WO1992019289A1 - Treatment of polyurethane surfaces - Google Patents

Treatment of polyurethane surfaces Download PDF

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Publication number
WO1992019289A1
WO1992019289A1 PCT/EP1992/000918 EP9200918W WO9219289A1 WO 1992019289 A1 WO1992019289 A1 WO 1992019289A1 EP 9200918 W EP9200918 W EP 9200918W WO 9219289 A1 WO9219289 A1 WO 9219289A1
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Prior art keywords
polymethacrylamide
article according
polyacrylamide
polyurethane
poly
Prior art date
Application number
PCT/EP1992/000918
Other languages
French (fr)
Inventor
Ian Philip Middleton
Ian Michael Harrison
Dennis Keith Gilding
Original Assignee
Polymedica Industries, Inc.
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Publication date
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Publication of WO1992019289A1 publication Critical patent/WO1992019289A1/en

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Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
    • C08G18/6266—Polymers of amides or imides from alpha-beta ethylenically unsaturated carboxylic acids
    • 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
    • C08J7/046—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
    • C08J7/056—Forming hydrophilic 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
    • C08J7/12—Chemical modification
    • 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
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers

Definitions

  • the present invention relates to an article having a polyurethane surface which has been rendered hydrophilic as well as to a method of rendering a polyurethane surface hydrophilic.
  • Articles having a polyurethane surface which has been rendered hydrophilic are useful in a number of applications.
  • various devices are used for insertion into the human body, e.g. catheters (such as urinary catheters, cardiovascular catheters, and radiological catheters), and anaesthia tubes (e.g. endotrachial tubes).
  • catheters such as urinary catheters, cardiovascular catheters, and radiological catheters
  • anaesthia tubes e.g. endotrachial tubes.
  • Such devices may be manufactured (over at least that part of their length which is inserted in the body) either of polyurethane or with a polyurethane coating and it is desirable that the polyurethane has a low coefficient of friction when in contact with aqueous body fluids. In other words, the wetted surface should feel "slippery" so that insertion of the device into the body is facilitated.
  • an article having a polyurethane surface provided with a coating of hydrophilic polyacrylamide or polymethacrylamide (other than poly(N-(monohydroxy)propyl methacrylamide) bonded to the polyurethane by residues of a compound having a first functional group reactive with the polyurethane and a second functional group reactive with the polyacrylamide or polymethacrylamide.
  • a method of rendering a polyurethane surface hydrophilic comprising treating the surface with a compound having first and second functional groups as defined in the preceding paragraph and with a hydrophilic polyacrylamide or polymethacrylamide (other than poly(N-(monohydroxy)propyl methacrylamide) whereby the latter is bonded to said surface by residues of said compound so as to provide a coating on the surface.
  • (N-(monohydroxy)propyl methacrylamide ) is intended to cover the compound having a propyl group which group has a hydroxy group as the sole substituent, which hydroxy group may be at the 1-, 2-, or 3- position.
  • poly(meth)acrylamide will be used herein as meaning either a polyacrylamide or polymethacrylamide.
  • poly(meth)acrylamide is also to be understood as covering homopoiymers of an acrylamide or methacrylamide monomer as well as (i) copolymers of such monomers with a further acrylamide or methacrylamide (thus a copolymer of an acrylamide and methacrylamid is covered), and (ii) copolymers with at least one monomer ether than an acrylamide or methacrylamide.
  • the amount of "non-(meth)acrylamide" comonomer preferably does not exceed 50% by mole.
  • the preferred poly(meth)acrylamides are homopoiymers.
  • the (meth)acrylamide from which this poly(meth)acrylamide is preferred is preferably a N-hydroxyalkyl (meth)acrylamide (other than N-(mono hydroxy) propyl methacrylamide.
  • the alkyl group has 1 to 4 carbon atoms.
  • the alkyl group is preferably bended by a terminal carbon atom to the nitrogen atom. It is also preferred that only one such N-hydroxyalkyl group is provided in the molecule.
  • the N-hydroxyalkyl group may contain more than one hydroxy group.
  • hydrophilicity of the poly(N-hydroxyalkyl (meth)acrylamide) will depend on the number of carbon atoms in the alkyl group and the number of hydroxy substituents. It is thus possible to "tailor" the poly(meth)acrylamide to the particular application.
  • N-hydroxyalkyl (meth)acrylamide monomers which may be used include the hydroxymethyl, hydroxy ethyl. and trishydroxyethyl compounds. Other hydroxy substituted alkyl groups may be used.
  • (meth)acrylamide monomers which may be used for producing the hydrophilic polymers include amino and carboxyl analogs of the hydroxy compounds.
  • one suitable monomer is N- aminopropyl (meth)acrylamide.
  • the poly(meth)acrylamide provides a coating which is a "glassy material" when dry and a hydrogel when wetted with aqueous fluids.
