens formulation comprises hydrogel formulations.
27. The lens of claim 24 wherein the uncured lens formulation comprises the formulations of acquafilcon A, balafilcon A, lotrafilcon A.
28. The lens of claim 24 wherein the uncured lens formulations comprise the formulation of etafilcon A, genfilcon A, lenefilcon A, polymacon, acquafilcon A, balafilcon A, galyfilcon A, or senofilcon A, or lotrafilcon A.
29. The lens of claim 24 wherein the uncured lens formulation comprises the formulations of acquafilcon A, balafilcon A, lotrafilcon A, galyfilcon A, or senofilcon A.
30. The lens of claim 24 wherein the front curve comprises an alicyclic co-polymer having a MFR of about 11.0 grams/10 minutes to about 18.0 grams/10 minutes, a specific gravity of 1.01 and a glass transition temperature of 105° C. and the back curve comprises polypropylene having a melt flow of less than about 21 g/10 min.
31. The lens of claim 24 wherein the front curve comprises an alicyclic co-polymer having a MFR of about 11.0 grams/10 minutes to about 18.0 grams/10 minutes, a specific gravity of 1.01 and a glass transition temperature of 105° C. and the back curve comprises polypropylene having a melt flow of less than about 21 g/10 min and an alicyclic co-polymer having a MFR of about 11.0 grams/10 minutes to about 18.0 grams/10 minutes, a specific gravity of 1.01 and a glass transition temperature of 105° C.
32. The lens of claim 31 wherein the ratio of alicyclic co-polymer to polyproylene in the back curve is about 20:80 to about 80:20.
33. The lens of claim 31 wherein the ratio of alicyclic co-polymer to polyproylene in the back curve is about 55:45.
34. A method for making a coated lenses comprising
(1) coating at least one lens forming surface of a lens mold with a coating effective amount of a high molecular weight coating composition wherein said lens mold comprises an alicyclic co-polymer, polypropylene having a melt flow of less than about 21 g/10 min, and at least one lens forming surface
wherein said alicyclic co-polymer comprises at lease two alicyclic monomers of different chemical structures;
(2) dispensing an uncured lens formulation onto said at least one lens forming surface; and
(3) curing said lens formulation and said coating composition using a dwell time of less than about 5 minutes and under conditions suitable to form a coated lens.
35. The method of claim 34 wherein the high molecular weight coating composition comprises poly(vinyl alcohol), polyethylene oxide, poly(2-hydroxyethyl methacrylate), poly(methyl methacrylate), poly(acrylic acid), poly(methacrylic acid), poly(maleic acid), poly(itaconic acid), poly(acrylamide), poly(methacrylamide), poly(dimethylacrylamide), poly(glycerol methacrylate), polystyrene sulfonic acid, polysulfonate polymers, poly(vinyl pyrrolidone), carboxymethylated polymers, such as carboxymethylcellulose, polysaccharides, glucose amino glycans, polylactic acid, polyglycolic acid, block or random copolymers of the aforementioned, and mixtures thereof.
36. The method of claim 34 wherein the high molecular weight coating composition comprises poly(2-hydroxyethyl methacrylate), poly(vinyl pyrrolidone), poly(acrylic acid), poly(methacrylic acid), poly(meth)acrylamide, or poly(acrylamide) and mixtures thereof.
37. The method of claim 34 wherein the lens forming surface of the front curve comprises an alicyclic co-polymer having a MFR of about 11.0 grams/10 minutes to about 18.0 grams/10 minutes, a specific gravity of 1.01 and a glass transition temperature of 105° C. and the lens forming surface of the back curve comprises polypropylene having a melt flow of less than about 21 g/10 min.
38. The method of claim 34 wherein the lens forming surface of the front curve comprises an alicyclic co-polymer having a MFR of about 11.0 grams/10 minutes to about 18.0 grams/10 minutes, a specific gravity of 1.01 and a glass transition temperature of 105° C. and the lens forming surface of the back curve comprises polypropylene having a melt flow of less than about 21 g/10 min and an alicyclic co-polymer having a MFR of about 11.0 grams/10 minutes to about 18.0 grams/10 minutes, a specific gravity of 1.01 and a glass transition temperature of 10520 C.
39. The method of claim 38 wherein the ratio of alicyclic co-polymer to polyproylene in the back curve is about 20:80 to about 80:20.
