EP1183282A1 - Procede de production de surfaces polymeres intrinsequement microbicides - Google Patents

Procede de production de surfaces polymeres intrinsequement microbicides

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Publication number
EP1183282A1
EP1183282A1 EP00922570A EP00922570A EP1183282A1 EP 1183282 A1 EP1183282 A1 EP 1183282A1 EP 00922570 A EP00922570 A EP 00922570A EP 00922570 A EP00922570 A EP 00922570A EP 1183282 A1 EP1183282 A1 EP 1183282A1
Authority
EP
European Patent Office
Prior art keywords
film
radiation
antimicrobial
substrate
minutes
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Withdrawn
Application number
EP00922570A
Other languages
German (de)
English (en)
Inventor
Peter Ottersbach
Friedrich Sosna
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Creavis Gesellschaft fuer Technologie und Innovation mbH
Original Assignee
Creavis Gesellschaft fuer Technologie und Innovation mbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Creavis Gesellschaft fuer Technologie und Innovation mbH filed Critical Creavis Gesellschaft fuer Technologie und Innovation mbH
Publication of EP1183282A1 publication Critical patent/EP1183282A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • C08J7/16—Chemical modification with polymerisable compounds
    • C08J7/18—Chemical modification with polymerisable compounds using wave energy or particle radiation
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
    • A01N25/10—Macromolecular compounds
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N33/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
    • A01N33/02—Amines; Quaternary ammonium compounds
    • A01N33/04—Nitrogen directly attached to aliphatic or cycloaliphatic carbon atoms
    • 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
    • A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/42—Use of materials characterised by their function or physical properties
    • A61L15/46—Deodorants or malodour counteractants, e.g. to inhibit the formation of ammonia or bacteria
    • 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
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L27/54—Biologically active materials, e.g. therapeutic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/60—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing nitrogen in addition to the carbonamido nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/04—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polycarbonamides, polyesteramides or polyimides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F291/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00
    • 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
    • A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/20—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing organic materials
    • A61L2300/204—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing organic materials with nitrogen-containing functional groups, e.g. aminoxides, nitriles, guanidines
    • 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
    • A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/40—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
    • A61L2300/404—Biocides, antimicrobial agents, antiseptic agents

Definitions

  • the invention relates to a process for the production of antimicrobial polymers by polymerizing amino-functionalized monomers and the use of the antimicrobial polymers thus produced
  • the invention further relates to a process for the production of antimicrobial polymers by graft polymerization of amino-functionalized monomers on a substrate and the use of the antimicrobial substrates thus produced
  • Bacteria must be kept away from all areas of life in which hygiene is important.This affects textiles for direct body contact, in particular for the genital area and for nursing and elderly care.In addition, bacteria must be kept away from furniture and device surfaces in care stations, particularly in the area of Intensive care and the care of small children, in hospitals, in particular in rooms for medical interventions and in isolation stations for critical infection cases and in toilets
  • Tert-butylaminoethyl methacrylate is a commercially available monomer of methacrylate chemistry and is used in particular as a hydrophilic component in copolymerizations.
  • EP-PS 0 290 676 describes the use of various polyacrylates and polymethacrylates as a matrix for the immobilization of bactericidal quaternary ammonium compounds
  • US Pat. No. 4,532,269 discloses a terpolymer of butyl methacrylate, tributyltin methacrylate and tert-butylaminoethyl methacrylate.
  • This polymer is used as an antimicrobial marine paint, the hydrophilic tert-butylaminoethyl methacrylate requiring the slow erosion of the polymer and thus the highly toxic tributyltin microbial methacrylate releases
  • the copolymer produced with aminomethacrylates is only a matrix or carrier substance for added microbicidal active ingredients which can diffuse or migrate from the carrier substance.
