EP0418247A1 - Oberfläche mit niedrigem reibungskoeffizient - Google Patents
Oberfläche mit niedrigem reibungskoeffizientInfo
- Publication number
- EP0418247A1 EP0418247A1 EP89903597A EP89903597A EP0418247A1 EP 0418247 A1 EP0418247 A1 EP 0418247A1 EP 89903597 A EP89903597 A EP 89903597A EP 89903597 A EP89903597 A EP 89903597A EP 0418247 A1 EP0418247 A1 EP 0418247A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- poly
- shaped structure
- hydrophilic polymer
- free radical
- vinyl
- 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.)
- Withdrawn
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
- B05D5/08—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L29/00—Materials for catheters, medical tubing, cannulae, or endoscopes or for coating catheters
- A61L29/08—Materials for coatings
- A61L29/085—Macromolecular materials
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/08—Materials for coatings
- A61L31/10—Macromolecular materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/054—Forming anti-misting or drip-proofing coatings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/056—Forming hydrophilic coatings
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D129/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Coating compositions based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Coating compositions based on derivatives of such polymers
- C09D129/10—Homopolymers or copolymers of unsaturated ethers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/10—Homopolymers or copolymers of methacrylic acid esters
- C09D133/12—Homopolymers or copolymers of methyl methacrylate
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D139/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Coating compositions based on derivatives of such polymers
- C09D139/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
Definitions
- This invention relates to shaped structures having low friction surfaces when wet.
- U.S. 4,585,666 discloses a process for coating a polymer surface with a hydrophilic coating having low friction in wet condition.
- the process consists of applying to the polymer surface a solution containing between 0.05 to 40% of a compound which contains at least two ⁇ nreacted isocyanate groups per molecule, evaporating the solvent, applying a solution containing between 0.5 to 50% of polyvinylpyrrolidone to the thus treated polymer surface, evaporating the solvent, and curing the coating at elevated temperature.
- U.S. 4,503,111 discloses a recording material, comprising a hydrophobic substrate material with a polymeric coating.
- a MylarTM film is coated with a 5% solution of 360,000 MW polyvinylpyrrolidone dissolved in a 50:50 (by volume) mixture of ethanol/water. The product was air dried and tested on an ink jet printer.
- U.S. 4,119,094 and U.S. 4,100,309 disclose a substrate coated with a polyvinylpyrrolidone polyurethane interpolymer.
- a polyisocyanate and a polyurethane in a solvent such as methyl ethyl ketone are applied to a substrate and the solvent is evaporated. If the substrate is a polyurethane, only the polyisocyanate need be employed.
- Polyvinylpyrrolidone in a solvent is then applied to the treated substrate and the solvent is evaporated.
- the substrate can be, for example, a tube such as a catheter, a condom or a peristaltic pump tube.
- U.S. 4,055,682 discloses a process whereby a silicone catheter is rendered hydrophilic by contacting it with N-vinyl pyrrolidone (NVP) in bulk or in solution and exposing the catheter and NVP to ionizing radiation at high dose rate. Penetration of the NVP beyond a thin surface layer is prevented by controlling the dosage of ionizing radiation and the concentration of NVP .
- NVP N-vinyl pyrrolidone
- U.S. 3,892,575 discloses a method of modifying the surface properties of substrates such as films of plastics material.
- the substrate is given a very thin coating of a mixture of modifying materials and the latter is then bonded to the substrate by irradiation with ultra-violet light.
- a 1% solution of polyvinylpyrrolidone with added saponin is coated in a thin layer on a sheet of poly(ethylene terephthalate) .
- the wet sheet is heated to about 100°C and irradiated for 1 minute with a germicidal ultraviolet lamp.
- the resulting hydrophilic coating resists moderate abrasion and cannot be removed by adhesive tape.
- U.S. 4,589,873 discloses a method of coating a polymeric substrate, the method comprising contacting a polymeric substrate with a solution of polyvinylpyrrolidone in an applying solvent selected from dimethyl formamide, butanone, methanol, tetrahydrofuran and dimethyl acetamide, and evaporating the solvent from the substrate so that the surface of the substrate retains a coating of the polyvinylpyrrolidone, to provide the surface of the coated substrate with lubricity when it is contacted with an aqueous-based liquid.
- solvent selected from dimethyl formamide, butanone, methanol, tetrahydrofuran and dimethyl acetamide
- the invention resides in a solid shaped structure, such as a tubing, film, containment vessel or fiber, having at least one surface coated with a crosslinked hydrophilic polymer, the coated surface of the shaped structure being durable and having a low coefficient of friction in wet condition for extended periods of time.
- wet is meant that the substrate is in contact with a liquid, such as but not limited to, water; low molecular weight alcohols, such as methanol and ethanol; salt solutions; blood; and body fluids.
- a liquid such as but not limited to, water; low molecular weight alcohols, such as methanol and ethanol; salt solutions; blood; and body fluids.