  • the invention is thus applicable particularly to devices (e.g. catheters; which are for insertion in the human body. Upon wetting of such a catheter by aqueous body fluids, the poly(meth)acrylamice provides the necessary low-friction coating which facilitates insertion and withdrawal of the catheter and prevents damage from "rubbing" between the catheter and the body of the patient.
  • catheter to which the present invention is applicable is a Foley balloon catheter in which the elongate body of the catheter is of a polyurethane material and the inflatable sleeve or balloon is of a natural or synthetic rubber coated with a layer of a soft polyurethane.
  • Other catheters to which the present invention is applicable are cardiovascular catheters, and radiological catheters.
  • the invention is also applicable to anaesthia tubes (e.g. endotrachial tubes).
  • the poly(meth)acrylamide provides several advantages. In particular, the wetted poly(meth)acrylamide provides low friction for insertion and low mechanical trauma to biological tissue. Additional advantages are better blood, urine and tissue compatibility as well as reduction of infection rates.
  • the poly(me th)acrylamide has a molecular weight (M n ) of at least 20,000 daltons as measured by GPC using polystyrene standard calibration.
  • M n molecular weight
  • the poly(meth)acrylamide is a homopolymer although comonomers can be included, preferably in an amount less than 10% by mole, or preferably less than 2% by mole.
  • a preferred such comonomer is methacrylic acid.
  • the compound (hereinafter referred to as the bridging agent) used for bonding the poly(meth)acrylamide to the polyurethane surface is preferably a compound having two or more functional groups each of which is capable of reaction with the polyurethane and the poly(meth)acrylamide.
  • the bridging agent may be an aliphatic, alicyclic aromatic or alicyclic compound.
  • bridging agents are di - or higher functionality isocyanates.
  • Suitable isocyanates are aliphatic diisocyanates having 3 to 10 carbon atoms, more preferably 5 to 7 carbon atoms.
  • a preferred aliphatic diisocyanate is hexamethylene diisocyanate (HDI).
  • HDI hexamethylene diisocyanate
  • the preferred compound is pure MDI or HMDI.
  • bridging agents which may be used include diacid halides (particularly diacid chlorides, e.g. ⁇ iacipcyl chloride and phthaloyl dichloride).
  • diimidazoies e.g. carbonyl diimidazole
  • carbodiimides e.g dicyclohexyl carbodiimide.
  • a further compound which is useful is cyanogen bromide.
  • the poiy(methiacrylamide coating may be applied to the polyurethane surface in a number of ways, examples of which are given below.
  • a solution of the isocyanate (eg. MDI) and poly(meth)acrylamide is formulated in a suitable solvent.
  • concentration of the diisocyanate in the solution will be in the range 0.5-5% whereas the concentration of the poly(meth)acrylamide will generally be 1-5%.
  • Suitable solvents include dimethyl formamide (DMF) as well as mixtures of DMF with lower boiling solvents eg. tetrahydrofuran or methyl ethyl ketone.
  • DMAC, DMSO and NMP may also be used.
  • the polyurethane surface is dipped into the abovedescribed solution, typically for a time of less than 10 seconds. After this dipping process, the surface is "dried” to leave the surface coating of poly(meth)acrylamide bonded to the polyurethane. surface by isocyanate compound residues. Typically the drying condition includes IR drying (eg. 4-8 mins at 65-70°C) followed by drying (in a fan oven) for several hours at 50-70°C, (e.g. 3-8 hrs at 60°C).
  • the polyurethane surface is initially dipped into a solution of the isocyanate (the isocyanate solution) so that isocyanate compound residues become bonded to the polyurethane surface, followed by dipping into a solution of the poly(meth)acrylamide (the poly(meth)acrylamide solution), preferably containing a catalyst for forming polyurethanes.
  • the solvent for the isocyanate solution is preferably a halocarbon, preferably one containing chlorine and/or fluorine.
  • Preferred examples of such solvents are low boiling liquids such as methylene chloride, chloroform etc.
  • the concentration of the isocyanate is preferably 1-5%.
  • the dipping time of the polyurethane surface in the isocyanate solution is preferably less than 10 seconds.
  • the polyurethane surface is removed from the solution and the solvent is allowed to evaporate in air prior to the surface being dipped in the poly(meth)acrylamide solution containing a polyurethane formation catalyst.
  • a suitable concentration range for the poly(meth)acrylamide is 0.5-5% and the preferred solvent is a mixture of DMF (50-75%) and THF (25-50%).
  • Other solvents which can be used include DMAC, DMSO, and NMP.
  • the polyurethane formation catalyst is preferably used in an amount of 1 part of catalyst per 500-10000 parts of poly(meth)acrylamide.
  • the catalyst may for example be stannous octoate, stannous chloride, diethyl zinc, diphenyl zinc, and other common organometallic catalysts used in polyurethane formation reactions. This dipping process is preferably effected for less than 10 seconds.
  • the surface Upon removal of the polyurethane surface from the poly(meth)acrylamide solution, the surface is dried preferably at a temperature of 65-70°C for 8-12 minutes. Finally the surface is washed with water and dried in warm air.
  • the poly(meth)acrylamide coating may include an antimicrobial agent or a drug for delivery to the body of the patient, eg. copper or silver compounds, chlorhexidine or other antiseptic, or an antibiotic.