40. The method of claims 38 wherein the ratio of alicyclic co-polymer to polyproylene in the back curve is about 55:45.
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US11/522,230 US20070216860A1 (en) | 2002-08-16 | 2006-09-15 | Molds for producing contact lenses |
US11/930,709 US20080064784A1 (en) | 2002-08-16 | 2007-10-31 | Molds for producing contact lenses |
US12/330,056 US20090091047A1 (en) | 2002-08-16 | 2008-12-08 | Molds for producing contact lenses |
US12/342,661 US7833443B2 (en) | 2002-08-16 | 2008-12-23 | Molds for producing contact lenses |
US12/887,685 US8292256B2 (en) | 2002-08-16 | 2010-09-22 | Molds for producing contact lenses |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US22237302A | 2002-08-16 | 2002-08-16 | |
US39575503A | 2003-03-24 | 2003-03-24 | |
US10/639,823 US20040075039A1 (en) | 2002-08-16 | 2003-08-13 | Molds for producing contact lenses |
US11/522,230 US20070216860A1 (en) | 2002-08-16 | 2006-09-15 | Molds for producing contact lenses |
Related Parent Applications (3)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US22237302A Continuation-In-Part | 2002-08-16 | 2002-08-16 | |
US39575503A Continuation-In-Part | 2002-08-16 | 2003-03-24 | |
US10/639,823 Continuation-In-Part US20040075039A1 (en) | 2002-08-16 | 2003-08-13 | Molds for producing contact lenses |
Related Child Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US11/930,709 Continuation US20080064784A1 (en) | 2002-08-16 | 2007-10-31 | Molds for producing contact lenses |
US12/342,661 Division US7833443B2 (en) | 2002-08-16 | 2008-12-23 | Molds for producing contact lenses |
Publications (1)
Publication Number | Publication Date |
---|---|
US20070216860A1 true US20070216860A1 (en) | 2007-09-20 |
Family
ID=31890920
Family Applications (6)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US10/639,823 Abandoned US20040075039A1 (en) | 2002-08-16 | 2003-08-13 | Molds for producing contact lenses |
US11/522,230 Abandoned US20070216860A1 (en) | 2002-08-16 | 2006-09-15 | Molds for producing contact lenses |
US11/930,709 Abandoned US20080064784A1 (en) | 2002-08-16 | 2007-10-31 | Molds for producing contact lenses |
US12/330,056 Abandoned US20090091047A1 (en) | 2002-08-16 | 2008-12-08 | Molds for producing contact lenses |
US12/342,661 Expired - Lifetime US7833443B2 (en) | 2002-08-16 | 2008-12-23 | Molds for producing contact lenses |
US12/887,685 Expired - Lifetime US8292256B2 (en) | 2002-08-16 | 2010-09-22 | Molds for producing contact lenses |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US10/639,823 Abandoned US20040075039A1 (en) | 2002-08-16 | 2003-08-13 | Molds for producing contact lenses |
Family Applications After (4)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US11/930,709 Abandoned US20080064784A1 (en) | 2002-08-16 | 2007-10-31 | Molds for producing contact lenses |
US12/330,056 Abandoned US20090091047A1 (en) | 2002-08-16 | 2008-12-08 | Molds for producing contact lenses |
US12/342,661 Expired - Lifetime US7833443B2 (en) | 2002-08-16 | 2008-12-23 | Molds for producing contact lenses |
US12/887,685 Expired - Lifetime US8292256B2 (en) | 2002-08-16 | 2010-09-22 | Molds for producing contact lenses |
Country Status (11)
Country | Link |
---|---|
US (6) | US20040075039A1 (en) |
JP (1) | JP4708023B2 (en) |
KR (2) | KR20100119802A (en) |
AR (1) | AR040997A1 (en) |
AU (2) | AU2003255279A1 (en) |
BR (1) | BR0313516A (en) |
CA (1) | CA2496024C (en) |
DE (1) | DE10393129T5 (en) |
GB (1) | GB2409683B (en) |
HK (1) | HK1078051A1 (en) |
WO (1) | WO2004016405A1 (en) |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20060051454A1 (en) * | 2004-08-26 | 2006-03-09 | Ansell Scott F | Molds for producing ophthalmic lenses |
US20070267765A1 (en) * | 2006-05-18 | 2007-11-22 | Ansell Scott F | Biomedical device mold |
US20090130295A1 (en) * | 2007-11-16 | 2009-05-21 | Julie Broguiere | High Definition Printing With Waterborne Inks on Non-Porous Substrates |
US20090321970A1 (en) * | 2008-06-30 | 2009-12-31 | Changhong Yin | Ophthalmic lens molds parts with siloxane wax |
US20100109176A1 (en) * | 2008-11-03 | 2010-05-06 | Chris Davison | Machined lens molds and methods for making and using same |
US20110101550A1 (en) * | 2002-08-16 | 2011-05-05 | Changhong Yin | Molds for producing contact lenses |
CN104029317A (en) * | 2014-05-19 | 2014-09-10 | 滁州迪蒙德模具制造有限公司 | Mold production method |
Families Citing this family (22)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6638451B1 (en) * | 1999-08-31 | 2003-10-28 | Novartis Ag | Plastic casting molds |