- the invention also resides in a process which provides a solid surface which is durably coated with a crosslinked hydrophilic polymer, the process comprising contacting the solid surface with a solution containing at least 0.1 t. % of uncrosslinked hydrophilic polymer and a free radical initiator selected from peroxides and ultraviolet (UV) ligh -ac i ated free radical initiators, air drying the coated solid surface, and heating the dried coated surface at the decomposition temperature of the free radical initiator or, when a UV light-activated free radical initiator is used, exposing the coated surface to UV radiation.
- the process can be carried out by contacting the solid surface with a solution containing at least 0.1 wt. % of uncrosslinked hydrophilic polymer, air drying the coated solid surface, and subjecting it to electron beam radiation of 1 to 20 megarads or corona discharge.
- the process of the invention is carried out by. (1) contacting, for at least one second, a surface of a solid shaped structure with a solution containing:
- the coated surface is heated to the decomposition temperature of the free radical initiator, to effect crosslinking of the hydrophilic polymer.
- the length of time that the coated surface is exposed to the elevated temperature is determined by the half-life of the initiator. The exposure time should be of a duration as to consume substantially all of the initiator.
- an ultraviolet light-activated free radical initiator such as benzoin or benzoin methyl ether
- the coated surface is subjected to ultraviolet radiation to effect crosshydrophilic polymer.
- the length of time that the coated surface is exposed to the UV light is determined by the intensity of the light source and the half-life of the initiator.
- the exposure time should be of a duration to consume substantially all of the initiator.
- the process of this invention can be carried out using a combination of thermal and UV-activated initiators .
- the ratio of the number of moles of initiator (thermal or UV-activated) per gram of uncrosslinked hydrophilic polymer used in the process usually is in the range 0.0002 to less than 0.0040, although it has been discovered that with some substrates higher ratios can be tolerated, for example, substrates comprised of EstaneTM or LycraTM, both of which substrates are exemplified herein. Stated more generally, an effective amount of initiator is employed, "effective amount” being that amount which provides the requisite crosslinking of crosslinkable hydrophilic polymer so " as to achieve a durable coating that exhibits a low coefficient of friction when wet.
- the process can be carried out by contacting the solid surface with a solution consisting of uncrosslinked hydrophilic polymer, air drying the coated surface, and subjecting it to electron beam radiation of 1 to 20 megarads or corona discharge for a period of 0.03 to 5 minutes, to effect crosslinking of the polymer.
- the crosslinking of hydrophilic polymer can be effected in air or in an inert atmosphere, such as nitrogen, helium, argon or carbon dioxide.
- the degree of crosslinking is important and is controlled by the operating conditions" chosen. Too much crosslinking reduces or completely eliminates the low friction surface property, and too little crosslinking negatively affects the durability of the coating.
- the crosslinking must be carried out on relatively dry hydrophilic polymer. It has been discovered that hydrophilic polymer crosslinked in the presence of water may produce an adhesive surface, rather • than a surface having a low coefficient of friction.
- crosslinkable hydrophilic polymers examples include, but are not intended to be limited to, poly(N- vinylpyrrolidones) , such as poly(Nviny1-2- pyrrolidone) , a preferred polymer herein, and poly(N-vinyl-3-pyrrolidone) ; substituted pol (N- vinyl-2- and 3-pyrrolidones) in which one or more of the hydrogen atoms of the ring are substituted with one or more substituents selected from -CH 3 , -C 2 H 5 , - OCH 3 and -OC 2 H 5 ; poly(N-vinyl-2-piperidone) ; poly(N- vinyl-3-piperidone) ; poly (N-vinyl-4- ⁇ iperidone) ; substituted poly (N-vinyl-2-, 3- and 4-piperidones) in which one or more of the hydrogen atoms of the ring are substituted with one or more substituents selected from -CH3,
- crosslinkable hydrophilic polymers of this invention may be blended with nonhydrophilic polymers prior to coating the solid substrate, for example in the coating solution.
- the proportions of hydrophilic and nonhydrophilic polymer should be such that a hydrophilic surface is ultimately formed on the solid substrate and would be readily apparent to one skilled in the art. It is preferred that the hydrophilic polymer be the major portion of the blend.
- a useful nonhydrophilic polymer is polyurethane.
- thermally-activated free radical initiators include, but are not intended to be limited to, peroxide initiators, such as benzoyl peroxide, peracetic acid, perbenzoic acid, hydrogen peroxide, t-butylhydroperoxide, bis (4-t-butylydicarbonate, t-butylperoxypivalate, t- butylperoctoate, diisopropylbenzene hydroperoxide, succinic acid peroxide, potassium persulfate and ammonium persulfate.