Abstract

The invention relates to an article having a polyurethane surface which has been rendered hydrophilic as well as to a method of rendering a polyurethane surface hydrophylic. According to the invention there is provided an article having a poyurethane surface provided with a coating of hydrophilic polyacrilamide or polymethacrylamide (other than poly(N-(mono hydroxy)propyl methacrylamide) bonded to the polyurethane by residues of a compound having a first functional group reactive with the polyurethane and a second functional group reactive with the polyacrylamide or polymethacrylamide.

Description

TREATMENT OF POLYURETHANE SURFACES
The present invention relates to an article having a polyurethane surface which has been rendered hydrophilic as well as to a method of rendering a polyurethane surface hydrophilic.
Articles having a polyurethane surface which has been rendered hydrophilic are useful in a number of applications. For example, in the medical field various devices are used for insertion into the human body, e.g. catheters (such as urinary catheters, cardiovascular catheters, and radiological catheters), and anaesthia tubes (e.g. endotrachial tubes). Such devices may be manufactured (over at least that part of their length which is inserted in the body) either of polyurethane or with a polyurethane coating and it is desirable that the polyurethane has a low coefficient of friction when in contact with aqueous body fluids. In other words, the wetted surface should feel "slippery" so that insertion of the device into the body is facilitated.
According to a first aspect of the present invention there is provided an article having a polyurethane surface provided with a coating of hydrophilic polyacrylamide or polymethacrylamide (other than poly(N-(monohydroxy)propyl methacrylamide) bonded to the polyurethane by residues of a compound having a first functional group reactive with the polyurethane and a second functional group reactive with the polyacrylamide or polymethacrylamide.
According to a second aspect of the present invention there is provided a method of rendering a polyurethane surface hydrophilic comprising treating the surface with a compound having first and second functional groups as defined in the preceding paragraph and with a hydrophilic polyacrylamide or polymethacrylamide (other than poly(N-(monohydroxy)propyl methacrylamide) whereby the latter is bonded to said surface by residues of said compound so as to provide a coating on the surface.
The term (N-(monohydroxy)propyl methacrylamide ) is intended to cover the compound having a propyl group which group has a hydroxy group as the sole substituent, which hydroxy group may be at the 1-, 2-, or 3- position.
For convenience the term poly(meth)acrylamide will be used herein as meaning either a polyacrylamide or polymethacrylamide. The term poly(meth)acrylamide is also to be understood as covering homopoiymers of an acrylamide or methacrylamide monomer as well as (i) copolymers of such monomers with a further acrylamide or methacrylamide (thus a copolymer of an acrylamide and methacrylamid is covered), and (ii) copolymers with at least one monomer ether than an acrylamide or methacrylamide. In such a copolymer (ii) the amount of "non-(meth)acrylamide" comonomer preferably does not exceed 50% by mole.
The preferred poly(meth)acrylamides are homopoiymers. The (meth)acrylamide from which this poly(meth)acrylamide is preferred is preferably a N-hydroxyalkyl (meth)acrylamide (other than N-(mono hydroxy) propyl methacrylamide. Preferably the alkyl group has 1 to 4 carbon atoms. The alkyl group is preferably bended by a terminal carbon atom to the nitrogen atom. It is also preferred that only one such N-hydroxyalkyl group is provided in the molecule. The N-hydroxyalkyl group may contain more than one hydroxy group. It will be appreciated that the hydrophilicity of the poly(N-hydroxyalkyl (meth)acrylamide) will depend on the number of carbon atoms in the alkyl group and the number of hydroxy substituents. It is thus possible to "tailor" the poly(meth)acrylamide to the particular application.
Examples of N-hydroxyalkyl (meth)acrylamide monomers which may be used include the hydroxymethyl, hydroxy ethyl. and trishydroxyethyl compounds. Other hydroxy substituted alkyl groups may be used.
Other (meth)acrylamide monomers which may be used for producing the hydrophilic polymers include amino and carboxyl analogs of the hydroxy compounds. For example, one suitable monomer is N- aminopropyl (meth)acrylamide.
The poly(meth)acrylamide provides a coating which is a "glassy material" when dry and a hydrogel when wetted with aqueous fluids. The invention is thus applicable particularly to devices (e.g. catheters; which are for insertion in the human body. Upon wetting of such a catheter by aqueous body fluids, the poly(meth)acrylamice provides the necessary low-friction coating which facilitates insertion and withdrawal of the catheter and prevents damage from "rubbing" between the catheter and the body of the patient. A particular example of catheter to which the present invention is applicable is a Foley balloon catheter in which the elongate body of the catheter is of a polyurethane material and the inflatable sleeve or balloon is of a natural or synthetic rubber coated with a layer of a soft polyurethane. Other catheters to which the present invention is applicable are cardiovascular catheters, and radiological catheters. The invention is also applicable to anaesthia tubes (e.g. endotrachial tubes). The poly(meth)acrylamide provides several advantages. In particular, the wetted poly(meth)acrylamide provides low friction for insertion and low mechanical trauma to biological tissue. Additional advantages are better blood, urine and tissue compatibility as well as reduction of infection rates.