US20050171232A1 (en) * | 2003-11-05 | 2005-08-04 | Ford James D. | Methods of inhibiting the adherence of lenses to their packaging materials |
US7805822B2 (en) * | 2003-12-15 | 2010-10-05 | Turbocombustor Technology, Inc. | Process for removing thermal barrier coatings |
US7799249B2 (en) | 2005-08-09 | 2010-09-21 | Coopervision International Holding Company, Lp | Systems and methods for producing silicone hydrogel contact lenses |
US7320587B2 (en) * | 2005-08-09 | 2008-01-22 | Cooper Vision, Inc. | Contact lens molds and systems and methods for producing same |
US8003024B2 (en) * | 2006-09-18 | 2011-08-23 | Coopervision International Holding Company, Lp | Polyolefin contact lens molds and uses thereof |
US7875217B2 (en) * | 2006-09-29 | 2011-01-25 | Johnson & Johnson Vision Care, Inc. | Excess polymer ring removal during ophthalmic lens manufacture |
JP5534817B2 (en) * | 2006-12-19 | 2014-07-02 | ノバルティス アーゲー | Premium optic ophthalmic lens |
US20080239237A1 (en) * | 2007-03-30 | 2008-10-02 | Ansell Scott F | Molds with thermoplastic elastomers for producing ophthalmic lenses |
US20080290534A1 (en) * | 2007-05-24 | 2008-11-27 | Changhong Yin | Ophthalmic lens mold surface energy differential |
JP5525816B2 (en) | 2007-09-14 | 2014-06-18 | ロート製薬株式会社 | Ophthalmic composition |
TWI430789B (en) * | 2007-11-22 | 2014-03-21 | Mitsubishi Plastics Inc | Plastic containers with cyclic polyolefin layers |
US20090146329A1 (en) * | 2007-12-06 | 2009-06-11 | Changhong Yin | Lens release |
US8333360B2 (en) * | 2008-06-20 | 2012-12-18 | 3M Innovative Properties Company | Polymeric molds and articles made therefrom |
BRPI0922802B1 (en) * | 2008-11-21 | 2019-09-17 | Hercules Incorporated | Cross-linked CARBOXYLIC ACID COPOLYMER |
JP5381827B2 (en) * | 2010-03-15 | 2014-01-08 | 日本ゼオン株式会社 | Composite resin mold for curable composition |
WO2012006488A2 (en) | 2010-07-09 | 2012-01-12 | Lee Darren Norris | Ophthalmic lens molds with low levels of uv light transmittance, ophthalmic lenses molded therein, and related methods |
EP2598321B1 (en) | 2010-07-30 | 2016-10-26 | CooperVision International Holding Company, LP | Ophthalmic lens molds, ophthalmic lenses molded therein, and related methods |
SG190057A1 (en) | 2010-12-01 | 2013-06-28 | Novartis Ag | Atmospheric plasma coating for ophthalmic devices |
US9358735B2 (en) | 2011-11-29 | 2016-06-07 | Novartis Ag | Method of treating a lens forming surface of at least one mold half of a mold for molding ophthalmic lenses |
CN108250586B (en) * | 2017-12-29 | 2021-02-02 | 青岛海尔新材料研发有限公司 | PP/PMMA alloy material and preparation method and application thereof |
US11426959B2 (en) | 2019-11-06 | 2022-08-30 | Innovega, Inc. | Apparatuses and methods for multistage molding of lenses |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3502634A (en) * | 1960-09-24 | 1970-03-24 | Phillips Petroleum Co | Process and catalyst for polymerization of alpha-monoolefins having three or more carbon atoms per molecule |
US5629398A (en) * | 1990-10-05 | 1997-05-13 | Idemitsu Kosan Co., Ltd. | Process for producing cyclic olefin based polymers, cyclic olefin copolymers, compositions and molded articles comprising the copolymers |
US6551531B1 (en) * | 2000-03-22 | 2003-04-22 | Johnson & Johnson Vision Care, Inc. | Molds for making ophthalmic devices |
Family Cites Families (146)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2089033A (en) * | 1937-01-16 | 1937-08-03 | Miller Chris | Foil applying device |
US3337659A (en) * | 1958-06-12 | 1967-08-22 | Lentilles Ophlalmiques Special | Method of producing mold elements for lenses |
US2965946A (en) * | 1958-10-02 | 1960-12-27 | Colgate Palmolive Co | Apparatus and process for pressing detergent bars and cakes |
US3077005A (en) * | 1959-04-17 | 1963-02-12 | Republic Aviat Corp | Method of molding synthetic resins |
US3056166A (en) * | 1959-07-20 | 1962-10-02 | Bausch & Lomb | Lens mold and apparatus |
NL285986A (en) * | 1961-12-27 | |||
US3212097A (en) * | 1962-04-12 | 1965-10-12 | Richard Wlodyga | Truncated prism ballast contact lens with indentation and fluid drainage channel at bottom edge |
US3422168A (en) * | 1964-12-01 | 1969-01-14 | Ppg Industries Inc | Process of casting resinous lenses in thermoplastic cast replica molds |
US3404861A (en) * | 1965-02-22 | 1968-10-08 | Optics Australia Pty Ltd | Optical casting gasket |
US3423486A (en) * | 1966-05-03 | 1969-01-21 | Olin Mathieson | Oxyalkylated 2,2-bis(chloromethyl)-1,3-propanediol-bis-phosphate |
US3423488A (en) * | 1966-05-11 | 1969-01-21 | Ppg Industries Inc | Process for casting resinous lenses in thermoplastic cast replica molds |