- peroxide initiators such as benzoyl peroxide, peracetic acid, perbenzoic acid, hydrogen peroxide, t-butylhydroperoxide, bis (4-t-butylydicarbonate, t-butylperoxypivalate, t- butylperoctoate, diisopropylbenzene hydroperoxide, succinic acid peroxide, potassium persulfate and ammonium persul
- any thermally-activated free radical initiator that produces a stabilized free radical such as one containing a -CN or -COOR ester group adjacent to the radical site, does not have sufficient energy to effect crosslinking of the hydrophilic polymer.
- Solvents which are suitable for dissolving the hydrophilic polymer include, but are not intended to be limited to, water, methylene chloride, chloroform, low molecular weight alcohols, such as methanol or ethanol, dimethylformamide (DMF) , dimethylacetamide, ethyl acetate, methylethylketone, ethylene dichloride, acetone,- esters of lactic acid, for example, ethyl lactate, diacetone alcohol, N-methylpyrrolidone, pyridine and the mono- and diethylene glycol ethers .
- concentration of uncrosslinked hydrophilic polymer in the solution is not critical.
- the use of higher concentrations can be used to produce thicker coatings of crosslinked hydrophilic polymer.
- the molecular weight of the uncrosslinked hydrophilic polymer is not critical,- although it is preferred to utilize uncrosslinked hydrophilic polymer having a molecular weight of at least 1,000, more preferably at least 10,000.
- the hydrophilic polymer is in solution, it is not essential that such be the case.
- the uncrosslinked hydrophilic polymer can be applied to the solid surface by any feasible means .
- the uncrosslinked hydrophilic polymer can be in the form of a dispersion, or it can be spray coated onto the surface, etc., all as will be apparent to one skilled in the art.
- the invention herein resides only in those coated substrate structures, and processes for producing such structures, wherein the crosslinked coatings have a low coefficient of friction when wet and are durably adhered to the substrate.
- the adherence of the hydrophilic crosslinked polymer to the surface of the substrate is believed to be by physical forces rather than by chemical bonding, as evidenced by the fact that crosslinked hydrophilic polymer adheres strongly to metal surfaces, such as steel and aluminum, provided the aforesaid initiator to polymer ratio is correctly chosen.
- the durability of the crosslinked hydrophilic polymer on the surface of the coated article is determined by soaking the article in water at 37°C and periodically testing the surface when wet for the coefficient of friction. If the coefficient of friction is unaffected after one hour, the coating is considered durable. The time of one hour has been arbitrarily chosen, since most non-durable coatings of the art, regardless of their type, will fail in less than one hour.
- the low coefficient of friction, when wet, of the coated surface can be determined qualitatively by rubbing one ' s fingers on the wetted sample and comparing it to the feel of an uncoated wet substrate.
- the kinetic coefficient of friction can be determined quantitatively by using a standard test, such as ASTM D1890-61T or ASTM D1894-78.
- Values of the coefficient of friction determined by these tests show quantitative differences in the dry and wet state of coated materials being tested.
- Mixtures of uncrosslinked hydrophilic polymer and other compatible polymers can be employed in carrying out the process of the invention.
- the amount of the compatible polymer which can be admixed with the uncrosslinked hydrophilic polymer can readily be determined experimentally, with the upper limit being just below that which substantially deleteriously affects the benefits achieved by the invention, that is, the production of a durable coated solid surface having a low coefficient of friction when wet .
- the solid substrates whose surfaces can be coated in accordance with this invention can be organic ' or inorganic and include polymers, metals, wood, natural fibers and synthetic fibers. More specifically, these substrates include polymers, such as polyurethanes, for example, EstaneTM, polyesters, for example, MylarTM or RyniteTM, fluoropolymers such as "Tefzel” Modified ETFE fluorocarbon and “Viton” fluoroelastomer, perfluoropolymers such as "Kalrez" perfluoroelastomer and “Teflon” fluorocarbon resin, - polyacetals such as "Delrin” acetal resins, polyamides, polyimides, polyolefins, polyvinyl halides- polycarbonates, cellulosics, cured epoxy resins, natural and synthetic rubbers, and silicones; metals, such as steel, stainless steel, aluminum, iron and copper; natural fibers such as cotton and wool; and synthetic fiber
- Preferred fluoropolymers and perfluoropolymers are homo- or copolymers of tetrafluoroethylene.
- Other preferred fluoropolymers include homo- and copolymers of vinylidene fluoride.
- Non-polar surfaces, such as polyolefins, should be made polar prior to the coating operation by pretreatment, for example, with corona discharge, flame treatment, or chemical etching with permanganate or chromium trioxide.
- the solid substrate is a polymer
- such polymers shall include, but not be limited to, crystalline, semicrystalline, glassy amorphous and elastomeric polymers .
- Polymers may contain additives such as filler, pigments, antioxidants, antiozonants, etc.
- Solid substrates shall also include any surface that is covered with a coating, such as paint. In this case, surface preparation, if needed, would be to the coating surface, not the substrate underneath. It has been discovered that if a surface is difficult to coat and render slippery, the advantageous effects of the invention can be realized by first coating the surface with a material which is known to provide the desirable results of the invention. For example, it has been found that PellethaneTM, a polyurethane which, for some unknown reason, is difficult to render slippery in accordance with this invention, can be coated with EstaneTM and then subjected to the process of the invention.