  • Polymers of this type lose their effect more or less quickly if the necessary “minimal inhibitory concentration” is found on the surface. (MIK) is no longer achieved
  • the present invention is therefore based on the object of developing novel, antimicrobial polymers which, if necessary, are intended as a coating to prevent the settling and spreading of bacteria on surfaces
  • the present invention relates to a process for the preparation of antimicrobial polymers, characterized in that aliphatically unsaturated monomers which are functionalized at least once by a primary amino group are polymerized.
  • the aliphatically unsaturated monomers functionalized at least simply by a primary amino group in the process according to the invention can have a hydrocarbon radical of up to 50, preferably up to 30, particularly preferably up to 22 carbon atoms.
  • the monomers can also be substituted by keto or aldehyde groups such as acryloyl or oxo groups or cyclic hydrocarbon groups such as substituted or unsubstituted phenyl or cyclohexyl groups.
  • the monomers used according to the invention should have a molar mass of less than 900, preferably less than 550 g / mol.
  • aliphatic unsaturated monomers of the general formula which are functionalized simply by a primary amino group are functionalized simply by a primary amino group
  • Ri branched, unbranched or cyclic, aliphatic unsaturated
  • Hydrocarbon radicals with up to 50 carbon atoms which can be substituted by O, N or S atoms, are used.
  • Suitable monomer building blocks are all aliphatic unsaturated monomers which have at least one primary amino function, such as, for example, l-amino-2-propene, N-6-aminohexyl-2- propenamide, N-3-aminopropyl methacrylamide hydrochloride, methacrylic acid-2-aminoethyl ester hydrochloride and 3-aminopropyl vinyl ether.
  • the process according to the invention can also be carried out by polymerizing the monomers which are functionalized at least once by a primary amino group on a substrate. A physisorbed coating of the antimicrobial copolymer is obtained on the substrate.
  • All polymeric plastics are suitable as substrate materials.
  • the method according to the invention can also be applied to surfaces of lacquered or otherwise plastic, metal, glass or wooden bodies.
  • the antimicrobial polymers can be obtained by graft-polymerizing a substrate with an aliphatic unsaturated monomer which is functionalized at least simply by a primary amino group.
  • the grafting of the substrate enables the antimicrobial polymer to be covalently bound to the substrate.
  • All polymeric materials, such as the plastics already mentioned, can be used as substrates.
  • the surfaces of the substrates can be modified a number of times before the graft copolymerization
  • Methods are activated. All standard methods for activating polymer surfaces can be used here; For example, the activation of the substrate before the graft polymerization by UV radiation, plasma treatment, corona treatment, flame treatment, ozonization, electrical discharge of the ⁇ radiation, methods used.
  • the surfaces are expediently removed beforehand in a known manner by means of a solvent
  • the substrates can be activated by UV radiation in the wavelength range 170-400 nm, preferably 170-250 nm.
  • a suitable radiation source is, for example, a UV excimer device HERAEUS Noblelight, Hanau, Germany.
  • mercury vapor lamps are also suitable for substrate activation if they are emit significant amounts of radiation in the areas mentioned
  • the exposure time is generally 0 1 seconds to 20 minutes, preferably 1 second to 10 minutes
  • the activation of the standard polymers with UV radiation can also be carried out with an additional photosensitizer.
  • the photosensitizer such as benzophenone
  • the substrate surface is irradiated. This can also be done with a mercury vapor lamp with exposure times of 0.1 seconds to 20 minutes, preferably 1 second up to 10 minutes
  • the activation can also be achieved by plasma treatment using an RF or microwave plasma (Hexagon, Fa Technics Plasma, 85551 Kirchheim, Germany) in air, nitrogen or argon atmosphere.
  • the exposure times are generally 2 seconds to 30 minutes, preferably 5 seconds up to 10 minutes
  • the energy input for laboratory devices is between 100 and 500 W, preferably between 200 and 300 W.
  • Corona devices SOFTAL, Hamburg, Germany
  • the exposure times in this case are generally 1 to 10 minutes, preferably 1 to 60 seconds
  • Activation by electrical discharge, electron or ⁇ -rays (e.g. from a cobalt 60 source) and ozonization enable short exposure times, which are generally 0 1 to 60 seconds
  • Flaming substrate surfaces also leads to their activation.