FR1552001A (en) * | 1967-10-20 | 1969-01-03 | ||
CH512980A (en) * | 1969-01-20 | 1971-09-30 | Ceskoslovenska Akademie Ved | Process for the production of rotationally symmetrical objects by centrifugal casting |
US3673055A (en) * | 1970-03-30 | 1972-06-27 | Bausch & Lomb | Laminated transparent bodies having mar resistant protective coatings |
FR2109470A5 (en) * | 1970-10-19 | 1972-05-26 | Silor | |
US3871803A (en) * | 1971-12-21 | 1975-03-18 | Beattie Dev Company | Apparatus for producing an optical molding plaque |
US3833588A (en) * | 1972-04-25 | 1974-09-03 | Sandoz Ag | Unsaturated-substituted tricyclic quinazolinones |
US3835588A (en) * | 1973-03-05 | 1974-09-17 | Warner Lambert Co | Lenticular contact lense lathe |
US3821333A (en) * | 1973-03-21 | 1974-06-28 | American Optical Corp | Gasket for lens mold from a blend of epdm and ethylene/vinyl acetate copolymer |
JPS5148664B2 (en) * | 1973-03-23 | 1976-12-22 | ||
US3861683A (en) * | 1973-04-18 | 1975-01-21 | Carl M Henry | Tubular shaped projectile for sporting games |
US3894710A (en) * | 1973-08-29 | 1975-07-15 | George M J Sarofeen | Mold forms coating synthetic resin lenses |
US3881683A (en) * | 1973-11-29 | 1975-05-06 | American Optical Corp | Gasket for lens mold |
US3915609A (en) * | 1974-03-18 | 1975-10-28 | American Optical Corp | Molds for casting silicone rubber contact lenses |
US4197266A (en) * | 1974-05-06 | 1980-04-08 | Bausch & Lomb Incorporated | Method for forming optical lenses |
US4103992A (en) * | 1975-01-20 | 1978-08-01 | Breger-Mueller Welt Corp. | Corneal contact lens and method of making the same |
US4008031A (en) * | 1975-08-22 | 1977-02-15 | Weber Hermann P | Apparatus for injection molding lenses |
US4121896A (en) * | 1976-03-24 | 1978-10-24 | Shepherd Thomas H | Apparatus for the production of contact lenses |
US4208364A (en) * | 1976-03-24 | 1980-06-17 | Shepherd Thomas H | Process for the production of contact lenses |
US4159292A (en) * | 1977-05-25 | 1979-06-26 | Neefe Optical Lab. Inc. | Method of controlling the release of a cast plastic lens from a resinous lens mold |
US4150073A (en) * | 1977-05-25 | 1979-04-17 | Neefe Charles W | Method of controlling the adhesion of a molded plastic lens to the mold |
CA1108797A (en) | 1977-09-16 | 1981-09-08 | Anthony J. Bell | Random copolymers of dicyclopentadiene and unsaturated monocyclic compounds |
US4361657A (en) * | 1978-11-30 | 1982-11-30 | Global Vision (U.K.) Ltd. | Cross-linked hydrogel copolymers for contact lenses |
FR2449522A1 (en) * | 1979-02-20 | 1980-09-19 | Essilor Int | MOLDING PROCESS AND CORRESPONDING MOLD, IN PARTICULAR FOR MOLDING OPHTHALMIC LENSES IN ORGANIC MATERIAL |
FR2477059A1 (en) * | 1980-02-28 | 1981-09-04 | Medicornea Sa | METHOD OF MANUFACTURING BY MOLDING CONTACT LENSES AND LENSES OBTAINED |
US4284591A (en) * | 1980-04-28 | 1981-08-18 | Neefe Optica Lab Inc. | Injection molding of optical lenses and optical molds |
US4565348A (en) * | 1981-04-30 | 1986-01-21 | Mia-Lens Production A/S | Mold for making contact lenses, the male mold member being more flexible than the female mold member |
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 |
US4640489A (en) * | 1981-04-30 | 1987-02-03 | Mia-Lens Production A/S | Mold for making contact lenses, either the male or female mold sections being relatively more flexible |
US4419483A (en) * | 1982-05-24 | 1983-12-06 | Sun Chemical Corporation | Process for preparing water-in-oil emulsions |
US4453916A (en) * | 1982-07-12 | 1984-06-12 | Osipov Anatoly A | Device for fusion of electrodeposited coating of printed-circuit boards |
US4530914A (en) * | 1983-06-06 | 1985-07-23 | Exxon Research & Engineering Co. | Process and catalyst for producing polyethylene having a broad molecular weight distribution |
CS239282B1 (en) * | 1983-08-17 | 1986-01-16 | Otto Wichterle | Preparation method of objects made from hydrophilic gelsnamely contact lences by polymer casting |
US4540534A (en) * | 1983-10-11 | 1985-09-10 | American Optical Corporation | Apparatus and method for injection molding lenses |
JPS61174128A (en) * | 1985-01-28 | 1986-08-05 | Sumitomo Electric Ind Ltd | Mold for molding lens |
US5179171A (en) * | 1985-05-24 | 1993-01-12 | Mitsui Petrochemical Industries, Ltd. | Random copolymer, and process for production thereof |
US4686267A (en) * | 1985-10-11 | 1987-08-11 | Polymer Technology Corporation | Fluorine containing polymeric compositions useful in contact lenses |
DE3767317D1 (en) * | 1986-02-13 | 1991-02-21 | Philips Nv | DIE FOR AN IMPRESSION PROCESS. |