- the process of this invention provides a solid substrate surface with a durable hydrophilic coating having a low coefficient of friction in wet condition.
- some of the coatings of the invention have been found to exhibit the properties of biocompatability, blood compatability, non- fouling and anti-fogging, with minimal change in profile (width, thickness, etc.) in either the wet or dry condition.
- Such coatings may be suitable for medical applications, for example, catheters; scopes, such as endo and laryngo; tubes, such as feeding, draining and endotracheal; wound dressings; . contact lenses; eye shields having improved cleanability; implants; condoms; extracorporeal blood conduits; hemodialysis membranes; blood filters; and circulatory assist devices.
- Other applications may include food packaging; boat hulls; razor blades; fishing nets; conduits for wiring; low friction coatings on torpedoes; internally coated pipes and tubes for moving large volumes of fluids; membranes for separations; glassware; sporting/recreational equipment; cosmetic additives (spreading agent); mold release agents; fishing lines and regenerable cookware coatings.
- PVP refers to poly(N-viny1-2- pyrrolidone) , a preferred hydrophilic polymer, as noted above.
- a polyurethane film [TexinTM 480 AR] was placed into a Petri dish and contacted with a solution containing 0.5 g of benzoyl peroxide, 48 g of methylene chloride and 1.5 g of PVP [MW 360,000] for 10 minutes.
- the film was air dried for 10 minutes at 25°C, placed in a one quart jar and purged with nitrogen for three h. The jar was sealed and heated at 90°C for one h.
- a polyurethane film [TexinTM 480 AR] was dipped into a 3% solution of PVP [M 360,000] in methylene chloride for 30 minutes. The film was drained and air dried for several h. It was then placed in a Petri dish contained in a glove bag under an atmosphere of argon. The film was then treated with 10 megarads of electron beam radiation.
- the film exhibited low friction in water at 37°C.
- the low friction in water at 37°C persisted undiminished for at least six days.
- the coatings remained slippery after four days in water at 23°C.
- the steel panel rusted extensively in the uncoated areas, but not under the crosslinked PVP.
- the aluminum foil was dried and the coating thickness was found to be about 0.1 mil (0.00254 mm) .
- the MylarTM film was rinsed, dried, placed in a polyethylene bag, and cooled to 0°C. The film was quickly removed from the bag and breathed upon. The coated area remained clear whereas the uncoated area became fogged.
- estaneTM commercially available polyurethane was hot pressed onto a steel panel measuring 4" x 12" (10.2 x 30.5 cm) .
- the polyurethane surface was coated by dipping for 20 seconds in a solution consisting of 1 g of benzoyl peroxide, 3 g of PVP [MW 360,000] and 96 g of methylene chloride. After drying under nitrogen overnight, the panel was heated one hour in air at 110°C, then washed in water at 37°C for one hour.
- the coated surface was rubbed with soft paper towed to remove any debris and tested for coefficient of friction [ASTM D1894-78] against polyurethane as the second surface.
- the coating solution consisted of 3 g of PVP (MW 360,000), 2 g of t-butylperoctoate, and 95 g of methylene chloride.
- PVP MW 360,000
- t-butylperoctoate a coating solution
- 95 g of methylene chloride a stainless steel sheet
- MylarTM 500D polyester film were coated with the solution using a 10 mil (0.254 mm) doctor knife.
- LycraTM films were coated with the following PVP [MW 360,000] solutions using a 10 mil (0.254 mm) doctor knife: 1) 3 g of PVP, 1 g of benzoyl peroxide, 96 g of methylene chloride
- the coated LycraTM was cured at 110°C for one hour. All three films were slippery in water for at least one day.
- a balloon made of the same LycraTM was similarly treated with Solution 1 and another with Solution 1 diluted with an equal volume of methylene chloride. Both balloons were very slippery in water.
- Too much crosslinking gives a non-slippery surface.
- EXAMPLE 9 Catheter tubes made of polyurethane filled with 30 wt. % BaS0 4 , 1 wt. % titanium dioxide and 0.5 wt . % green pigment were coated by dipping for 20 seconds into a solution consisting of 1 g of benzoyl peroxide, 3 g of PVP [MW 360,000] and 96 g of methylene chloride. After drying under nitrogen overnight, the tubes were heated one hour in air at 110°C, then washed in water at 37°C for one hour. The coated tubes were tested for coefficient of friction using the ASTM D1890-61T procedure against plasticized polyvinyl chloride as the second surface. The results are shown below. Kinetic Coefficient of Friction
- the coating solutions consisted of 3 g of poly-acrylic acid [solution 1: MW 90,000; solution 2: MW 250,000], 0.5 g of succinic acid peroxide, and 96.5 g of water.