  • Suitable devices especially those with a barrier flame front, can be easily built or, for example, obtained from ARCOTEC, 71297 Monsheim, Germany. They can be operated with hydrocarbons or hydrogen as fuel gas In In any case, damaging overheating of the substrate must be avoided, which is easily achieved by intimate contact with a cooled metal surface on the surface of the substrate facing away from the flame side.
  • Activation by flame treatment is accordingly limited to relatively thin, flat substrates.
  • the exposure times are generally 0 1 second to 1 minute, preferably 0 5 to 2 seconds, all of which are non-luminous flames and the distances between the substrate surfaces and the outer flame front are 0 2 to 5 cm, preferably 0 5 to 2 cm
  • the substrate surfaces activated in this way are produced using known methods, such as dipping,
  • solvents Water and water-ethanol mixtures have been used as solvents, but other solvents can also be used, provided that they have sufficient bulk for the monomers and wet the substrate surfaces well.
  • Other solvents are, for example, ethanol, methanol, methyl ethyl ketone, diethyl ether, dioxane, hexane, Heptane, benzene, toluene, chloroform, dichloromethane, tetrahydrofuran and acetonitrile. Solutions with monomer contents of 1 to 10% by weight, for example about 5% by weight, have been found to be effective in practice and generally give coherent coatings covering the substrate surface in one pass with layer thicknesses that can be more than 0 1 ⁇ m
  • the graft copolymerization of the monomers applied to the activated surfaces can expediently be initiated by radiation in the short-wave segment of the visible region or in the long-wave segment of the UV region of the electromagnetic radiation.
  • radiation from a UV excimer of the wavelengths 250 to 500 nm is very suitable. preferably from 290 to 320 nm
  • mercury vapor lamps are suitable, provided they emit considerable amounts of radiation in the areas mentioned.
  • the exposure times are generally 10 seconds to 30 minutes, preferably 2 to 15 minutes
  • a graft copolymerization can also be achieved by a process which is described in the European patent application 0 872 512 and is based on a graft polymerization of swollen monomer and initiator molecules
  • further aliphatic unsaturated monomers can be used, in addition to the monomers functionalized by a primary amino group.
  • an aliphatic unsaturated monomer functionalized at least simply by a primary amino group with acrylates or methacrylates for example acrylic acid, tert-butyl methacrylate or methyl methacrylate, can be used as the monomer mixture.
  • acrylates or methacrylates for example acrylic acid, tert-butyl methacrylate or methyl methacrylate
  • Styrene, vinyl chloride, vinyl ether, acrylamides, acrylonitriles, olefins (ethylene, propylene, butylene, isobutylene), allyl compounds, vinyl ketones, vinyl acetic acid, vinyl acetate or vinyl esters can be used
  • the antimicrobial polymers made from aliphatic unsaturated monomers, which are functionalized at least simply by a primary amino group, produced by the process according to the invention show a microbicidal or antimicrobial behavior even without grafting onto a substrate surface
  • customary free-radical initiators can be added.
  • the initiators are azonitriles, alkyl peroxides, hydroperoxides, acyl peroxides, peroxoketones, peresters, peroxocarbonates, peroxodisulfate, persulfate and all customary photoinitiators such as acetophenones, ⁇ -Hydroxyketone, Dimethylketale and and use benzophenone
  • the polymerization can also be initiated thermally or, as already stated, by electromagnetic radiation, such as UV light or ⁇ -radiation
  • the present invention furthermore relates to the use of the antimicrobial polymers produced according to the invention for the production of antimicrobially active products and the products thus produced as such.
  • the products may contain or consist of modified polymer substrates according to the invention.