CS260213B1 (en) * | 1986-03-05 | 1988-12-15 | Jiri Sulc | Method of polymerization casting of articles especially lenses from hydrophilic gels and equipment for realization of this method |
US4622347A (en) * | 1986-04-07 | 1986-11-11 | Atlantic Richfield Company | Expandable polypropylene interpolymer particles |
US4661573A (en) * | 1986-04-14 | 1987-04-28 | Paragon Optical Inc. | Lens composition articles and method of manufacture |
US4822238A (en) * | 1986-06-19 | 1989-04-18 | Westinghouse Electric Corp. | Robotic arm |
US4780515A (en) * | 1987-02-05 | 1988-10-25 | Bausch & Lomb Incorporated | Continuous-wear lenses having improved physical properties |
EP0284708B1 (en) * | 1987-04-03 | 1996-01-31 | Fina Technology, Inc. | Metallocene catalyst systems for olefin polymerization having a silicon hydrocarbyl bridge. |
US5070169A (en) * | 1988-02-26 | 1991-12-03 | Ciba-Geigy Corporation | Wettable, flexible, oxygen permeable contact lens containing block copolymer polysiloxane-polyoxyalkylene backbone units and use thereof |
US5096626A (en) * | 1988-06-10 | 1992-03-17 | Asahi Kogaku Kogyo Kabushiki Kaisha | Process of molding a coated plastic lens |
US4983702A (en) * | 1988-09-28 | 1991-01-08 | Ciba-Geigy Corporation | Crosslinked siloxane-urethane polymer contact lens |
ES2076216T3 (en) * | 1988-11-02 | 1995-11-01 | British Tech Group | CASTING FOR CASTING AND PACKAGING OF CONTACT LENSES. |
AU637361B2 (en) | 1989-04-24 | 1993-05-27 | Novartis Ag | Polysiloxane-polyoxyalkylene block copolymers and ophthalmic devices containing them |
US5070215A (en) * | 1989-05-02 | 1991-12-03 | Bausch & Lomb Incorporated | Novel vinyl carbonate and vinyl carbamate contact lens material monomers |
AT391371B (en) * | 1989-05-12 | 1990-09-25 | Avl Ag | METHOD AND DEVICE FOR DETERMINING BIOLOGICAL ACTIVITIES IN A SAMPLE |
US5034461A (en) * | 1989-06-07 | 1991-07-23 | Bausch & Lomb Incorporated | Novel prepolymers useful in biomedical devices |
US5115056A (en) | 1989-06-20 | 1992-05-19 | Ciba-Geigy Corporation | Fluorine and/or silicone containing poly(alkylene-oxide)-block copolymers and contact lenses thereof |
DE3922546A1 (en) * | 1989-07-08 | 1991-01-17 | Hoechst Ag | METHOD FOR THE PRODUCTION OF CYCLOOLEFINPOLYMERS |
US4983332A (en) * | 1989-08-21 | 1991-01-08 | Bausch & Lomb Incorporated | Method for manufacturing hydrophilic contact lenses |
WO1991004283A1 (en) | 1989-09-14 | 1991-04-04 | Chang Sing Hsiung | Soft gas permeable contact lens having improved clinical performance |
US5369183A (en) | 1989-10-09 | 1994-11-29 | Sanyo Chemical Industries, Ltd. | Composite and molding from the composite |
JPH04218557A (en) | 1990-04-13 | 1992-08-10 | Nippon Zeon Co Ltd | Molding of thermoplastic saturated norbornene-based polymer |
JPH03294818A (en) | 1990-04-13 | 1991-12-26 | Seiko Epson Corp | Soft contact lens |
US5480946A (en) * | 1990-04-26 | 1996-01-02 | Ciba Geigy Corporation | Unsaturated urea polysiloxanes |
US5874557A (en) * | 1990-06-11 | 1999-02-23 | Nexstar Pharmaceuticals, Inc. | Nucleic acid ligand inhibitors to DNA polymerases |
US5158718A (en) * | 1990-08-02 | 1992-10-27 | Pilkington Visioncare, Inc. | Contact lens casting |
US5160749A (en) * | 1990-10-30 | 1992-11-03 | Minnesota Mining And Manufacturing Company | Three piece mold assembly for making an ocular device |
ES2071888T3 (en) * | 1990-11-12 | 1995-07-01 | Hoechst Ag | BISINDENILMETALOCENOS SUBSTITUTED IN POSITION 2, PROCEDURE FOR ITS PREPARATION AND USE AS CATALYSTS IN THE POLYMERIZATION OF OLEFINS. |
US5264161A (en) | 1991-09-05 | 1993-11-23 | Bausch & Lomb Incorporated | Method of using surfactants as contact lens processing aids |
US5271875A (en) * | 1991-09-12 | 1993-12-21 | Bausch & Lomb Incorporated | Method for molding lenses |
US5310779A (en) * | 1991-11-05 | 1994-05-10 | Bausch & Lomb Incorporated | UV curable crosslinking agents useful in copolymerization |
US5352714A (en) * | 1991-11-05 | 1994-10-04 | Bausch & Lomb Incorporated | Wettable silicone hydrogel compositions and methods for their manufacture |
US5567776A (en) * | 1992-05-26 | 1996-10-22 | Mitsui Petrochemical Industries, Ltd. | Cycloolefin copolymer composition and method for the preperation thereof |
TW294669B (en) | 1992-06-27 | 1997-01-01 | Hoechst Ag | |
US5260000A (en) * | 1992-08-03 | 1993-11-09 | Bausch & Lomb Incorporated | Process for making silicone containing hydrogel lenses |
EP0588208A3 (en) | 1992-09-12 | 1994-07-06 | Hoechst Ag | Polyolefin moulding composition with broad melt range, process and use therefore |
