AU629203B2 - Low coefficient of friction surface - Google Patents

Low coefficient of friction surface

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Publication number
AU629203B2
AU629203B2 AU32198/89A AU3219889A AU629203B2 AU 629203 B2 AU629203 B2 AU 629203B2 AU 32198/89 A AU32198/89 A AU 32198/89A AU 3219889 A AU3219889 A AU 3219889A AU 629203 B2 AU629203 B2 AU 629203B2
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Australia
Prior art keywords
process
poly
shaped structure
hydrophilic polymer
vinyl
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AU32198/89A
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AU3219889A (en
Inventor
Edward George Howard Jr.
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E I du Pont de Nemours and Co
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E I du Pont de Nemours and Co
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Priority to US17218388A priority Critical
Priority to US172183 priority
Application filed by E I du Pont de Nemours and Co filed Critical E I du Pont de Nemours and Co
Publication of AU3219889A publication Critical patent/AU3219889A/en
Application granted granted Critical
Publication of AU629203B2 publication Critical patent/AU629203B2/en
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Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING LIQUIDS OR OTHER FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05DPROCESSES FOR APPLYING LIQUIDS OR OTHER FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B05D5/08Processes 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
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L29/00Materials for catheters, medical tubing, cannulae, or endoscopes or for coating catheters
    • A61L29/08Materials for coatings
    • A61L29/085Macromolecular materials
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L31/00Materials 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
    • A61L31/08Materials for coatings
    • A61L31/10Macromolecular materials
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G
    • C08J7/00Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04Coating
    • C08J7/047Coating with only one layer of a composition containing a polymer binder
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; MISCELLANEOUS COMPOSITIONS; MISCELLANEOUS APPLICATIONS OF MATERIALS
    • C09DCOATING 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
    • C09D129/00Coating 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
    • C09D129/10Homopolymers or copolymers of unsaturated ethers
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; MISCELLANEOUS COMPOSITIONS; MISCELLANEOUS APPLICATIONS OF MATERIALS
    • C09DCOATING 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
    • C09D133/00Coating 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
    • C09D133/02Homopolymers or copolymers of acids; Metal or ammonium salts thereof
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; MISCELLANEOUS COMPOSITIONS; MISCELLANEOUS APPLICATIONS OF MATERIALS
    • C09DCOATING 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
    • C09D139/00Coating 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
    • C09D139/04Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member

Description

Lg_ OPI DATE 16/10/89 wl AOJP DATE 09/11/89 APPLN. ID 32198 89 PCr PCT NUMBER PCT/US89/00720 INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT.COOPERATION TREATY (PCT) (51) International Patent Classification 4: (11) International Publication Number: WO 89/ 09246 CO9D 3/00,5/00, CO8J 7/04 Al 3/00, C08L 39/06 (43) International Publication Date: 5 October 1989 (05.10.89) (21) International Application Number: PCT/US89/00720 (72) Inventor; and Inventor/Applicant (for US only) HOWARD, Edward, (22) Ir:rnational Filing Date: 27 February 1989 (27.02.89) George, Jr. [US/US]; RD 2, Box 100, Hockessin, DE 19707 (US).

(31) Priority Application Number: 172,183 (74) Agent: CONNER, Michael; E.I. du Pont de Nemours and Company, 1007 Market Street, Wilmington, DE (32) Priority Date: 23 March 1988 (23.03.88) 19898 (US).

(33) Priority Country: US (81) Designated States: AT (European patent), AU, BE (Eu.

ropean patent), CH (European patent), DE (Euro- Parent Application or Grant pean patent), DK, FR (European patent), GB (Euro- (63) Related by Continuation pean patent), IT (European patent), JP, KR, LU (Eu- US 172,183 (CIP) ropean patent), NL (European patent), NO, SE (Eu- Filed on 23 March 1988 (23,03.88) ropean patent), US.

(71) Applicant (for all designated States except US): E.I. DU Published PONT DE NEMOURS AND COMPANY [US/US]; With international search report.

1007 Market Street, Wilmington, DE 19898 6 629 203 (54) Title: LOW COEFFICIENT OF FRICTION SURFACE (57) Abstract Solid shaped structure having a surface coated with crosslinked hydrophilic polymer, and process for preparing such structure, the coating being durable and exhibiting a low coefficient of friction when wet.