  • modified polymer substrates according to the invention are preferably based on polyamides, polyurethanes, polyether block amides, Polyester amides or imides, PVC, polyolefms, silicones, polysiloxanes, polymethacrylate or polyterephthalates, which have surfaces modified with the polymers produced according to the invention
  • Antimicrobial products of this type are, for example, and in particular machine parts for food processing, components of air conditioning systems, roofing, bathroom and toilet articles, cake articles, components of sanitary facilities, components of animal cages and dwellings, toys, components in water systems, food packaging, operating elements (touch panel ) of devices and contact lenses
  • the present invention also relates to the use of the polymer substrates modified on the surface with the antimicrobial polymers produced according to the invention for the production of hygiene products or medical articles.
  • hygiene products are, for example, toothbrushes, toilet seats, combs and packaging materials also other objects that may come into contact with many people, such as a telephone receiver, handrails of stairs, door and window handles, and holding straps and handles in public transport.
  • Medical technology items include catheters, tubes, cover foils, and surgical cutlery
  • copolymers or graft copolymers produced according to the invention can be used wherever bacteria-free, ie microbicidal surfaces or surfaces with non-stick properties are important.
  • examples of uses for the copolymers or graft polymers produced according to the invention are, in particular, paints, protective coatings or coatings in the following areas
  • Heat exchangers bioreactors, membranes, medical technology, contact lenses, diapers, membranes, implants, utensils, car seats, clothing (stockings, sportswear), hospital facilities, door handles, telephone receivers, public transport, animal cages, cash registers, carpets, wallpapers
  • a polyamide 12 film is exposed for 2 minutes at a pressure of 1 mbar to 172 nm radiation from an excimer radiation source from Heraeus.
  • the film activated in this way is placed in an irradiation reactor under protective gas and fixed thereupon the film is countercurrently flowed with 20 ml of a mixture of 3 g of 3-aminopropyl vinyl ether (from Aldrich) and 97 g of methanol are coated.
  • the radiation chamber is closed and placed at a distance of 10 cm under an excimer radiation unit from Heraeus, which has an emission of the wavelength 308 nm.
  • the radiation is started, the exposure time is 15 minutes
  • the film is then removed and rinsed with 30 ml of methanol.
  • the film is then dried in vacuo for 12 hours at 50 ° C.
  • the film is then extracted 5 times for 6 hours at 30 ° C., then dried at 50 ° C. for 12 hours
  • a coated piece of film from Example 1 (5 ⁇ 4 cm) is placed in 30 ml of a test microbial suspension of Staphylococcus aureus and shaken. After a contact time of 15 minutes, 1 ml of the test microbial suspension is removed, and the number of bacteria in the test batch is determined more detectable from Staphylococcus aureus
  • a coated piece of film from Example 1 (5 ⁇ 4 cm) is placed in 30 ml of a test microbial suspension of Pseudomonas aeruginosa and shaken. After a contact time of 60 minutes, 1 ml of the test microbial suspension is removed, and the number of bacteria in the test mixture is determined dropped from 10 7 to 10 3
  • a polyamide 12 film is exposed for 2 minutes at a pressure of 1 mbar to 172 nm radiation from an excimer radiation source from Heraeus.
  • the film activated in this way is placed in an irradiation reactor under protective gas and fixed thereupon the film is exposed to 20 ml of a mixture in a protective gas countercurrent 3 g of methacrylic acid-2-aminoethyl ester hydrochloride (Aldrich) and 97 g of methanol are coated.
  • the radiation chamber is closed and placed at a distance of 10 cm under an excimer radiation unit from Heraeus, which has an emission of 308 nm.
  • the radiation is started, the Exposure time is 15 minutes.
  • the film is then removed and unwound with 30 ml of methanol.
  • the film is then dried in vacuo at 50 ° C. for 12 hours.