- MylarTM, EstaneTM and aluminum foil were coated with the above solutions. The excess solvent was allowed to drain off. After air drying, the ilms were cured by heating at 100°C for one hour in air. The surface of the coated materials when in contact with water exhibited a low coefficient of friction for at least seven days at room temperature.
- a repeat of the above experiment using 1, 2, and 3 wt. % of succinic acid peroxide in the coating solution gave similar results.
- the coating solution consisted of 3 g of methyl cellulose, 0.5 g of succinic acid peroxide, - and 96 g of water. EstaneTM and aluminum foil were coated with the above solution. The excess solvent was allowed to drain off. After air drying, the films were cured by heating at 100°C for one hour in air. The surface of the coated materials when in contact with water exhibited a low coefficient of friction for at least two hours. A repeat of the above experiment using 1 g, 2 g, and 3 g of succinic acid peroxide in the coating solution gave similar results.
- the coating solution consisted of 3 g of poly-(methylvinyl ether), 0.5 g of benzoyl peroxide, and 96.5 g of toluene.
- EstaneTM and aluminum foil were coated with the above solution. The excess solvent was allowed to drain off. After air drying, the films were cured by heating at 100°C for one hour in air. The surface of the coated materials when in contact with water exhibited a low- coefficient of friction.
- a repeat of the above experiment using 1, 2, and 3 wt. % of benzoyl peroxide in the coating solution gave similar results.
- a panel of smooth, gel coated, polyester/glass boat hull was coated with a solution consisting of 3 wt. % of PVP [MW 360,000] and 2 wt. % of benzoyl peroxide in methylene chloride by dipping the panel for 30 seconds.
- the excess solution was drained off by placing the panel vertically in a large beaker saturated with methylene chloride vapors. The vapors were allowed to escape slowly until the coating was dry; it was then cured at 100°C for 20 minutes.
- the high points on the finish were removed by light sanding with extremely fine sandface of the coated panel when in contact with water exhibited a low coefficient of friction.
- a MylarTM film coated with crosslinked PVP was tested for coefficient of friction using methanol and ethanol as the wetting agents.
- the film when in contact with ethanol or methanol exhibited a low coefficient of friction.
- EXAMPLE 17 Using the same procedure as Example 15 pieces of Hytrel 4056 polyester elastomer (available from E. I. du Pont de Nemours) were dipped in the PVP solution for 5 sec. After air drying overnight they were heated at 110 deg. for 70 min. After 2 hr. in an agitated water bath at 38 deg., they were very slippery. EXAMPLE 18
- PVP 50% aqueous solution
- the PVP was admixed with a polyurethane to facilitate swelling of the coating, so as to provide intimate contact between the coating and the water in which it is subsequently soaked.
- the final solution had increased viscosity but no phase separation.
- a film was prepared by casting the solution at 145°C. There was no phase separation. The film had a 99.6% weight gain after soaking 7 hours in water at 25°C, and a 118% weight gain after 72 hours.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Epidemiology (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Heart & Thoracic Surgery (AREA)
- Surgery (AREA)
- Vascular Medicine (AREA)
- Laminated Bodies (AREA)
- Treatments Of Macromolecular Shaped Articles (AREA)
- Paints Or Removers (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US17218388A | 1988-03-23 | 1988-03-23 | |
US172183 | 1988-03-23 |
Publications (1)
Publication Number | Publication Date |
---|---|
EP0418247A1 true EP0418247A1 (de) | 1991-03-27 |
Family
ID=22626685
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP89903597A Withdrawn EP0418247A1 (de) | 1988-03-23 | 1989-02-27 | Oberfläche mit niedrigem reibungskoeffizient |
Country Status (7)
Country | Link |
---|---|
EP (1) | EP0418247A1 (de) |
JP (1) | JPH03503379A (de) |
KR (1) | KR900700550A (de) |