WO 89/09246 PCT/US89/00720 1' Low Coefficient Of Friction Surface BACKGROUND OF THE INVENTION Field of the Invention This invention relates to shaped structures having low friction surfaces when wet.

Background 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 unreacted isocyanate groups per molecule, evaporating the solvent, applying a solution containing between 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 coanting. In a typical example a Mylar T film is coated with a 5% solution of 360,000 MW polyvinylpyrrilidone 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. In the method, a polyisocyanate and a polyurethane in a solvent such WO 89/09246 PCT/US89/00720 2 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.

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.

In a typical example 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 10000C 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 cf coating a polymeric substrate, the method comprising contacting a polymeric substrate with a solution of polyvinylpyrrolidone in an applying solvent 3 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.

None of the above references either teaches or suggests the use of crosslinked hydrophilic polymers for the preparation of a solid shaped structure with a durable surface having a low coefficient of friction in wet condition.

SUMMARY OF THE INVENTION The invention resides in a solid shaped structure, such as a tubing, film, containment vessel or 15 fiber, having at least one surface coated with a crosslinked hydrophilic polymer, the coated surface of the shaped structure being durable and having a coefficient of friction when wet that is lower than the coefficient of Sfriction of the uncoated shaped structure when wet.

By "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.

The invention also resides in a process which 25 provides a solid surface which is durably coated with a crosslinked hydrophilic polymer, the process comprising contacting the solid surface with a WO 89/09246 PCT/US89/00720 4 solution containing at least 0.1 wt. of uncrosslinked hydrophilic polymer and a free radical initiator selected from peroxides and ultraviolet (UV) light-activated 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.

Alternatively, 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.

DETAILED DESCRIPTION OF THE INVENTION In amplification of the above summary, the process of the invention is carried out by: contacting, for at least one second, a surface of a solid shaped structure with a solution containing: at least 0.1 wt. of a crosslinkable hydrophilic polymer; and optionally containing a thermally-activated free radical initiator; or (ii) an ultraviolet light-activated free radical initiator; drying, for example, air drying, the coated surface; and crosslinking the hydrophilic polymer of the dried coated surface, as further described below.

L- I i li-; WO 89/09246 PCT/US89/00720 If a thermally-activated free radical initiator is used in the coating solution, 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.

If an ultraviolet light-activated free radical initiator, such as benzoin or benzoin methyl ether, is used in the coating solution, 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 LycraT, both of which substrates are exemplifi'i herein, Stated more generally, an effective amount of initiator is employed, "effective amount" being that amount which provides the requisite crosslinking of crosslinkable WO 89/09246 PCT/US89/00720 6 hydrophilic polymer so as to achieve a durable coating that exhibits a low coefficient of friction when wet.

Alternatively, 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 fo:c 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. In addition, it is to be noted that 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.

Examples of crosslinkable hydrophilic polymers that can be used herein include, but are not intended to be limited to, poly(Nvinylpyrrolidones), such as poly(Nvinyl-2pyrrolidone), a preferred polymer herein, and poly(N-vinyl-3-pyrrolidone); substituted poly(Nvinyl-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 -C2H 5

OCH

3 and -OC 2

H

5 poly (N-vinyl-2-piperidone); poly(N- WO 89/09246 PCT/US89/00720 7 vinyl-3-piperidone); poly (N-vinyl-4-piperidone); 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 -CH 3

-C

2

H

5

-QCH

3 and -OC 2

H

5 poly(methylvinyl ether/; polyacrylic acid; polymethacrylic acid; polyethylene oxide; partially esterified polymethacrylic acid; polymethacryl amide; partially esterified polyacrylic acid; polyacrylamide; methyl cellulose; poly(2 hydroxyethyl methacrylate); and mixtures of the above.

The 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 polyter be the major portion cf the blend, A useful nonhydrophilic polymer is polyurethane.

Examples of thermally-activated free radical.

initiators that can be used herein include, btit are not intended to be limited to, peroxide initiators, such as benzoyl peroxide, peracetic acid, perbenzoic acid, hydrogen peroxide, t-butyfhydroperoxide, bis(4-t-butylydic4bonate, t-butylperoxypivalate, tbutylperoctoate, diisoapopylbenzene hydroperoxide, succinic acid peroxide, potassium pesulfate and amionium persulfate, Although not wishing to be bouad by this explanation, it is believed that any thermnally-activated free radical initiator that 1, WO 89/09246 PCT/US89/00720 8 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.