Preferably the poly(me th)acrylamide has a molecular weight (Mn) of at least 20,000 daltons as measured by GPC using polystyrene standard calibration. The preferred Mn range is 50,000-150,000 daltons. Preferably the poly(meth)acrylamide is a homopolymer although comonomers can be included, preferably in an amount less than 10% by mole, or preferably less than 2% by mole. A preferred such comonomer is methacrylic acid.
The compound (hereinafter referred to as the bridging agent) used for bonding the poly(meth)acrylamide to the polyurethane surface is preferably a compound having two or more functional groups each of which is capable of reaction with the polyurethane and the poly(meth)acrylamide. The bridging agent may be an aliphatic, alicyclic aromatic or alicyclic compound.
Examples of bridging agents are di - or higher functionality isocyanates. Suitable isocyanates are aliphatic diisocyanates having 3 to 10 carbon atoms, more preferably 5 to 7 carbon atoms. A preferred aliphatic diisocyanate is hexamethylene diisocyanate (HDI). Of the aromatic diisocyanates which may be used, the preferred compound is pure MDI or HMDI.
The b o n ding o f a c o atin g o f p o ly( N - ( 2 -hydroxyethyl)methacrylamide (HEMA) to a polyurethane using a diisocyanate compound is illustrated somewhat schematically below.
Figure imgf000006_0001
Although the above illustration shows the isocyanate residues being bonded to the oxygen atom of the poly(meth)acrylamide, it is also possible it is bonded to a nitrogen atom.
Further examples of bridging agents which may be used include diacid halides (particularly diacid chlorides, e.g. άiacipcyl chloride and phthaloyl dichloride). diimidazoies (e.g. carbonyl diimidazole), carbodiimides (e.g dicyclohexyl carbodiimide. A further compound which is useful is cyanogen bromide.
The poiy(methiacrylamide coating may be applied to the polyurethane surface in a number of ways, examples of which are given below. In one method, a solution of the isocyanate (eg. MDI) and poly(meth)acrylamide is formulated in a suitable solvent. Typically the concentration of the diisocyanate in the solution will be in the range 0.5-5% whereas the concentration of the poly(meth)acrylamide will generally be 1-5%. Suitable solvents include dimethyl formamide (DMF) as well as mixtures of DMF with lower boiling solvents eg. tetrahydrofuran or methyl ethyl ketone. DMAC, DMSO and NMP may also be used.
The polyurethane surface is dipped into the abovedescribed solution, typically for a time of less than 10 seconds. After this dipping process, the surface is "dried" to leave the surface coating of poly(meth)acrylamide bonded to the polyurethane. surface by isocyanate compound residues. Typically the drying condition includes IR drying (eg. 4-8 mins at 65-70°C) followed by drying (in a fan oven) for several hours at 50-70°C, (e.g. 3-8 hrs at 60°C).
In an alternative method of applylng the poly(meth)acrylamide coating, the polyurethane surface is initially dipped into a solution of the isocyanate (the isocyanate solution) so that isocyanate compound residues become bonded to the polyurethane surface, followed by dipping into a solution of the poly(meth)acrylamide (the poly(meth)acrylamide solution), preferably containing a catalyst for forming polyurethanes.
The solvent for the isocyanate solution is preferably a halocarbon, preferably one containing chlorine and/or fluorine. Preferred examples of such solvents are low boiling liquids such as methylene chloride, chloroform etc.
The concentration of the isocyanate is preferably 1-5%. The dipping time of the polyurethane surface in the isocyanate solution is preferably less than 10 seconds.
After this dipping process, the polyurethane surface is removed from the solution and the solvent is allowed to evaporate in air prior to the surface being dipped in the poly(meth)acrylamide solution containing a polyurethane formation catalyst. A suitable concentration range for the poly(meth)acrylamide is 0.5-5% and the preferred solvent is a mixture of DMF (50-75%) and THF (25-50%). Other solvents which can be used include DMAC, DMSO, and NMP. The polyurethane formation catalyst is preferably used in an amount of 1 part of catalyst per 500-10000 parts of poly(meth)acrylamide. The catalyst may for example be stannous octoate, stannous chloride, diethyl zinc, diphenyl zinc, and other common organometallic catalysts used in polyurethane formation reactions. This dipping process is preferably effected for less than 10 seconds.
Upon removal of the polyurethane surface from the poly(meth)acrylamide solution, the surface is dried preferably at a temperature of 65-70°C for 8-12 minutes. Finally the surface is washed with water and dried in warm air.
As a result of the abovedescribed treatments, there is a surface of poly(meth)acrylamide covalently bonded to the polyurethane surface. This covalent bonding ensures that the poly(meth)acrylamide is firmly bonded to the polyurethane surface and so can repeatedly be made hydrophilic. When wet, the poiy(meth)acrylamide becomes a hydrogel and can expand with the balloon.
If desired, the poly(meth)acrylamide coating may include an antimicrobial agent or a drug for delivery to the body of the patient, eg. copper or silver compounds, chlorhexidine or other antiseptic, or an antibiotic.