AU (1) | AU629203B2 (de) |
DK (1) | DK228690A (de) |
IL (1) | IL89694A (de) |
WO (1) | WO1989009246A1 (de) |
Families Citing this family (57)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DK146790D0 (da) * | 1990-06-15 | 1990-06-15 | Meadox Surgimed As | Fremgangsmaade til fremstilling af en ved befrugtning friktionsnedsaettende belaegning samt medicinsk instrument med en friktionsnedsaettende belaegning |
EP0612253A4 (de) * | 1991-11-12 | 1995-08-09 | Nepera Inc | Anklebenok hydrogele mit verlängerter lebensdauer und verfahren zu ihrer herstellung. |
US5576072A (en) * | 1995-02-01 | 1996-11-19 | Schneider (Usa), Inc. | Process for producing slippery, tenaciously adhering hydrogel coatings containing a polyurethane-urea polymer hydrogel commingled with at least one other, dissimilar polymer hydrogel |
US5919570A (en) * | 1995-02-01 | 1999-07-06 | Schneider Inc. | Slippery, tenaciously adhering hydrogel coatings containing a polyurethane-urea polymer hydrogel commingled with a poly(N-vinylpyrrolidone) polymer hydrogel, coated polymer and metal substrate materials, and coated medical devices |
WO1996023834A1 (en) * | 1995-02-01 | 1996-08-08 | Schneider (Usa) Inc. | Process for hydrophilicization of hydrophobic polymers |
US6017577A (en) * | 1995-02-01 | 2000-01-25 | Schneider (Usa) Inc. | Slippery, tenaciously adhering hydrophilic polyurethane hydrogel coatings, coated polymer substrate materials, and coated medical devices |
US5662960A (en) * | 1995-02-01 | 1997-09-02 | Schneider (Usa) Inc. | Process for producing slippery, tenaciously adhering hydrogel coatings containing a polyurethane-urea polymer hydrogel commingled with a poly (n-vinylpyrrolidone) polymer hydrogel |
US5731087A (en) * | 1995-06-07 | 1998-03-24 | Union Carbide Chemicals & Plastics Technology Corporation | Lubricious coatings containing polymers with vinyl and carboxylic acid moieties |
US5620738A (en) * | 1995-06-07 | 1997-04-15 | Union Carbide Chemicals & Plastics Technology Corporation | Non-reactive lubicious coating process |
US6083230A (en) | 1997-07-30 | 2000-07-04 | Allergan | Method for making IOL insertion apparatus |
FR2758990B1 (fr) * | 1996-09-19 | 1999-05-28 | Hospal Ind | Appareil pour le traitement du sang par circulation extracorporelle et procede de fabrication |
ATE295748T1 (de) * | 1996-11-01 | 2005-06-15 | Medtronic Minimed Inc | Pumpe zur medikamentösen infusion mit einer durch ein protein stabilisierten beschichtung |
EP0879607A3 (de) * | 1997-05-23 | 1999-05-19 | Hüls Aktiengesellschaft | Verfahren zur Veminderung des Reibungswiderstandes hydrophiler Oberflächen |
WO1998058989A1 (en) | 1997-06-20 | 1998-12-30 | Coloplast A/S | A hydrophilic coating and a method for the preparation thereof |
ATE227754T1 (de) * | 1997-06-20 | 2002-11-15 | Coloplast As | Hydrophile beschichtung und verfahren zu ihrer herstellung |
WO1998058990A1 (en) * | 1997-06-20 | 1998-12-30 | Coloplast A/S | A hydrophilic coating and a method for the preparation thereof |
US6500481B1 (en) | 1998-06-11 | 2002-12-31 | Johnson & Johnson Vision Care, Inc. | Biomedical devices with amid-containing coatings |
US6087415A (en) | 1998-06-11 | 2000-07-11 | Johnson & Johnson Vision Care, Inc. | Biomedical devices with hydrophilic coatings |
US6329488B1 (en) | 1998-11-10 | 2001-12-11 | C. R. Bard, Inc. | Silane copolymer coatings |
CN1291762C (zh) | 1998-11-20 | 2006-12-27 | 科洛普拉斯特公司 | 对具有亲水涂层的医疗器械进行消毒的方法 |
US6986868B2 (en) | 1998-11-20 | 2006-01-17 | Coloplast A/S | Method for sterilizing a medical device having a hydrophilic coating |
US6478423B1 (en) | 1999-10-12 | 2002-11-12 | Johnson & Johnson Vison Care, Inc. | Contact lens coating selection and manufacturing process |
DE10053554B4 (de) * | 2000-10-28 | 2007-07-05 | Fresenius Medical Care Deutschland Gmbh | Beschichtungsverfahren zur Erhöhung der Wärmestandfestigkeit und Hydrophilierung der Oberflächen von Substraten und damit erhaltene Werkstücke |
JP2002146273A (ja) * | 2000-11-10 | 2002-05-22 | Nippon Shokubai Co Ltd | コーティング用樹脂組成物 |
JP2006510756A (ja) | 2002-12-20 | 2006-03-30 | コロプラスト アクティーゼルスカブ | 親水性コーティング及びそれらを調製するための方法 |