The concentration of uncrosslinked hydrophilic polymer in the solution is not critical.

It will readily be understood that the use of higher concentrations can be used to produce thicker coatings of crosslinked hydrophilic polymer.

Likewise, 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.

Although the above description recites that the hydrophilic polymer is in solution, it ;s not essential that such be the case. More specifically, the uncrosslinked hydrophilic polymer can be applied to the solid surface by any feasible means. For example, 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.

It is to be understood that the invention i i~i_ 1 WO 89/09246 PCT/US89/00720 9 herein y ides 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, Although not wishing to be bound by this explanation, 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 1 0 fact that crosslinked hydrophilic polymer adheres strongly to metal surfaces, such as steel and aluminum, provided the aforesaid initiatoe 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 370C 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 wett 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 DI890-6iT or ASTM DI894-78., 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 WO 89/09246 PCT/US89/00720 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 substraces 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, siah as polyurethanes, for example, EstaneTM, polyesters, for example, MylarT™ 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 fibers, such as Dacron

T

M polyester 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 WO 89/09246 PCT/US89/00720 11 pretreatment, for example, with corona discharge, flame trea ;.ent, or chemical etching with permanganate or chromium trioxide.

If the solid substrate is a polymer, such polymers shall include, but not be limited to, crystalline, semicrystalline, glassy amorphous and elastomeric polymers. Polym6rs may contain additives such as filler, pigments, antioxidants, antiozonants, etc.

Solid substrates shall also include any surface that is covered with a coating, such es 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 bee;1 found that Pellethane

T

M, 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 frictionl in wet condition. In addition, some of the coatings of the invention have been found to exhibit the properties of biocompatability, blood compatability, nonfouling and anti-fogging, with minimal change in profile (width, thickness, etc,) in either the wet or dry condition. Such coatings may be suitable for WO 89/09246 PCT/US89/00720 12 medical applications, for example, catheters; scopes, such as endo and laryngo; tubes, such as feeding, draining and endotracheal; wound1 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.

The invention is illustrated in the fQllowing examples. In the examples and comparative experiments, PVP refers to poly(N-vinyl-2pyrrolidone), a preferred hydrophilic polymer, as noted above.

EXAMPLE 1 A polyurethane film [TexinT m 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 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.

The film exhibited low friction. in water at 37°C. The low friction in water at 37C persisted undiminished for at least three days, WO 89/09246 PCT/US89/00720 13 EXAMPL~e 2 A polyurethane film [Texin

T

m 480 AR] was dipped into a 3% solution of PVP [MW 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 flm exhibited low friction in water at 37°C. The low friction in water at 37°C persisted undiminished for at least six days.

EXAMPLE _a Crosslinked PVP Films on Metals and Plastics The coating solution consisted of 3 g of PVP (MW 360,000], 1 g of benzoyl peroxide, and 96 g of methylene chloride. The materials being tested were dipped one-half of their length into the solution and removed. The excess solvent was allowed to drain off. After air drying, the films were cured by heating at 110 0 °C for one hour in air. The materials coated were: 1. Steel panel [type used for paint testing] 2. MylarTM [polyethylene terephthalate film] 3. Aluminum foil [l mil (0.0254 mm) thick] All exhibited a low coefficient of friction in water. 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. After four days, the aluminum foil was drjd and the coating thickness was found to be about 0.1 mil (0.00254 mm). The Mylar'r film was rinsed, dried, placed in a polyethylene bag, and cooled to 0°C. The film was quickly removed from the 6 WO 89/09246 PCT/US89/00720 14 bag and breathed upon. The coated area remained clear whereas the uncoated area became fogged.

This example shows that the invention is useful with metals and plastics, where there is no polymer penetration of the solid surface.

Therefore, there need be no concern with polymer supports about grafting of the two polymers.

1 0 Dependence on the Molecular Weight of the Uncrosslinked Polymer There seems to be no dependence on molecular weight as illustrated by the following experiments.

Solutions consisting of 3 g of PVP, 96 g of 1 5 methylene chloride, and 1 g of benzoyl peroxide were coated onto I mil (0.0254 mm) aluminum foil. After drying and curing' at 110C for one hour, they were soaked in water at 23 0

C.