  • the film is then extracted 5 times for 6 hours at 30 ° C., then at 50 ° C. 12 Hours dried
  • a coated piece of film from Example 2 (5 ⁇ 4 cm) is placed in 30 ml of a test microbial suspension of Staphylococcus aureus and shaken. After a contact time of 15 minutes, 1 ml of the test microbial suspension is removed, and the number of bacteria in the test batch is determined more detectable from Staphylococcus aureus
  • a coated piece of film from Example 2 (5 ⁇ 4 cm) is placed in 30 ml of a test microbial suspension of Pseudomonas aeruginosa and shaken. After a contact time of 60 minutes, 1 ml of the test microbial suspension is removed, and the number of bacteria in the test batch is determined dropped from 10 7 to 10 ⁇
  • a polyamide 12 film is exposed for 2 minutes at a pressure of 1 mbar to 172 nm radiation from an excimer radiation source from Heraeus.
  • the film activated in this way is placed in an irradiation reactor under protective gas and fixed thereupon the film is exposed to 20 ml of a mixture in a protective gas countercurrent 3 g of N-3-aminopropyl methacrylamide hydrochloride (from Polysciences Ine) and 97 g of methanol are coated.
  • the radiation chamber is closed and placed at a distance of 10 cm under an excimer radiation unit from Heraeus, which has an emission of the wavelength 308 nm.
  • the radiation is started, the exposure time is 15 minutes.
  • the film is then removed and unwound with 30 ml of methanol.
  • the film is then dried in vacuo for 12 hours at 50 ° C.
  • the film is then extracted 5 times for 6 hours at 30 ° C., then at 50 ° C. Dried for 12 hours
  • a coated piece of film from Example 3 (5 ⁇ 4 cm) is placed in 30 ml of a test microbial suspension of Staphylococcus aureus and shaken. After a contact time of 15 minutes, 1 ml of the test microbial suspension is removed, and the number of bacteria in the test mixture is determined more detectable from Staphylococcus aureus
  • a coated piece of film from Example 3 (5 ⁇ 4 cm) is placed in 30 ml of a test microbial suspension of Pseudomonas aeruginosa and shaken. After a contact time of 60 minutes, 1 ml of the test microbial suspension is removed, and the number of bacteria in the test mixture is determined dropped from 10 7 to 10
  • a polyamide 12 film is exposed for 2 minutes at a pressure of 1 mbar to 172 nm radiation from an excimer radiation source from Heraeus.
  • the film activated in this way is placed in an irradiation reactor under protective gas and fixed thereupon the film is exposed to 20 ml of a mixture in a protective gas countercurrent 3 g of 3-aminopropyl vinyl ether (from Aldrich), 2 g of methyl methacrylate (from Aldrich) and 95 g of methanol are covered.
  • the radiation chamber is closed and placed at a distance of 10 cm under an excimer radiation unit from Heraeus, which has an emission of the wavelength 308 nm
  • the irradiation is started, the exposure time is 15 minutes.
  • the film is then removed and unwound with 30 ml of methanol.
  • the film is then dried in vacuo at 50 ° C. for 12 hours.
  • the film is then extracted 5 times 6 hours at 30 ° C. in water. then dried at 50 ° C for 12 hours
  • a coated piece of film from example 4 (5 ⁇ 4 cm) is placed in 30 ml of a test germ suspension of Staphylococcus aureus and shaken. After a contact time of 15 minutes, 1 ml of the test germ suspension is removed, and the number of germs in the test mixture is determined. After this time there are no germs more detectable from Staphylococcus aureus
  • a coated piece of film from Example 4 (5 ⁇ 4 cm) is placed in 30 ml of a test germ suspension from Pseudomonas aeruginosa and shaken. After a contact time of 60 minutes, 1 ml of the test germ suspension is removed, and the number of bacteria in the test mixture is determined dropped from 10 7 to 10 4
  • a polyamide 12 film is exposed for 2 minutes at a pressure of 1 mbar to 172 nm radiation from an excimer radiation source from Heraeus.
  • the film activated in this way is placed in an irradiation reactor under protective gas and fixed thereupon the film is exposed to 20 ml of a mixture in a protective gas countercurrent 3 g of methacrylic acid-2-aminoethyl ester hydrochloride (Aldrich), 2 g of methyl methacrylate (Aldrich) and 95 g of methanol are coated.
  • the radiation chamber is closed and placed at a distance of 10 cm under an excimer radiation unit from Heraeus, which emits wavelength 308 nm.