EP1833889A2 (de) * | 2004-12-30 | 2007-09-19 | Coloplast A/S | Vorrichtung mit hydrophiler beschichtung, die p-toluolsulfonamid enthält, sowie verfahren zur ihrer herstellung |
ATE456381T1 (de) * | 2005-05-02 | 2010-02-15 | Coloplast As | Verfahren zur sterilisierung einer medizinischen vorrichtung mit hydrophiler beschichtung |
US8814861B2 (en) | 2005-05-12 | 2014-08-26 | Innovatech, Llc | Electrosurgical electrode and method of manufacturing same |
DE102005048675A1 (de) * | 2005-10-11 | 2007-04-12 | Invendo Medical Gmbh | Medizintechnische Vorrichtung mit selbstschmierendem Element |
DE102005054106A1 (de) * | 2005-11-12 | 2007-05-16 | Fresenius Medical Care De Gmbh | Verfahren zum Beschichten von Oberflächen mit Hydrogelen und mit Hydrogelbeschichtungen versehene Polymersubstrate |
EP1968792B1 (de) | 2005-12-30 | 2013-12-11 | 3M Innovative Properties Company | Funktionalisierte substrate |
AU2007209856B2 (en) | 2006-02-01 | 2013-06-13 | Hollister Incorporated | Methods of applying a hydrophilic coating to a substrate, and substrates having a hydrophilic coating |
WO2008002657A2 (en) | 2006-06-28 | 2008-01-03 | Surmodics, Inc. | Microparticles containing active agent dispersed in a polymer matrix as implant or as coating for medical devices |
RU2009106445A (ru) * | 2006-07-25 | 2010-08-27 | Колопласт А/С (Dk) | Фотоотверждающиеся термопластичные покрытия |
EP2679254A1 (de) * | 2006-07-25 | 2014-01-01 | Coloplast A/S | Lichthärtung thermoplastischer Beschichtungen |
EP2104523B1 (de) * | 2006-12-15 | 2015-08-26 | Coloplast A/S | Beschichtungen aus poly(ethylenoxid) und einen lichtinitiator enthaltende gerüste |
DE102007000214A1 (de) * | 2007-04-10 | 2008-10-16 | Invendo Medical Gmbh | Verfahren zur Reibungsverringerung eines medizintechnischen Kautschukschlauchs |
EP2310059B1 (de) * | 2008-05-29 | 2016-11-16 | Numat Biomedical S.L. | Mit pufa beschichtete implantate |
EP2294118B1 (de) | 2008-05-30 | 2012-07-04 | 3M Innovative Properties Company | Verfahren zur herstellung von ligandenfunktionalisierten substraten |
DK2198897T3 (en) * | 2008-12-19 | 2016-11-14 | Dentsply Ih Ab | PROCESS FOR THE PREPARATION OF A medical device having a crosslinked hydrophilic coating |
BRPI1011747A2 (pt) | 2009-06-23 | 2018-02-27 | 3M Innovative Properties Co | artigo não tecido funcionalizado. |
KR101133078B1 (ko) * | 2009-09-16 | 2012-04-04 | 부산대학교 산학협력단 | 마찰저항 저감 코팅 조성물 |
US8377672B2 (en) | 2010-02-18 | 2013-02-19 | 3M Innovative Properties Company | Ligand functionalized polymers |
CN102844662B (zh) | 2010-03-03 | 2015-04-29 | 3M创新有限公司 | 配体胍基官能化聚合物 |
JP4896245B2 (ja) * | 2010-03-31 | 2012-03-14 | 朝日インテック株式会社 | ガイドワイヤ |
JP6188114B2 (ja) * | 2010-06-23 | 2017-08-30 | 国立研究開発法人 海上・港湾・航空技術研究所 | 摩擦抵抗低減塗料、摩擦抵抗低減塗膜および船舶 |
PL2461767T3 (pl) | 2010-07-30 | 2013-09-30 | Novartis Ag | Soczewki silikonowo-hydrożelowe z powierzchniami bogatymi w wodę |
US8541498B2 (en) | 2010-09-08 | 2013-09-24 | Biointeractions Ltd. | Lubricious coatings for medical devices |
JP5690631B2 (ja) * | 2011-03-30 | 2015-03-25 | 日本コヴィディエン株式会社 | 潤滑性を有する医療用具およびその製造方法 |
EP2890414B1 (de) | 2012-08-29 | 2019-01-16 | Cardiac Pacemakers, Inc. | Verbesserte reibungsarme beschichtung für medizinische ableitungen und herstellungsverfahren dafür |
AU2013347996B2 (en) | 2012-11-21 | 2016-08-11 | Cardiac Pacemakers, Inc. | Medical electrodes with layered coatings |
WO2014095690A1 (en) | 2012-12-17 | 2014-06-26 | Novartis Ag | Method for making improved uv-absorbing ophthalmic lenses |
CN105829081B (zh) | 2013-12-17 | 2017-12-19 | 诺华股份有限公司 | 具有交联的亲水性涂层的硅水凝胶镜片 |
US9968965B2 (en) | 2014-04-25 | 2018-05-15 | Toyo Seikan Group Holdings, Ltd. | Structure having liquid film on the surface thereof |
US11002884B2 (en) | 2014-08-26 | 2021-05-11 | Alcon Inc. | Method for applying stable coating on silicone hydrogel contact lenses |
CN108369291B (zh) | 2015-12-15 | 2021-07-20 | 爱尔康公司 | 用于将稳定的涂层施加在硅酮水凝胶接触镜片上的方法 |
KR20200098540A (ko) | 2017-12-13 | 2020-08-20 | 알콘 인코포레이티드 | 한 주 및 한 달 착용용 워터 그래디언트 콘택트 렌즈 |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1420064A (en) * | 1971-12-13 | 1976-01-07 | Minnesota Mining & Mfg | Coating of plastics materials |