1. PVP molecular weight 10,000 2. PVP molecular weight 24,000 3. PVP molecular weg-7ht 40,000 4. PVP molecular wei 160,000 All films were slippery in water, that is, exhibited a low coefficient of friction.

Coefficient of riction Data A film of 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 RO seconds in a solution consisting of I g of benzoyl peroxide, 3 g of PVP (MW 360,000] and 96 g of methylene chloride. After drying under nitrogen WO 89/09246 PCT/US89/00720 overnight, the panel was heated one hour in air at 110 0 C, then washed in water at 37 0 C for one hour.

The coated surface was rubbed with soft paper towed to remove any debris and tested for coefficient of friction [ASTM D1894-781 against polyurethane as the second surface.

The experiment was repeated, using polytetrafluoroethylene and polyvinyl chloride instead of the steel.

Kinetic Coefficient of Friction of Untreated EstaneT' Dry Wet 2.35 0.59 Kinetic Coefficient of Friction of Crosslinked PVP- Coated EstaneTt Dry Wet 0,30 0.09 Kinetic Coefficient of Friction of Untreated Estane T M on polytetrafluoroethylene (PTFE) Dry Wet 0.27 0.17 Kinetic Coefficient of Friction of Crosslinked PVP- Coated EstaneTM on PTFE Dry Wet 0.20 0.10 Kinetic Coefficient of Friction of Untreated EstaneTM on polyvinyl chloride (PVC) Dry Wet 0.55 0.39 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 WO 89/09246 PCT/US89/00720 16 Kinetic Coefficient of Friction of Crosslinked PVP- Coated Estane

T

m on PVC Dry Wet 0.22 0.10 PVP Crosslinked With t-Butyl Peroctoate The coating solution consisted of 3 g of PVP (MW 360,000), 2 g of t-butylperoctoate, and 95 g of methylene chloride. A stainless steel sheet and Mylar T M 500D polyester film were coated with the solution using a 10 mil (0.254 mm) doctor knife.

After air drying, the coatings were cured at 100- 15 O110 0 C for one hour. Their slippery nature persisted undiminished for at least seven days in water at 370C Crosslinked Coatinas Of Polyvinylpyrrolidone (PVP) On Lycra T M Film A. Lycra T m 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 2) 3 g of PVP, 2 g of benzoyl peroxide, 95 g of methylene chloride 3) 3 g of PVP, 3 g of benzoyl peroxide, 94 g of methylene chloride.

After the solvent had evaporated, the coated Lycra

T

M was cured at 110 0 C for one hour. All three films were slippery in water for at least one day.

B. A balloon made of the same Lycra T M was rE WO 89/09246 PCT/US89/00720 17 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.

Effect of Usingr Too Much Peroxide A. Solutions containing 3% PVP in methylene chloride with: 1) 1% benzoyl peroxide, and 2) 3% 1 0 benzoyl peroxide were coated onto Mylar

T

I 5000 film, air dried, and cured at 110 0 C for 1 hour. Solution 1 gave a slippery film in water, but Solution 2 did not give a slippery surface in water, B. Solution 2 did not give a slippery film in water on aluminum foil or stainless steel.

Too much crosslinking gives a non-slippery surface.

EXMLE2 Catheter tubes made of polyurethane filled with 30 wt. BaSO 4 1 wt. titanium dioxide and wt. green pigment were coated by dipping for seconds into a solution consisting of 1 g of benzoyl peroxide, 3 g of PVP (MW 360,000] and 96 g of methylene ohloride. After cIry,"ng under nitrogen overnight, the tubes were heated one hour in air at 110'C, then washed in water at 37 0 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.

drying, for example, air drying, the coated surface; and crosslinking the hydrophilic polymer of the dried coated surface, as further described below.

V

WO 8909246PCT/US89/00720 18 Kinetic Coefficient of Friction Dry Wet [Average of 5 samples] 0.22 0.03 EXAMPLE 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. Mylarm, Estane Tm and aluminum foil were coated with the above solutions. 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 1 5 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 rcesults.