Claims

Claims
1. Article having a polyurethane surface characterized in a coating of hydrophilic polyacrylamide or polymethacrylamide other than poly(N-(mono hydroxy) propyl methacrylamide) bonded to the polyurethane by residues of a compound having a first funcitonal group reactive with the polyurethane and a second functional group reactive with the polyacrylamide or polymethacrylamide.
2. Article according to claim 1 characterized in that the polyacrylamide or polymethacrylamide has a molecular weight (Mn) of at least 20,000 daltons.
3. Article according to claim 2 characterized in that the polyacrylamide or polymethacrylamide has a molecular weight (Mn) range of 50,000-150,000 daltons.
4. Article according to one of the claims 1-3 characterized in that the polyacrylamide or polymethacrylamide is a homopolymer.
5. Article according to claim 4 characterized in that
comonomers are included in an amount less than 50% by mole, preferably less than 10% by mole and more pre ferably less than 2% by mole.
6. Article according to claim 5 characterized in that the comonomer is methacrylic acid.
7. Article according to one of the claims 1-6 characterized in that the polyacrylamide or the polymethacrylamide is a poly(N-hydroxyalkyl acrylamide) or a poly(N-hydroxyalkyl methacrylamide) other than poly(N-(mono hydroxy) propyl methacrylamide), that the alkyl group preferably has 1 to 4 carbon atoms and that the alkyl group is preferably bonded by a terminal carbon atom to the nitrogen atom.
8. Article according to claim 7 characterized in that the N-hydroxy alkyl group contains more than one hydroxy group.
9. Article according to one of the claims 1-8 characterized in that the compound with said first and second functional groups has two or more functional groups each of which is capable of reaction with the polyurethane and the polyacrylamide or the polymethacrylamide and that this compound is an aliphatic, alicyclic aromatic or alicyclic compound.
10. Article according to claim 9 characterized in that the compound with said first and second functional groups is a di or higher functionality isocyanate, a diacid
halide, a diimidazole, a carbodiimide or cyanogen
bromide.
11. Article according to one of the claims 1-10 charac terized in that the polyacrylamide or polymethacrylamide coating includes an antimicrobial agent or a drug for delivery to the body of the patient.
12. Method of rendering a polyurethane surface hydrophilic characterized in that said surface is treated with a compound having first and second functional groups as definded in one of the preceding claims and with a hydrophilic polyacrylamide or polymethacrylamide other than poly (N-mono hydroxy)propyl methacrylamide) whereby the latter is bonded to said surface by residues of said compound so as to provide a coating on the surface.
13. Use of an article according to one of the claims 1-11 as catheter.
PCT/EP1992/000918 1991-04-25 1992-04-27 Treatment of polyurethane surfaces WO1992019289A1 (en)