US5294379A (en) * | 1992-09-18 | 1994-03-15 | Johnson & Johnson Vision Products, Inc. | Laser assisted demolding of ophthalmic lenses |
AU4639293A (en) | 1992-09-29 | 1994-04-26 | Bausch & Lomb Incorporated | Method of making plastic molds and process for cast molding contact lenses |
GB9224876D0 (en) | 1992-11-27 | 1993-01-13 | Exxon Chemical Patents Inc | Improved processing polyolefin blends |
JPH06170857A (en) * | 1992-12-03 | 1994-06-21 | Seiko Epson Corp | Production of contact lens and mold therefor |
US5573715A (en) | 1992-12-21 | 1996-11-12 | Johnson & Johnson Vision Products, Inc. | Method for treating an ophthalmic lens mold |
US5374662A (en) | 1993-03-15 | 1994-12-20 | Bausch & Lomb Incorporated | Fumarate and fumaramide siloxane hydrogel compositions |
US5440534A (en) * | 1994-01-10 | 1995-08-08 | Eastman Kodak Company | Method and apparatus for maintaining a recording light beam in an on-track position on a recording medium |
US5436212A (en) * | 1994-04-15 | 1995-07-25 | Phillips Petroleum Company | Organoaluminoxy product, preparation, and use |
US5540410A (en) * | 1994-06-10 | 1996-07-30 | Johnson & Johnson Vision Prod | Mold halves and molding assembly for making contact lenses |
US5597519A (en) | 1994-06-10 | 1997-01-28 | Johnson & Johnson Vision Products, Inc. | Ultraviolet cycling oven for polymerization of contact lenses |
US5837314A (en) | 1994-06-10 | 1998-11-17 | Johnson & Johnson Vision Products, Inc. | Method and apparatus for applying a surfactant to mold surfaces |
ATE188967T1 (en) | 1994-06-13 | 2000-02-15 | Targor Gmbh | TRANSITION METAL JOINTS |
DE4420456A1 (en) | 1994-06-13 | 1995-12-14 | Hoechst Ag | Neutral zwitterionic transition metal cpds. |
US5843346A (en) * | 1994-06-30 | 1998-12-01 | Polymer Technology Corporation | Method of cast molding contact lenses |
JPH0825378A (en) | 1994-07-20 | 1996-01-30 | Seiko Epson Corp | Resin mold for producing contact lens and production of contact lens |
US5760100B1 (en) | 1994-09-06 | 2000-11-14 | Ciba Vision Corp | Extended wear ophthalmic lens |
US5690865A (en) * | 1995-03-31 | 1997-11-25 | Johnson & Johnson Vision Products, Inc. | Mold material with additives |
US5849209A (en) * | 1995-03-31 | 1998-12-15 | Johnson & Johnson Vision Products, Inc. | Mold material made with additives |
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 |
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 |
US5997881A (en) * | 1995-11-22 | 1999-12-07 | University Of Maryland, Baltimore | Method of making non-pyrogenic lipopolysaccharide or A |
DE69615393T2 (en) | 1995-12-07 | 2002-07-04 | Bausch & Lomb | MONOMERS FOR REDUCING THE MODULE OF SILOXYNHYDROGELS |
US5952244A (en) * | 1996-02-15 | 1999-09-14 | Lam Research Corporation | Methods for reducing etch rate loading while etching through a titanium nitride anti-reflective layer and an aluminum-based metallization layer |
US5779943A (en) * | 1996-03-19 | 1998-07-14 | Johnson & Johnson Vision Products, Inc. | Molded polymeric object with wettable surface made from latent-hydrophilic monomers |
GB9607749D0 (en) * | 1996-04-15 | 1996-06-19 | Blatchford & Sons Ltd | Specification of an artifical limb |
US5820895A (en) * | 1996-06-04 | 1998-10-13 | Johnson & Johnson Vision Products, Inc. | Conductive probe for heating contact lens mold assemblies during demolding |
US6090888A (en) | 1996-06-06 | 2000-07-18 | Hoechst Celanese Corporation | Cyclic olefin polymer blends exhibiting improved impact resistance and good transparency |
US5975694A (en) * | 1996-07-01 | 1999-11-02 | Bausch & Lomb Incorporated | Contact lens and method for making the same |
JPH1071190A (en) * | 1996-08-30 | 1998-03-17 | Tomey Technol Corp | Liquid agent for contact lens |
US5972251A (en) * | 1996-10-16 | 1999-10-26 | Bausch & Lomb Incorporated | Method for blocking a contact lens button |
EP0860213A3 (en) * | 1997-01-03 | 2002-10-16 | Therapol SA | Bioactive coating on surfaces |
US6218492B1 (en) | 1997-01-03 | 2001-04-17 | Huels Aktiengesellschaft | Water insoluble bacteriophobic polymers containing carboxyl and sulfonic acid groups |
CA2228961C (en) * | 1997-02-05 | 2007-06-19 | Johnson & Johnson Vision Products, Inc. | Base curve mold designs to maintain hema ring/base curve adhesion |
DK0866080T3 (en) * | 1997-03-01 | 2002-09-09 | Vestolit Gmbh & Co Kg | Molds having anticoagulant properties, their preparation and processing into articles which can be used in the medical technique |
JP3817015B2 (en) * | 1997-04-14 | 2006-08-30 | 三井化学株式会社 | Cyclic olefin copolymer and use thereof |
US5952444A (en) * | 1997-05-22 | 1999-09-14 | Chisso Corporation | Polyurethane coating resin composition |