EXAMPLE 11 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 of f. After air drying, the films were cured by heating at 100 0 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.

substrates are exemplifitd herein. Stated more generally, an effective amount of initiator is employed, "effective amount" being that amount which provides the requisite crosslinking of crosslinkable i PCT/US89/0072 0 wo 89/09246 19 EXAMPLE 12 The coating solution consisted of 3 g of poly-(methylvinyl ether), 0.5 g of benzoyl peroxide, and 96.5 g of toluene. Estane T M 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 l00 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.

consisting of 3 wt. of PVP (MW 360,0001 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.

EXAMALE 14 A MylarT m film coated with crosslinked PVP i poly(N-vinyl-3-pyrrolidone); substituted poly(Nvinyl-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 -0C 2

H

5 poly(N-vinyl-2-piperidone); poly(N- 1 l l 1 WO 89/09246 PCT/US89/00720 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 A solution containing 3% PVP (molecular weight 360,000) and 2% of benzoyl peroxide in methylene chloride was prepared. Two samples of 1 0 silicone tubing, one untreated and other plasma treated, were dipped into the above solution for sec. The tubes were purged with nitrogen and then allowed to air dry for 3 days. The coating was then crosslinked by heating at '0 deg. for 70 min.

1 5 After two hours in a 38 deg. agitated water bath, both silicone tubing samples were slippery when wet.

EXAMPLE 16 Using the same procedure as Example strips of "Delrin" 100ST acetal resin (available from E. I. du Pont de Nemours) were dipped into the PVP solution. After air drying, the strips were heated 110 deg. for 70 min. After 2 hr, in a 38 deg. agitated water bath the surfaces were still slippery.

ZXAMPLE 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.

WO 89/09246 PCT/US89/00720 21 EXAMPLE 18 Using the procedure of Example 15, pieces of "Kalrez" perfluoroelastomer (available from E. I. du Pont de Nemours) were treated with the PVP solution for 5 min. After air drying overnight the pieces were heated at 100 deg. for 70 min. After immersion in a 38 deg. agitated water bath for 2 hr., the pieces were slippery.

EXMPLE 19 Using the same procedure as Example pieces of "Rynite" 530-NC-10 polyester engineering thermoplastic were immersed in the PVP solution for about 4 min. "Rynite" 530-NC-10 (available from E. I. du Pont de Nemours) is poly(ethylene terephthalate) containing 30% by weight glass fiber, After air drying 3 days, the pieces were heated at 100 deg, for 70 min. T.he resulting pieces were very slippery after wetting with distilled water.

COMPARATIVE EXPERIMENT 1 PVP [20% aqueous solution] was poured into Petri dishes, placed in polyethylene bags, and purged with nitrogen. The sealed bags were passed under an electron beam. After 1 megarad exposure, the viscosity increased; after 2 megarad exposure, the solution was a gel. The gels receiving 2, 5, or 20 megarads were strongly adhesive; even wet fingers stick strongly to them. This is in contrast to films that have been crosslinked in a dry state which are very slippery when wet. A catheter coated with PVP crosslinked in the presence of water would be so adhesive it could not be inserted into the body, WO 89/09246 PCT/US89/00720 22 COMPARATIVE EXPERIMENT 2 Ir, this experiment, 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 following two solutions were combined: 1. 2 g of PVP [MW 360,000] in 13 mL of DMF 2. 2 g of Texin T m 480 [polyurethane] in 13 mL of DMF 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 0 C, and a 118% weight gain after 72 hours, When dried, the film had lost 3% of its weight due to the PVP that had been extracted.

The results of this experiment show that the amount of swelling which will be realized may have to be taken into consideration when selecting the hydrophilic polymer for certain applications.

COMPARATIVE EXPERIMENT 3 The following experiment shows the importance of crosslinkinq the PVP, and the absence of durability in a coating which is comprised of uncrosslinked PVP.

3 0 POlyurethane film was coated with 3 3 wt. solution of PVP [MW 360,000] in methylene chloride. The film was dried at 25 0 C for 24 hours, then at IO0OC for one hour, The surface of the coated material when in I- WO 89/09246 PCT/US89/00720 23 contact with water exhibited a low coefficient of friction. However, when the film was immersed in water at 37 0 C, the low coefficient of friction was lost in about one hour, demonstrating the nondurability of non-crosslinked polymer.