JPS51101077A (de) * | 1975-03-04 | 1976-09-07 | Konishiroku Photo Ind | |
SE430696B (sv) * | 1982-04-22 | 1983-12-05 | Astra Meditec Ab | Forfarande for framstellning av en hydrofil beleggning samt en enligt forfarandet framstelld medicinsk artikel |
US4589873A (en) * | 1984-05-29 | 1986-05-20 | Becton, Dickinson And Company | Method of applying a hydrophilic coating to a polymeric substrate and articles prepared thereby |
DE3814135A1 (de) * | 1987-05-06 | 1988-11-24 | Wilkinson Sword Gmbh | Verfahren zur herstellung einer hydrophilen beschichtung auf einem formteil und unter anwendung des verfahrens hergestellter rasierapparat |
-
1989
- 1989-02-27 KR KR1019890702169A patent/KR900700550A/ko not_active Application Discontinuation
- 1989-02-27 WO PCT/US1989/000720 patent/WO1989009246A1/en not_active Application Discontinuation
- 1989-02-27 AU AU32198/89A patent/AU629203B2/en not_active Ceased
- 1989-02-27 JP JP1503309A patent/JPH03503379A/ja active Pending
- 1989-02-27 EP EP89903597A patent/EP0418247A1/de not_active Withdrawn
- 1989-03-21 IL IL89694A patent/IL89694A/xx unknown
-
1990
- 1990-09-21 DK DK228690A patent/DK228690A/da not_active Application Discontinuation
Non-Patent Citations (1)
Title |
---|
See references of WO8909246A1 * |
Also Published As
Publication number | Publication date |
---|---|
WO1989009246A1 (en) | 1989-10-05 |
IL89694A0 (en) | 1989-09-28 |
AU3219889A (en) | 1989-10-16 |
DK228690D0 (da) | 1990-09-21 |
AU629203B2 (en) | 1992-10-01 |
KR900700550A (ko) | 1990-08-16 |
IL89694A (en) | 1992-12-01 |
DK228690A (da) | 1990-09-21 |
JPH03503379A (ja) | 1991-08-01 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0418247A1 (de) | Oberfläche mit niedrigem reibungskoeffizient | |
EP0887369B1 (de) | Verfahren zur Hydrophilierung der Oberfläche polymerer Substrate mit einem Makroinitiator als Primer | |
US4589873A (en) | Method of applying a hydrophilic coating to a polymeric substrate and articles prepared thereby | |
JP3115590B2 (ja) | 湿潤摩耗に耐性な潤滑親水性被膜 | |
US5100689A (en) | Surface modified surgical instruments, devices, implants, contact lenses and the like | |
US5094876A (en) | Surface modified surgical instruments, devices, implants, contact lenses and the like | |
US4961954A (en) | Surface modified surgical instruments, devices, implants, contact lenses and the like | |
US5429839A (en) | Method for grafting preformed hydrophillic polymers onto hydrophobic polymer substrates | |
EP0106004B1 (de) | Verfahren zur Bildung einer hydrophilen Beschichtung auf einem Substrat | |
CA1324920C (en) | Process for coating polymer surfaces and coated products produced using such process | |
US20020133072A1 (en) | Graft polymerization of substrate surfaces | |
US8029562B2 (en) | Wettable ePTFE medical devices | |
US20010007694A1 (en) | Process for the preparation of antimicrobial plastics | |
CN1171412A (zh) | 在聚合物基体表面上进行亲水涂层 | |
WO1998058990A1 (en) | A hydrophilic coating and a method for the preparation thereof | |
IE862473L (en) | Hydrophilic coated polymer articles | |
DE10053555C2 (de) | Verfahren zur Erhöhung der Heißdampfstabilität polymerer Substrate | |
JPH03250034A (ja) | プラスチック表面への含フッ素高分子皮膜の形成方法 | |
DE19700079A1 (de) | Verfahren zur Herstellung hydrophilen Beschichtungen auf polymeren Substraten | |
CN115607748A (zh) | 一种血液相容性的类液体超滑表面及其制备方法 | |
JPH06287335A (ja) | ヒドロゲルおよびその製造方法 | |
JPH06116433A (ja) | 表面改質された高分子材料 | |
JPH08319329A (ja) | ヒドロゲルの製造方法 | |
Siao et al. | Surface Modified of Silicone rubber by Atmospheric pressure plasma jets and UV Induced-Graft Polymerization of Anti-Bacterial Hydrogels | |
SWANSON et al. | Polymer Surface Modification: Relevance to Adhesion, pp. 319-325 KL Mittal (Ed.)© VSP 1995. |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 19900917 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE CH DE FR GB IT LI LU NL SE |
|
17Q | First examination report despatched |
Effective date: 19920422 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN |
|
18D | Application deemed to be withdrawn |
Effective date: 19940614 |