US6228795B1 (en) | 1997-06-05 | 2001-05-08 | Exxon Chemical Patents, Inc. | Polymeric supported catalysts |
US6943203B2 (en) | 1998-03-02 | 2005-09-13 | Johnson & Johnson Vision Care, Inc. | Soft contact lenses |
US5998498A (en) * | 1998-03-02 | 1999-12-07 | Johnson & Johnson Vision Products, Inc. | Soft contact lenses |
US5962548A (en) * | 1998-03-02 | 1999-10-05 | Johnson & Johnson Vision Products, Inc. | Silicone hydrogel polymers |
US6308314B1 (en) | 1998-03-11 | 2001-10-23 | International Business Machines Corporation | Mechanism and method for flexible coupling of processes in an object oriented framework |
ID23894A (en) | 1998-03-17 | 2000-05-25 | Bausch & Lomb | PRINTING METHOD OF CONTACT LENSES |
US6087415A (en) | 1998-06-11 | 2000-07-11 | Johnson & Johnson Vision Care, Inc. | Biomedical devices with hydrophilic coatings |
US6153715A (en) * | 1998-09-17 | 2000-11-28 | Idemitsu Petrochemical Co., Ltd. | Propylenic resin and blow molded article made therefrom |
US5981675A (en) * | 1998-12-07 | 1999-11-09 | Bausch & Lomb Incorporated | Silicone-containing macromonomers and low water materials |
MXPA01012579A (en) | 1999-06-11 | 2002-04-10 | Bausch & Lomb | Lens molds with protective coatings for production of contact lenses and other ophthalmic products. |
US6135715A (en) * | 1999-07-29 | 2000-10-24 | General Electric Company | Tip insulated airfoil |
JP3956552B2 (en) * | 1999-10-27 | 2007-08-08 | 日本ゼオン株式会社 | Contact lens mold |
US6582631B1 (en) * | 1999-11-09 | 2003-06-24 | Novartis Ag | Method for cast molding contact lenses |
US6416690B1 (en) | 2000-02-16 | 2002-07-09 | Zms, Llc | Precision composite lens |
JP3929014B2 (en) * | 2000-02-24 | 2007-06-13 | Hoyaヘルスケア株式会社 | Contact lens material comprising a macromer having a polysiloxane structure in the side chain |
WO2001074576A1 (en) * | 2000-03-31 | 2001-10-11 | Bausch & Lomb Incorporated | Method and device to control polymerization |
AU2001252985A1 (en) * | 2000-03-31 | 2001-10-15 | Bausch And Lomb Incorporated | Methods and devices to control polymerization |
US6419858B1 (en) | 2000-06-13 | 2002-07-16 | Zms, Llc | Morphology trapping and materials suitable for use therewith |
MXPA03003542A (en) * | 2000-10-24 | 2004-08-12 | Bausch & Lomb | Prevention of bacterial attachment to biomaterials by cationic polysaccharides. |
US6839042B2 (en) | 2000-10-27 | 2005-01-04 | Advanced Laser Technologies, Inc. | Light beam display with interlaced light beam scanning |
US20020197299A1 (en) * | 2000-12-21 | 2002-12-26 | Vanderlaan Douglas G. | Antimicrobial contact lenses containing activated silver and methods for their production |
US20030044447A1 (en) | 2000-12-21 | 2003-03-06 | Diana Zanini | Antimicrobial contact lenses and methods for their production |
US20020080327A1 (en) * | 2000-12-22 | 2002-06-27 | Clark Douglas G. | Tinted contact lenses |
KR20040043178A (en) | 2001-08-02 | 2004-05-22 | 존슨 앤드 존슨 비젼 케어, 인코포레이티드 | Antimicrobial lenses and methods of their use |
US7879267B2 (en) * | 2001-08-02 | 2011-02-01 | J&J Vision Care, Inc. | Method for coating articles by mold transfer |
US20040044106A1 (en) * | 2001-11-08 | 2004-03-04 | Portnoy Robert C. | Polypropylene for precision injection molding applications |
US20040075039A1 (en) | 2002-08-16 | 2004-04-22 | Dubey Dharmesh K. | Molds for producing contact lenses |
-
2003
- 2003-08-13 US US10/639,823 patent/US20040075039A1/en not_active Abandoned
- 2003-08-13 BR BR0313516-0A patent/BR0313516A/en not_active Application Discontinuation
- 2003-08-13 WO PCT/US2003/025235 patent/WO2004016405A1/en active Application Filing
- 2003-08-13 KR KR1020107021006A patent/KR20100119802A/en not_active Application Discontinuation
- 2003-08-13 GB GB0505217A patent/GB2409683B/en not_active Expired - Lifetime
- 2003-08-13 KR KR1020057002621A patent/KR101021433B1/en active IP Right Grant
- 2003-08-13 JP JP2004529326A patent/JP4708023B2/en not_active Expired - Lifetime
- 2003-08-13 DE DE10393129T patent/DE10393129T5/en not_active Ceased
- 2003-08-13 CA CA2496024A patent/CA2496024C/en not_active Expired - Fee Related
- 2003-08-13 AU AU2003255279A patent/AU2003255279A1/en not_active Abandoned
- 2003-08-15 AR ARP030102975A patent/AR040997A1/en active IP Right Grant
-
2005
- 2005-11-10 HK HK05110062A patent/HK1078051A1/en not_active IP Right Cessation
-
2006
- 2006-09-15 US US11/522,230 patent/US20070216860A1/en not_active Abandoned
-
2007
- 2007-10-31 US US11/930,709 patent/US20080064784A1/en not_active Abandoned
-
2008