Claims (25)

1. Solid shaped structure having a surface coated with crosslinked hydrophilic polymer, the coating being durable as hereinbefore defined and exhibiting a coefficient of friction when wet that is lower than the coefficient of friction of the uncoated shaped structure when wet.
2. Solid shaped structure of Claim 1 wherein the crosslinked polymer is selected from poly(N-vinyl-3- pyrrolidone); substituted poly-(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- 15 piperidone); 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 -CH 3 -C 2 H 5 -OCH 3 and -OC 2 H 5 poly(methylvinyl ether); polyacrylic acid; polymethacrylic acid; 20 polyethylene oxide; partially esterified polymethacrylic acid; polymeth-acrylamide; partially esterified polyacrylic acid; polyacrylamide; methyl cellulose; poly(2-hydroxyethyl methacrylate); and mixtures thereof.
3. The structure of Claim 1 wherein the Ir sslinked hydrophilic polymer is blended with a nonhydrophilic polymer prior to coating.
4. Shaped structure of Claim 1 wherein the polymer is poly(N-vinyl-2-pyrrolidone). Shaped structure of Claim I in the form of a tube.
6. Shaped structure of Claim 1 in the form of a fiber.
7. Shaped structure of Claim i in the form of a containment vessel.
8. Shaped structure of Claim 1 in the form of a film.
9. Shaped structure of Claim 1 comprising an organic substrate coated with crosslinked hydrophilic polymer. i 25 Shaped structure of Claim 1 comprising an inorganic substrate coated with crosslinked hydrophilic polymer.
11. Shaped structure of Claim 9 wherein the organic substrate is polymeric.
12. Shaped structure of Claim 9 wherein the organic substrate is a polyurethane.
13. Shaped structure of Claim 10 wherein the inorganic substrate is a metal.
14. Shaped structure of Claim 13 wherein the metal is aluminum. Shaped structure of Claim 13 wherein the metal is stainless fteel.
16. The structure of Claim 3 wherein the hydrophilic 15 polymer is the major portion of the blend. 17, The structure of Claim 16 wherein the nonhydrophilic p .ymer is polyurethane.
18. Shaped structure of Claim 9 wherein the organic substrate is a perfluoropolymer. 20 19. Shaped substrate of Claim 9 wherein the organic substrate is a fluoropolymer. shaped structure of Claim 9 wherein the organic substrate is a polyacetal.
21. Process of adherably coating a surface of a solid 25 shaped structure with a crosslinkable hydrophilic polymer, i said process comprising: contacti.ng said srface with a solution containing at least 0.1 weight of uncrosslinked hydrophilic polymer and a free radical initiator selected from peroxides and ultraviolet (UV) light- activated free radical initiators; drying the resulting hydrophilic polymer- coated solid surface; and crosslinking the polymeric coating by the application of heat or UV radiation,
22. Process of Cla r 21 wherein the crosslinkable v. Wvv ILU/ ±it- viy.ar*" riLm was rinsed, dried, placed in a polyethylene bag, and cooled to OoC. The film was quickly removed from the L 26 hydrophilic polymer is selected from poly(N-vinyl-2- pyrrolidone); poly(N-vinyl-3-pyrrolidone); substituted poly(N-vinyl-2- ard 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-piperidone); 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 -CH 3 -C 2 H 5 poly(methylvinyl ether); polyacrylic acid; polymethacrylic acid; polyethylene oxide; partially esterified polymethacrylic acid; polymethacrylamide; partially esterified polyacrylic acid; polyacrylamide; 15 methylcellulose; poly(2-hydroxyethyl methacrylate); and mixtures thereof.
23. Process of Claim 21 wherein the crosslinkable hydrophilic polymer is in solution, and the resulting coated surface is dried to remove the solution solvent. 20 24. Process of adherably coating a surface of a solid shaped structure with a crosslinkable hydrophilic polymer, said process comprising: contacting said surface with a solution containing at least 0.1 weight of uncrosslinked hydrophilic polymer; I I I I *1 I *r I.1 drying the resulting hydrophilic polymer- coated solid surface; and crosslinking the polymeric coating by the application of electron beam radiation of 1 to 20 megarads or corona discharge. Process of Claim 24 wherein the crosslinking is effected in an inert atmosphere.