  • the irradiation is started, the exposure time is 15 minutes.
  • the film is then removed and rinsed with 30 ml of methanol.
  • the film is then dried in vacuo for 12 hours at 50 ° C.
  • the film is then 5 times 6 hours at 30 ° C. in water extracted, then dried at 50 ° C for 12 hours
  • a coated piece of film from Example 5 (5 ⁇ 4 cm) is placed in 30 ml of a test microbial suspension of Staphylococcus aureus and shaken. After a contact time of 15 minutes, 1 ml of the test microbial suspension is removed, and the number of bacteria in the test batch is determined more detectable from Staphylococcus aureus
  • a coated piece of film from Example 5 (5 ⁇ 4 cm) is placed in 30 ml of a test germ suspension from Pseudomonas aeruginosa and shaken. After a contact time of 60 minutes, 1 ml of the test germ suspension is removed, and the number of bacteria in the test mixture is determined dropped from 10 7 to 10 4

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Toxicology (AREA)
  • Plant Pathology (AREA)
  • Wood Science & Technology (AREA)
  • Environmental Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • Zoology (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Epidemiology (AREA)
  • Dentistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Transplantation (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Dermatology (AREA)
  • Molecular Biology (AREA)
  • Biomedical Technology (AREA)
  • Hematology (AREA)
  • Materials Engineering (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

L'invention concerne un procédé de production de polymères antimicrobiens par polymérisation de monomères aliphatiquement insaturés qui sont fonctionnalisés au moins une fois par un groupe amino primaire. Les polymères antimicrobiens ainsi obtenus peuvent être utilisés comme revêtement microbicide, entre autres sur des articles d'hygiène ou dans le domaine médical, ainsi que dans des peintures et revêtements protecteurs.
EP00922570A 1999-05-12 2000-03-30 Procede de production de surfaces polymeres intrinsequement microbicides Withdrawn EP1183282A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19921898A DE19921898A1 (de) 1999-05-12 1999-05-12 Verfahren zur Herstellung inhärent mikrobizider Polymeroberflächen
DE19921898 1999-05-12
PCT/EP2000/002783 WO2000069925A1 (fr) 1999-05-12 2000-03-30 Procede de production de surfaces polymeres intrinsequement microbicides

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EP1183282A1 true EP1183282A1 (fr) 2002-03-06

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AU (1) AU7236200A (fr)
DE (1) DE19921898A1 (fr)
WO (1) WO2000069925A1 (fr)

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WO2006042161A2 (fr) 2004-10-07 2006-04-20 E.I. Dupont De Nemours And Company Adhesif tissulaire polymere a base de polysaccharide destine a un usage medical
JP5539725B2 (ja) 2006-11-27 2014-07-02 アクタマックス サージカル マテリアルズ リミテッド ライアビリティ カンパニー 分岐末端反応物及びそれから製造されるポリマーヒドロゲル組織接着剤
EP2214731B1 (fr) 2007-11-14 2014-05-14 Actamax Surgical Materials LLC Adhésif tissulaire polymère à base de polysaccharide cationique oxydé, à usage médical
DE102008005875A1 (de) 2008-01-24 2009-07-30 Georg-August-Universität Göttingen Stiftung Öffentlichen Rechts Verwendung von Polymeren mit Amino- bzw. Ammoniumgruppen zur Erhöhung der Dauerhaftigkeit von Holz gegenüber holzbesiedelnden Pilzen
US8551136B2 (en) 2008-07-17 2013-10-08 Actamax Surgical Materials, Llc High swell, long-lived hydrogel sealant
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US9044529B2 (en) 2008-11-19 2015-06-02 Actamax Surgical Materials, Llc Hydrogel tissue adhesive formed from aminated polysaccharide and aldehyde-functionalized multi-arm polyether
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AU7236200A (en) 2000-12-05
WO2000069925A1 (fr) 2000-11-23
DE19921898A1 (de) 2000-11-16

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