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EP0611576A1 (en) * 1993-02-08 1994-08-24 Terumo Kabushiki Kaisha Medical tool having lubricious surface in a wetted state and method for production thereof
EP0892008A1 (en) * 1997-07-18 1999-01-20 Ucb, S.A. Coating composition for a plastic film
US5869127A (en) * 1995-02-22 1999-02-09 Boston Scientific Corporation Method of providing a substrate with a bio-active/biocompatible coating
US6179817B1 (en) 1995-02-22 2001-01-30 Boston Scientific Corporation Hybrid coating for medical devices
US6197051B1 (en) 1997-06-18 2001-03-06 Boston Scientific Corporation Polycarbonate-polyurethane dispersions for thromobo-resistant coatings
US6723121B1 (en) 1997-06-18 2004-04-20 Scimed Life Systems, Inc. Polycarbonate-polyurethane dispersions for thrombo-resistant coatings
US20130323291A1 (en) * 2012-05-31 2013-12-05 Biocoat Incorporated Hydrophilic and non-thrombogenic polymer for coating of medical devices
WO2018126796A1 (en) * 2017-01-05 2018-07-12 华南理工大学 Method for preparing anti-bacterial surface on medical material surface
US20180361031A1 (en) * 2015-06-15 2018-12-20 Rheinisch-Westfalische Technische Hochschule (Rwth) Aachen Method for Bonding a Polyurethane Polymer to a Substrate, in Particular for the Manufacturing of Stents
US11167064B2 (en) 2016-07-14 2021-11-09 Hollister Incorporated Hygienic medical devices having hydrophilic coating

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US5441488A (en) * 1993-02-08 1995-08-15 Terumo Kabushiki Kaisha Medical tool having lubricious surface in a wetted state and method for production thereof
EP0611576A1 (en) * 1993-02-08 1994-08-24 Terumo Kabushiki Kaisha Medical tool having lubricious surface in a wetted state and method for production thereof
US6099563A (en) * 1995-02-22 2000-08-08 Boston Scientific Corporation Substrates, particularly medical devices, provided with bio-active/biocompatible coatings
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US5869127A (en) * 1995-02-22 1999-02-09 Boston Scientific Corporation Method of providing a substrate with a bio-active/biocompatible coating
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US6197051B1 (en) 1997-06-18 2001-03-06 Boston Scientific Corporation Polycarbonate-polyurethane dispersions for thromobo-resistant coatings
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US20130323291A1 (en) * 2012-05-31 2013-12-05 Biocoat Incorporated Hydrophilic and non-thrombogenic polymer for coating of medical devices
US20180361031A1 (en) * 2015-06-15 2018-12-20 Rheinisch-Westfalische Technische Hochschule (Rwth) Aachen Method for Bonding a Polyurethane Polymer to a Substrate, in Particular for the Manufacturing of Stents
US11167064B2 (en) 2016-07-14 2021-11-09 Hollister Incorporated Hygienic medical devices having hydrophilic coating
WO2018126796A1 (en) * 2017-01-05 2018-07-12 华南理工大学 Method for preparing anti-bacterial surface on medical material surface
US11426496B2 (en) 2017-01-05 2022-08-30 South China University Of Technology Method for preparing anti-bacterial surface on medical material surface

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AU1650792A (en) 1992-12-21

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