26. Process of Claim 25 wherein the inert atmosphere is selected from nitrogen, argon, helium and carbon dioxide.
27. Process of Claim 24 wherein the crosslinking is effected in air. f~,fj C WO 89/09246 PCT/US89/00720 27
28. Process of Claim 23 wherein the solution of crosslinkable hydrophilic polymer includes an effective amount of a free radical initiator selected from thermally-activated and ultraviolet light-activated free radical initiators.
29. Process of Claim 28 wherein the ratio of the number of moles of initiator per gram of polymer is within the range 0.0002 to less than 0.0040. Process of Claim 28 wherein the thermallyradical initiator is a peroxide,
31. Process of Claim 28 wherein the initiator is a thermally-activated free radical initiator and crosslinking is effected in an inert atmosphere by heating to decompose the free radical initiator.
32. Prcce.s of Claim 31 wherein the inert atmosphere is selected from nitrogen, argon, helium and carbon dioxide.
33. Process of Claim 28 wherein the crosslinkinig is effected in air,
314. Process of Claim 31 wherein the free radical initiator is selected from benzoyl peroxide, peracetic acid, perbenzoic acid, hydrogen peroxide, t-butylhydroperoxide, bis(4-t- butylcyclohexyl) peroxy-dicarbonate, t- butylperoxypivalate, t-butylperoctoate, diisopropylbenzene hydroperoxide, succinic acid peroxide, potassium persuifate and ammonium persulfate, Process of Claim 33 wherein the free Nadical initiator is selected from benzoy. peroxide, p4aracetic acid, perbenzoic acid, hydrogen peroxide, t- butylhydroperoxide, bis (4-t- butylcyclobexyl) peroxy-dicarbonate, butylperoxypivalate, t-butylperoctoate, Ohl I I Dry Wet 0.55 0.39 '1 WO 89/09246 PCT/US89/00720 28 diisopropylbenzene hydroperoxide, succinic acid peroxide, potassium persulfate and ammonium persulfate. 36. Process of Claim 28 wherein the free radical initiator is an ultraviolet light-activated initiator and crosslinking is effected by means of ultraviolet radiation which activates the free radical initiator. 37. Process of Claim 36 wherein the crosslinking is effected in an inert atmosphere. 38. Process of Claim 37 wherein the inert atmosphere is selected from nitrogen, argon, helium .and carbon dioxide. 39. Process of Claim 36 wherein the crosslinking is effected in air. Process of Claim 36 wherein the free radical initiator is benzoin or benzoin methyl ether, 41. Process of Claim 21 further comprising: contacting, for at least one second, a surface of a solid shaped structure with a solution containing: at least 0,1 wt. of a crosslinkable hydrophilic polymer; and a thermally-activated free radical initiator; or (ii) an ultraviolet light-activated free radical initiator; drying the coated surface; and crosslinking the hydrophilic polymer of the dried coated surface. I. INTERNATIONAL SEARCH REPORT International Application No PCT/US 89/00720 1. CLASSIFICATION OF SUBJECT MATTER (it veveral Ctassi11ficlstion Symbol$ Apply, Indicate 4ii)a According to International Potent Classification (IPC or to buth National Classiication and IPC IC4 1C 09 D 3/00; C 09 D 5/00; C 08 J 7/04; B 05 D 3/00; C-08 L 39/06 11. FIELDS SEARCHED Minimum Documentation Searched I Classification System IClaselialior, Symbols IPC 4 C 09 D; C 08 J; B 05 D Documentation S Iarc~1sd other than minimum Documentation to the Extent that auth 'Documents are Included In the Fields SearchedI Ill. DOCUMENTS CONSIDERED To BE RELEVANTII Category 'I Citation of Document, II with Indication. where appropriate, of the relevant psassages I Relevant to Claim No. ill X EP, A, 0093094 (ASTRA, MEDITEC AB) 1,2,3,5,9, 2 November 1983 11,12,16,17 see claims 1-10; page 2, line 15 21,22e23 page 6, line 2 Y 1-6,8-17, 21-23,28, 36,41 X DE, k, 2608827 (KONISEIROKU PHOTO 21-23,28-30, INDUSTRY CO. LTD) 36,39 23 September 1976 see claims; page 7, line 1 page 8, line 1; page 11, line 1.9 page 12, line I Y US, A, 3892575 WATTS et al.)1-8-7 1 July 1975 21-23,28, see claims 1-4; column 1, line 30 36,41 column 2, line 56; column 3, line 44- column 5, line 2; column 6, lines 14-26; example 7 3 peclil categories of cited documents: If "T later document published after the international filung date A" dcumnt efiingthe eneal tat oft~, rt hic Ianotor priority dais and not in conflict with the application but cA oncmetdon to e b ealsae of paricla relevances no cited to understand the principle or theory underlying the consdere tobe o paticuar elevnceInvention earlier document but published on or after the international x" document of particular relevance: the claimed Invention filing dale cannot be considered novel of cannot be considered to document which may throw doubts on priority claimws or Involve an Inventive step which Is cited to establish the publication date of another 1y" document of particular raloeancei'the claimed invention citation or other special reason (as specified) cannot be considered to Involve an Inventive step whon the document referring to an oral disclosure, use, exhtibition or document Is combined with one or more other such docu. other means ments. such combination being obvious to a parson skilled *1P'1 document Pubiished prior to the International filing dteo but in the art. later than the Priority date ci~med WA decumerit member of the same patent family IV. CERTIFICATION Date of the Actusl Completion of the International Search Date of Mailting of this Initernational search Report 8th June 1989 1 U, 11 International Searching Authority Sign cot EUROPEAN PATENqT OFFICE E RUN Form PCT/ISA 1210 (second sheeit) IJanuary INS) ~Y7 2, International Application No, PCT/ US 89 /00720 Ill. DOCUMENTS CONSIDERED To 31 RELEVANT (COWFI~fuEi) FROM THE SECOND SHEET) Category Citation of Document, with Indication, wflwe appropriatoi 0f the relevant pssages Relevant to Claim No US, A, 4589873 SCHWARTZ et al.) May 1986 see claims 1-5,8,9, 11 r 2,18, 19,21,22, 23 Form PCT ISA'210 (astra *hest) (January Iiffl) EXAPLE14 A MylarTM film coated with crosslinked PVP p.- ANNEX TO THE INTERNATIONAL SEARCH REPORT ON INTERNATIONAL PATENT APPLICATION NO. US 8900720 SA 27375 T"his annex lists the patent family members relating to th,, patent documents cited in the above-mentioned international search report. The members are as contained in the European Patent 0tigce EDP ile on 23/06/89 The European Patent Office is in no way liable for thcse particulars which are merely given for the purpose of information. Patent document Publication Patent family Publication cited in search report date member(s) -Tdate EP-A- 0093094 02-11-83 SE-B- 430696 05-12-83 AU-B- 556350 30-10-86 AU-A- 1326683 27-10-83 CA-A- 1215598 23-12-86 GB-A,B 2119283 16-11-83 JP-A- 58193766 11-11-83 SE-A- 8202524 23-10-83 US-A- 4459317 10-07-84 US-A- 4487808 11-12-84 OE-A- 2608827 23-09-76 JP-A- 51101077 07-09-76 GB-A- 1549317 01-08-79 US-A- 4051302 27-09-77 US-A- 3892575 01-07-75 GB-A- 1420064 07-01-76 US-A- 4589873 20-05-86 None CI Q For more details about this anlieg see Official Journal of the European Patent Office, No. 12/82
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US3892575A (en) * 1971-12-13 1975-07-01 Minnesota Mining & Mfg Method of modifying the surface properties of a substrate
US4051302A (en) * 1975-03-04 1977-09-27 Konishiroku Photo Industry Co., Ltd. Method of improving adhesive property of plastic supports
AU604883B2 (en) * 1987-05-06 1991-01-03 Wilkinson Sword Gesellschaft Mit Beschrankter Haftung Process to produce a hydrophilic coating on a moulded part and shaver manufactured by using the process

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU655589B2 (en) * 1990-06-15 1995-01-05 Meadox Medicals, Inc. A method of providing a medical instrument with a hydrophilic, low-friction coating and medical instrument having such a coating

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IL89694D0 (en) 1989-09-28
EP0418247A1 (en) 1991-03-27
JPH03503379A (en) 1991-08-01
AU3219889A (en) 1989-10-16
IL89694A (en) 1992-12-01
DK228690D0 (en) 1990-09-21
WO1989009246A1 (en) 1989-10-05
DK228690A (en) 1990-09-21

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