- 2008-12-08 US US12/330,056 patent/US20090091047A1/en not_active Abandoned
- 2008-12-23 US US12/342,661 patent/US7833443B2/en not_active Expired - Lifetime
-
2010
- 2010-03-02 AU AU2010200783A patent/AU2010200783B2/en not_active Ceased
- 2010-09-22 US US12/887,685 patent/US8292256B2/en not_active Expired - Lifetime
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3502634A (en) * | 1960-09-24 | 1970-03-24 | Phillips Petroleum Co | Process and catalyst for polymerization of alpha-monoolefins having three or more carbon atoms per molecule |
US5629398A (en) * | 1990-10-05 | 1997-05-13 | Idemitsu Kosan Co., Ltd. | Process for producing cyclic olefin based polymers, cyclic olefin copolymers, compositions and molded articles comprising the copolymers |
US6551531B1 (en) * | 2000-03-22 | 2003-04-22 | Johnson & Johnson Vision Care, Inc. | Molds for making ophthalmic devices |
Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20110101550A1 (en) * | 2002-08-16 | 2011-05-05 | Changhong Yin | Molds for producing contact lenses |
US8292256B2 (en) | 2002-08-16 | 2012-10-23 | Johnson & Johnson Vision Care, Inc. | Molds for producing contact lenses |
US20060051454A1 (en) * | 2004-08-26 | 2006-03-09 | Ansell Scott F | Molds for producing ophthalmic lenses |
US20070267765A1 (en) * | 2006-05-18 | 2007-11-22 | Ansell Scott F | Biomedical device mold |
US20090130295A1 (en) * | 2007-11-16 | 2009-05-21 | Julie Broguiere | High Definition Printing With Waterborne Inks on Non-Porous Substrates |
US8025918B2 (en) * | 2007-11-16 | 2011-09-27 | Rhodia, Inc. | High definition printing with waterborne inks on non-porous substrates |
US20090321970A1 (en) * | 2008-06-30 | 2009-12-31 | Changhong Yin | Ophthalmic lens molds parts with siloxane wax |
WO2010002674A1 (en) * | 2008-06-30 | 2010-01-07 | Johnson & Johnson Vision Care, Inc. | Opthalmic lens mold compounded with siloxane wax |
WO2010062520A3 (en) * | 2008-11-03 | 2010-07-08 | Coopervision International Holding Company, Lp | Machined lens molds and methods for making and using same |
WO2010062520A2 (en) * | 2008-11-03 | 2010-06-03 | Coopervision International Holding Company, Lp | Machined lens molds and methods for making and using same |
US20100109176A1 (en) * | 2008-11-03 | 2010-05-06 | Chris Davison | Machined lens molds and methods for making and using same |
CN102202875A (en) * | 2008-11-03 | 2011-09-28 | 库柏维景国际控股公司 | Machined lens molds and methods for making and using same |
CN104029317A (en) * | 2014-05-19 | 2014-09-10 | 滁州迪蒙德模具制造有限公司 | Mold production method |
Also Published As
Publication number | Publication date |
---|---|
AR040997A1 (en) | 2005-04-27 |
KR20050048607A (en) | 2005-05-24 |
AU2010200783A1 (en) | 2010-03-25 |
US20090091047A1 (en) | 2009-04-09 |
AU2010200783B2 (en) | 2011-11-17 |
US20040075039A1 (en) | 2004-04-22 |
DE10393129T5 (en) | 2005-09-01 |
CA2496024A1 (en) | 2004-02-26 |
US20080064784A1 (en) | 2008-03-13 |
JP4708023B2 (en) | 2011-06-22 |
CA2496024C (en) | 2010-05-25 |
AU2003255279A1 (en) | 2004-03-03 |
JP2005535478A (en) | 2005-11-24 |
WO2004016405A1 (en) | 2004-02-26 |
KR20100119802A (en) | 2010-11-10 |
GB2409683A (en) | 2005-07-06 |
GB2409683B (en) | 2006-03-29 |
HK1078051A1 (en) | 2006-03-03 |
GB0505217D0 (en) | 2005-04-20 |
BR0313516A (en) | 2005-06-14 |
KR101021433B1 (en) | 2011-03-15 |
US20090121368A1 (en) | 2009-05-14 |
US7833443B2 (en) | 2010-11-16 |
US20110101550A1 (en) | 2011-05-05 |
US8292256B2 (en) | 2012-10-23 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US8292256B2 (en) | Molds for producing contact lenses | |
JP5671138B2 (en) | Vinyl alcohol ophthalmic lens mold, ophthalmic lens molded therein, and related methods | |
EP2483737B1 (en) | Silicone hydrogel contact lenses and methods of making silicone hydrogel contact lenses | |
AU2002322750B2 (en) | Method for in mold coating hydrogel articles | |
EP2590809B1 (en) | Polar thermoplastic opthalmic lens molds, opthalmic lenses molded therein, and related methods | |
US20070267765A1 (en) | Biomedical device mold | |
AU2007265662A1 (en) | Water soluble ophthalmic lens mold | |
EP2598321B1 (en) | Ophthalmic lens molds, ophthalmic lenses molded therein, and related methods | |
CN100519124C (en) | Molds for producing contact lenses |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: JOHNSON & JOHNSON VISION CARE, INC., FLORIDA Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:YIN, CHANGHONG;ANSELL, SCOTT F.;REEL/FRAME:018722/0323;SIGNING DATES FROM 20061219 TO 20061221 |
|
STCB | Information on status: application discontinuation |
Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION |